A METHOD FOB THE Identification of Pure Organic Compounds By a Systematic Analytical Procedure Based on Physical Properties and Chemical Reactions In Three Volumes. (Vols. I and III now ready.) By SAMUEL P. MULLIKEN, Ph.D. Associate Professor of Organic Chemical Research, Massachusetts Institute of Technology Vol. I contains Classified Descriptions of about 2300 of the more important Compounds of Carbon with Hydrogen and with Hydrogen and Oxygen. Large 8vo, xil+264 pages. Cloth, 84.50 net Vol. II, containing Classified Descriptions of the more Im- portant Compounds of Carbon with the Elements Nitrogen, Hydrogen, and Oxygen, Exclusive of the Dyestuffs. (Zn Prep- aration.' Vol. III. "Identification of the Commercial Dyestuffs," con- taining Classified Original Descriptions of most of the Com- mercially Important Synthetic and Natural Pure Dyestuffs used in the Arts, arranged for the use of Color Chemists, Dyers, and Analysts. Large 8vo, vi+274 pages. Cloth, 84.50 net A METHOD FOR THE IDENTIFICATION OF PURE ORGANIC COMPOUNDS BY A SYSTEMATIC ANALYTICAL PROCEDURE BASED ON PHYSICAL PROPERTIES AND CHEMICAL REACTIONS Vol. I CONTAINING CLASSIFIED DESCRIPTIONS OF ABOUT 2300 OF THE MORE IMPORTANT COMPOUNDS OF CARBON WITH HYDROGEN AND WITH HYDROGEN AND OXYGEN BY SAMUEL PARSONS MULLIKEN, Ph.D. Associate Professor of Organic Chemical Research at the Massachusetts Institute of Technology, Boston, Mass, FIRST EDITION THIRD THOUSAND NEW YORK JOHN WILEY & SONS, Inc. London : CHAPMAN & HALL, Limited Copyright, 1904, BY SAMUEL PARSONS MULLIKEN Entered at Stationers' Hall. PRESS OF BRAUNWORTH &. CO. BOOK MANUFACTURERS BROOKLYN, N. Y. PREFACE. At the time of writing the only general and fairly systematic procedure for the identification of previously described organic compounds of all classes is that which may be conveniently designated the Method of the Empirical Formula. In following this procedure a determination of the percentage composition is first made. The molecular weight is next determined or conjectured. From these data an empirical formula is calculated. The properties of the substance are then compared with those of all the known compounds possessing this formula by refer- ence to their scattered literature, for which Richter's " Lexicon der Kohlenstoff- Verbindungen " with its supplements now furnishes a very complete index. Resting, as it chiefly does, on the two fundamental properties, percentage composition and molecular weight-which alone among the chemical constants can be readily cal- culated for every compound in advance of its discovery-it is probable that this method will long remain the last resort in all earnest attempts to establish the identity of compounds which have been previously undescribed or very imper- fectly characterized through their physical and chemical properties. Nevertheless, when we turn to the great body of well-characterized compounds that occur with some frequency in the products of Nature, the useful arts, and the scientific labo- ratory, there is good reason to raise the question whether the Method of the Empir- ical Formula is from the practical standpoint a sufficiently satisfactory one. It is evidently not if any substitute can be found that will lead the analyst to the same results with less expenditure of time and effort, and without requiring unusual knowledge or skill on his part; and it is not to be denied that in these respects this method makes a very poor showing. The indispensable key to its use is pro- ficiency in ultimate organic analysis, whose difficult technique is fully mastered only by long practice. The performance of the combustions, which must be made in duplicate to secure certainty, is at best a time-consuming operation; and even after reliable results have been obtained, it is further necessary, in order to fully identify a compound, to resort to a study of its physical properties, chemical behavior, and perhaps to a molecular-weight determination. The consequence of this has been that the identification of organic compounds by this general method has been practi- cally limited to its occasional employment in laboratories devoted to synthetic organic research, and that such identifications when attempted elsewhere are usu- ally accomplished, often with uncertain results, by the use of disconnected desultory tests. Through these considerations, and with the belief that a path of less resist- ance could be broken out for the analyst, the writer began more than eight years ago the studies whose first results appear in this volume. III IV PREFACE. The present method, as contrasted with that just described, gives fuller recog- nition to the important truths that percentage composition and molecular weight are merely two among many highly significant characteristics of every compound; and that without recourse to them, by the use of the more easily determined prop- erties like qualitative elementary composition, color, melting-point, boiling-point, solubility, specific gravity, alkali neutralizing power, and chemical behavior under prescribed conditions, entirely satisfactory identifications may be made -provided a sufficient number of these facts which are at the disposal of the systematist are carefully verified and suitably coordinated in a classified system. The new method therefore rests, as will be more fully explained in the intro- ductory chapter, upon a classification designed to secure for the carbon compounds those advantages which have been already so long enjoyed in Botany and other branches of Natural History through the use of systematized descriptions of salient characteristics. The compounds, or chemical "species," have been first grouped into "orders" on the basis of their qualitative elementary composition; then into "genera" (aldehydes, acids, phenols, etc.), usually on the basis of behavior in simple chemical tests; and, finally, arranged within each genus according to the increasing value of some readily-determined constant like the melting-point or boiling-point. The name of each species is followed in the tables by a brief specific characterization enumerating some of the simpler properties of the substance that have genuine analytical significance, and then, whenever possible, by detailed directions for preliminary and corroborative chemical tests which can be performed with small quantities of material. The phrase "More Important Compounds" used in the title is unavoidably indefinite; but the intention has been to admit all substances to the tables for which there is more than a remote chance that they may come into the hands of the analyst as unknown compounds. Such a list naturally includes: first, all com- pounds that may be isolated in a state of purity and without excessive difficulty from materials used in the arts, or from substances which occur somewhat abun- dantly in Nature; second, compounds of minor importance which may easily be formed in the laboratory as by-products in reactions between substances of more common occurrence; third, many rare compounds which have acquired a general scientific interest either on account of their properties or as representatives of peculiar types. Very few compounds that could be purchased in the market in a state of purity have been omitted except through oversight. The most important intentional omissions are: substances whose claims to recognition as distinct chemical species are not generally accepted; uncrystallizable syrups that cannot be distilled without decomposition; the oily and fatty glycerides; those glucosides and synthetic sugars of which specimens could not be obtained for examination. The claims for admission to this volume of every compound of carbon with hydrogen, or with hydrogen and oxygen, that receives mention in the second edi- tion of Beilstein's great " Handbuch der organischen Chemie" and in its supple- ments issued prior to January, 1902, have been separately passed upon, and about 2300 selected as deserving mention in the tables. All copied data used in the manuscript sent to the publisher have been twice compared with their source by the author and once by Dr. Heyward Scudder. PREFACE. V Obviously the attempt to establish an analytical system of the proposed char- acter on any less secure foundation than an extended first-hand study of a very large number of representative compounds so selected as to cover all important types, would be to invite the fate of "the foolish man which built his house upon the sand"; for existing descriptions of the reactions of even the most familiar com- pounds very rarely state the experimental conditions and phenomena in terms that are immediately available for the purposes of a systematic analytical classification. The chemical tests that have been relied upon for arranging the chemical species in genera are therefore the result of many hundred original experiments made upon several hundred compounds in the laboratories of the Massachusetts Institute of Technology, the preparations used being supplied for the most part from the valu- able Institute collection. Yet in spite of the considerable labor expended in this way, since it has been physically impossible to examine personally every species described, it would be absurd to deny that some may be wrongly located in the classification. To safeguard the analyst as far as possible against errors arising from such imperfect descriptions, every reasonable precaution that has suggested itself has been taken during the construction of the procedures and tables. The names of those compounds whose generic positions have been established by original experiments in the author's laboratory are distinguished from others by being preceded by the mark f, though it is not true that every property ascribed to a sub- stance thus marked is necessarily an original or guaranteed datum. Of the "num- bered specific tests" it may, however, be said that each one has been performed at least several times in accordance with the directions contained in the manu- script; that they have all been used on more than one occasion; and that they have proved successful in the hands of two or more persons. The specific characterizations are all quite brief because the work is intended to be used as a compact practical analytical guide and index, and not as a hand- book of descriptive Organic Chemistry; and because the value of a specific descrip- tion to the analyst never increases, beyond a certain point, directly in proportion to the number of properties and tests included-long descriptions often becoming unwieldy and confusing through suggesting too many alternatives of unequal merit. To obtain all the new material required for these pages single-handed would have proved a disheartening labor. The writer's grateful acknowledgments are therefore due to the many friends (most of whom are or have been connected with the chemical department of the Massachusetts Institute of Technology) who have rendered assistance in the work. Some of the most important contributions from this source are recorded in the unpublished "thesis" investigations of the writer's students. Valuable information has thus been furnished by Messrs. A. P. Norris, C. L. M. Pettee, H. M. Loomis, H. Scudder, B. R. Rickards, A. R. S. Booth, J. W. Brown, J. R. Odell, and Misses E. M. Chandler and A. F. Blood. The writer has also been ably assisted at different times by Dr. Paul Chapin and Messrs. A. C. Davis and Herbert Walker. To his friend, Dr. Heyward Scudder, the author's thanks are however especially due for generous and untiring cooperation during a considerable part of this undertaking. Many of the best methods, particularly among the " specific tests," are the fruits of his research, or have been improved VI PREFACE. in consequence of his suggestions, while nearly the whole of the manuscript, as well as the proof-sheets, have received the benefit of his criticism. It is regretted that the necessary practice of omitting, for the sake of simplicity and compact- ness in tabulation, those bibliographical references which, while they have aided the writer, would not be of obvious advantage to the analyst, has prevented that full acknowledgment of aid from many earlier investigators that would other- wise have been gladly rendered. In closing, a word should be added in regard to the proposed extension of this "Method" to the other organic compounds. It is planned to describe the carbon compounds containing nitrogen, or nitrogen and oxygen-exclusive of the dye- stuffs-in Vol. II, as Order II of the analytical system. Although the prepara- tion of material for Vol. II is quite far advanced, it is probable that Vol. Ill, which is to be devoted to the identification of the organic dyestuffs, will be ready for publication first. The completion of the system will then await the prepara- tion of a fourth volume to include the remaining "orders." S. P. M. Massachusetts Institute of Technology, December, 1903. CONTENTS. PAGES Preface iii-vi Table of Abbreviations xi-xii CHAPTER I. Classification of Compounds and the Analytical Procedure 1-8 Explanation of Classification.-Orders, Genera, Divisions, Sections, Species, 1-2. General Directions for Examination of Unknown Compounds.-Evidences of Homo- geneity; Examination of Physical Characteristics; Determination of Order; Determination of Genus; Tabular Summary of Generic Tests; Determina- tion of Division and Section; Determination of Species. 3-7. Examples illustrating the Analytical Procedure. 7-8. CHAPTER II. Ordinal Tests 9-14 Procedure for Detection of the Elements in Organic Compounds.-Carbon and Ash Con- stituents; Sulphur, Nitrogen, and the Halogens; Ignition with Sodium; Sul- phur; Nitrogen; Nitrogen and Sulphur together; Pohsphorus; Halogens; Iodine; Bromine; Chlorine. CHAPTER HI. Genus I (Subord. I, Ord. I).-Aldehydes 15-25 Generic Characterization.-Generic Test I; Observations on Test; Aldehyde Char- acteristics, 15-16. Analytical Tables.-Div. A (Solid Species), 17-18; Div. B (Liquid Species), 19-21. Numbered Specific or Semi-specific Aldehyde Tests.-(101)* Compounds reducing Tollen's Reagent; (111) Acetaldehyde; (112) Acrolein; (113) Benzaldehyde; (114) Formic Aldehyde; (115) Furfurol. 22-25. CHAPTER IV. Genus II (Subord. I, Ord. I).-Carbohydrates. . • 26-34 Generic Characterization.-Generic Test II; Generic Subdivisions; Carbohydrate Characteristics. 26-28. Analytical Tables.-Section 1 (Soluble Species), 29; Section 2 (Insoluble Spe- cies), 31. Numbered Sectional and Specific Carbohydrate Tests.-(201) Osazone Precipita- tions; (202) Reduction of Fehling's Solution; (203) Furfurol; (204) Phloro- glucine Reaction; (205) Oxidations to Mucic or Saccharic Acids. 32-34. * The numerals in parentheses refer to test numbers-not pages. VII VIII CONTENTS. CHAPTER V. PAGES Genus III (Subord. I, Ord. I).-Acids 35-86 Generic Characterization.-Generic Test III; Observations on Test; Acid Charac- teristics; Generic Subdivisions. 35-38. Analytical Tables.-Div. A, Sec. 1 (Solid Soluble Species), 39; Div. A, Sec. 2 (Solid but not Soluble Species), 52; Div. B, Sec. 1 (Liquid Soluble Species), 73; Div. B, Sec. 2 (Liquid but not Soluble Species), 75. Numbered Specific or Semi-specific Tests.-(301) Neutralization Equivalent; (302) a-Oxyacids; (303) Acids losing Carbon Dioxide at 200; (304) Unsaturated Acids; (305) Esters with characteristic Odors; (306) Metallic Salts; (307) Acid Anhydrides of Genus III; (311) Acetic, Propionic, Butyric, and Isobutyric Acids; (312) Benzoic Acid; (313) Cinnamic Acid; (314) Citric, Malic, and Tartaric Acids; (315) Formic Acid; (316) Glutaric Acid; (317) Oxalic Acid; (318) Phthalic Acid, Isophthalic Acid and Terephthalic Acid; (319) Salicylic Acid; (320) Succinic Acid. 77-86. CHAPTER VI. Genus IV (Subord. I, Ord. I).-Phenolic Compounds 87-110 Generic Characterization.-Generic Test IV. Observations on Test; Phenolic Char- acteristics. 87-90. Analytical Tables.-Div. A (Solid Species), 91; Div. B (Liquid Species), 104. Numbered Specific or Semi-specific Tests.-(401) Ferric-chloride Colorations; (402) Phthaleine Fusion; (411) Hydroquinone; (412) a-Naphthol; (413) /?-Naphthol; (414) Phenol; (415) Phloroglucine; (416) Pyrocatechin; (417) Pyrogallol; (418) Resorcine; (419) Thymol. 107-110. CHAPTER VII. Genus V (Subord. I, Ord. I).-Esters 111-127 Generic Characterization.-Generic Test V, 111; Saponification and Saponification Equivalent (Rapid Method), 111; Saponification to obtain both Acid and Neutral Products (Longer Method), 113; Examination of the most Important Neutral Saponification Products, 113; Examination of the Acid Products, 116; Observations on Test V. 117. Analytical Tables.-Div. A (Solid Esters), 118; Div. B (Liquid Esters), 120. CHAPTER VIII. Genus VI (Subord. I, Ord. I).-Acid Anhydrides and Lactones. 128-132 Generic Characterization, 128. Analytical Tables.-Div. A (Solid Species), 129; Div. B (Liquid Species), 131. CHAPTER IX. Genus VII (Subord. I, Ord. I).-Ketones 133-150 Generic Characterization.-Generic Test VII; Procedures 1 and 2; Observations on the Test. 133-135. Analytical Tables.-Div. A (Solid Species), 136; Div. B (Liquid Species), 141. Numbered Specific or Semi-specific Ketone Tests.-(701) Colorations with Sodium Nitroprusside; (702) Oxidations with Chromic Acid; (703) Pyrrol-red Reaction of f-Diketones; (711) Acetone; (712) Acetophenone; (713) Benzoin; (714) Benzophenone; (715) Camphor. 146-150. CONTENTS. IX CHAPTER X. PAGES Genus VIII (Subord. I, Ord. I).-Alcohols 151-172 Generic Characterization.-Generic Test VIII; Procedures 1, 2, and 3; Observations on the Test. 151-154. Analytical Tables.-Div. A, Sec. 1 (Solid "Soluble" Species), 155; Div. A, Sec. 2 (Solid and not "Soluble" Species), 158; Div. B (Liquid Species), with Sp. Gr. less than 0.90), 160; Div. B, Sec. 2 (Liquid Species, with Sp. Gr. greater than 0.90), 164. Numbered Specific or Semi-specific Tests.-(801) The Iodoform Test; (811) Allyl Alcohol; (812) Benzyl Alcohol; (813) Butyl Alcohol; (814) Ethyl Alcohol; (815) Ethylene Glycol; (816) Glycerine; (817) Isobutyl Alcohol; (818) Iso- propyl Alcohol; (819) Methyl Alcohol; (820) Propyl Alcohol. 166-72. CHAPTER XI. Genus IX (Subord. I, Ord. I).-Hydrocarbons, etc 173-203 Generic Characterization, and the Sectional Tests, 173. Analytical Tables.-Div. A (Solid Species), 174; Div. B, Sec. 1 (Liquid Species. Sp. Gr. below 0.85, not giving Tests 901-903), 182; Div. B, Sec. 2 (Liquid Spe- cies, Sp. Gr. below 0.85, but attacked in Tests 901, 902, or 903), 184; Div. B, Sec. 3 (Liquid Species, Sp. Gr. above 0.85), 189. Numbered Specific or Semi-specific Tests.-(901) Bromine Test for Unsaturation, etc.; (902) Action of Fuming Sulphuric Acid; (903) Action of Fuming Nitric Acid; (904) Colorations with Aluminium Chloride; (905) Oxidation of Side- chains (1) with Permanganate, (2) with Chromic Acid, (3) with Nitric Acid; (906) Test for C-CH Group; (907) Saturated Ethers of Div. B; (911) Ace- naphthene; (912) Anthracene; (913) Benzene; (914) Mesitylene; (915) Naphthalene; (916) Phenanthrene; (917) Pseudocumene; (918) Toluene; (919) m-Xylene; (920) p-Xylene; (921) o-Xylene. 195-203. CHAPTER XII. Suborder II of Order I.-Colored Compounds of Order I 204-216 Subordinal Characterization, 204. Analytical Tables.-Div. A, Sec. 1 (Solid Species of Determined Melting-point), 205; Div. A (Supplementary), Sec. 2, 212; Div. B (Liquid Species), 215. Numbered Specific Tests.-No. 1011, Anthraquinone; 1012, Benzoquinone; 1013, n-Naphthoquinone; 1014, Phenanthrenequinone, 216. CHAPTER XIII. Special Methods, Apparatus, and Reagents 217-237 Melting- and Boiling-points.-Usual and Special Methods for Determining; Sources of Error and Corrections, 217-223. Thermometric Indications of Chemical Purity.-Fractionation Tests; Sharpness Tests; Fusion and Boiling Intervals. 223-227. Specific Gravities.-Determination with the Capillary Pycnometer or the Pipette, 227-229. Color.-Color Terminology; Pigmentary Color Standards; Color Symbols; Color Comparisons, 230-234. X CONTENTS. PAGES The Manipulation of Small Quantities.-Solid Precipitates: Liquids. 234-236. List of Special Reagents and Apparatus, 236-237. Alphabetical Index 239-243 Formula Index 244-264 Color Standard In the back cover. TABLE OF ABBREVIATIONS. a. = above. Before a melting-point or boiling-point indicates that the change occurs above the tem- perature given. abt. = about. Indicates that the value _ following is only approximate. A (standing after the symbol for a metal) represents the acid residue of the acid in whose description it occurs; e.g., PbA2 in a descrip- tion of benzoic acid would rep- resent lead benzoate. Ac. = acetic acid or acetate. ac. = acid. ale. - alcohol or alcoholic. aid. = aldehyde. alm. = almost. alk. = alkaline. anhyd. = anhydride. aq. -water or aqueous^ as. = asymmetrical. b.p. -boiling-point. Bu. -butyl, C^H^, without regard to structure of the radical. bz. = benzene. c. -corrected (not necessarily correct); also cold. chlf. = chloroform. cone. = concentrated. cryst. -crystals, crystalline, or crystallizes. d. = decomposes. Standing after a number indicates the tempera- ture at which a substance melts or boils with decomposition. Standing before a number it indi- cates the temperature at which decomposition occurs without necessarily implying that the substance either melts or boils. Standing before the name of a compound means dextro-gyra- tory. d. a. - decomposes above. Is used in the same way as d. d. w. m. = decomposes without melting, deliq. = deliquescent or deliquesces, dil. = dilute. In expressions like " dil. ale. (3:1)," the first term of the numerical ratio between paren- theses always refers to the sub- stance directly mentioned, and the second term to the water used as diluent or solvent. dif. = difference. dist. -distils; also, may be distilled, without stating the tempera- ture. d. s. -difficultly soluble. See page 38. Et. = ethyl, C,H6. Eth. = ether, (ethyl oxide). e. s. = easily soluble. See page 38. fr. = from. floc. - flocculent. h. = hot. i. = insoluble; also, in name of a com- pound, optically inactive. (i. v.) = in vacuo. G. = specific gravity. gran. = granula r. I. = hrvo-gyratory. liq. ~l qu 'd. Igr. = ligroin. m- = meta. mic. = microscopic. Me. =methyl, CH3 . misc. = miscible. m. p. -melting-point. k N.Eq. = " neutralization equivalent." (De* fined on page 77.) n. f. = non-fusible. n. v. - non-volatile. o- = ortho. o.p. =ordinary atmospheric pressure. o. t. = ordinary room temperature. oxid. = oxidize, oxidizes, or oxidation. p- = para. Ph. = phenyl, CtpP- Pr. = propyl, CsHi (without indicating the structure of the radical). ppt. -precipitate or precipitates. pt. =part or parts. pulv. = pulverulent. (r. h.) = rapidly heated. (See page 220.) s. = soluble. (See page 38.)-Before the name of a compound signi- fies symmetrical. sbl. = sublimes. s. d. = slightly decomposed. (Signifies that the substances melts or boils with slight decomposition at the temperature given.) Sap. Eq. = saponification equivalent. (Defined on page 113.) sol. = solution. s.f. = softens. Indicates that the sub- stance softens at the tempera- ture stated. Sbl. w. m. = sublimes without melting. (Often followed by specification of the temperature.) tbl. -tabular crystals. (Th. i.) = thermometer immersed in the vapor. u. c. = uncorrected. unsat. = unsaturated. v. = vicinal or adjacent. vol. -volume. volat. = volatile. vol. w. st. = volatile with steam. w. =with. x. s. = excess. XI XII SIGNS.-BIBLIOGRAPHICAL. [a]# Specific rotary power (using monochromatic sodium light). For the carbohy- drates the values given are the "permanent" rotations at 20° C. obtained with aqueous solutions. Index of refraction (using monochromatic sodium light). + placed after a number in a column of boiling- or melting-points indicates that the substance melts or boils slightly above the temperature given. [+]or[-] placed before the name or symbol for a compound indicates that the substance is optically active. f placed before the name of a compound indicates that the position of the latter in the analytical system has been experimentally determined in the author's laboratory. The "specific descriptions" for such compounds are also based, for the most part, on experimentally verified data. SIGNS. BIBLIOGRAPHICAL. Abbreviation. Title. A. Liebig's Annalen dor Chemie. A. ch. Annales de chimie et de physique. A. ch. an. Annales de chimie analytique. Allen. Allen's Commercial Organic Analysis, 3d Edition (BJackiston's Son). Anl. The Analyst. Am. American Chemical Journal. Am. Soc. Journal of the American Chemical Society. Ar. Archiv der Pharmacie. B. Berichte der deutschen chemischen Gesellschaft. Bl. Bulletin de la Society Chimique de Paris. C. Chemisches Centralblatt. C. r. Comptes rendus de 1'Academic des Sciences. Ch. Ind. Journal of the Society of Chemical Industry. Ch. Z. Chemiker Zeitung (Cbthen). Ch. N. Chemical Nevs. Fr. (Fresenius') Zeitschrift fur analytische Chemie. G. Gazzetta Chimica italiana. H. (Hoppe-Sevier's) Zeitschrift fiir physiologische Chemie. J. Jahresbericht der Chemie. J. pr. Journal fiir praktische Chemie. M. Monatshefte fiir Chemie. Pin Ch. Zeitschrift fiir phvsicalische Chemie. R. Recueil des travaux chimiques des Pavs-Bas. Soc. Journal of the Chemical Society of London. IDENTIFICATION OF ORGANIC COMPOUNDS. CHAPTER I. CLASSIFICATION OF COMPOUNDS AND THE GENERAL ANALYTICAL PROCEDURE. To facilitate their identification, the pure compounds or chemical species described in this work are systematically arranged in genera, orders, and various minor groups. The general analytical procedure can be applied intelligently only after the underlying principles of this classification are clearly understood. The order of any species is determined by its qualitative elementary compo- sition. Compounds made up of the same elements belong to the same order. The compounds of carbon and hydrogen, and of carbon, hydrogen, and oxygen, con- stitute Order I of the system, and are the only ones described in the present volume. Order I contains two suborders, Suborder I including all colorless, and Suborder II all colored species. Tests having as their object the determination of the order of a species, i.e. tests for the elements, are called ordinal tests. They will be fully treated in Chapter II. A genus is a group of species characterized by showing a common behavior in certain prescribed and carefully defined generic tests. With few exceptions generic tests are based on chemical reactions rather than differences in physical properties. The experimental details for each generic test are to be found at the beginning of the chapter devoted to the genus whose number it bears. Typographically generic tests are distinguished from other numbered tests by being printed in Roman instead of Arabic numerals. Test III, for instance, means the test prescribed (page 35) for the recognition of species of Genus III (Acids). The genera are so arranged that no species shall give the generic test for any genus preceding it in the same suborder. A concise summary of the generic tests of Suborder I, Order I, is given on page 5. All genera, including both solid and liquid species, contain two divisions. Division A contains the solid, and Division B the fluid species. Gaseous species are so few in number that they are treated in division B with the species that are liquid under the ordinary conditions of temperature and pressure. The " divisions" of some genera are composed of smaller groups of species called sections. The term section is also, though less frequently, applied to small arti- ficial groups of species, like the two sections of Suborder II, when the chemical 2 CLASSIFICATION OF COMPOUNDS. relationships between the members of the group are not sufficiently intimate to warrant their erection into genera. Sectional tests when based upon chemical reactions are referred to by numbers, and described just before the true specific tests, and immediately after the tabulated descriptions of the species of the genus. The chemical species or compounds, the fundamental units in the classification, are, whenever practicable, arranged within their respective genera, divisions, or sections according to the numerical values of their melting-points, if they are solids; or of their boiling-points, under standard conditions, if they are liquids. Genus II of Suborder I, and Supplementary Section 2 of Suborder II, furnish the only examples in this volume, of groups of compounds whose arrangement within their respective sections of the tables is not dependent on the values of these constants. ^Specific tests are primarily designed to distinguish a species from others situated near it in the same subdivision of its genus, and in the regular course of analysis should follow the ordinal, generic, and sectional tests. Very few of them have much significance if applied directly to an entirely unknown compound. It is conceivable, for instance, that there may be a number of organic liquids which will give a white crystalline derivative melting at 92°-93° when treated as directed in Specific Test 814; but if it is also shown that the unknown substance is a colorless compound of carbon, hydrogen, and oxygen belonging to Genus VIII, Division 2, and boiling at 78°, the proof that the species is ethyl alcohol is overwhelming. The most satis- factory specific tests are usually those in which a few centigrams of a compound are quickly converted into a well-characterized derivative. The directions for many specific tests form a part of the specific characterizations of the tables, but some of the more important tests in each genus are described together immediately after the tables of the genus to which they relate, and referred to in the characterization by test numbers. In Order I, one hundred numbers are reserved for the description of the sectional, semi-specific, and specific tests of each genus, the first ten numbers in each hundred being set aside for the sectional and semi-specific,* and the last ninety for the true specific tests. Any numbered test in Order I may be easily found without consulting the index, if it be remembered that the numeral denoting the hundreds in the test number (e.g. 3 in 321) is also the number of the genus to which the compound concerned in the test belongs. The last two numerals in the test number indicate the position of the test among its fellows. Test 302 will accordingly be recognized at a glance as either a sec- tional or semi-specific test of Genus III (Acids). By turning to page 78 it will be found to be a reaction for the recognition of n-hydroxy acids. In the same way Test 319 will be seen to be a specific test for some particular acid. It is actually a description of two reactions for the identification of salicylic acid. The tests connected with the nine genera of Suborder I, Order I, are assigned numbers 100-900. Suborder II, not being divided into genera, has its specific tests numbered as if it were the tenth genus of its order; i.e. they are represented by the numbers 1000 to 1100. * By a semi-specific test is meant one employing some general experimental procedure that leads to similar results with a number of compounds, but which enables a partial selec- tion between some of the species situated in the same smallest subdivision of a genus. Tests 301, 302, and 303 are semi-specific tests. GENERAL ANALYTICAL PROCEDURE. 3 GENERAL DIRECTIONS FOR THE IDENTIFICATION OF AN UNKNOWN COMPOUND. The numbered paragraphs in heavy type which follow form an analytical key to the use of the " Method ", They indicate the successive considerations that should receive the attention of the analyst in the investigation of every unknown compound. With the explanatory remarks in ordinary type which accompany them, they give a comprehensive view of the general analytical procedure disen- cumbered of detailed descriptions of special operations and tests which can be more advantageously discussed elsewhere. It will be assumed that the reader has already acquainted himself with the classification of the 11 Method ". i. PURITY. ESTABLISH A PRESUMPTION THAT THE UNKNOWN SUBSTANCE IS REALLY A PURE COMPOUND BEFORE ATTEMPTING TO IDENTIFY IT. IF IT IS NOT HOMOGE- NEOUS, PURIFY IT. THE CONSTITUENTS OF AN UNKNOWN ORGANIC MIXTURE CAN NOT BE SATISFACTORILY IDENTIFIED PREVIOUS TO THEIR SEPARATION. THE HOMOGENEITY OF COMPOUNDS WHICH EXIST ONLY IN THE FORM OF UNCRYSTALLIZABLE SYRUPS THAT CAN NOT BE DISTILLED WITHOUT SERI- OUS DECOMPOSITION, IS SO DIFFICULT TO ESTABLISH, THAT SUCH SPECIES ARE, AS A RULE, EXCLUDED FROM THE TABLES. To prove absolutely that a substance is chemically homogeneous, it would have to be shown that the physical and chemical properties of all the parts into which a given mass of it can be separated by methods of fractionation that do not affect it chemically, are identical; or, in other words, that no substance can be thus isolated from it whose melting-point, boiling-point, solubility, specific gravity, crystalline structure, chemical behavior, etc., is different from that of the original body. This absolute proof is of course impossible in practice. But if the properties whose identity in the several fractions has been ascertained are very few in number, they may still afford a presumption in favor of chemical homogeneity so strong as to closely approximate to the absolute proof, pro- vided they are judiciously selected and are of a kind that permit of exact measurement. The decision of the analyst as to just how many and what purity tests it will be profit- able to apply to any particular substance, will be influenced by a variety of circumstances, among which will be included the importance of the identification, the extent of his knov 1- edge of the methods employed in the preparation and purification of the substance, and the quantity of material that is available. If the supply is so small as to barely suffice for the tests of the regular procedure exclusive of special homogeneity tests, there will be no alternative between abandoning the examination altogether, and hazarding the loss of all the substance in what may at the end prove to be fruitless experiments upon a mix- ture. Whenever it is decided in such a case to proceed with the examination, it must be remembered that the results will be worthless unless the final specific tests are most unequivocal. Of all the methods affording indications of purity, those which depend upon constancy or sharpness in melting-and boiling-point have been the most widely used. Indeed, it is altogether probable that for a majority of the organic compounds which have been described, the only direct evidence of purity that it has been considered necessary to secure, pre- liminary to the first ultimate analysis,-aside from that incidentally gained from their general' appearance and behavior towards solvents-has been that furnished by these simple thermometric methods. The use and interpretation of these purity tests will be discussed somewhat fully in Chapter XIII (pp- 223-227). The truth of the proposition that "The constituents of an unknown mixture cannot be satisfactorily identified previous to isolation," may, at the first glance, appear to be 4 GENERAL ANALYTICAL PROCEDURE invalidated by the existence of direct tests for organic adulterants in foods, for abnormal constituents in the urine, and the like. These tests, however, all owe their usefulness to the fact that the mixtures to which they are applied-except as regards the compound sought-are, virtually, known mixtures, in the sense that the combined effect of all their customary constituents-known and unknown-upon the test, has been carefully ascer tained by previous investigations. Their value accordingly becomes problematical as soon as any substance not usually present in such a mixture is added to it. The preliminary treatment of unknown mixtures is, undoubtedly, that part of most organic analyses which makes the greatest demands on the originality and patience of the analyst. While the number and peculiarities in chemical behavior of the organic compounds are so great as to forbid the expectation that a general scheme for their separa- tion comparable in simplicity and comprehensiveness to that used in qualitative analysis for the elements can ever be realized, it is reasonable to anticipate that this important branch of Analytical Chemistry will eventually be so far systematized that much less will be left to chance and individual dexterity than at present. The omission from this volume of suggestions for methods of separation occurs, not because the importance of the matter has been underestimated, but because sufficient data for comprehensive and practical generalizations on the subject have not yet accumulated. It is, however, the author's hope to present such recommendations as can be given for the systematic treatment of mixtures in a later volume. IF THE SUBSTANCE IS A SOLID, DETERMINE ITS MELTING-POINT; IF A LIQUID, ITS BOILING-POINT AND ITS SPECIFIC GRAVITY AT 20°/4°. IN EITHER CASE NOTE ITS ODOR, COLOR, TASTE, AND OTHER SALIENT PHYSICAL CHARAC- TERISTICS, AND DETERMINE ITS APPROXIMATE SOLUBILITY IN WATER. 2. PHYSICAL PROPERTIES. The determination of melting-points is discussed on pages 217-221. Most of the melting-points recorded in the tables are probably "uncorrected." The boiling-points, on the contrary, are in general to be regarded as corrected for stem-exposure, and have been approximately reduced to their values under the standard pressure of 760 millimeters whenever possible. The determination of boiling-points is treated on pages 221-223. Whenever small distilling flasks are employed in making these determinations, the use of the asbestos diaphragm shown in Fig. 6 should never be neglected. The specific gravity of liquids, if the quantity available is very small, is best determined by aid of the capillary pyknometer described on page 22S. 0.2 cc. of the liquid will be enough to enable a satisfactory determination in this apparatus. Color comparisons should be expressed in terms of the color standard placed in the back cover of this volume and described on pages 230-234. The determination of solubility in water at the temperature of the laboratory may be quickly made by the approximate method of page 38. These tests are made so early in the procedure, because, unlike most of those which follow, they consume little or no material which can not be recovered, while the informa- tion which they furnish is almost certain to be required at some later period in the investi- gation. 3. ORDER. DETERMINE THE ORDER OF THE COMPOUND BY APPLYING THE ORDINAL TESTS IN THE SUCCESSION AND MANNER DIRECTED IN CHAPTER II, PAGE 9 ET SEQ. IF THE COMPOUND CONTAINS ANY ELEMENTS OTHER THAN CARBON, HYDROGEN, AND OXYGEN, IT IS NOT DESCRIBED IN THIS VOLUME. IF IT CONTAINS CARBON AND HYDROGEN, OR CARBON, HYDROGEN, AND OXY- GEN, AND IS COLORLESS, IT BELONGS TO SUBORDER I, ORDER I. IN THIS CASE TURN TO PARAGRAPH 4 BELOW. IF IT BELONGS TO ORDER I, BUT IS COLORED (I.E., BELONGS TO SUBORDER II), TURN TO PAGE 204. GENERAL ANALYTICAL PROCEDURE. 5 4. GENUS. [For Species of Suborder I, Order I.]-APPLY GENERIC TESTS I-IX SUCCESSIVELY UNTIL THE GENUS OF THE COMPOUND IS ASCERTAINED. DO NOT VARY THE ORDER OF THE TESTS, NOR OMIT ANY WHICH ARE NOT KNOWN FROM THE CIRCUM- STANCES TO BE POSITIVELY UNNECESSARY. BEFORE PERFORMING ANY GENERIC TEST FOR THE FIRST TIME, READ CAREFULLY THE "OBSERVA- TIONS" WHICH FOLLOW THE DIRECTIONS. THE PAGES ON WHICH DIREC- TIONS FOR THE SEVERAL GENERIC TESTS ARE TO BE FOUND, ARE GIVEN IN THE "TABULAR SUMMARY OF GENERIC TESTS" BELOW. When a generic test is subdivided into parts, a statement of the sequence in which they should be applied, or of the circumstances under which certain of them are to be omitted, is always conspicuously placed near the head of the chapter devoted to the genus. Test Number and Page. Condensed Description of Test. I (P- 15) Aldehydes.-A color reaction with a fuchsine solution decolorized by sulphur- ous acid. Requires 5 cgr. of substance. Time, about 3 minutes. II (p. 26) Carbohydrates.-The Molisch color reaction with a-naphthol, followed by three short supplementary tests to exclude glucosides in case the proper color is obtained. The Molisch reaction requires 5 mgr. of substance and can be applied in 5 minutes. The supplementary tests, when made, require in all 11 cgr. of substance and can be applied in 5 minutes. in (P. 35) Acids.-A titration with decinormal sodium hydroxide and phenolphthalein. Requires 1 decigr. of substance. Time about 30 minutes when a neutrali- zation equivalent is determined; in other cases (cf. note on p. 35) 5 minutes. IV (p. 87) Phenolic Compounds.-The test has two parts: (1) a color test with ferric chloride consuming 5 to 10 mgr. of substance,, which can be applied in less than 5 minutes; (2) a solubility test with aqueous alkali, which can be made with 10 cgr. of substance in 5 minutes. Part 2 is used only for solids that fail to give part 1. V and VI Esters and Anhydrides.-A saponification experiment with 10 cgr. of substance, (pp. 111-128) which is heated with 2 cc. of alcoholic potash solution for 30 minutes. (During the heating, preparations for Tests VII and VIII will be made.) [A second longer and more difficult saponification procedure (cf. p. 113) with aqueous potash and a gram or two of substance is required when it is wished to isolate the neutral saponification products from an ester, and thus distinguish certainly between species of Genera V and VI. It is never applied when the first procedure has given a negative result; and its use is generally inadvisable when the total supply of substance does not exceed 2 grams. When omitted, Genera V and VI have to be treated as a single composite genus.] VII (p. 133) Ketones.-Solid compounds melting above 30° are tested with hot alkaline hydroxylamine solution; all compounds liquid at temperatures below 30°, with phenylhydrazine solution. The test with hydroxylamine requires 10 cgr. of substance; that with phenylhydrazine about 5 cgr. Time in either test about 15 minutes. vm (p. i5i) Alcohols.-To this genus belong: (A), all species not included in earlier genera that are soluble in less than 30 parts of water at 20°; (B), all compounds liquid below 75° that evolve hydrogen on treatment with sodium; (C), all compounds solid at 75° that are not acetylated by acetic anhydride under certain prescribed conditions. Test A has been already made in the pre- liminary examination. Tests B and C require about 20 cgr. and 10 cgr. of substance respectively. Test B can be performed in 10 or 15'minutes; C can not be completed" in less than about 50 minutes. [In dealing with insoluble solids time will often be saved by referring directly to the appro- priate division and section in the tables of both Genus VIII and IX with- out applying test C.] IX (p. 173) Hydrocarbons, etc.-Genus IX includes all species not giving Tests I to IX, and hence has no special generic test of its own. TABULAR SUMMARY OF GENERIC TESTS I-IX IN SUBORDER I, ORDER I. 6 GENERAL ANALYTICAL PROCEDURE. 5. GENERIC SUBDIVISIONS. TURN TO THE PROPER DIVISION (A FOR SOLIDS, AND B FOR LIQUIDS) IN THE TABLES OF THE GENUS. IF THE DIVISION CONTAINS SECTIONS, THE DE- SCRIPTIVE DIVISIONAL HEADINGS WILL INDICATE WHAT ADDITIONAL TESTS, IF ANY ARE NECESSARY, MUST BE MADE TO ASCERTAIN THE SECTION. As the divisions in many genera are not subdivided, and as many of the sections are distinguished fiom one another by differences in solubility or specific gravity which are already known from the preliminary examination of paragraph 2, additional tests at this point are usually unnecessary. The following table gives a general view of the subdi- visions of the genera of Suborder I, together with page numbers or each divisional heading. Genus Page No. Number -_____ and of Division of Basis of Sectional Distinctions. Divisions. Head. Sections. I A 17 0 B 19 0 II III X A 29 39 Solubility in water at 20°, with special chemical tests for B 73 2 ) subsections. IV A 91 0 B 104 0 V A 118 0 B 120 2 VI A 129 0 B 131 0 VII A 135 0 B 141 0 VIII A 155 2 Solubility in water at 20°. B 160 2 Sp. gr. (20°/4°) greater or less than 0.90. IX A 174 0 B 182 3 Sp. gr. (20°/4°) in sections 1 and 2 less than 0.85; in 3 greater than 0.85. Sec. 1 is distinguished from 2 by chemical tests. SUBDIVISIONS OF THE GENERA IN SUBORDER I, ORDER I. COMPARE THE PROPERTIES OF THE SUBSTANCE WITH THE PROPERTIES OF ALL SPECIES THAT MELT OR BOIL WITHIN FIVE OR TEN DEGREES OF ITS MELT- ING- OR BOILING-POINT AND ARE DESCRIBED IN THE SUBDIVISION OF THE GENUS TO WHICH IT HAS BEEN FOUND TO BELONG. 6. SPECIES. The published data concerning melting- and boiling-points are, unfortunately, not always based upon exact determinations. (Seepage 217.) Hence the necessity for extending the inspection of the tables to include species that are described as melting or boiling a number of degrees from the temperature actually observed. The 5° limit is sufficient for most species whose melting- or boiling-points are below 150°; but the limit of 10° is none too large for compounds that melt or boil at 300°. When the recorded and observed temperatures are both "corrected" ones, the limit may be safely much reduced. The mode of procedure in the few sections in which the species are not arranged according to melting- or boiling-points, will always be sufficiently indicated in the sectional headings of the tables. The specific characteristics most serviceable in making a first partial choice between compounds having nearly the same melting-points or boiling-points are: properties like color, taste, and odor, which are obvious from a casual inspection; properties like specific gravity, solubility, boiling-point (for solids), refractive index, and neutralization equivalent, for which numerical values can be deter- GENERAL ANALYTICAL PROCEDURE. 7 mined quickly, or which are already known in consequence of the preliminary examination and the generic, divisional, and sectional tests that have been made; and, lastly, simple semi-specific tests, such as number 901 with bromine for unsatu- ration, or 302 with ferric chloride for a-oxyacids. Undue weight should not be attached to statements concerning crystalline form which are unaccompanied by exact crystallographic measurements; the general appearance of crystals of the same compound being often strongly influenced by the solvent, temperature, and other conditions accompanying crystallization. The final confirmatory specific tests of the tables are not all of equal merit or conclusiveness. Many which have been inserted on the strength of apparently good authority, but not verified by the author, may be deficient in essential details. Those introduced by the words ' ' Apply Test -" or " Identify by Test -" have been carefully studied in the author's laboratory, and may be accepted as thoroughly reliable. The basis for the recommendation of such as begin with the phrase 1 ' Gives Test -" or1 ' Gives - in Test -" (e.g.' ' Gives isophthalic acid in Test 905") is either experiments made in the author's laboratory, or positive published statements that the result specified has been produced under conditions which it is reasonably certain will be supplied by the method of the numbered test cited. To complete the identification of any compound for which adequate specific confirmatory tests are not suggested in the tables, recourse to the original litera- ture of the body and its derivatives will frequently be necessary. These descrip- tions have now been made so accessible, and are so well summarized in " Beilstein's Handbuch ", that suggestions for the desired tests will often be quite readily found. Some general remarks on the selection of suitable derivatives for use in such impromptu specific tests are given on page 234. The properties of many of the species whose names appear in the chemical literature have, however, been either so imperfectly determined or described, that their identifica- tion by any purely analytical method, without some knowledge of the reactions leading to their formation, is an impossibility. All that can be done analytically with such com- pounds, when the quantity of material is limited, is to ascertain whether their percentage compositions and molecular weights harmonize with any hypothesis that we may be in a position to make concerning them. In such cases it will usually make little difference whether we begin or close the examination of the body with the determination of an em- pirical formula; for when all has been done that is possible under the circumstances, the labor performed will be the same, whichever procedure is chosen. Substantial justifica- tion for the subordination of the method of identification by properties and reactions to that founded on the empirical formula, exists in one case only. This is met with when there are strong reasons for suspecting the unknown substance to be a new compound, or one very unlikely to appear in the tables of this work, and when its quantity is less than about two grams. It would then be unfortunate, in view of the anticipated failure of the attempt at identification by properties and reactions, to forego the possible advan- tages that might be derived from a knowledge of the empirical formula. Examples Illustrating the Analytical Procedure. The following examples of identifications by the procedure of this "Method" are the records of actual experiments made in a laboratory where the apparatus and reagents required were all in readiness. The contents of each numbered paragraph are a record of the results obtained by following that part of " General Directions for the Identification 8 ILLUSTRA TIVE EX A M PLES. of an Unknown Compound " summarized in the paragraph in heavy type designated by the same number. The compounds being known to be pure, the description of operations begins with the examination of physical properties referred to in paragraph " (2)," page 4, of the "General Directions". EXAMPLE 1. (HYDROQUINONE.) (2).-The compound crystallizes in thin colorless needles melting in a capillary tube at 168°-169° (uncor.). It is odorless; tastes faintly bitter-sweet; and is soluble in ap- proximately 20 parts of cold water. (Time 28 minutes.) (3).-Ignited on platinum foil it leaves no ash. The tests after ignition with sodium in the iron tube show the absence of sulphur, nitrogen, and the halogens. It is therefore to be considered a species of Order I; and, because colorless, of Suborder I. (Time 20 minutes.) (4).-It does not give Generic Tests I or II. In the titration of Generic Test III, some alkali is consumed, but the final color transition is not sharp, and the slightly alkaline solution soon acquires a brownish color. The substance is therefore not'an acid, but may be a phenol. Test IV-1 gives a yellow-orange coloration. Test IV-2 gives a solution that rapidly turns brown on standing. The compound is hence a phenol. Turn to the analytical tables of Division A, Genus IV. (Time 22 minutes.) (5 and 6).-Of the ten phenolic species in the tables (p. 99) that melt between 163° and 173°, hydroquinone (m. p. 169°) appears to be the only one easily soluble in cold water. (The solubility given is 17 parts of water at 15°.) The solubility in alcohol and ether, taste, YO coloration with ferric chloride in Test 401, power to reduce silver-nitrate solution on warming, and browning of the alkaline solution in the air, are found to be all properties of the substance which agree with those described for hydroquinone. The final confirmatory Test 411 (cf. p. 108) is next applied, and by oxidation with ferric-chloride solution, quinone is obtained. The quinone is recognized by its odor, and by conversion into quinhydrone, which forms green-black needles melting to a dark-red liquid at about 170°, after previously beginning to soften at about 150°. (Time 40 minutes.) All the tests in the identification of hydroquinone were completed within 1 hour and 50 minutes, and 0.85 gram of hydroquinone was consumed. (2).-The compound is a colorless liquid which boils sharply between 163° and 163.5° (uncor.). Its specific gravity (determined in a capillary pyknometer (cf. p. 228) of known capacity, at 25°/4°) is 0.860. Its odor is aromatic; its taste slightly burning. It is in- soluble in cold water. (Time 30 minutes.) (3).-Ash constituents, sulphur, nitrogen, and the halogens are absent. The com- pound is to be sought among the species of Suborder I, Order I. (Time 18 minutes.) (4).-Negative results are obtained in Generic Tests I, III, IV-1, VI, VII, and VIII, which are the only ones required for liquids. The compound must therefore be sought in Section 3 of Division B, Genus X (Liquid Hydrocarbons with Specific Gravity greater than 0.85 at 20°/4°). (Time 1 hour and 7 minutes.) Turning to the sections designated, it is found that of the six species mentioned with boiling-points between 159° and 169°, only two, p-methylethylbenzene, of B. P. 162°, mesitylene of B. P. 164.5° (cor.), and possibly tert, butylbenzene, B. P. 168°-8.5°, have specific gravities approximating that of the unknown compound. Specific Test 914 (cf. p. 201) for mesitylene is therefore applied, and a white crystalline nitro derivative melting at 235° (uncor.) is obtained. The formation of this derivative, trinitromesitylene, proves the unknown substance to be mesitylene. (Time 60 minutes.) All the tests in this identification of mesitylene were completed in two hours and fifty-five minutes, with an expenditure of 0.87 gram of substance. EXAMPLE 2. (MESITYLENE.) CHAPTER IL ORDINAL TESTS. DIRECTIONS FOR THE DETECTION OF THE ELEMENTS IN AN ORGANIC COMPOUND. To determine the Order in which an unknown chemical species belongs usually involves a systematic qualitative examination for its component elements. This examination can be safely omitted only when the analyst's knowledge of the origin of the compound is so complete that it is in itself demonstrative proof that certain elements must be, and alone can be, present. The qualitative procedure that will be given in this chapter makes provision for the detection of all the elements * that are of common occurrence in pure organic compounds, and will ensure the ready determination of the order of all species to be included in the "Method". Whenever a complete qualitative examination is called for, the several tests should be applied in the order in which they appear in the following lettered paragraphs: (a) Ignition Test for Carbon and Ash Constituents.-If reducible metals are probably absent, ignite a little of the substance on platinum foil; otherwise in a porcelain crucible. If the substance burns with a flame, or leaves a black carbon- aceous residue which gradually burns away, it may be considered organic. Care must, however, be taken not to mistake a permanent black residue consisting of a metallic oxide, like copper oxide, or of a reduced metal, like platinum, for carbon. If an incombustible ash is formed, incinerate a larger quantity of the substance in a crucible, and make a complete qualitative examination of the ash by the usual analytical methods. Should the ash contain a metallic element, it is probable that the original compound is a salt of some organic substance of acidic character. Since the "Method" only provides for the identification of metallic salts through the acids from which they are derived, it will be necessary, in dealing with a salt, to isolate its acid in a state of purity, preparatory to the location of the latter in the tables. (a') Ignition Test for Carbon and Hydrogen.-It is rarely necessary to make any other test for carbon than that already given under (a); but the following more exact method is occasionally required: Place 0.1 gram of the substance mixed with five times its bulk of freshly ignited, dry, powdered copper oxide in an ignition-tube of hard glass, having an internal diameter of about 5 mm., and a length of 12 cm. Fill half the space remaining above the mixture with granulated copper oxide, and connect the open end of the tube with a bent gas-delivery tube leading into a narrow test-tube containing a few cubic * Oxygen and hydrogen form important exceptions to this general statement. A simple qualitative test for oxygen in combination, although much to be desired, is at present lacking. A test for hydrogen might always be applied, but the numerical preponderance of the hydrogen- containing species is so great-the present volume being without a single example of a com- pound in which this element is missing-that its general employment is unnecessary. 9 10 ORDINAL TESTS. centimeters of baryta solution. Support the ignition-tube in a horizontal position, and begin by heating that portion which contains the granulated copper oxide nearly to the temperature at which the glass begins to soften. This may be conveniently accomplished by use of a single Bunsen burner whose flame has been extended by a wing-top spreader. Next heat the mixture of substance and copper oxide by a second burner held in the hand, manipulating the flame so as to decompose the substance very gradually. The condensa- tion of drops of water on the glass at the cold end of the tube indicates the presence of hydrogen in the substance; the precipitation of barium carbonate in the test-tube, the presence of carbon. The above test, when applied to sulphur compounds, gives a precipitate of barium sulphate. In this case, allow the precipitate to settle without exposing to the air; decant the clear solution; cover the precipitate with a concentrated solution of potassium per- manganate; acidify with dilute sulphuric acid; and test the gas evolved for carbon dioxide. (The permanganate serves to oxidize the sulphur dioxide, thus preventing its escape when the solution is acidified.) SULPHUR, NITROGEN, PHOSPHORUS, CHLORINE, BROMINE, AND IODINE. Before applying the tests for these elements it is necessary to bring them into inorganic combination by fusing the organic substances containing them with metallic sodium. The analysis is then easily and quickly accomplished with an insignificant expenditure of material, even in the unusual case when all six elements are simultaneously present, and the product of the fusion consists of a mixture of alkaline sulphide, cyanide, (sulphocyanide), phosphide, chloride, bromide, and iodide. The manipulations connected with these tests, when once learned, will be found to offer no difficulties. The reliability of the process has been established by several years' practical trial in the author's laboratory. (b) Directions for the Ignition with Sodium.-Prepare an ignition-tube 8-10 cm. in length from a piece of hard-glass * combustion tubing. Support it in an * The employment of an iron or steel instead of a glass tube is usually permissible and preferable. Fig. 1 represents such a tube in use, suspended by the flange A through the per- forated asbestos-board screen B. The dimensions of these tubes should be: length, 9 cm.; internal diame- ter, 1.3 cm.; thickness of walls, 1.6 mm. They may now be obtained from the firm of Eimer & Amend of New York, by whom they are for sale under the name of "Iron Ignition-tubes for Use in Organic Analysis." Unlike glass tubes they may be used for many successive fusions. After each experiment they should be allowed to stand filled with strong hydrochloric acid for several minutes, and then thoroughly cleaned by use of a test- tube brush and water. The manipulations in the test are the same as with glass tubes, except that an iron tube may be rapidly cooled after the ignition by the application of cold water to its outer surface, as soon as its temperature falls below visible redness. The time required to complete a test is thus materially shortened; and even when the tubes are iron castings, this practice, in the writer's experience, has not been the cause of any accidents. [As the opacity of the iron tube makes it impossible to observe just when the free sodium is com- pletely destroyed after adding alcohol to it, the operator using this method should always be on his guard against the slight explosions that will follow a premature treat- ment of the residue with water.] Since it is well known that nitrogen is fixed as cyanide when a mixture of sodium, iron powder, and carbona- ceous matter is strongly ignited with free access of air, it might be anticipated that iron would Fig. 1. ORDINAL TESTS. 11 exactly vertical position by a narrow metal clamp whose jaws are protected by being wrapped about by one or two layers of asbestos paper permanently wired on. Warm the closed end of the tube gradually before adding the sodium to lessen the danger of cracking the glass. Then drop in the sodium, which should be freshly cut from a large piece that has been wiped free from all adhering oil by filter-paper. The sodium should weigh about a quarter of a gram, and will be of about the size of a pea. Place a burner flame directly underneath the tube and heat its lower end quickly to redness. As soon as the purple vapor of the melted metal is seen to form a layer more than a centimeter in depth, allow five drops of the substance if a liquid, or an equivalent quantity in fragments if a solid, to fall at intervals of one or two seconds directly upon the red-hot bottom of the tube without touching its side walls. The ensuing decomposition is almost instantaneous, and is some- times accompanied by slight but harmless explosions. The face of the operator should not be brought too close to the mouth of the tube during the reaction.^f" When the ignition-tube has become cold, remove the excess of sodiurmmy adding 3 cc. of alcohol. Immediate addition of water is liable to cause explosions. As soon as the reaction between alcohol and sodium ceases, stir with a glass rod, and then pour cold water in cautiously^, in small portions, until the tube is about two-thirds full. Finally stir again with a glass rod and rinse into a test-tube. Boil and filter. Dilute the alkaline filtrate, which will be nearly colorless if the fusion has been satisfactory, to about 20 cc. Separate portions of this filtrate, which will be designated as " S," will be used in making the following tests: (c) Tests for Sulphur.-To 1 cc. of the alkaline ' ' solution S", add two or three drops of a dilute sodium-nitroprusside solution. The presence of sulphur will be indicated by the immediate appearance of an intense, but not very permanent, purple coloration.-[It is best to prepare the reagent at the time when it is to be used, by dissolving a small crystal of nitroprusside in a little distilled water. Nitroprusside solutions do not keep well, though in the dry condition the sodium salt is very stable.] As an alternative test for sulphur, prepare a clear alkaline solution containing lead, by mixing two or three drops of lead-acetate solution with several cubic prove an unsatisfactory substitute for glass in these ignition tests. But experiments have shown that even when the ignition is prolonged (unnecessarily) for five minutes after the addition of the last portion of the organic compound, only a scarcely perceptible blue stain is formed on the filter-paper in test (d) for nitrogen. The tests for sulphur and halogens are not interfered with by the iron. The use of an iron tube is, however, not permissible when the test for phosphorus is to be applied; for sodium appears always to take up some phosphorus or silicon when ignited in contact with cast iron. * The preliminary examination and the ignition test (a) will have given warning of danger if the substance under examination is a high explosive. Accidents from other compounds, if ordinary caution is observed, need not be feared. Liquids are best dropped into the tube from a medicine-dropper or small pipette. If the liquid is very volatile, its introduction will be much facilitated by passing the ignition-tube through a tight-fitting circular hole cut in the middle of a square screen of asbestos-board. This screen, resting on the iron ring of a lamp-stand, shields the hand and dropper from the heat of the flame, and at the same time may be made to serve as a substitute for the clamp which would otherwise be used for holding the ignition-tube in position. The same screen may be used with tubes of smaller diameters if the tube is first fitted with a circular disc or washer cut from heavy asbestos paper. When in use, such a tube will be suspended from a point near the upper end by its washer, which will rest on the upper surface of the asbestos-board screen. By employing such screens, liquids whose boiling-points are very near the temperature of the labora- tory may be successfully treated. An improvement in the method for testing for nitrogen in small quantities of volatile or explosive substances in given in Vol. II, p. 3. 12 ORDINAL TESTS. centimeters of a solution of sodium hydroxide [1 : 10], and add to 1 cc. of "S." The presence of sulphur will be shown by the appearance of a black precipitate of lead sulphide. (d) Test for Nitrogen.-Boil 2 cc. of solution "S" for a minute or two with five drops of sodium-hydroxide solution and five drops of ferrous-sulphate solution. Then add just enough dilute hydrochloric acid to dissolve the precipitate of iron hydrates, and finally, a slight excess of ferric-chloride solution. A single drop of the last-named reagent will be enough, unless the solution should happen to contain much sodium sulphide, which would act on the ferric salt as a reducing agent. If no blue precipitate appears at once, allow the mixture to stand for a few minutes; then throw on a filter and wash with water. Presence of nitrogen will be indicated by a precipitate of Prussian blue. This precipitate, if scanty, may remain for some time in suspension, giving a turbid greenish appearance to the solution, which, in the absence of nitrogen, should merely show a pale yellow color due to the iron salts that have been added. After filtration, the Prussian blue in such a mixture will appear as a precipitate, or a very pronounced blue stain on the filter-paper. Test (d), so far as known, is universally applicable to all nitrogenous com- pounds except the diazo salts. These bodies when heated lose their nitrogen as a gas at such a low temperature that none of it reaches the sodium in a form that is convertible into cyanide. Diazo salts are, however, so well characterized by their physical and chemical properties, that they are not likely to be mistaken for species of the non-nitrogenous orders. (e) Test for Nitrogen and Sulphur when Present together.-Faintly acidify 1 cc. of "S " with hydrochloric acid, and add two or three drops of ferric-chloride solution. A red coloration (ferric sulphocyanide) indicates the presence of sul- phur and nitrogen. This test may be omitted when (c) and (d) have both given a positive result. When a sufficient excess of sodium is used * for the fusion, no sulphocyanide will ever be met with at this point, as, at the temperature of the fusion, sulpho- cyanides are decomposed by the alkali metal to form sulphide and cyanide. It therefore rarely happens that sulphur and nitrogen are not detected by tests (c) and (cl). (f) Test for Phosphorus.-Boil 1 cc. of solution "S" with 3 cc. of concen- trated nitric acid. Cool; mix with two volumes of the ordinary acid ammonium- molybdate reagent; warm to 50°; and allow to stand for ten or fifteen minutes. A pulverulent yellow precipitate indicates phosphorus-(in the absence of arsenic). A portion of the phosphorus originally combined as sodium phosphide is lost as phosphoretted hydrogen when the solution "S" is prepared from the fused mass. Enough, however, remains to give a satisfactory phosphomolybdate pre- cipitate in test (f). (g) Tests for Halogens.-Two cases are to be distinguished:- (1) When sulphur and nitrogen are both absent, acidify 1 cc. of solution "S" with nitric acid and add silver nitrate. If a precipitate of silver halide appears, * Cf. Tauber, Ber. 32, 3150. ORDINAL TESTS. 13 place the remainder of "S" in a very small porcelain dish; add dilute sulphuric acid to faint acid reaction; and boil down to one third of the initial volume. The boiling is to remove alcohol, which may interfere with test (i), in which chromic acid is employed. Dilute the concentrated solution to 20 cc. Under the name of solution " H" it will be used for tests (h), (i), and (j). (2) If either sulphur or nitrogen has been found, prepare solution "H" first, and use 1 cc. of it instead of " S" in making test (1) with silver nitrate. In the preparation of "H" the sulphur will usually have been completely expelled as hydrogen sulphide, and the nitrogen as hydrocyanic acid, so that if no precipitate is obtained, it will be safe to conclude that the halogens are all absent. To detect several halogens in presence of one another, the following analytical scheme, based on the principles used in Carnot's method for their quantitative separation, is recommended as direct and reliable. The complications and mistakes which are liable to occur in using other procedures when a solution contains sulpho- cyanide, or when all hydrocyanic acid and sulphuretted hydrogen have not been removed in the preparation of " solution H," are here rendered impossible in conse- quence- of the complete oxidation or expulsion of the disturbing compounds that occurs during the operations in the test for bromine in (i). (h) Test for Iodine.-Place "solution H" in a 50-cc. separatory funnel, add 3 drops of the nitrosyl-sulphate solution whose preparation is described in the foot- note,* and shake out thoroughly with 5 cc. of carbon disulphide. If iodine is present it will he liberated and taken up by the disulphide, which will acquire an amethys- tine purple color. Shake out with fresh portions of the disulphide until the last portion added is removed colorless. Then add two or three more drops of the nitrosyl-sulphate solution, and repeat the operations described until it is certain that all the iodine has been removed. (i) Test for Bromine.-After the separation of iodine by the method described in the last paragraph, filter the solution through a wet filter to remove the last of the carbon disulphide and transfer to a 75- or 100-cc. round-bottomed flask. Support the latter in a slightly inclined position by means of a clamp, and add to its contents 0.7 grm. of powdered potassium dichromate (free from chloride) and 6 cc. of dilute sulphuric acid. Rinse out the neck of the flask with a little distilled water. Drop in an ebullator tube (cf. p. 223), and then boil the solution briskly over a free flame. Just before boiling begins, insert a short roll of fluorescein * Nitrosyl-sulphuric Acid Solution-Grind together in a mortar 15 grms. of starch and an equal weight of water. Pour the thick cream into a 300-cc. distilling-flask, heated by a boiling water-bath, and then add to it 30 cc. of pure nitric acid (sp. gr. 1.35). The flask is to be pro- vided with a dropping-funnel, and with a delivery-tube for conveying the oxides of nitrogen that will be evolved, into 30 cc. of concentrated sulphuric acid, in which they are to be absorbed. The sulphuric acid should be placed in a small flask surrounded by cold water. A small empty bottle should be interposed between the distilling-flask and the sulphuric acid to condense most of the water and nitric acid that pass over with the gases. Heat the mixture in the flask until a vigorous evolution of gas sets in. When this begins to slacken, gradually admit into the flask through the dropping-funnel 60 cc. more of the nitric acid of 1.35 specific gravity, and continue the heating as long as the oxides of nitrogen are given off freely. The product is a nearly saturated solution of nitrosyl-sulphuric acid in sulphuric acid. In a closed bottle it keeps indefinitely. 2H2SO4 + N2O3=H2O + 2NO.O.SO2.OH. 14 ORDINAL TESTS. paper * for half its length into the mouth of the flask. If the solution contains bromide, bromine vapors will be liberated. These vapors mixed with the hot steam change the lemon-yellow color of the test-paper to a rose-pink. Chlorine is not set free. The test with fluorescein must be repeated at intervals of two minutes, using fresh portions of the test-paper each time, until it is certain that the last trace of bromine has been expelled. (j) Test for Chlorine.-Dilute " H," after the removal of iodine and bromine, to at least 50 cc.; add 2 or 3 cc. of dilute nitric acid; bring to a boil and test for chlorine with silver nitrate. If a precipitate which remains reddish after washing is formed, it is probably colored by silver chromate. In such a case it should be redissolved in a little warm ammonia, and after dilution reprecipitated by nitric acid. The precipitate, if silver chloride, will now be white. The colorless species of every order form its first suborder, and its colored species its second suborder. The position in the classification of compounds that are only very slightly colored is fixed by rules stated on page 204. Determination of the Suborder. * Fluorescein Paper.-This is prepared by soaking filter-paper in a filtered solution con- taining one part of fluorescein in two hundred parts of 50 per cent acetic acid. The paper, which should then have a clear lemon-yellow color, is quickly air-dried, cut in strips, and pre- served in stoppered bottles. It keeps well when not exposed to bright sunlight. The change in color produced in this paper in test (i) by the mixture of bromine vapor and dry steam is due to the formation of eosine (tetrabromfluorescein). CHAPTER III. GENUS I. ALDEHYDES OF SUBORDER I, ORDER I. (Colorless Compounds of Carbon, Hydrogen, and Oxygen.) This genus is by definition made to include all species of the suborder which give Generic Test I. The definition admits to the group in addition to the true aldehydes those acetals that are partially hydrolyzed to aldehydes under the conditions of the test, but excludes the aldose carbohydrates. GENERIC TEST I. ADD 0.05 GRM. OF THE FINELY POWDERED SUBSTANCE, IF IT IS A SOLID, OR ONE DROP, IF IT IS A LIQUID, TO 5 CC. OF A FUCHSINE ALDEHYDE REAGENT * THAT HAS BEEN PREPARED BY THE METHOD DESCRIBED BELOW. IF THE SUBSTANCE DISSOLVES, ALLOW THE SOLUTION TO STAND TWO MINUTES AND THEN OBSERVE THE COLOR. IF THE SUBSTANCE DOES NOT DISSOLVE, SHAKE THE TEST-TUBE CONTAINING IT GENTLY FOR TWO MINUTES AND THEN OBSERVE THE COLOR. NEVER APPLY HEAT. THE APPEARANCE OF A DISTINCT PINK, RED, PURPLE, OR BLUE COLORATION IN THE SOLUTION WITHIN THE TIME LIMIT INDICATES THAT THE COMPOUND TESTED SHOULD BE SOUGHT FOR IN THE TABLES OF THIS GENUS. IF THE SUBSTANCE IS A SOLID, AND NO COLORATION IS OBTAINED, PASS ON TO GEN- ERIC TEST II; IF A LIQUID, TO GENERIC TEST III. Observations on Generic Test I. Soluble aldehydes usually color the fuchsine reagent within a few seconds; those which are difficultly soluble and of high molecular weight sometimes require the full two minutes. Solid substances which for any reason are suspected to be polymerized aldehydes should be boiled with 5 cc. of water containing a drop of strong hydrochloric acid, if no color appears, within the time limit, and a few drops of the cooled solution then added to the reagent. Enough of the compound (e.g. metaldehyde) may thus be depolymerized to give a good reaction. Ordinary acetone and some other soluble ketones prepared by destructive distillation gradually redden the reagent if added to it in large quantity, or allowed * [The Fuchsine Aldehyde Reagent.-Dissolve 0.2 grm. of rosaniline, or, if the free base can not be obtained, of the hydrochloride or acetate, in 10 cc. of a freshly prepared, cold, saturated aqueous solution of sulphur dioxide. Allow the solution to stand until all signs of pink dis- appear and it becomes colorless or pale yellow. This will require several hours. Then dilute with water to 200 cc. and preserve for use in a tightly stoppered bottle. This reagent keeps well if not unnecessarily exposed to air and light, and should always be kept on hand. The directions for its preparation should be followed with care, since any large increase of sulphurous acid above the quantity specified diminishes its sensitiveness so much as to render it unserviceable in testing for the less reactive aromatic aldehydes like sali- cylic aldehyde, vanilline, etc. A reagent that has been in use many months and is found to have lost sensitiveness may be re-sensitized by the cautious addition of sodium acetate, stop- ping at the moment when a faint pink coloration begins to appear, and then discharging this color by a few drops of the oxidized solution held in reserve for the purpose. In this connec- tion it should be stated, by way of caution, that free alkali, or the alkali salts of any weak acid, organic or inorganic, will redden the reagent like an aldehyde. It is also reddened by heat or when exposed in small quantities to the air for some hours at the ordinary temperature. Min- eral acids greatly diminish its sensitiveness.] 15 16 CHARACTERISTICS OF THE ALDEHYDES. to remain in contact with it for a number of minutes; but the color is due chiefly, if not wholly, to the presence of traces of aldehydes or acetals. The limits set upon the quantity of material used, and the time allowed for the development of a distinct coloration, are, therefore, both conditions that must not be disregarded. The reaction is so delicate that the traces of aldehydes occurring as impurities in many commercial preparations may make trouble if their preliminary purification is neglected. But if the conditions prescribed for the test are carefully observed, the best commercial preparations of bodies belonging to other genera rarely give any color within two minutes.* General Physical and Chemical Characteristics of the Aldehydes. Nearly all aldehydes of the liquid division are distinguished by characteristic odors, which, for the more volatile species, may be described as ethereal and at the same time irri- tating or pungent; and for the higher boiling ones, as aromatic, fragrant, or spicy. The solid aldehydes are either odorless or have odors similar to those of the higher boiling liquid aldehydes, though as a rule less intense. Genus I is notable chemically for the great reactivity of its species. Brief contact with small quantities of concentrated mineral acids, alkalies, or certain metallic salts often causes gradual or sudden polymerization of aldehydes to more stable " para" or " meta " modifications, which would entirely fail to give aldehydic reactions were it not for their tendency to dissociate to some slight extent, under the influence of reagents, to the parent compounds. Since the liquid aldehydes are gradually oxidized to acids by exposure to the air, commercial preparations of the species of Division 2 will often be found to react acid towards litmus or phenolphthalein. Aldehydes are readily oxidized by alkaline permanganate in Test 304, and by ammoniacal silver nitrate in Test 101. The latter reaction, which is accompanied by the formation of a silver mirror, or a precipitate of finely divided metallic silver, is a simple and valuable test. Aldehydes usually dissolve in concentrated sulphuric acid with decomposition. Hot solutions of caustic alkali attack them with greater or less ease, according to the species, forming salts of organic acids that are sometimes accompanied by other products. Bro- mine reacts with them readily, hydrobromic acid being evolved. Metallic sodium attacks them much as it does alcohols or phenols, hydrogen being sometimes liberated. Phenylhy- drazine, hydroxylamine, and aniline condense with them to hydrazones, oximes, and anils, compounds which often crystallize well and are very valuable in the identification of in- dividual species. Phenylhydrazine, applied in the manner directed in generic Test VII-2 for ketones, is also a very sensitive general reagent for the detection of the carbonyl radical in aldehydes; but many species in the genera intervening between I and VII likewise react with it. Towards certain reagents like sodium bisulphite, many aldehydes, as well as ketones act like unsaturated compounds. A concentrated bisulphite solution, when vigorously shaken in a test-tube with an equal volume of a liquid aldehyde, or with a concentrated ethereal solution of a solid aldehyde, frequently evolves heat and solidifies, either at once, or after being cooled and shaken, to a thick crystalline magma of the composition R.C.H(OH)(SO3Na), from which the original aldehyde maybe recovered by treatment with an alkali or an acid. A negative result from this test does not prove that a sub- stance is not an aldehyde, for many bisulphite addition-products are too soluble in water to appear as precipitates, while others do not combine readily with the reagent. Many ketones, moreover, show the same behavior with the reagent as aldehydes. * Thus, among the alcohols prepared by Kahlbaum, benzyl and allyl alcohols were the only iwrs which were found to be sufficiently contaminated with an aldehyde to give this test. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER II. GENUS I, ALDEHYDES. Melting-point (C.°). ALDEHYDES.-Colorless and Solid. 35 o-Methoxybenzoic Aid., MeO.CGH4.CHO.-After fusion remelts at 3°.-I. aq • e. s. eth.; s. ale. B. p. 243°-4° C. 37 Acetylsalicylic Aid., o-C2H3O.O.CBH4.CHO.-B. p. 253° (si. dec.). Cryst. mass v. s. ale. or eth. 37 t Piperonal (Heliotropine), CH?.O2.C,H,.CHO.-B. p. 263°. Odor of helio- trope! Ndl. fr. h. aq.; s. 500-600 pts. c. aq.; e. s. ale. or eth.-f Warm 0.1 grm. gently with nitric acid (sp. gr. 1-40); precipitate nitro comp, with cold water; cryst. fr. h. aq.; m. p. of dry, pale-yellow silky ndl. 95-5°. 40 Propionylpropionic Ald.,Et. CO.CHMe.CHO.-B. p. 164-6°. Tbl. s. aq.; v. s. ale. Ale. sol. dark violet w. FeCl3. 44-5 Lauric Aid., CnH?3.CHO.-Cryst. mass. 45-6 t Metacrolein, (C(H4O)3.-Cryst.; odor spicy.-Distill. Pass irritating acro- lein vapors liberated into 2 cc. aq., and apply Test 112. 51 Furfuracrolein, CGHs0.CH0.-B. p. a. 200° w. dec.-Cinnamon odor.-D. s. aq.; e. s. ale. or eth.; s. glacial Ac. containing aniline w. green color! ' 52 i, 2, 3-Trimethylbenzoic Aid., Me3.CGH2.CHO.-Ndl. fr. dil. ale. 52-5 Myristic Aid., C13H,7.CHO.-B. p. 168°-169° (22 mm.). 52-53 Polycenanthylic Aid., (C7Hl4O)a.-I. aq.; v. s. ale. or eth. Dist. gives oenan- thylic aldehyde. 54 o-Oxy-p-toluic Aid., Me.CGH3(OH)CHO.-B. p. 222°-3°.-Violet w. FeCl3.- Sol. in ammonia w. deep-yellow color. 56 o-Oxy-m-toluic Aid., Me.CGH3(OH)CHO.-B. p. 217°-8°.-Deep-blue color w. PeCl3.-Ammon, sol. deep yellow. 58-5 j- Palmitic Aid., C1SH31.CHO.-B. p. 192°-3° (22 mm.). Pearly scales d. s. c. eth. 59-60 Paraisobutyric Aid., (C4H8O)3.-B. p. 195° C. Ndl. fr. aq. or ale. Heated w. H2SO4 gives isobutyric aldehyde. 61 /?-Naphthoic Aid., CJ0H7.CHO.-Lfts. fr. h. aq.; v. s. ale. or eth. 63-5 Stearic Aid., C17H35.CHO.-B. p. 212°-3° (22 mm.). Scales fr. eth. 80-81 f Vanilline, C0H3.(MeO)(OH)(CHO)(3 ; 4 : 1).-Slender ndl. fr. h. aq.; s. in 20 pt. h. aq. or in 90-100 pt. c. aq ; e. s. ale., eth., or CHC13. Strong vanilla odor ! Taste at first burning, then like vanilla ! Aq. sol. (1 : 200) gives immediate blue coloration w FeCh in Test 401.-Dissolve 0.05 grm. in 10 cc. aq. Add 2 drops cone. HC1 and 2 drops FeCl3 sol. (1 :10). Boil one minute. Filter hot. Wash. Boil residue w. 5 cc strong alcohol. Filter; dry at 100° and determine melting-point The product, dehy- drodivanilline, forms slender, nearly colorless, silky microcrystalline ndl. melting w. dec. at abt 304° (uncor.). 97-2 o-Aldehydobenzoic Ac., CO2H.CGH4.CHO.-Lfts. v. s. aq., ale. or eth. Ag salt cryst. in ndl. fr. h. aq -NH3 gas passed into ale. sol. gives cryst. cornu, m p. 187°. [Gives Test I w. the fuchsine reagent, (A. 239, 82) ] 104 m-Oxybenzoic Aid., HO.C„H4.CHO.-B. p. 240° Ndl. fr. h. aq.-Sol. violet w„ FeCl3; gives ppt. w. Pb.Ac2. Heating w. X's acetic anhydride gives diacetate, m. p. 76°. 105-6 Trimethyl-o-oxybenzoic Aid., Me3.CGH(0H).CH0.-Pale-yellow ndl.; i. aq. or KOH; s. ale. or eth. Sublimes. DIVISION A-SOLID ALDEHYDES. 17 18 GENUS I, DIV. A, Melting-point (C/). ALDEHYDES.-Colorless and Solid. 110 p-Oxy-o-toluic Aid., Me.C6H3OH.CHO.-Tbl. s. h. aq.; e. s. ale., or eth. Rose red w. FeCl3. Ammonia sol. colorless. Sbl. 112-15 j-Metaldehyde, (CJI^j)^.-I. aq.; d. s. eth., ale. Dist. w. dil. H2SO4 gives acetaldehyde (Test 111). For behavior toward reagents cf. remark on page 15. 115 p-Oxy-m-toluic Aid., Me.C6H3(OH)CHO.-Pr. fr. aq.-Blue-violet color w. FeCl3. 115-16 p-Oxybenzoic Aid., H0.CGH4.CH0 -Sbl. undec. D. s. c. aq.; e. s. ale., eth. Pale-violet color w. FeCl3.-For derivative cf. Paal, Ber. 28, 2409. Sbl. abt. 120 f Paraformaldehyde (commercial), (CH,O)X.-Odor and reactions like form- aldehyde. White amorphous powder.-Apply Test 114-1. 128 Disalicylic Aid., CI4HI0O3.-Sbl. undec. Almost i. aq. or KOH; e. s. ale., eth. Cold cone. H2SO4 gives salicylic aid. 130 Dialdane, CSH14O3.-Cryst. v. d. s. aq., eth.; e. s. h. ale. 164-6 m-Aldehydobenzoic Ac., CO2H.C0H4.CHO.-Cu salt green-blue ndl. Oxime m. p. 165°d. 175 Helicine, C13H1GO7.-(Cryst. w. |H2O, which is lost at 100°.) Small ndl. s. 64 pt. aq. at 8°; i. eth.-No color w. FeCl3. Dil. min. acids hydrolyze to dextrose and salicylic aldehyde. Opt. act. 179 (v-)m-Aldehydosalicylic Ac., (HO)(CO2n).CGH3.CHO.-Sbl. S. h. aq.; s. w. yellow color in NaOH-Sol. red w. FeCl3. 180 Metapropionic Aid., (C3H6O)X.-Sbl. fr. 160°. I. aq.; v. d. s. ale. 221-2 Aldehydovanillic Ac., MeO.CGH2.(OH)(CO,H)(CHO).-Silky ndl. v. d. s. c. aq.; s. -Yellow sol. in NaOH. Dingy-violet color w. FeCl3. 234 p-Aldehydo-m-oxybenzoic Ac., CHO.C6H3(OH)CO,H,-Ndl. d. s. h. aq.; e. s. ale. or eth.-Sol. in NaOH is deep yellow.--Gives violet color w. FeCl3. 237-8d. Aldehydo-(v)-oxyisophthalic Ac., CHO.CGH2.(OH)(CO2H)2.-S. h. aq.; e. s. eth.-Sol. cherry-red w. FcCl3.NaOH sol. colorless! 243-4 m-Aldehydo-p-oxybenzoic Ac., CHO.CGH3(OH)CO,H.-D. s. aq.; e.s. eth. Aq. sol. brick-red w. FeCl3. NaOH sol. deep yellow! 247 p-Aldehydocinnamic Ac., CHO.CGH4.C2H2.CO,H.-Sbl. in Ifts. D. s. eth. 248-9 (a-)m-Aldehydosalicylic Ac., CHO.CGH3fOH)CO.H.-D. s. h. aq.; e. s. eth. NaOH sol. colorless. FeCl3 gives red color to aq. sol. 260d. Aldehydo-(a)-oxyisophthalic Ac., CHO.CGH,OH.(CO2H)2.-Ndl. fr. h. aq., e. s. eth. Does not sublime. Blood-red color w. FeCl3. Alkali solutions are yellow w. green fluorescence. 285 p-Aldehydobenzoic Ac., CHO.CGH4.CO2H.-Sbl. in small ndl. D. s. eth. or h. aq.-Ndl. fr. aq. (ORDER I, SUBORDER I.) COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I]. GENUS I, ALDEHYDES. DIVISION B-LIQUID ALDEHYDES. Boiling-point (CM. ALDEHYDES.-Colorless and Liquid. 20-8 t Acetic Aid., Me.CHO.-G. 0-8056%. Odor pungent-ethereal, stifling! Mise. w. aq., ale., or eth.-Apply Test 111! 45-5 t Methylal, CH2.(OMe)2.-G. 0 • 872J%. Odor alcoholic.-E. s. aq.-Apply formic aldehyde Test 114-1 to dil. aq. sol. 48-8c. t Propionic Aid., Et.CHO.-G. 0 -80662%. S. in 5 pts. aq. at 20°. Odor pun- gent.-Warm w. 2 pts. phenylhydrazine; wash hydrazone w. dil. acetic acid; then heat w. an equal wt. ZnCl2 at 180°. Disgusting skatol odor is produced. 52-4 f Acrolein, CH2 :CH.CHO.-G. 0-84. Vapor excessively irritating; in traces provokes flow of tears. E. s. aq.-Polymerizes to i. solid so readily that it can not long be preserved liquid.-Apply Test 112 ! 59-61 Propargyl Aid., CH':C.CHO.-E. s. aq. Very irritating to mucous mem- branes. Gives orange ppt. with ammon. Cu2Cl2 sol ! 63-4 t Isobutyric Aid., C3H7.CHO.-G. 0 • 79382%. S. in 9 vol aq.-NaHSO3 comp, pearly Ifts. rather d. s. aq. 64 Dimethylacetal, Me.CH.(0Me)2.-G. 0-866 at 22°. 73-4 n-Butyric Aid., Pr.CHO.-G. 0-81702%. S. in 27 pt. aq.-NaHSO3 comp. e. s. aq. or ale. 74-5 Trimethylacetic Aid., Me3.C.CHO.-G. 0-7927 (18°). 89c. Methylene-diethyl Ether, CH2.(OEt)2.-G. 0-851 (0°). S. in 11 vol. aq.-Not acted on by h. KOH. 92-5 f Isovalerianic Aid., C4H9.CHO.-G. 0-82 (0°). Odor when free fr. valerianic ac. sweet and aromatic. Shaken w. cone, ammonia solidifies to cryst. comp. (m. p. 56°-8°). 97-8 j-Formic Aid., (commercial "40 per cent solution" in water). Distillation leaves white residue of "paraformaldehyde" in flask. Odor pungent. Apply Test 114! 103-4 n-Valerianic Aid., C4H9.CHO.-G. 0-82 (11.2°). 104 j-Acetal, Me.CH.(OEt)2.-G. 0-83142%. Odor-agreeable and refreshing-not irritating.-S. in 18 vol. c. aq. The dil. aq. sol. if first mixed with a few drops of HC1 gives acetaldehyde (Test 111). (Boiling with NaOH gives no acetaldehyde.) 104-5 a-Crotonic Aid., Me.CH :CH.CHO.-G. 1-033%. Odor fruity, then irritat- ing. Absorbs O, and adds Br2 easily. 115-17 Tetramethylene Aid., C4H7.CHO. 116-6c. Tiglic Aid., Me.CH :CMe.CHO.-G 0-87 (15°). Odor like bitter almonds. S. in 40-50 pt. aq. Air oxid. easily. 121-7 Isobutylacetic Aid., C4H9.CH2.CHO.-Odor aromatic. 124c. t Paraldehyde, (C2H4O)3.-G. 0-9992 at 15°. M. p. 10°.5. Odor ethereal, agreeable. S. in 10 pt. aq. Heated with a very little cone. H2SO4 gives off acetic aldehyde freely. Pure, does not give acetic aldehyde (Test 111) distinctly. Solidified by freezing mixture. M. p. +12.5° 129c. n-Caproic Aid., C6Hn.CHO.-G. 0-8498 at 0°. 137-3c. Methylethylacrolein, Et.CH :CMe.CHO.-G. 0-8577 at 20°. Almost i. aq. Odor penetrating. 19 20 GENUS I, DIV. B. (ORDER I, SUBORDER I.) Boiling-point (C.°). ALDEHYDES.-Colorless and Liquid. 146-8 Ethylidenedipropyl Ether, CH3.CH.(OPr)2.-G. 0-825 at 22°. I. aq.; s. cone. HC1. Reduces ammon. AgNO3 sol.-Not attacked by hot KOH. 155 f CEnanthic Aid., C6H13.CHO.-G. 0-84952%. Odor aromatic. 160-2 Ethyl Methylformylacetate, CO2Et.CH.Me.CHO.-Gives intense red-violet coloration w. FeCl3. 161 f Furfurol, C4H3O.CHO.-G. 1 • 159 4 20/4. Darkens on exposure to light. Odor remotely resembles that of bitter almonds and cinnamon.-Apply Test 115. 161-2d. [Glycid, cf. Genus VIII.]-Dist. w. dec. giving acrolein (Test 112). 166-2c. Propylidinedipropyl Ether, Et.CH.(OPr)2.-G. 0-8495 at 0°. 169-6 Isocapric Aid., C9HI9.CHO.-G. 0-828 at 0°. NaHSO3 gives no comp. 169-70 Parapropionic Aid., (C3H6O)3.-I. aq. Dist. w. a drop or two of cone. H2SO4 gives much propionic aid. 170-ld- J4, "-Dihydrobenzaldehyde, C7H8O.-G. 1-0327 at 0°. Oil w. penetrating odor. 179-5 t Benzaldehyde, Ph.CHO.-G. l-0504.15/4. Bitter-almond odor. S. in abt. 300 pt. aq.-Apply Test 113. 186-8d. Laevulinic Aid., Me.CO.(CH2)2.CHO.-G. 1-0156 at 16°. "Odor aldehydic." Mise. w. aq.-Reduces Fehling's sol. in the cold. Colored red by cone. H2SO4. 186-8 Tetrahydrobenzaldehyde, C7HlnO.-G. 1-0091 at 0°. I. aq. Odor like ace- tone and bitter almonds. Reduces Fehling's sol. in cold. 187 (th. i.) Methylfurfurol, Me.C4H2O.CHO.-G. 1-1087 at 18°. S. in 30 pt. aq.-1 drop in 5 cc. ale. +1 cc. cone, sulphuric acid gives green color. Cone, ammonia gives the furfuramide (m. p. 86-7°, ndl. fr. dil. ale.). 188-92 Diisovalerianic Aid., C10H18O.-G. 0-861 at 0°. I. aq.; e. s. ale. Odor aromatic. 193-4 Phenylacetic Aid., Ph.CH2.CHO.-G. 1-085. Phenylhvdrazone ndl. fr. Igr. m. p. 58°. 196-5c f Salicylic Aid., o-HO.Cf)H4.CHO.-G. 1 • 173 at 13°. Odor faint aromatic. D. s. aq.; v. s. ale. or eth. Aq. sol. gives w. FeCl3 intense violet color.-Con- vert into the phenylhydrazone. 199 m-Toluic Aid.. Me.C0H4.CHO.-G. 1-037 at 0°. Bitter-almond odor. Pre- pare corresponding phenylhvdrazone, m. p. abt. 90°. 200 o-Toluic Aid., Me.CcH4.CHO.-M. p. of oxime 48°-49°. 204 p-Toluic Aid., Me.C6H4.CH0.-Odor pepper-like.-M. p. of oximes 79°-80°, and 108°-110°. 205-8 t Citronellal, C9Hi7.CHO.-G. 0-8538 at 17.5°. Strong geranium-like odor! Opt. active. Identify by conversion into its semicarbazide of m. p. 84°. (Cf. Ber. 31, 3307.) 208 Hydrocinnamic Aid., Ph.C2H4.CHO. 208-9 (v)-o-Oxy-m-toluic Aid., Me.CGH3OH.CHO.-M. p. 17°. D. s. aq.; e. s. eth.-• Sol in ammonia yellow. Sol. in FeCl3 bluish. 210-8c. Ethylidene-diisoamyl Ether, Me.CH.(OC5Hn)3.-G. 0-8347 at 15°. 228-9 f Citral, C9Hlfi.CHO.-G. 0-8972 at 15°. Odor of oil of lemon! Opt. active. -Identify by converting into the semicarbazide of m. p. 164° (cf. Ber. 31, 3331). 230 m-Oxybenzoicaldehydemethylether, MeO.CGH4.CHO.-G. 1 • 1187 20/4. Forms a d. s. NaHSO3 comp. 230 /?-Diisobutylene Aid., C8H14O.-G. 0-9575 at 0°. Thick oil of agreeable odor. Resinified by h. NaOH sol. 235 t Cuminic Aid., p-Me2.CH.CcH4.CHO.-G. 0-9832 at 0°. Odor aromatic and characteristic. Gives terephthalic ac.( cf. Test 318).-Color reaction with H2SO4 (A. 137, 104). f Phenylhydrazone deriv. white but unstable (m. p 127^129°). 235-40 i, 3, 5-Trimethylbenzoic Aid., Me3.C6H2.CHO. GENUS I, DIV. B. 21 (ORDER I, SUBORDER I.) Boiling-point (C.°). ALDEHYDES.-Colorless and Liquid. 245 m-Oxybenzoicaldehyde-ethylether, EtO.C0H4.CHO.-G. 1 • 076820/4. Yellow oil. 248c. f Anisic Aid., p-MeO.CfHpCHO.-G. 1-1228 at 18°. M. p. 0°. Odor aro- matic. Hot ale. KOH gives anisic ac. and anisic alcohol.-f Prepare the phenylhydrazone, a pearly-white ppt., m. p. 120° (uncor.). Procedure exactly as in Test 113-1, except that only half the quantity of dilute alcohol there prescribed should be used in each operation. 279 Dioenanthylic Aid., C14H2oO.-G. 0-8494 at 15°. Oil with faint odor. [Important aldehydes that can be distilled only under reduced pressure.] 128-30 (20 mm.) f Cinnamic Aid., Ph.C2H2.CHO.-G. l-049724/4. Odor like cinnamon, changed by shaking w. excess of permanganate sol. [1 : 10] to odor of benzaldehyde.-f Prepare the phenylhydrazone by method given in Test 113-1, except that the product should be boiled up three times with 15 cc. of 50 per cent alcohol, instead of twice with 12 cc. This hydrazone is yellow (YT1-YT2), and melts at 168° (uncor.). NUMBERED SPECIFIC AND SEMI-SPECIFIC ALDEHYDE TESTS. [TESTS 101-200.] ioi. Compounds Reducing Silver from Tollen's Reagent. Place 1-2 drops, or about 0.05 grm., of the finely powdered substance in a test-tube with 2-3 cc. of the reagent (whose preparation is described below*). Shake and allow to stand without warming for about five minutes. A black or brownish-black precipitate of metallic silver, or a silver mirror adhering to the walls of the tube, shows that the compound has silver-reducing power and may be an aldehyde. Outside of Order I, Genus I, many scattered species reduce silver from Tollen's reagent. Representative bodies of this description are glucose among the carbohydrates, and hydroquinone among the polyacidic phenols. So far as it is known, this reaction fails among the aldehydes only in the case of a few aromatic oxy-aldehydes like salicylic aldehyde and vanilline. It is generally a very delicate and satisfactory reaction. in. Acetaldehyde. (Properties tabulated on p. 19.) 1. Boil 1 cc. of a clear aqueous solution of the aldehyde that is concentrated enough to have a distinctly pungent odor with 5 cc. of sodium hydroxide solution (1:10) for a minute or two. The solution, which at first assumes a clear-yellow color, soon becomes turbid, opaque, and yellow orange (YOSI) from separation of finely divided acetaldehyde resin. At the same time a peculiar, penetrating and rather persistent odor is given off. Although many other aldehydes give colorations to boiling soda solution, and emit odors during treatment, this reaction when applied comparatively, or when the odor and color are both familiar from earlier experience, is a delicate and characteristic preliminary test. Propionic aldehyde, which resembles acetaldehyde more closely in its physical proper- ties than any other species in its genus, gives a somewhat similar odor and turbidity; but the turbidity is less conspicuous in dilute solutions, is nearly white instead of yellow- orange and entirely disappears if the boiling is long continued. Half a drop of acet- aldehyde, for instance, when boiled with 5 cc. of the soda solution is enough to give the test^as described; while three drops of propionic aldehyde under the same circumstances give only a milky-white precipitate which disappears on continued boiling with emission of a strong lemon-like odor. The lemon odor is usually noticeable in testing acetaldehyde, but is not the dominant odor. * Tollen's Ammoniacal Silver Nitrate Reagent.-This reagent is prepared by mixing equal volumes of a 10 per cent solution of silver nitrate in ammonia, and of a 10 per cent aqueous sodium hydroxide solution. The ammonia solution used for dissolving the silver nitrate should be a mixture of one volume of the most concentrated aqua ammonia of commerce (sp. gr. 0.90) with one volume of water. The solution of silver nitrate in the diluted ammonia should always be kept in stock, but must not be mixed with the caustic soda until it is needed for an experi- ment, since the mixture on long standing deposits a highly explosive black precipitate. It also gives a black precipitate immediately, and without the addition of any reducing compound, when heated to boiling. It is a much more senstive reagent for aldehydes than a simple solu- tion of silver nitrate in ammonia. 22 NUMBERED SPECIFIC TESTS OF GENUS I. 23 2. Shake in a three-inch test-tube 0.18-0.25 grm. of 5-naphthol, 2 drops of concen- trated hydrochloric acid, and about 2.0 cc. of glacial acetic acid, until the naphthol is nearly all dissolved. Add one drop of the aldehyde and shake again. Heat at 50°-60° for about five minutes. Then boil for one minute. Cool and shake vigorously until a crystalline precipitate separates. Because of its tendency to form supersaturated solutions, this precipitate sometimes comes down slowly. Allow to stand until the precipitate has begun to settle. Filter through a small filter wet with glacial acetic acid. Wash with 1 cc. of cold glacial acetic acid. Boil with a mixture of 3 cc. alcohol and 1 cc. of water for half a minute or so. Most of the precipitate will remain undissolved. Cool thoroughly and shake. Filter. Wash with 1 cc. of cold dilute alcohol (1:1). Dry 15-30 minutes at 100°. The product in this test-which is not directly applicable to very dilute solutions of acetaldehyde-is ethylidene-/?-dinaphthyl oxide, melting at 172.5°-173.5°. ii2. Acrolein. (Properties tabulated on p. 19.) The following tests for acrolein are to be applied to dilute aqueous solutions strong enough to possess a distinctly irritating odor. (Such a solution, for instance, as is obtained from the distillation of one drop of glycerine with acid potassium sulphate in Test 816-2.) 1. Add 2 cc. of the acrolein solution to 5 cc. of the fuchsine aldehyde reagent pre- pared as described under Test I. (Addition of sodium acetate will never be necessary.) Allow the mixture to stand overnight at the ordinary temperature. It will then appear opaque by reflected light with a deep violet-blue color like cobalt glass. In very thin layers the color will be approximately VR. Add to the blue solution an equal volume of hydrochloric acid, sp. gr. 1.2. Within half a minute the color will change to an impure OYS2. Gradually dilute 2 cc. of this solution to 30 cc. with water. The color on dilution will change, passing through yellow-green and blue-green to about VB of the color standard (the comparison being made against a white background in a test-tube about 2 cm. in diameter). These color changes, collectively, distinguish acrolein from all other common volatile aldehydes, although the initial coloration alone is not characteristic. A dilute acetalde- hyde solution, such as would be obtained in applying the distillation test for glycerine (Test 816) to a drop of ethylene glycol, gives a quite similar coloration at the beginning of the test, but this fades, sometimes almost to colorlessness, on standing overnight, while the surface of the solution becomes covered with a thin cantharides-green scum. At the end of the experiment when an acetaldehyde solution is used, after the treatment with acid and dilution with water, the final color will be an exceedingly pale tint of VR, having an intensity about half or one third of the VRT2 of the standard. 2. Mix one drop of the acrolein solution with six drops of a cold saturated alcoholic solution of gallic acid, and dilute with water to 2 cc. Pour the mixture gently down the side of an inclined test-tube containing 3 cc. of pure concentrated sulphuric acid, in such a manner that the two liquids shall not mix. Allow to stand for some minutes. A very distinct red-orange (RO) ring will appear at the plane of contact between the liquids. 113. Benzaldehyde. (Properties tabulated on p. 20.) 1. Dissolve one drop of the aldehyde in 12 cc. of 50% alcohol. Add one drop of pure phenylhydrazine and boil for half a minute. Cool. Shake well, and collect the bulky pre- cipitate on a small filter. Wash with 5 cc. of cold 50% alcohol. Redissolve the washed precipitate in 12 cc. of boiling 50% alcohol. Cool. Filter, and again wash with 5 cc. of cold 50% alcohol. Dry the well-drained precipitate on the opened filter for fifteen minutes in an oven at 100°. Determine its melting-point. The precipitate, benzalphenylhydrazone, is a crystalline white or faintly yellowish compound melting at 156° (uncor.) and changing in color to OT2-* after exposure for one hour to diffuse daylight from a clear sky. The yield is very good. 24 NUMBERED ALDEHYDE TESTS. 2. In a small dry test-tube mix, in the order given, one drop each of melted phenol, the aldehyde, and concentrated sulphuric acid. Dissolve as much as possible of the colored product in 2-3 cc. of 10% sodium hydroxide solution by stirring with a glass rod. Benzaldehyde gives immediately a beautiful, intensely violet-red (VR) solution. 3. Prepare a cold saturated aqueous solution of the aldehyde and /?-naphthol by shaking together one drop of the aldehyde, a pinch of /3-naphthol and 10 cc. of water. Filter, and pour 2-3 cc. of the clear solution down the side of an inclined test-tube containing 3 cc. of concentrated sulphuric acid. A violet-red (VRT1) colored zone will appear at the plane of contact between the acid and aqueous layers. 114. Formic Aldehyde. (Properties tabulated on p. 19.) 1. Mix one drop of a one-half per cent aqueous solution of resorcine with 1 cc. of a dilute aqueous solution of the aldehyde of such a concentration (about 1:500) that the irritating odor of the aldehyde is just barely perceptible in the cold, though rather un- pleasantly strong when the solution is heated to 100°. Allow the mixture to flow gently down the side of an inclined test-tube containing 3-5 cc. of pure concentrated sulphuric acid. Impart a gentle rotary motion to the liquids by cautiously swaying the lower end of the tube through a circle about a decimeter in diameter in such a manner as not to cause the disappearance of the two layers. If formic aldehyde is present a red (R) ring, slightly tinged with violet, will soon appear. Above this ring a light flocculent precipitate, at first nearly white on its upper surface, and red-violet beneath, but soon changing to flocks that are red (R) throughout, will be seen suspended in the aqueous upper layer. 2. Repeat part I of the test, substituting six drops of a cold saturated alcoholic solu- tion of gallic acid for the resorcine. A pure blue (B) ring will be formed. [In either of the preceding color tests it would be a serious mistake to employ too concentrated aldehyde solutions. Such solutions yield deep-colored precipitates that obscure the purer and more characteristic hues that it is desired to produce.] 3. (Applicable to concentrated aqueous solutions like the commercial "formalin".) Place in a test-tube three drops of the solution, 3 cc. of dilute alcohol (1:2), 0.04- 0.06 gram of ^-naphthol, and three to five drops of concentrated hydrochloric acid. Boil gently until the liquid fills with an abundant precipitate of small white needles. Filter while hot. Wash with 1 cc. of dilute alcohol (1:2). Boil the precipitate with 4 cc. of dilute alcohol (1:1). (It is not necessary that all should dissolve.) Cool, and filter off the precipitate. Wash with 1 cc. of dilute alcohol (1:1). Dry on porous tile in a warm place and determine the melting-point. Methylene-di-/?-naphthol, the product, forms white needles, which, when the tempera- ture in the neighborhood of its melting-point is raised at the rate of 1° in 15 seconds, begins to turn brown at 180°. It melts with decomposition to a brown-red liquid at 189°-192° (uncor.). The directions for part (3) of this test are specially intended for use with solutions containing 30-40% of formic aldehyde, but they become applicable to much weaker solutions, if the quantity of the aldehyde solution taken in such cases is proportionately increased. In working with a 10% solution, for example, ten drops instead of three should be used. A moderate excess of the aldehyde produces no injurious results. 115. Furfurol. (Properties tabulated on p. 20.) 1. Mix in a dry test-tube one drop of the aldehyde and two drops of phenylhydrazine. Dissolve the pasty reaction product in 3 cc. of boiling 50% alcohol. Cool well in running water, and shake until the precipitate, which often appears at first in an amorphous con- dition, separates in pearly crystalline scales. Collect on a small filter. Wash with 5 cc. NUMBERED SPECIFIC TESTS OF GENUS I. 25 of a cold mixture of two volumes of water and one of strong alcohol. Transfer the pre' cipitate to a test-tube and redissolve in 5 cc. of a boiling mixture of one volume of strong alcohol and two of water. If a few dark-colored droplets should separate at this point, allow them to settle, and decant the clear hot -solution into another tube. Cool and shake the solution until pearly scales are again separated. Collect on a small filter and wash with 5 cc. of a cold mixture of two parts of water and one of strong alcohol. Drain. Dry in an oven at 85°, and then determine the melting-point. Furfurolphenylhydrazone, the product of this test, melts at 97° (uncor.). The crystals have a pale-yellow color and a conspicuously pearly lustre. 2. Boil in a test-tube a mixture of one drop of the aldehyde and 2-3 cc. of water. Moisten a strip of paper with a mixture of equal parts of aniline and glacial acetic acid, removing any excess of the mixture with blotting-paper. Hold a roll of test-paper in the steam issuing from the tube. If the furfurol is present, the paper will be immediately colored a bright light red (RTI). The test is simple and delicate. CHAPTER IV. GENUS II. CARBOHYDRATES OF SUBORDER I, ORDER I. (Colorless Compounds of Carbon, Hydrogen, and Oxygen.) This genus includes all the carbohydrates treated in the work, but no glucosides. The species described when pure are all solid at the ordinary temperature. GENERIC TEST II. THIS TEST CONSISTS OF TWO PARTS, THE MOLISCH CARBOHYDRATE REACTION, AND THREE SUPPLEMENTARY TESTS. APPLY THE MOLISCH REACTION FIRST; THEN, IF THE RESULT SHOULD BE NEGATIVE, OMIT THE SUPPLE- MENTARY TESTS. THE REASON FOR APPLYING THE LATTER, WHEN THEY ARE REQUIRED, IS TO EXCLUDE CERTAIN SPECIES OF OTHER GENERA WHICH GIVE COLORATIONS IN THE MOLISCH REACTION, AND MIGHT CONSEQUENTLY BE MISTAKEN FOR CARBOHYDRATES. The Molisch Carbohydrate Reaction.*-Place about 5 mgr. of the substance with 10 drops of water in a small narrow test-tube, and mix with 2 drops of a 10 per cent chloroform solution of a-naphthol. Allow 1 cc. of pure concentrated sulphuric acid to flow slowly from a pipette down the lower inclined side of the tube, so that the acid may form a layer beneath the aqueous solution without mixing with it. If a carbohydrate is present, a red ring will appear within a few seconds at the line of separation between the two layers. The color soon changes on standing or shaking, a very dark-purple solution being formed. Shake, and allow to stand for one or two minutes; then dilute with 5 cc. of cold water. In presence of a carbohydrate, a dull-violet precipitate will immediately appear. Addition of an excess of strong ammonia will change the color to a rusty-yellowish brown. Any substance that gives the dull-violet and rusty-brown precipitate, as well as the purple coloration, under the circumstances described, may be assumed to be a carbohydrate. Observations.-On account of the delicacy of the Molisch Reaction it is very essential that the substance examined shall be entirely free from all traces of filter- paper, particles of woody fibre, or dust. The purity of the reagents employed should also be placed beyond question. The presence of nitrous acid in the sul- phuric acid is specially objectionable. The reagents may be tested by shaking one drop of a-naphthol solution with ten drops of water and 1 cc. of concentrated sulphuric acid. The mixture should be of a golden-yellow color. If dark green, the reagents are not sufficiently pure. The naphthol solution does not keep well, and so should not be prepared in large quantities. * Modified from Molisch, M. 7, 198 (1888). 26 GENUS II. CARBOHYDRATES. 27 The immediate cause of the colorations observed in the Molisch Reaction is supposed to be the formation of an unstable condensation product of furfurol and a-naphthol. The Supplementary Tests.-(1) Test the reaction of a little of the substance, which has been dissolved or suspended in powdered form in a few drops of water, with litmus. If the reaction is distinctly acid, the compound is not a carbohydrate. (2) Place about 5 mgr. of the substance in a small test-tube, cover with 10 drops of water, and then mix with 1 cc. of concentrated sulphuric acid. If a red or purple coloration, or indeed any coloration other than a yellow or brown to black, makes its appearance, the compound is not to be sought among the carbohydrates. (This test results in the exclusion of several glucosides like salicin and coniferin.) (3) Add one drop of a one tenth per cent ferric-chloride solution to 1 cc. of a 1 per cent aqueous solution of the substance; or if the latter is very insoluble, to its cold saturated aqueous solution. Unless the solution remains colorless, or, at most, shows a pale-yellow or orange-yellow coloration, the compound is not to be looked for in this genus. (This test excludes certain glucosides like arbutin and esculin.) Subdivisions and Contents of Genus II. The principles guiding the selection and arrangement of species in this genus differ materially from those followed in the case of other genera. The carbohy- drates, that have been obtained in a pure condition up to the present time are all solids. The genus therefore contains only a single "Division," which is subdivided into two "Sections," and several small "Subsections," whose relations to one another will be readily understood from an inspection of the tables. Section 1 includes all species giving clear solutions in less than ten parts of cold water. It contains all the sugars, monosaccharide and polysaccharide. Many, but not all of them, have a sweet taste. The species of Sec- tion 2 are either insoluble in ten parts of cold water, or dissolve to solutions that remain opalescent or turbid after repeated filtration. This is the section of starch, glycogen, and cellulose. The members of both sections are colorless, odorless, and neutral towards indicators. It will be noticed that the number of species described is comparatively small. The names of a majority of the rare synthetic sugars, such as the glucoses and taloses, 1-glucose and 1-fructose, the heptoses, octoses, and nonoses, are lacking, as are also many of those of the less accessible natural carbohydrates. The cause of these omissions is the nature of the scheme of analytical procedure adopted. This is simple and systematic, but of such a character that the position of every species described had to be determined by actual experiment. It will not be amiss to remind the reader that the direct application of the tests recommended in this chapter to unknown mixtures is not allowable. Generic Characteristics.-The carbohydrates seldom melt sharply, because fusion is nearly always preceded by slight decomposition. Their melting-points are accordingly of minor importance as specific properties, and worthless as indications of chemical purity. When determined they should be observed by the capillary-tube method (cf. p. 220) in a bath whose temperature is rising somewhat rapidly. The instability of the sugars towards heat is further manifested by their tendency to pass into the state of uncrystallize- able syrups when their solutions are concentrated by boiling down under the ordinary atmospheric pressure. The specific rotations of the soluble carbohydrates cover a wide range in their values; are the most characteristic of their physical constants; and will usually be determined 28 GENUS IL CARBOHYDRATES. in any laboratory that is equipped with the requisite apparatus. The deficiency of many laboratories in this respect is the only reason for not employing the specific rotation as the chief means for fixing the arrangement of the soluble carbohydrate species within their "sections." The description for any sugar in the tables is always for the more com- mon of the two optical isomers bearing the name. The description for the " optical anti- pode," if it were given, would be the same as that for its isomer, except that the specific rotation would have the opposite algebraic sign. Many of the soluble carbohydrates reduce Tollen's ammoniacal silver nitrate reagent (cf. p. 22) in the cold, and Fehling's solution (cf. Test 202) on heating; but none of them, even such as have been shown to contain the aldehydic grouping, redden the fuch- sine aldehyde reagent of Test I. Heated with normal potassium hydroxide under the conditions prescribed for the saponification of esters (cf. Test V), some carbohydrates are rapidly attacked, giving dark brown or black solutions and neutralizing much alkali; others, like cane-sugar, remain practically unchanged after long-continued treatment. Some of the reactions of the group that have been found most valuable for diagnostic purposes, such as those leading to the formation of osazones, furfurol, etc., and the use of Fehling's solution, are described in the numbered reactions beginning on page 32. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I], GENUS II, CARBOHYDRATES. CARBOHYDRATES SOLUBLE IN LESS THAN TEN PARTS OF WATER AT 20°, GIVING SOLUTIONS WHICH ARE NOT OPALESCENT AFTER FILTRATION. SECTION 1. SECTIONAL PROCEDURE.-Apply Test 201 ("Rapidity of Osazone Formation") to 0.1 grm. of the substance.-Then: (1) if a white crystalline precipitate appears within less than one minute, see Subsection A; (2) if no precipitate separates from the hot solution within twenty minutes, see Subsection B; (3) if a yellow or orange-yellow precipitate sepa- rates within less than twenty minutes, see Subsection C. Subsection A. [Test 201 gives a nearly white precipitate within 1 minute f d-Mannose, C6H12Oh.-Hard amorph. mass, or pr. fr. 90% ale.; s. 0.4 pt. c. aq.; d. s. c. ale.; i. eth.-[«]D= + 14-4°.-Taste sweet.-Reduces Fehling's sol. (Test 202).-Test 201 gives a nearly white cryst. ppt. of the phenylhydrazone after | min. heating, which after recryst. fr. boiling aq. melts at 195°-200° (r. li.) ! (The last test is characteristic.) Subsection B. [Test 201 gives no precipitate after heating for 20 min.\ SUBSECTIONAL PROCEDURE.-Test with Fehling's solution by Test 202. If a heavy red precipitate is obtained, see maltose, lactose, and dextrin; if none appears, or if it is yellowish and very scanty, see saccharose, raffinose, and gum arabic. f Maltose, C]2H22On+ H,O.-Fine white ndl., losing aq. at 100-10°. V. s. c. aq.; v. d. s. c. ale.- Tastes as sweet as cane-sugar.-[«]D = +137-7°.--In Test 201 no osazone separates fr. the sol. while hot, even after 2 hours' heating.-Oxidation by Test 205 gives saccharic ac., but no mucic ac. f Lactose (Milk-sugar), C12H22Olt + H2O.-Large, hard, white cryst., losing aq. at 130°; turns yellow abt. 160° and melts abt. 200° d.-S. 6 pt. c., or 21 pt. h. aq.; i. ale. or eth.-[a]D = + 52-5°.-In Test 201 no osazone separates fr. the h. sol. even after 2 hours'heating. Taste only faintly sweet.-Oxid. by Test 205 gives mucic ac. and saccharic ac. f "Dextrin."-Although commercial dextrin is not a true chemical species, being a mixture of several hydrolytic decomposition products of starch, its practical importance renders some mention of its properties and reactions in this place desirable. It is usually a white or slightly brownish powder of insipid mucilaginous taste; v. s. in h. aq. and for the most part also in c. aq ; though in the latter case the sol. is apt to be somewhat milky or turbid. Test 201 usually gives no ppt. of osazone in the hot solution after 20 minutes.-Unless unusually free from reducing sugars, Test 202 with Fehling's sol. gives a red ppt.-[a]D = + 200° (approximately).-Unless so much starch is present as to give a blue color, a very dilute sol. of I in KT produces a strong brown coloration. Unlike gum arabic it does not give Test 204 with phloroglucine.-For additional tests cf. Allen, vol. 1, p. 419. t Saccharose (Cane-sugar), Cl2H22Ou.-Colorless monoclinic cryst. s. in | pt. c. aq.; d. s. c. ale.; 100 cc. c. abs. methyl ale. dissolve 0-4 grm.-M. p. abt. 160°-70° d.-[«]D = +66°-5. Taste very sweet.- In Test 201 the yellow osazone ppt. begins to separate fr. the hot sol. if the heating is continued for abt. 30 min.-Oxid. by Test 205 gives saccharic ac., but no mucic ac. j Raffinose, C1SH32O16 + 5H2O.-Ndl., losing all aq. at 110°; when anhydrous melts at 118°-19°.- S. in 7 pt. aq. at 20°; 100 cc. abs. methyl ale. dissolve 9-5 grm. of the anhydrous sugar (dif. fr. saccharose); alm. i. c. ethyl ale.-Taste not noticeably sweet.-[a],= +104-5°. In Test 201 the yellow osazone does not separate fr. the. hot sol. unless the heating is con- tinued for abt. 60 min.-Oxid. by Test 205 gives both saccharic and mucic acids. | Gum Arabic.-Although not a true chemical species, this substance gives many of the reac- tions of this section and may be sometimes sought at this point. It consists in part of calcium arabate, and is a hard gum having a faint odor and insipid mucilaginous taste. It dissolves slowly in about 2 pts. of c. aq. to a thick transparent mucilage, but is i. in ale. It gives Generic Test II, and Specific Tests 203 and 204.-It gives no osazone ppt. in the h. sol. after 20 min. heating in Test 201, and gives little or no ppt. in Test 202 with Fehling's sol.-Oxid. by Test 205 gives mucic ac.-Ammonium oxalate and ammonia ppt. calcium oxalate fr. the aq. sol. For other tests cf. Allen, vol. 1, p. 426. 29 30 GENUS II, CARBOHYDRATES. SECTION 1. Subsection C. [Test 201 gives a yellow or orange- yellow precipitate from the hot solution within 20 minutes. All species also give a heavy red precipitate with Fehling's solution in Test 202.] SUBSECTIONAL PROCEDURE.-Apply Test 203. If no test for furfurol is obtained, see dextrose and galactose. If, on the other hand, furfurol is formed, apply Test 204 with hydrochloric acid and phloroglucine. If the precipitate from Test 204 is of a dark-purple color, see arabinose and xylose; if brown, see levulose, sorbinose, and rhamnose. f d-Glucose (Dextrose or Grape-sugar), C0H12O6.-Ndl. or crusts fr. ale. (m. p. 146°), or in tbL w. 1H2O fr c. aq. (m. p. abt. 85°-90°).-Anhydrous dextrose is s. in 1-2 pt. aq. at 17-5°; d. s. c. 90% ale., but v. s. h.; i. eth.-[«]□= +52-8°. Tastes half as sweet as cane-sugar. In Test 201 a heavy yellow ppt. of the osazone [m. p. 204°-5° (r. h.)] separates suddenly from the hot sol. after abt. 4-5 min. heating ! Test 205 gives saccharic but no mucic ac. t d-Galactose, CGH12O6.-Small hexagonal tbl. fr. abs. ale., m. p. 168° (r. h.); cryst. fr. aq. w. 1H2O, m. p. abt. 118°-20°. E. s. c. aq.; d. s. c. ale.-[a]D=+80-3°. Tastes about as sweet as dextrose.-Test 201 gives a heavy yellow to orange-yellow ppt. of the osazone, m. p. abt. 196° (r. h.), separating fr. the hot sol. after about 15-19 min. heating ! Oxid. by Test 205 gives mucic ac.! f 1-Arabinose, C5H10O5.-Pr. fr. ale., m. p. abt. 160°. V. s. c. aq.; v. d. s. ale.; i. eth.-[a]o = +104°-5°. The orange-yellow osazone, m. p. 160°, separates fr. the hot sol. in Test. 201 after abt. 10 min. heating; unless the sugar is very pure the osazone often separates in part in the form of brownish-yellow oily drops. Test 204 gives a purplish-black ppt.- Arabinose is best distinguished from xylose by preparing the p-bromphenylhydrazone as described by Fischer [Ber. 27, 2491]. t Xylose, C5H10O5.-Ndl. v. s. c. aq.; alm. i. c. ale. or eth.; m. p. abt. 150°-3°.-[a]D = + 18.7°. -The orange-yellow osazone, m. p. abt. 160°, separates fr. the hot sol. in Test 201 after abt. 7 min. heating. Test 204 gives a purplish-black ppt.-f Xylose may be quite easily distinguished from arabinose by conversion into cadmium xylonate by the method of Ber- trand [Bull. Soc. [3], 5, 556], f d-Fructose (Levulose), C6H12OS.-Somewhat hygroscopic cryst. or crusts fr. ale.; m. p. 94°I Also in ndl. w. |H2O fr. aq. V. s. aq.; s. 5 pt. c. abs. ale.; s. eth.!-[a]D = -90-2°. Tastes as sweet as cane-sugar.-A heavy yellow ppt. of the osazone, m. p. 204° (r. h.), separates from the hot sol. after abt. 2 min. heating in Test 201.-Gives dark, rusty-brown ppt. in Test 204. f Sorbinose, C0H12O0.-Rhombic cryst. s. in | pt. c. aq.; d. s. h. ale.; m. p. 164°!-[a]D = - 43 • 4°. Tastes as sweet as cane-sugar.--The yellow osazone, m. p. abt. 164° (r. h.), separates from the hot sol. in Test 201 after abt. 3| min. heating; it usually separates partly in the form of oily drops, but is easily purified by recryst. from a mixture of acetone and ether.-Test 204 gives a dark, rusty-brown ppt. f Rhamnose (Isodulcite), C0H]2O5 + H2O.-Hard, glassy cryst. fr. aq. or ale., m. p. below 100°. S. in 2 pt. c. aq.; v. d. s. c. ale.-[a]D = +9-43°. Tastes faintly sweet.-The osazone separates from the hot sol. in Test 201 after abt. 9 min., as a heavy yellow ppt. (ndl. fr. bz., m. p. abt. 180° d.). GENUS II, CARBOHYDRATES. SECTION 2. 31 SECTION 2. CARBOHYDRATES WHICH EITHER ARE,NOT SOLUBLE IN TEN PARTS OF COLD WATER, OR WHICH DISSOLVE, GIVING SOLUTIONS THAT REMAIN STRONGLY OPALESCENT AFTER FILTRATION. t Starch, (CcH10O5)a;.-Ordinary air-dried starch is a white, tasteless powder, containing about 18% of water. Under the microscope it is seen to consist of granules showing concen- trically stratified structure whose size and shape are often characteristic of the plant by which they were 'produced. (For details concerning the microscopic identification, cf. Allen, vol. I, p. 405.)-Starch is undissolved and unacted upon by c. aq., ale., or eth. A few cgrms. of the powder rubbed to a thin cream with cold water and then gradually stirred into 100 cc. of boiling water quickly dissolve to a nearly clear solution. This solution, after being cooled, gives a white ppt. with tannin or with much alcohol.-A few drops of a very dilute solution of I in KI gives an intense deep-blue coloration! The blue solution is tem- porarily decolorized by warming, or permanently by traces of free alkali. In an alkaline solution the color may be restored by acidifying with dil. HC1. (This characteristic color reaction will be masked by the presence of much erythrodextrine, which gives a deep red- dish-brown color with the reagent, unless care is taken to use a very weak iodine solution, and to add it gradually.) f Cellulose, (CflH10O6)x.-A white, tasteless, amorphous solid, insoluble in water and all ordinary organic solvents, either cold or hot, but dissolving in Schweitzer's reagent, i.e., in ammonia that has been saturated with cupric hydroxide (obtained by precipitating a cold solution of copper sulphate with an excess of caustic soda and washing the ppt. well with cold water), giving a viscid solution, from which it may be reprecipitated in a flocculent state by neu- tralization with acid.-After a few seconds' immersion in a cold mixture of 2 vol. cone. H2SO4 and 1 vol. aq., cellulose assumes a deep-blue color if wet (either immediately or after hastily rinsing with cold water), with a few drops of 2% iodine solution containing KI. [Unless it has been previously treated with such reagents as ZnCl2 or cone. H2SO4, cellu- lose is not colored blue by the iodine solution.] t Inulin, C36H02O3] (dried at 130°).-A tasteless white powder; m. p. 178° d. Under the micro- scope it is seen to consist of spheroidal cryst. aggregates. Alm. i. c. aq.; v. s. h. aq. giving clear solution which shows tendency to remain supersaturated for a long time; alm. i. ale. [a]D = - 39-5°. Easily hydrolyzed by h. dil. HC1, chief product being levulose. Does not reduce Fehling's sol. (Test 202). Test 201 gives a yellow osazone which begins to sep- arate from the hot sol. after abt. 25 min. heating. Gives no coloration with dil. I sol. t Glycogen, CBH10O5.-White amorphous powder, m. p. abt. 240°. E. s. c. aq. to intensely opalescent sol.! This opalescence is not destroyed by repeated filtration, but is removed by addition of acetic acid. I. ale.-[a]D = 198°.-Test 202 w. Fehling's sol. gives no ppt. Test 201 gives no ppt. of osazone after heating for one hour. f Commercial Dextrin.-Cf. Subsection B. (Filtered sol. in c. aq. often somewhat milky; usually reduces Fehling's sol.) SECTIONAL AND SPECIFIC CARBOHYDRATE TESTS. [TESTS 201-300.] 20i. Osazone Precipitation. Place in a dry test-tube having an internal diameter of 13 mm., 0.100 grm. of the carbohydrate, 0.200 grm. of pure phenylhydrazine hydrochloride* (cf. Note below), 0.300 grm. crystallized sodium acetate, and 2.00 cc. of distilled water. The errors in measurement should not much exceed 1 per cent. Close the tube loosely with a cork stopper to prevent evaporation, and stand it upright in a tall narrow beaker containing two or three inches of water that is already briskly boiling. Note the exact moment of immersion. Shake the tube occasionally without, however, removing it from the beaker. If a precipitate finally separates, note the number of minutes that have elapsed up to the moment of its appearance. The precipitate usually separates out quite suddenly, so that duplicate experiments will generally give results that agree within about half a minute. Note also whether the precipitate is white, yellow, or orange-yellow, and whether it is crystalline, flocculent, or tends to rise to the surface in oily drops. The properties enumerated are all used either as subsectional or as specific tests in the tables. If a melting-point of the osazone is desired, and it will often be found an important specific constant, cool the hot solution; collect the precipitate on a very small filter; wash with a little cold water; dissolve in the smallest possible volume of boiling 50 per cent alcohol, and filter hot. If the quantity of precipitate which separates on cooling permits, recrystallize once more in the same manner. Dry the precipitate, first on a bit of porous tile, or between filter-papers, and finally at 100°, and determine the melting-point in a bath whose temperature is rising rapidly. The fact that the rate of osazone formation is very different for the various sugars was first clearly indicated by Marquenne,f but seems not to have been hitherto very gener- ally known or taken advantage of by analysts. The conditions for the test in its present form are so planned that the monosaccharide sugars (the pentoses and hexoses) all give precipitates in from thirty seconds to twenty minutes. Of the polysaccharide sugars, some, like maltose, give products which do not separate until the hot solution is cooled; others, like saccharose, are gradually hydrolyzed to monosaccharides, which then give the corresponding osazones, but naturally require a longer time for the reaction than when the simple sugar was originally present. The times given in the table for the appearance of precipitates in different cases are based on experiments by several observers, and except for xylose and mannose, several distinct preparations were used for examina- * [Note on Phenylhydrazine Hydrochloride.-This salt, unless very pure and dry, rapidly decomposes and darkens on keeping. Only a perfectly white and dry salt should be used for the foregoing test. Although the commercial hydrochloride often fails to meet these require- ments, a very satisfactory reagent is easily prepared by dissolving a light-colored sample of phenylhydrazine in twelve volumes of strong alcohol, and then precipitating out the hydro- chloride by the addition of a sufficient excess of the most concentrated hydrochloric, acid. Wash the precipitate thoroughly on a suction-plate, first with alcohol and ether, and then with ether, until it is snow-white throughout. Dry on filter-paper in a warm place for half an hour, and then for at least an hour at 100°. Such a preparation, if white at the start, may be preserved for many months if placed in a tightly stoppered bottle, and not freely exposed to the light]. t Compt. rend. 112, 799. 32 NUMBERED SECTIONAL AND SPECIFIC TESTS OF GENUS II. 33 tion. Variations of a minute or two from the stated time-values will occasionally occur however, and this should not be overlooked -when it is a question of selecting between two species whose values lie close together. The precipitates are all phenylosazones, i.e., di-phenylhydrazones, except that from mannose, which is a simple phenylhydrazone, and is easily distinguished from its associates in being white instead of yellow. 202. Reduction of Fehling's Solution. Add eight drops of Fehling's Solution * to a solution of approximately 0.03 grm. of the carbohydrate in 3 cc. of water. Boil for two minutes if no precipitate appears before. Arabinose, xylose, rhamnose, mannose, glucose, galactose, fructose, sorbinose, malt- ose, and lactose give almost immediately a red to yellow-orange precipitate of cuprous oxide on heating. Inulin, raffinose, saccharose, and gum arabic give only a scanty yellowish turbidity after two minutes' boiling. Glycogen, starch, and cellulose give no precipitate after two minutes' boiling. The behavior of commercial dextrin is quite variable. 203. Aniline Acetate Test for Carbohydrates giving much Furfurol with Acid. Dissolve 0.3-0.4 grm. of the carbohydrate in 5 cc. of hydrochloric acid prepared by mixing one volume of an acid of sp. gr. 1.20 with three volumes of water. Boil for one minute. Then insert a cylindrical roll of freshly prepared aniline-acetate paper,t two inches long,- for half its length into the upper end of the test-tube from which the vapors of steam and furfurol are issuing. Continue the boiling one minute longer if necessary. Certain carbohydrates of Section 1, Subsection C, viz., arabinose, xylose, rhamnose, fructose, and sorbinose, give enough furfurol when thus treated to communicate a bright pink color to the test-paper. The other carbohydrates of this subsection do not occasion noticeable colorations. The coloration sometimes appears in streaks and blotches, but often covers the entire surface of the paper. 204. Color Reactions with Phloroglucine. Boil 3 cc. of the phloroglucine reagent described below J with about 0.03 grm. of the carbohydrate in a small test-tube. Note the color when boiling is about to begin. Continue to boil until the color darkens very considerably, and the solution begins to appear slightly turbid. This will occur within a minute from the moment when boiling begins. Pour the hot solution without delay onto a wet filter, and rinse the scanty pre- cipitate with a little cold dilute alcohol. Note the color of the precipitate while moist; it is the most characteristic result of the test. This test is used to distinguish between certain carbohydrates of Section 1, Subsec- tion C. The first coloration on heating with arabinose and xylose is a pure red to violet-red * Preparation of Fehling's Solution.-Dissolve 34.64 grms. of pure crystallized copper sulphate in distilled water, and dilute the solution to 500 cc. Dissolve 70 grms. of caustic soda of good quality, and 180 grms. of the best crystallized Rochelle salt (potassium-sodium tartrate) in about 400 cc. of water, and dilute to 500 cc. Keep the solutions in separate bottles, and prepare the Fehling's solution fresh before each series of experiments by mixing the two together in equal volumes. f Preparation of Aniline Acetate Paper.-This is prepared as required for use by wetting strips of thick filter-paper in a mixture of 5 cc. of aniline and 10 cc. of 50 per cent acetic acid, pressing out all excess of the solution between blotting-papers. It should be used while still slightly moist. Xylidine-acetate paper, which has also been recommended by Sohiff [A. 239, 380] for the detection of furfurol, is somewhat more sensitive than the paper prepared from aniline acetate. The latter is, however, thoroughly satisfactory for use in the present test. I Preparation of Phloroglucine Reagent.-This reagent is made by shaking an excess of powdered phloroglucine with a mixture of equal volumes of concentrated hydrochloric acid and water, until the solution is saturated. The clear solution, unless freshly prepared, is slightly yellow, but remains serviceable for many months and should be kept in stock. 34 NUMBERED CARBOHYDRATE TESTS. (R-VR), which rapidly intensifies and darkens. The color of thfe precipitate varies according to the duration of the boiling from a very dark purple (VRT2 or RVT2) to black if the boiling is too long continued. With rhamnose, fructose, and sorbinose the first colora- tion is yellow-orange (YO), quickly passing through dark orange to dingy brown. The precipitate is of a rusty brown, or dark broken shade of yellow-orange or orange (YO or 0), which will easily be changed to a dull black if the boiling is too long continued. 205. Oxidation to Mucic or Saccharic Acid. Galactose is the only hexose yielding mucic acid on oxidation with dilute nitric acid, and glucose the only one, with the exception of the artificial sugar gulose, that gives sac- charic acid. The reaction has the merit of being applicable to carbohydrate mixtures, as well as to the simple sugars and their polysaccharide and glucoside derivatives. Several grams of the carbohydrate must be oxidized to ensure satisfactory results if saccharic acid is to be sought. The method is fully described by Gans and Tollens, A. 249, 215 (1888), and more briefly by Allen, Vol. I, p. 270. A close adherence to all details given in these directions is necessary. CHAPTER V. GENUS III. ACIDS OF SUBORDER I, ORDER I. (Colorless Compounds Containing Carbon, Hydrogen, and Oxygen.) This large and important genus includes all non-aldehydic species of the suborder that contain the carboxyl radical, together with a few acid anhydrides and easily sapon- ified esters that show the same behavior as acids when titrated with decinormal alkali by the method of Generic Test III. Many compounds whose solutions in water or alcohol redden blue litmus, including a few like "carbolic acid," are popularly known as acids, but are too feebly acidic to meet the requirements of this test. Such species are accord- ingly treated elsewhere, most of them in Genus IV. GENERIC TEST III. APPLY PROCEDURE 1 OF THIS TEST FIRST TO EVERY COMPOUND, SOLID OR LIQUID, REGARDLESS OF SOLUBILITY. APPLY PROCEDURE 2 ONLY TO SOLID COM- POUNDS INSOLUBLE IN WATER WHICH IT IS FOUND DO NOT TITRATE LIKE ACIDS IN PROCEDURE 1. PROCEDURE 1. (Titration in Water.)* Weigh out accurately about 0.10 grm. of the dry substance, finely powdered if it is a solid, into a beaker of 50 cc. capacity. Add 10-15 cc. of cold distilled water, and one drop of a solution of phenolphthalein made by dissolving one part of the indicator in three hundred parts of 50 per cent alcohol. Place the beaker on a sheet of white paper, and titrate cautiously with decinormal soda or baryta until the pink color produced by an excess of one drop of the alkali, after exact neutralization, persists for more than one minute when the solution is constantly stirred. PROCEDURE 2. (Titration in Alcohol.)* If less than 2 cc. of the alkali were required for neutralization in Procedure 1, and if the substance at the same time did not go into solution, and is a solid, repeat the titration, replacing the distilled water by about 25 cc. of strong alcohol of the best * Shorter Alternative Procedure.-Whenever the substance is not very valuable and is not believed to be an acid, it is allowable to take a small unweighed pinch, or three drops (about 0.1 grm.) of the substance for the titrations. If not more than three or four drops of alkali are neutralized, or if the color transition in the end reaction is not '1 sharp," the time otherwise required for weighings and calcu- lations will be saved. 35 36 GENUS III. ACIDS. quality, using three or four drops of phenolphthalein instead of one, and disregard- ing any precipitate that may form.-[The best commercial alcohol usually reacts acid. This acidity should be exactly neutralized by alkali in each experiment before adding the substance to be titrated.] Any compound that consumes more than 2 cc. of decinormal alkali in either titration, and that also gives a sharp and normal color transition in the end reaction, should be sought in Genus III. The sharpness of the color transition, and the alkali consumption, are phenomena of coordinate importance. The phrase ' ' sharp color transition in the end reaction" is here used with the restricted, definite mean- ing given to it in the explanatory observations below. Any compound that yields a solution at the end of the titration that has a pronounced color other than pink is likely to be a species of Genus IV. Observations on Generic Test III.-Never titrate hot solutions nor substitute some other indicator for phenolphthalein. Never omit to reduce the substance to a uniformly fine powder before beginning a titration, unless it is known in advance that it dissolves quickly in cold water. All but the weakest and most insoluble acids may, with a little patience, be success- fully titrated without the use of alcohol if this injunction is observed and the suspended powder is persistently stirred. Even terephthalic acid, which is said to require 67,000 parts of cold water for solution, gives little trouble. But if an acid is at once almost absolutely insoluble and very weak, like stearic and other higher solid fatty acids, an aqueous suspension will not neutralize the alkali, and the use of alcohol becomes indispensable. The sharpness of the color change at the end of a titration is usually more striking in aqueous than in alcoholic solutions. The end reaction in Generic Test III may be defined as being sharp in the sense intended, when a single drop of decinormal alkali, added at the moment when the solution is exactly neutral but still colorless, suffices to develop a full strong pink color which is not greatly intensified if the quantity of free alkali is increased. Some phenols, /?-diketones, and similar compounds, consume more than 2 cc. of the alkali before the appearance of a pink color, but they may be distinguished from the species of Genus III by the lack of sharpness in their '' end reactions." That is to say, an excess of a single drop of the alkali, added at the end of the titration of such a substance, produces only an almost imperceptible pinkish coloration, that then gradually increases in intensity when more alkali is added. There is no abrupt transition such as is observed in titrating a true acid whose salts are not hydrolyzed in solution. The quantity of alkali consumed in titrating from colorlessness to a full pink, has been found to diminish as the strength of the acid (as indicated by its ' ' affinity constant ") increases. The limits vary from a fraction of a drop to several cubic centimeters. Presence of carbonate in the alkali, or of carbon dioxide in the water, increases the transition interval, and is very detrimental to sharpness whenever the impurity is at all considerable. A decinormal alkali prepared from the purest commercial caustic soda and ordinary distilled water will, however, be found sufficiently pure for practical use. A blank titration of two or three drops of acetic acid will quickly determine the condition of any doubtful alkali solution. Within quite wide limits, the abruptness of the color change in an end reaction is independent of the quantity of substance dissolved. An acid GENUS III. ACIDS. 37 containing an appreciable quantity of a phenol as an impurity will titrate like a phenol, the pink color appearing gradually after the acid has been neutralized. Aromatic oxyacids (e.g. salicylic acid) titrate as sharply as other acids of the same strength that do not contain phenolic hydroxyl. Polybasic acids with several carboxyl groups also titrate sharply, the end reaction first appearing when all the carboxylic hydrogens have been replaced. Although a small bottle of approximately decinormal alkali, and a glass tube medicine-dropper with a rubber nipple, are all the apparatus that is absolutely necessary for the performance of Test III as a generic reaction, it is strongly recom- mended that the alkali should be carefully standardized, and used from a burette mounted in the manner to be described in Test 301. Accurate neutralization equivalents of an unknown acid may then be quickly determined while making the generic test, without involving any additional manipulations, and will be found nearly or quite as useful as melting-point or boiling-point data in completing the identification. The time limit stated in the direction to ' ' Titrate to a pink color that does not disappear after stirring for one minute," is imposed for several reasons. The first of these is, that nearly insoluble acids, towards the end of a titration when the quantity in suspension has become small, neutralize the dilute alkali very slowly. Yet, if the stirring were to be continued for a much longer period, the color would eventually fade away through absorption of carbonic acid from the air; or,, in the case of many esters, from the gradual neutralization of alkali by saponification. A few esters like methyl formate, dimethyl oxalate, and some esters of hydroxyacids, do neutralize decinormal alkali within the time limit selected, and are, in consequence, described with the acids; but this behavior is very excep- tional, as has been found by a large number of ester titrations. Isolated cases may, however, occur in the tables, in which esters or lactones that should have been placed in this genus have been wrongly assigned other positions through this cause. In titrating acid anhydrides a very characteristic, and at first sight surprising phenomenon, will often be noticed. The solution, instead of becoming pink when the neutral point is passed and alkali is present in excess, remains colorless; but after standing for some time gradually becomes pink. The explanation seems to be that the anhydride attacks the hydroxyl groups of the indicator, as in the Schotten-Baumann Reaction, so that the power to form colored alkali salts is lost. The colorless reaction product is, however, gradually saponified by the excess of alkali present after the titration, and the colored salt of the indicator is again formed. Confirmation of this explanation is found in the fact that direct titrations of acid anhydrides may be successfully made by testing the neutrality of the solution from time to time with fresh pieces of phenolphthalein paper. The indicator under these conditions is always present in the free state, and so performs its proper function. General Physical and Chemical Characteristics of the Acids.-The odors of the liquid acids vary greatly. The sharp penetrating quality, so familiar in the odor of acetic acid, is perhaps the most characteristic element that can be traced in any considerable number of species; but even this property is not common to all species. 38 GEN VS III. ACIDS. The solid acids are in a majority of cases odorless or nearly so, though there are many ex- ceptions to the rule. A sour taste and the power to redden blue litmus are properties common to all acids that are sensibly soluble in water. The power of acids, when dis- solved in water or alcohol, to instantly and completely neutralize alkalies, is their most striking chemical characteristic, and has been discussed in the preceding paragraphs. The melting-points, boiling-points, and neutralization equivalents of the tables always have reference to the dry acids when these can be obtained free from water of crystallization by drying in an oven at 100°-110°. For a few species which can not be easily freed from water of crystallization, the data relate to the air-dried acid. In these exceptional cases the hydrated condition of the acid is always made evident in the tables by the context. The number of acid species that occur com- bined with water of crystallization which may be expelled below 110° is large. Genus III has a Division A of solid, and a Division B of liquid, species. Of these divisions A is much the larger. Each division comprises two sections, 1 and 2, of which 1 contains 11 soluble acids," i.e. such as are soluble in less than fifty parts of cold water, and 2 the " difficultly soluble acids." Where serious doubts have arisen as to the sectional position of an acid it has been mentioned in two sections. The solubilities of the acids have, however, been more carefully studied than those of any other equally important group of compounds. To find the section in which an unknown acid is to be sought, it is always necessary to at least roughly determine its solubility. This may be rapidly accom- plished as follows: Weigh out 0.2 grm. of the acid-in the form of an impalpable powder, if it is a solid, in a five-inch test-tube. Add cold water in small measured portions from a graduate or pipette, shaking thoroughly and persistently after each addi- tion. If complete solution is effected by 1 cc., the substance will be described* as " very soluble," or " v. s."; if by 1-4 cc., as " easily soluble," or "e. s."; if by 4-10 cc., as "soluble," or "s."; if by more than 10 cc., but less than about 30 cc., as 11 difficultly soluble," or " d. s." Greater degrees of insolu- bility are expressed by the terms " very difficultly soluble," or " v. d. s.," and " in- soluble," or " i." If the supply of the acid is very limited, it is possible to make the solubility determination in a smaller test-tube, using only half the quantities of substance and solvent that have been recommended. * It is impossible to be entirely consistent in the use of this approximate solubility ter- minology, because many of the solubility data incorporated in the tables are merely literal quotations from authorities who have given no numerical values, and who have probably attached a different and less definite meaning to the terms of this solubility scale. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I]. GENUS III, ACIDS. DIVISION A, SECTION 1-SOLID ACIDS "SOLUBLE" IN COLD WATER. Melting-point (C.°j. Neut. Equiv. SOLID ACIDS.-Colorless and generally Soluble (see note, p. 38) in 50 parts of cold water. 15 86 Methacrylic Ac.-Cf. Div. B, Sec. 1, b. p. 162°-3°. 15-5 86 f Isocrotonic Ac.-Odor like butyric ac.-Cf. Div. B, Sec. 1, b. p. 169°. 17 86 Trimethylenecarbonic Ac., C3Hfl.CO2H.- B. p. 182°-2-5°. G. l-08792%.-"Somewhat" s. aq. 18 90 t i-Lactic Ac., Me.CH0H.C02H.-B. p. (12 mm.) 119°.-Ordinarily a hygroscopic syrup containing some anhydride, and hence giv- ing too high a neut. eq.-Mise. w. aq., ale., or eth.-Heated in test- tube decomposes, gives off white vapors and leaves a viscous residue. Gives a-hydroxyacid Test 302 !--Warm sol. quickly decol- orizes neutral permanganate w. effervescence.-f Heat nearly to dryness 1 cc. lactic acid in a large test-tube over a moderate flame, using an inverted closed capillary to prevent bumping. Conduct the vapors through a glass tube abt. 25 cm. long into 2 cc. aq. in a test-tube surrounded by cold water. Test this sol. (no odor of acetaldehyde) by Test 111 for acetaldehyde.- Neutral salts all s. aq.-[d. and 1. lactic acids are likewise soluble acids giving the same reactions]. 27 112 Propylacetylenecarbonic Ac., Pr.C:C.CO2H.-Violet color w. FeCl3 -AgA ppt. 29-30 158 Octanon(7)-oic Ac., Me.CO.C5H10.CO2H.-Tbl. e. s. aq.-AgA, tbl. e. s. h. aq. 31 118 a-Oxyvalerianic Ac., Me.(CH2),.CHOH.CO2H.-Hygroscop. ndl.; v. s. aq., ale., or eth. Gives Test 302! Gives anhydride easily.- AgA, scales, d. s. c. aq.; CaA2, ndl., s. in 28 pt. aq. at 15°; ZnA24- 2 aq. s., in 136 pt. aq. at 15°. 32-3 130 ^-Propionylpropionic Ac., Et.CO.(CH2)2.CO2H.-V. s. aq., ale., or eth. Violet color w. FeCl3.-AgA ppt. 33 116 J Laevulinic Ac., Me.CO.(CH2)2.CO2H.-B. p. 245°-6°.-Deliquescent; usually met with in liq. state. E. s. aq., ale., or eth. Easily oxid. by CrO3 mixture.-Gives iodojorm by Test 801 immediately in the 'cold. In CHC13 sol. 4Br gives stable C3H6Br2O3, which cryst. fr. aq. w. m. p. 114°-15°.-Ca and Ba salts e. s. aq.; AgA characteristic Ifts., s. in 150 pt. aq. at 17°. 35-5 102 Trimethylacetic Ac., Me3.C.CO2H.-B. p. 163-7° (th. i.).-S. in 45 pt. aq.-Ag, Zn, and Pb salts all ppts. fr. moderately cone. sols. 40-2 144 w-Acetylvalerianic Ac., Me.CO.(CH2)4CO2H.-B. p. 250°-53° at 280 mm.-Cryst. e. s. aq., ale., or eth. AgA ppt. 1ft. fr. h. aq. 43 104 f a-Oxybutyric Ac., Me.CH2.CHOH.CO2H.-B. p. 255°-60° d. Salts generally deliq. and v. s.-Gives a-hydroxyacid Test 302 1 43-4 166 o-Oxyphenylglycollie Ac., HO.C0H4.CO.CO2H.--Ndl. fr. bz.; s. aq. (?); e. s. ale. or eth.-Dist. gives CO2 and salicylic ac. (Test 319). 45 100 a-Ethylacrylic Ac., CH2: CEt.CO2H.-B. p. 180°.-AgA, 1ft., s. h* aq.-Unsaturated (Test 304). 45-5 100 Angelic Ac.-Cf. Div. A, Sec. 2.-B. p. 185° (th. i.). 48'5 156 Diallyloxalic Ac.-Cf. Div. A, Sec. 2. 39 40 GENUS III, DIV. A, SECT. 1. (ORDER I, SUBORDER I.) Melting-point (C.°). Neut. Equiv. SOLID ACIDS.-Colorless and generally Soluble (see note, p. 38) in 50 parts of cold water. 54 118 f Dimethyl Oxalate, C2O4Me2.-B. p. 163-3° (cor.). Monoclin. tbl. Titrates like a monobasic ac.-Add several vols. strong NH40H to cone. aq. sol.; a heavy cryst. ppt. of i. oxamide immediately forms. 55-6 192 5-Phenyllaevulinic Ac., Ph.CH2.CO.C2H4.CO2H.-Silky ndl.; s. aq.: e. s. ale.-BaA2 + l$ aq. e. s. aq.; AgA curdy ppt., Ifts. fr. h. aq. 57-8 130 Paraconic Ac., C4H5O2.CO,H.-Deliq. mass. Heated gives citraconic anhydride. 60-2 132 a-Oxycaproic Ac., Me.(CH,)3.CHOH.CO2H.-Gives Test 302. On long heating at 100° partly sbl. and is slowly changed to a syrupy anhydride i. aq.-Warmed w. CrO3 mixture gives valerianic alde- hyde and acid (odor). 64-5 100 f Tiglic Ac., Me.CH :CMe.CO2H.-Pr. or tbl. rather d. s. c. aq.; e. s. h. aq.-B. p. 198-5° (th. i.).-Peculiar sharp "spicy" odor.- Gives Test 304 (w. KMnO4 instantly-w. Br2 only upon heat- ing).-CaA2 + 3 aq., s. c. aq. and, unlike the angelate, more s. h. than c.; mod. s. ale. (unlike angelate).-AgA cryst. scales fr. h. aq. 64-5 144 2-Methylhexanql(4)-oic(6) Ac., C7HI4O3.-Lustrous 1ft., e. s. c. aq. or eth.-AgA scales, e. s. h. aq. 65-6 150 Benzoylformic Ac., Ph.CO.CO2H.-Heated gives benzoic ac. (Test 312), CO2, and benzaldehyde (odor).-V. s. aq.-Ba, Pb, and Ag salts d. s. ppts. The acid ppts. oily fr. salts and solidifies on standing in desiccator. It gives the ketone reactions. Warmed w. cone. H2SO4, it gives benzoic Ac. and CO2.-Cf. Ber. 12, 1505, for additional specific reactions. 66-8 118 a-Methyl-a-oxybutyric Ac., Et.CH(MeOH).CO2H.-Cryst. sbl. at 90° in ndl. V. s. aq., ale., or eth. Gives Test 302.-BaA2 v e. s. aq. : AgA s. aq. 69-5-70 50 ,5-Dimethylacrylic Ac., Me2.C: CH.C02H.-B. p. 195°.-Sbl. in ndl. -PbA2+H2O 1ft., e. s. aq.-Unsaturated. 70 114 2, 3-Dimethyl-buten(2)-oic(i) Ac., C(iH)0O2.-Ndl. fr. aq.; 100 pt. aq. dissolve 5.15 pt. at 19°.-BaA2 + 3| aq., powder, e. s. aq. Turns yellow in air. Unsat. 72 43 f a-Crotonic Ac., HCMe :HC.CO,H.-B. p. 185° c.-S. in 12 pt. aq. at 15°.-Ba and Ca salts e. s. aq.; AgA curdy ppt.-Reduction of boiling aq. sol. by Na amalgam gives butyric ac. easily.-Gives Test 304! 73 132 [ -], 2-Methyl-pentanol(4)-oic(s) Ac., C0H12O3.-Ndl. sbl. at 100°. At 225° gives syrupy anhydride.-V. s. aq., ale., or eth.-Zn salt, scales, s. in 300 pt. aq. at 16°, or 204 pt. at 100°.-Gives Test 302. 74 144 Mesitonic Ac., Me2.C(CO2H).CH2.CO.Me.-Small pr. fr. aq.-S. aq.; v. s. ale. or eth.-Dist. gives an anhydride w. m. p. 24° and b. p. 167°.-Salts v. s. aq. 74-5 138 a/?-Dioxybutyric Ac., C4HsO4 + aq.-Long deliq. pr.; v. s. aq. and ale.; i. eth. Effloresces over H2SO4. Gives Test 302. 74-5 120 /?-Methylisoglyceric Ac., Me.(CHOH)2.CO,H.-Pr.; e s. aq. or ale., d. s. eth. Cryst. w. 1 aq. Effloresces over H2SO4.-AgA, fr. h. aq., v. stable.-Gives Test 302. 74-6 87 (/?)-s-Dimethyladipic Ac., CO2H.CHMe.(CH2)2.CHMe.CO,H.-B. p 321°.-E. s. c. aq., ale., or eth. Heated w. dil. HC1 at 200° gives a acid w. m. p. 140°. 76 84 Tetrolic Ac., MeC: C.CO2H.-B. p. 203°.-Broad tbl., s. aq., eth., or CS2. Sbl.-Gives Test 304. Dec. at 202° to CO2 and allylene.- Salts all s. and reduce Au and Hg sols.-Heat w. cone. aq. KOH sol. at 105°. Distil, and test for acetone in the distillate (Test 711). 76 80 Sec.-Butylmalonic Ac., Bu.CH.(CO2H)2.-Cryst. fr. bz. E. s. aq., ale., or eth.--Gives Test 303.-AgA ppt. GENUS III, DIV. A, SECT. 1. 41 (ORDER I, SUBORDER I.) Melting-point Neut. Equiv. SOLID ACIDS.-Colorless and generally Soluble (see note, p- 38) in 50 parts of cold water. 77-8 73 a-Methylglutaric Ac., CO2H.CHMe.(CH2)2.CO,H.-Pr. v. s. aq., ale., or eth. Boiled 20 min. gives oily anhydride, b. p. 272°-75°. 76-80 81 [+ or - ] Ethoxysuccinic Ac., CO2H.CH2.CIIOEt.CO2H.-Pr. v. s. aq. Opt. active.-CaA (100°) v. s. c. aq. 78-9 76 f GlycoIlic Ac., CH2OH.CO2H.-Lft. fr. eth.; deliq. if not absolutely pure. S. aq. and not easily extracted by eth.-Long heating at 100° gives anhydride, C4HGO5, in. p. 128°-30°, i. eth., ale., and c. aq.-Gives _Test 302 ! Solubilities of salts in water:-BaA2, 1:79; CaA2, I : 82 at 10° (easily supersaturates); PbA2, 1 : 32 at 15°; CuA2, 1 ; 134; AgA + 1| aq., e. s. c. aq., e. dec. by h. aq. 79 after Sbl. at 50° 104 a-Oxyisobutyric (Acetonic) Ac., Me2.COH.CO2H.-Hygroscopic pr. v. s. aq., ale., or eth. Gives Test 302.-CaA2 v. s. aq.; AgA scales, s. in 14 pt. c. aq.-Fusion w. KOH gives acetone (Test 711). 80 65 f Citraconic Ac., Me.C(CO2H) :HC.C02H.-Dist. gives anhydride, b. p. 213°-4°. Deliq. 4-sided pr. s. in 0.42 aq. at 15°. Aq. sol. boiled w. HC1 gives mesaconic acid, which is also formed on evaporating sol. containing mineral acids.-(NH4)2A, boiled w. FeCl3 sol. (avoid excess), gives red ppt.-Ba salt, tbl. v. d. s. c. aq.; PbA, ppt. fr. h. sol.; Ag2A ndl. fr. h. aq.-Unsat., but gives Test 901 only w. boiling aq. Br sol. 80 132 Oxydiethylacetic Ac., Et2.COH.CO2H.-Triclin. cryst. SblL fr. 50°. V. s. aq., ale., or eth.-BaA2 v. s. aq., ale., or eth. ZnA2, scales s. in 301 pts. aq. at 16°, less s. hot.-Gives Test 302. 82 87 Pentylmalonic Ac., C5H1].CH.(CO2H)2.-Clear pr. Dec. at 140° giv- ing CO2 and oenanthic ac. (Test 303).-V. s. aq., ale., or eth. 82-3 166 o-Hydrocumaric Ac. (Melilotic Ac.), HO.CfiH4.(CH2)2.CO2H.-(In Melilotus officinalis). Dist. gives anhydride.--S. in 20 pt. aq. at 20°; e. s. ale., eth., and h. aq.-FeCl3 gives transient bluish color in aq. sol.-Fusion w. KOH gives acetic and salicylic ac. (Test 319).-CaA2 v. d. s. c. aq.; BaA2 + 3 aq. e. s.; PbA2 cryst. ppt.; AgA curdy ppt. (ndl. fr. h. aq.). 84 166 m-Methylmandelic Ac., Me.CGH4.CHOH.CO2H.-Lust. pr. fr. bz.; e. s. aq., ale., or eth. Gives Test 302. 83-6 118 «-Oxy iso valerianic Ac., Me2.CH.CH2OH.CO,H.-Rhomb, tbl. volatile at 100°. V. s. aq., ale., or eth.-Oxid. by CrO3 mixture.-Dil. H2SO4 at 130°-40° gives formic ac. (Test 315) and isobutyric alde- hyde.-Ca, Zn, and Ag salts d. s. c. aq. 84 80 2, 2-Dimethylpentanedioic-(i, 5)Ac., C7H12O4.-Woolly, ndl. fr. cone- HC1, e. s. aq.-M. p. of anhydride 38°; b. p. abt. 265°. 85-6 73 3-Methylpentanedioic(i, 5) Ac., Me.CH.(CH2.CO2H)2.-Glassy cryst. e. s. aq., ale., or eth. DistiL gives anhydride, m. p. 46°; b. p. 283°. -CaA. (at 150°) s. aq.; Ag2A ppt. i. aq. 86 81 i-Ethoxylsuccinic Ac., CO2H.CH2CHOEt.CO2H.-V. s. aq., ale., or eth.-CaA v. s. aq. 87 73 Isopropylmalonic Ac., Me2.CH.CH.(CO2H)2.-Dist. gives CO2 and iso- propylacetic ac. (Test 303).--E. s. ale. or eth.-Cryst. fr. bz. w. 2CGHG in long ndl. which effloresce.-Ag2A cryst. powder, i. aq. 87-8-5 79 trans.-Pentamethylenedicarbonic(i, 3) Ac., C5H8.(CO2H)2.-Flat. pr. fr. CC14, s. in 1 pt. c. aq.-Ag2A v. d. s. aq., stable. 88 134 Tigliceric Ac., C4H7(OH)2.CO2H.-Tbl. fr. eth.; v. s. aq.; i. CHC13.- CaA2, (at 100°), hard white mass, v. s. aq.; s. abs. ale. 89 166 [ -]-Arabonic Ac., HO.CH,.(CHOH)3.CO2II.-Evaporation of aq.. sol. gives syrupy anhydride solidifying in dessicator (m. p. 95°-8°)»- BaA2 ppt'd cryst. fr. aq. sol. by ale.-Gives Test 302. 89 166 Methoxylphenylglyoxylic Ac., MeO.CGH4.CO.CO2H.-Ndl. fr. bz. v. s. ale. or eth. 90 108 n-Heptylsuccinic Ac., CnH20O4.-Scales, e. s. aq. or CHC13.-Ag2A i. aq.; CaA 4 aq., d. s. white powder. 42 GENUS III, DIV. A, SECT. 1. (ORDER I, SUBORDER I.) Melting-point (C.°). Neut. Equiv. SOLID ACIDS.-Colorless and generally Soluble (see note, p. 38) in 50 parts of cold water. 90 178 Monoethyl Tartrate, CO2Et.(CHOH)2LCO2H.-Deliq. rhombic pr. s. in aq.-PbA2 1ft. d. s. c. aq.; BaA2 + 2 aq. s. c. aq.-Gives Test 302.-Saponification gives tartaric acid. 90 Terpenylic Ac., C8H12O4.-Cryst. w. 1 aq. (m. p. 57°).-(An oxidation product of oil of turpentine.)-Cryst. s. aq. or eth.-Sbl. at 130°- 40°. Heat dec. to CO2, etc.-CrO3 easily oxid. to acetic acid (cf. Tests 702 and 311), CO2, etc., but may be evaporated w. HN03 (sp. gr. 1-30) without change.-Monobasic to carbonates; dibasic to hot alkalies.-BaA d. s. h. aq.; BaA2 v. e. s. aq. 91 80 Propylsuccinic Ac., CO2H.CH2.CHPr.CO2H.-Cryst. fr. aq. 2-83 pt. s. in 100 pt. c. CHC13. 90-1 193 Atrolactic Ac., (Me)(Ph)(OH).C.CQ2H + 1$H2O.-NdL or pr. e. s. c. aq.-Ba salt d. s., and Zn salt v. d. s. in c. aq.-Boiled w. cone. HC1 gives atropic ac.-Boiling BaO2H2 has no action. 92 160 2, 2, 4-Trimethyl-pentanol(3)-oic(i) Ac., C8H16O3.-Cryst. s. in 50 pt. c. aq.-Ba and Ca salts e. s. aq. 93 166 Phenyl-/?-lactic Ac., Ph.CHOH.CH2.CO2H.-Pr. v. s. c. aq.-At 180°> or by boilmg w._BaO2H2 or dil. H2SO4 gives cinnamic ac. (Test 313).-BaA2, ZnA2, 1| aq. and AgA, d. s. c. aq. 93 87 Isoamylmalonic Ac., C5H„.CH.(CO2H)2.-Silky ndl. fr. bz.-E. s. aq., ale., or eth. Loses CO2 on fusion (Test 303).-CaA and Ag2A. amorph. ppts. 93-4-5 80 [ + ]-/?-Methyladipic Ac., C,H10.(CO2H)2.-B. p. 210°-2° (15 mm.). V. s. ale.; e. s. Igr.-Ag2A ppt. 95 180 Methyl-/?-phenyllactic Ac., Ph.CHOH.CHMe.CO2H.-V. s. ale., eth., or warm aq.-At 280° gives CO2 and allylbenzene.-AgA cryst. ppt. 95 74 P~Qxyglutaric Ac., CO2H.CH2.CHOH.CH2.CO2H.-Ndl. e. s. aq. or ale. -Boiled w. 60% H2SO4 gives glutaric acid. 95 79 d-Citramalic Ac., C5H8O5.-Very deliq. cryst. mass. Gives Test 302. 96 152 Phenoxyacetic Ac., PhO.CH,.CO2H.-B. p. 285° w. si. dec.-Silky ndl. e. s. aq., ale., or eth.-FeCl3 gives yellow ppt.-Cryst. ppt. w. Br aq.-BaA2 + 3 aq., s. aq.; AgA, d. s. ndl. 96 73 Propylmalonic Ac., Pr.CH.(CO2H)2.-Tbl. fr. bz. which contain no bz. of cryst. (dif. fr. isopropyl comp.).-Gives Test 303. 97-5 68-5 f Glutaric Ac., CO2H.(CH2),.CO2H.-Monoclinic pr.; 100 cc. aq. sol. contain 42-9 grms. at 0°; v. s. ale. or eth. Boils w._little dec. at 302°-4°.-CaA. 4 aq. and BaA. 5 aq., v. s. aq.; PbA cryst. ppt.; Ag2A ndl. s. h. aq.-Apply Test 316! 95-100d. 54-5 cis-i, 2, 3-trans-i-Trimethylenetetracarbonic Ac., CTHcO8.-E. s. aq., ale., or eth. Gives Test 303. 97-8 166 Phenyl-a-lactic Ac., Ph.CH2.CHOH.CO2H.-Thick pr. fr. aq.-BaA2 e. s. aq. Gives Test 302. * Heated above 140° gives formic acid and a-toluic aldehyde. 98d. 87 Isoamylmalonic Ac., C5Hn.CH.(CO2H)2.-Silky ndl. (fr. bz. + lgr.); v. s. c. aq. Gives Test 303: CaA amorph. ppt. 98 73 Ethylsuccinic Ac., CO2H.CHEt.CH,.CO2H.-Pr. v. s. aq., ale., eth., or CHC13. Dist. gives liquid anhydride b. p. 243°.-Ba and Zn salts e. s. aq. 99 63 t Oxalic Ac. (Cryst.), (CO2H)2 + 2H2O.-Monoclinic pr. After fusion subl. at 150°-60°. S. in 10.46 pt. aq. at 14-5°; e. s. c. ale.; s. in 79 pt. abs. eth. at 15°; v. d. s. CHC13.-Apply Test 317! 100 70 t Citric Ac. (Cryst.), CO2H.CH2.C(OH)(CO2H).CH2.CO2H + H2O.-Cf. Citric Ac. m. p. 153°. Gives Test 302! Apply Test 314! 100 80 3, 3-Dimethylpentanedioic(i, 5) Ac., C7H,2O4.-Pearly ndl. fr. bz.; e. s. aq., eth., or h. bz.-Dist. or action of acetyl chloride gives anhydride, m. p. 124°-5°. GENUS III, DIV. A, SECT. 1. 43 (ORDER I, SUBORDER I.) Melting-point (C.°). N eut. Equiv. SOLID ACIDS.-Colorless and generally soluble (see note, p. 38) in . 50 parts of cold water. 100 57 t[+ or - ] Malic Ac., CO2H.CH2.CHOH.CO2H.-Deliq. ndl.; cryst. w. difficulty. V. s. aq.; s. ale. or eth. Gives Test 302 ! Gives with PbAc2 a voluminous white ppt. which melts to resinous mass on boiling w. a little aq.-Salts give no ppt. w. BaCl2. White ppt. w. AgNO3. At 175°-200° gives fumaric and maleic acids and maleic anhydride.-Apply color test 314! 100 120 2-Methyl-2, 3-propanedioic(i) Ac., C4H8O4.-Slowly cryst. syrup; e. s. aq.; d. s. eth.-CaA2 s. aq. 100-1 72 Ethylmaleic Ac., CO2H.EtC :CH.CO2H.-Thick pr. e. s. aq. or eth.- Unsat. (Test 304). Heated gives a liquid anhydride. Na amal- gam reduces to ethylsuccinic acid. 101-2 80 s-Methylethylsuccinic Ac. (fumaroid), CO2H.CHMe.CHEt.CO2H.- Ndl. fr. aq.; e. s. c. aq. Heating gives liquid anhydride, b. p. 245°. 101-5 80 Butylmalonic Ac. Me.(CH2)3.CH.(CO2H)2.-Pr. e. s. aq., ale., or eth. Gives Test 303. At 150° gives CO2 and caproic acid (disagree- able odor). 102-3 98 Pentinoic Ac., C4H5.CO2H.-Monoclinic tbl. fr. eth.; ndl. fr. bz. V. s. aq.-BaA2, scales fr. dil. ale.; v. s. aq.-Unsat. (Test 304). 103 72 Allylmalonic Ac., C3H61CH.(CO2H)2.-E. s. aq. or eth. Adds Br2.- CaA, d. s. aq.; BaA + aq. pearly Ifts. s. in 1 pt. h. aq.; Ag2A, i. aq.-Gives Tests 303 and 304. 103-4 132 a-Hydroxylasvulinic Ac., Me.CO.CH2.CHOH.CO2H.-E. s. aq.; d. s. eth. Reduces Fehling's sol. At 100° gives an anhydride (ndl. m. p. 263° d.). 103-4 80 3-Methyl-3-carboxyl-pentanoic (i) Ac., C7H12O4.-Clear pr. fr. aq.; e. s. aq., ale., or eth. 100 pt. aq. at 15° dissolve 15-4 pt. acid. Heating at 200° gives an anhyd., b. p. 239°-45°. 105 80 f n-Pimelic Ac., (CO2H).(CH2)5.CO2H.-Tbl. fr. aq. s. in 24 pt aq. at 20°; e. s. eth.-Sbl. without dec.-BaCl2 gives no ppt.; AgA cryst. ppt.; CaA separates as gran. floc, ppt.when saturated sol. is boiled. 106-7 80 Methylpropylmalonic Ac., (Me)(Pr).C.(CO2H)2.-E. s. aq., eth., or CHC13.-Gives Test 303. 107 80 Isobutyl Malonic Ac., Me2.CH.CH2.CH.(CO2H)2.-E. s. aq. or eth.- CaA and Ag2A, i. ppts.-Gives Test 303. 107 87 Isobutylsuccinic Ac., C4H9.C2H3.(CO2H)2.-Cryst. e. s. aq. or eth.- CaA e. s.; BaA d. s.-The anhydride is liquid. 110-1 134 Angliceric Ac., C4H7.(OH)2.CO2H.-Ndl. fr. eth. V. s. aq.; i. CHC13. -Ca salt amorphous, v. s. aq.; i. abs. ale. 111 144 Hexahydrosalicylic Ac., o-HO.C0H,0.CO2H.-4-sided tbl. or ndl. e. s. aq. or eth. 111 166 m-Hydrocumaric Ac., HO.C6H4.(CH2)2.CO2H.-"E. s. usual solvents." 111-5 66 Ethylmalonic Ac., Et.CH.(CO2H)2.-Cryst. w 1H2O. Pr v s. aq. or eth.-Gives Test 303, being completely dec. to CO2 and butyric ac. (odor) at 160°!-Na2A gives no ppt w FeCl3 (dif. fr. pyro- tartaric acLbelow).-CaA less s. h. than c ; BaA + | aq., finepr. d. s. aq.; ZnA, 2| aq. characteristic 6-sided tbl. s. in 456 pt. aq. 112 66 Pyrotartaric Ac., Me.CH(CO,Hi.CH,.CO2H.-Triclinic pr. e s c. aq. or eth. At 200 gives an anhydride.-ZnA, v e. s. aq.; BaA-2aq. e. s. aq.; Ag2A, ppt., v. d. s. h. aq. 113-5 72 i-Methylcyclopropanedicarbonic(2, 2) Ac., Me.C3H3.(CO2H)2.-Silky ndl. fr. bz. S. in 1 pt. c. aq.; e. s. eth.-Distillation gives valero- lactone.-Gives Test 303 at 140° -Stable towards KMnO4.- CaA+ 5 aq., glassy pr., e. s. aq.; Ag2A, floc. ppt. (at 70°). 113-5 200 Naphthoylformic Ac., C10H7.CO.CO2H.-Ndl., e. s. aq. or eth. Oxid. by, KMnO4 to a-naphthoic ac.-BaA2, e. s. c. aq.; AgA, amorph. ppt. 112-15 192 Ethylbenzoylacetic Ac., Ph.CO.CHEt.CO2H.-E. s. ale. or eth. Boil- ing w. cone, alcoholic potash gives mixture of potassium benzoate and butyrate! 44 GEN VS III, DIV. A, SECT. 1. (ORDER I, SUBORDER I.) Melting-point (C.°). Neut. Equiv. SOLID ACIDS.-Colorless and generally soluble (see note, p. 38) in 50 parts of cold water. 114-5d. 91 Dioxytartaric Ac., CO2H.[C(OH),]2.CO,H.-Cryst. mass fr. eth. V. s. aq. Gives Test 303.-The aq. sol., when heated, dec. quantita- tively to CO2 and tartronic ac ! Therefore gives theoretical neut. eq. only at 0°. Salts unstable. 115-16 74 a-Ethyltartronic Ac., E_t.COH.(CO2H)2.-Cryst. w. 1 aq. in tbl. w. m. p. 64°-70°.-Ag2A, mic. pr. fr. h. aq. 116 136 Trioxyisobutyric Ac., (CH,OH)2.COH.CO2H.-Pr. fr. ale. v. s. aq.; d. s. ale. or eth.-Gives Test 302.-CaA2 + 4 aq., s. aq.; PbA2.Aq., d. s. h. aq. 116-5 164 Hydrocumarilic Ac., CSH7O.CO2H.-Pearly 1ft. fr. aq.; s aq.; v. e. s. alc._ or eth. Dist. w. dec. at abt. 300°.-AgA, v. d. s. h. aq.; BaA2 + 2 aq., e. s. aq. 117 80 Isopropylsuccinic Ac., CO2H.CHPr.CH2.CO2H.-Cryst. crusts e. s. aq., ale., eth., or CHC13.-On distill, gives liq. anhydride, b. p 245°-50°. -Fuse w. KOH and acidify w. H2SO4. (Odor of butyric ac.). -BaCl2 no ppt. Ag salt, d. s. 117 97 Benzylmalonic Ac., Ph.CH,.CH. (CO2H)2.-Triclinic, e. s. aq. or eth. Test 303 at 180° gives CO, and hydrocinnamic ac 117-8 166 Tropic Ac., Ph.CH(CH,OH).CO2H. (prepared fr. atropine).-Ndl. or tbl. s. 49 pt aq. at 14 5°; v d. s c. bz and CS2. Gives Test 302.-CaA2-4 aq., rhombic tbl.-Long boiling w. Ba(OH), gives atropic ac. 118 73 Methylethylmalonic Ac., (Me)(Et)C.(CO2H)2.-Pr e. s. aq. or eth.- Ag2A, d. s. cryst. powder.-Gives Test 303. 118 152 f Mandelic Ac., Ph.CHOH.CO,H.-Rhombic cryst., 16 pt s in 100 pt. aq. at 20°; s. eth.-Gives Test 302!-Dist. or boiled w aq. and MnO2 gives odor of bitter almonds!-AgA cryst. ppt., tbl. fr. h. aq.; BaA2, s. 12 pt aq. at 24°. 119 74 Citramalic Ac. (racemic), CO?H.CH2.C(OH,Me).CO2H.-Glassv deliq. cryst. v. s. aq -At 200° gives citraconic anhydride.-Gives Test 302.-CaCl, added to NH4 salt gives floc. ppt. in cone. sol.-Scaly fr h. dil. sol. 119-20 68 Mesoxalic Ac., (HO)2.C.(CO,H)2.-Deliq. ndl., v s. aq.; s. eth.-Re- duces ammon. AgNO3 sol. when warmed.-Ba, Ca, Pb, and Ag salts v. d. s. c aq.-Ag2A dec. by boiling w. aq., oxalic ac. being among the products. 120d. 85 J'-Tetrahydrophthalic Ac., CsH10O4 (dried i. v).-Lfts fr aq.; e. s. aq.-Oxid by alk. KMnO4 to adipic ac -At 100° gives anhy- dride, m. p. 74°.-BaA + aq., gran. ppt.-Gives Test 304. 120-1 94 2, 3, 3-Trimethylpentanediol(2, 4)-dioic(i, 5) Ac. (racemic), C6H12O6. -(An oxid product of camphoric acid ) Lust lfts., e s aq., ale., or eth.-Heated to 220° dec to water, isobutyric ac. (odor and Test 311!), CO, etc -Ag,A ppt. 123 74 ^-Methylmalic Ac., COH.CHMe.CHOH.COH.-Pr. fr. acetic eth., v. s. aq. or ale -Gives Test 302 -Heat gives citraconic anhy- dride, etc -BaA + 2J aq 1ft d s aq. 123 166 [ -]-Tropic Ac., Ph. CH(CH2OH).CO2H.-Cryst. somewhat s. aq.-M. p. of quinine salt 178°. 121-5 80 Diethylmalonic Ac., Et2.C.(CO2H),.-Pr , v s. aq. or eth.-Gives Test 303 at 170o-80°, forming CO2 and diethylacetic acid.-Zn salt cryst. ppt.--CaCl, precipitates cone sol of NH, salt. 124 80 Methylisopropylmalonic Ac., (Me)(Pr).C.(CO2H)2.-S. aq.-Gives Test 303.-CaA, v. d. s aq.: Ag2A ppt. 127-8 166 [ + ] Tropic Ac., Ph.CH(CH,OH)CO,H.-Pr. fr. eth. S. h. aq. M. p. of quinine salt 186°-7°. Less s. dil. ale than salt of [ -1 tropic ac. 128 80 s-Dimethylglutaric Ac. (malenoid), CO,H.C5H1G.CO,H.-Triclinic cryst.-100 pt. aq. at 17° dissolve 4.1 pt.-Acetylchloride gives anhydride in the cold, b. p. 272°. GENUS III, DIV. A, SECT. 1. 45 (ORDER I, SUBORDER I.) Melting-point Neut. Equiv. SOLID ACIDS.-Colorless and generally soluble (cf. note, p. 38) in. 50 parts of cold water. 128c. 90 [+ or -]-Trioxyglutaric Ac., CO2H.(CHOH)3.CO2H.-Cryst. fr. ace- tone; v. s. aq. or ale.-Ag-A ppt., m. p. w. dec. 173°.-Gives Test 302. 129 87 s-Diethylsuccinic Ac., CO2H.EtCH.CHEt.CO2H.-Warty masses; v. e. s. h. aq. or eth.-ZnA more s. c. than h.-At 180° gives anhydride. 129 152 m-Oxyphenylacetic Ac., HO.CGH).CH2.CO2H.-V. s. aq. or eth. Gives transient violet color w. FeCI3. 129 73 s-Dimethylsuccinic Ac. (malenoid), (MeCH)2.(CO2H)2.-Pr. s. in 3-3 pt. aq. at 14°.-W. Cone. HC1 at 180° gives much of the malenoid ac., m. p. 209°. 129 166 Phloretic Ac., p-HO.C0H4.CH(Me)(CO2H).-S. c. aq. or eth. Gives green color w. FeCl3!-Pb salt bulky ppt. 129-31 81 /?-Dimethylmalic Ac., CO2H.CHOH.CMe2.CO2H.-Cryst. fr. acetic eth. E. s. aq.; s. eth.-Ag2A, ndl. d. s. h. aq. Gives Test 302 ! 130 58 f Maleic Ac., CO2H.CH :CH.CO2H.-Monoclinic pr. s. in 2 pt. aq. at 10°. Gives Test 901 w. h. bromine water, but does not add Br easily in CC14 sol.-Heating in vacuo above 100° gives solid anhy- dride, m. p. 56°-7°.--At 200° in tube gives fumaric acid (d. s. aq., sbl. at 200°).-Aq. sol. gives ppt. w. BaO2H2; PbAc2 gives ppt. No ppt. w. CaCl2.-f Place 0-1 grm. acid w. 0-2 cc. aniline in a test-tube w. 10 cm. glass tube as return condenser. Heat 1 hr. at 190°-200°. Cryst. fr. 15 cc. boiling ale. Cool, filter, wash w. 2 cc. cold ale. and recrystallize fr. 10 cc. boiling ale. Dry at 100°- 110°. Gives phenylaspartic-anil. white cryst., m. p. 209°-10°. 131 194 PhenyI-/?-oxy valerianic Ac., Ph.C2H4.CHOH.CH2.CO2H.-E. s. aq.; d. s. c. eth.-Dec. on dist.-BaA2 + aq., Ifts. d. s. aq.; AgA curdy ppt. 131 72 trans-Tetramethylenedicarbonic(i, 2) Ac., C4H0.(CO2H)2.- Lust. ndl. fr. HC1. Goes easily into anhydride, m. p. 75°. 132 78 s-Methylethylmalic Ac., CO2H.CHEt. (Me)C(OH).CO2H.-Pr. e. s. aq. Dec. on dist. Gives Test 302. 132 52 t Malonic Ac., CH2.(CO2H)2.-Cryst. s. in less than 1 pt. aq.; s. eth.- Test 303 gives CO2 and acetic ac.!-Fuming nitric acid causes evolution of CO2.-f Boil 1-2 cgrm. in a test-tube w. 3 cc. acetic anhydride for 3 minutes; then dilute w. 3 cc. acetic ac. A yel- lowish-red sol. w. yellowish-green fluorescence will be obtained.-■ Ag2A stable cryst. ppt.; CaA + 2H2O, alm. i. c. aq. 132 65 Glutaconic Ac., CO,H.CH2.HC :HC.CO2H.--Pr. e. s. aq. or eth.- ZnA less s. h. than c.-Ag2A d. s. h. aq.-Long boiling w. x's acetvl chloride gives anhydride, m. p. 87°.-Reduction w. Na amalgam gives glutaric ac. 133 57 i-Malic Ac., C4HnO,.-Cryst. Not deliq.-Reactions as for [ + ac.] (Cf. m. p. 100°.) 133 92 Diallylmalonic Ac., (C3H5)_2.C.(CO3H)2.-Pr. e. s. aq. or eth. Gives Test 303 and 304.-CaA (at 100°) e. s. aq.; Ag,A d. s. c. aq. 132-4c. 112 Pyromucic Ac., C4H3O.CO2H.-Sbl. fr. 100° in ndl.-S. in 28 pt. aq. at 15°. V. s. h. aq.; e. s. ale. or eth.-Pine splinter, soaked in cone. HC1 and held in vapor evolved on heating dry NH4 salt in test-tube, becomes deep red!--Sol. in cone. H2SO4 warmed w. trace of isatin becomes violet-blue.-Aq. sol. gives reddish-yellow ppt. w. FeCl3.-CaA2 and BaA2 cryst. and s. aq. or ale.-PbA2 + aq. d. s. c. aq.-AgA 1ft. 135d. 59 Isosuccinic Ac., Me.CH.(CO2H),.-Pr. v. s. aq.; 100 cc. aq. sol. at 0° contains 44.3 grm.-Test 303 gives CO2 and propionic ac. (Test 311)!-Ca, Ba, Pb, and Ag salts v. d. s.; Pb salt s. in x's of pre- cipitant. 46 GENUS III, DIV. A, SECT. 1. (ORDER I, SUBORDER I.) Melting-point (C.°). Neut. Equiv. SOLID ACIDS.-Colorless and generally soluble (cf. note, p. 38) in 50 parts of cold water. 135d. 73(?) t Acetonedicarbonic Ac., CO.(CH2.CO2H)2.-Ndl. fr. acetic eth. which effloresce in the air.-V. s. aq. or ale.; d. s. eth.-Aq. sol.+ FeCls gives violet color! Gives Test 303!-Distil a neutral aqueous solution of the sodium salt and apply tests for acetone (Test 711) to distillate! 130-8 72 Cis-i, 2-Tetramethylenedicarbonic Ac., C4H6.(CO2H)2.-Feathery cryst. v. s. aq., ale. or eth.-Heated above 300° gives anhydride, m. p. 76°-8°.-Oxid. by KMnO4 to oxalic ac.-BaA separates as 6-sided tbl. on boiling a sol. in ammonia'w. BaCl2 sol. 137 72 Methylglutaconic Ac., Me.CH.(CO2H).CH: CH.CO2H.-E. s. aq., ale., or eth.-Unsaturated. 137 152 o-Oxyphenylacetic Ac., HO.CGH4.CH2.CO2H.-Ndl. fr. eth.; s. aq.- Dist. gives anhydride, m. p. 49°; b. p. 236°-8°.-Aq. sol. colored violet by FeCl3! 138-9 210 Veratrinketonic Ac., (MeO)2.C(H3.C2O3H (dried).-E. s. aq., ale., or eth.-KOH fusion gives protocatechuic ac.-Pb salt d. s. ppt. 138-9 72 Cis-Tetramethylenedicarbonic(i, 3) Ac., C4Hfi.(CO,H)2.-Pr. v. s. c. aq.-BaA+ 2 aq. s. in 150 pt. c. aq., less s. in h. aq. 139 87 Dimethylethylsuccinic Ac., CO2H.CHEt.CMe2.CO2H.-S. in 27 pt. c. aq.; e. s. ale. or eth.-B. p. 235°-40°. 139 Anhydrocamphoric Ac., C9H]2O5.-Sbl. undec.-E. s. aq., ale., or eth Can be recryst. fr. aq. 139-40 73 a-Dimethylsuccinic Ac., CO,H.CMe2.CH2.CO2H.-Thick glassy pr. fr. bz.-100 pt. aq. at 14° dissolve 7-52 pt.; e. s. ale. or eth.-At 165°-70° gives anhydride, m. p. 29°.-Ca salt separates from ammon. sol. by CaCl2 only when warmed. 139 101 Tetrahydroxy terephthalic Ac., (OH)4.C6.(CO2H)2.-E. s. aq. or ale.; i. eth. No color w. FeCl3.-BaA e. s. aq. 139 182 Hydrocaffeic Ac., (OH)2.CGH3.(CH2)„.CO2H.-6-sided tbl. fr. aq. E. s. aq. Aq. sol. gives intense green color w. FeCl3! Reduces Fehling's sol. and AgNO3 easily. 140 74 Ethylenemalonic Ac., C2H4.C.(CO2H)2 + aq.-Ndl. fr. eth., v. s. aq. or eth.; s. CHC13.-Gives Test 303 and 304.-(NH4)2A + BaCl2 gives ppt. almost i. c. aq. 140 79 Cis-Pentamethylenedicarbonic(r, 2) Ac., Cr,H8.(CO2H)2.-Ndl. At 160° gives anhydride (tbl. fr. Ac., m. p. 140°). abt. 140<L 67 Isomalic Ac., Me.COH.(CO2H)2.-Cryst., e. s. aq., ale., or eth.-Opt. i.-At abt. 160° gives Test 303 yielding CO, and lactic acid.- BaA+ 2 aq., d. s. h. aq. 140- 80 s-Dimethylglutaric Ac. (fumaroid), C7H12O4.-Pr.-100 pt. aq. at 17° dis. 4.4 pt.-CaA2 floc. ppt. 141d. 63-3 2, 3-Dicarboxyl-pentanoic(i) Ac., C7HI0Oc.- Cryst. fr. acetone, v. s. aq., ale., or eth.-Heated loses CO2.-Ba3A2, i. aq. or ale. 140-3 84 Mesotartaric Ac., (HO)2.C,H,.(CO2H)2.-(Cryst. w. 1 aq.)-Tbl. s. in less than 1 pt. c. aq.-KHa much more s. than acid tartrate or racemate.-Does not ppt. CaSO4 sol. (dif. fr. racemic ac.). Gives Test 302.-Opt. i.-For microchemical tests cf. R. 17.69. 143-4s.d. 182 Phenylglyceric Ac., Ph.(CHOH)2.CO,H.-V. s. aq. or ale.; d. s. abs. eth.-Gives Test 302, decomposing-at 160° to CO2 and a-toluylic aldehyde.-CaA2-4 aq. d. s. c. aq. 145-6d. 64 Glutinic Ac., CO?H.Cj C CH2.CO2H.-E. s. aq., ale., or eth.; i. bz. -Gives Test 303 and 304.-PbA ppt. GENUS III, DIV. A, SECT. 1. 47 (ORDER I, SUBORDER I.) Melting-point (C.°). Neut. Equiv. SOLID ACIDS.-Colorless and generally soluble (cf. note, p. 38) in 50 parts of cold water. 145 226 Galactosecarbonic Ac., HO.GH2.(CHOH)5.CO2H.-Ndl., s. aq.-Fusion gives an anhydride.-Gives Test 302. 147 168 Homogentisic Ac., (HO)2.C6H3.CH2.CO2H.-V. s. aq., ale., or eth.- Fusion gives anhydride of m. p. 191°.-Gives transient-blue color w. dil. FeCl3.-KOH fusion gives hydroquinone, etc.-Cryst. effloresce over H2SO4. 148 152 p-Oxyphenylacetic Ac., HO.C0H4.CH2.CO2H.-Flat ndl., s. c. aq.; v. e. s. h. aq.; s. ale. or eth.-Sol. gives pale-violet color w. FeCl3, changing quickly to a dirty grayish green. Dist. w. CaO gives CO2 and p-cresol. (From urine.) 148 76 Diglycollic Ac., CO2H.CH2.O.CH2.CO2H +Aq.-Rhomb, pr., e. s. aq. or ale.-Dist. w. dec. giving glycoIlic ac., trioxymethylene, CO and CO2.-BaA, i.aq.; Ag2A, gray ppt.; CuA blue ppt. abt. 150d. 72-7 1-Camphoronic Ac., C9H14O6.-Cryst. s. in 17 pt. c. aq.; v. s. ale.; e. s. eth.-CO2 and isobutyric ac. are among products of slow dist. 150-3 58 cis-i, 2, 3-Trimethylenetricarbonic Ac., C3H3.(CO2H)3 (dried at 120°)- -E. s. aq. or ale.-Ca salt less s. h. than c.; Ag3A amorphous ppt. 151 81 a-Oxyadipic Ac., CO2H.C3H0.CHOH.CO2H.-Sbl. undec. E. s. aq. ale., or eth. 152 80 Trimethylsuccinic Ac., CO2H.CMe,CHMe.CO2H.-E. s. aq. or bz.- ZnA, mic. pr. e. s. c. aq., but ppt'd by boiling the sol.-Prepare the anilic ac., m. p. 134°, and the anil. m. p. 129°. 152d. 90 i-Trioxyglutaric Ac., CO2H.(CHOH)3.CO2H.-Tbl. fr. acetone. V. s. aq. or h. ale. Gives Tests 101 and 302. 152-3 72 Hexamethylenetricarbonic (i, 4, 4) Ac., C9H12OG.-S. aq.; d. s. eth.-• Dec. at 200°. Gives Test 303. 152-3d. 90 Phenylmalonic Ac., Ph.CH.(CO2H)2.-Pr., e. s. aq., ale., or eth.-CaA cryst. ppt.; Ag2A curdy ppt.-Fusion gives CO2 and phenylacetic ac. (Test 303). 153 64 f Citric Ac., CO2H.CH2.C(OH)(CO2H).CH2.CO2H.-Cryst. w. 1 aq. in rhombic pr. (Dry at 130° for m. p.) S. in 0-75 pt. c. aq.; v. s. ale.: 100 pt. c. eth. dissolve 2-26 pt.-Gives Test 302.-Hot cone. H2SO4 gives yellow color, but does not char.-CaCl2 gives a white cryst. ppt. with neutral alkali citrates when the sol. is boiled for a few min.,-otherwise only after some hours; an alkali citrate sol. after being made strongly alkaline w. NaOH gives _an amorphous ppt. immediately.-Ca2A3 is soluble in HC1, in Ac, in citric ac., in NH4C1, and in alkaline citrates.-[Neutral alkali tartrates and oxalates give an immediate ppt. w. CaCl2; calcium oxalate is insoluble in acetic acid. Malic ac. and neutral malates give no ppt. w. CaCl2 unless ale. is also added. A cone. sol. of citric ac., or of an alkali citrate acidified w. acetic ac., gives no ppt. ■when treated w. a 5% potassium acetate sol. and ale. (dif. fr. tartrate)].-Gives color reac. 314! 154-5c. 90 (rac.)-Trioxyglutaric Ac., CO2H.(CHOH)3.CO2H.-Cryst. fr. acetone v. s. aq. or h. ale. 157 72 1, i-Tetramethylenedicarbonic Ac., C4HG.(CO2H)2.-Pr. fr. eth. E. s. aq.; s. eth.-Gives Test 303 at 210°.-Ba, Pb, and Ag salts are ppts. 158d. 105 [4- or -] Talomucic Ac., CtH10Os.--Mie. 1ft. fr. acetone; e. s. c. aq. or h. ale.-CaA (at 105°), d. s. h. aq. 159d. 54 Ethenyltricarbonic Ac., (CO,H),.CH.CH2.CO2H.-Pr. e. s. aq., ale., or eth._ Test 303 gives CO2 and succinic ac. (Test 320!). Ca3A2 and Zn3A2 are more s. in c. than in h. aq.; Ag3A is an amorphous ppt. d.160 101 Diacetylsuccinic Ac., CO2H.CH(MeCO).CH(MeCO).CO2H.-Ndl. s. aq. or ale.; d. s. eth.-Heated w. HC1 gives carbopyrotritaric ac. 158-9d. 60 Tartronic Ac.-See m. p. 185°-7°. 48 GENUS III, DIV. A, SECT. 1. (ORDER I, SUBORDER I.) Melting-point Neut. Equiv. SOLID ACIDS.-Colorless and generally soluble (cf. note, p. 38) in 50 parts of cold water. 161d. 65 + Itaconic Ac., CH2:C(CO2H).CH2.CO2H.-Rhombic octahedra, s. aq. (1 : 2 at 20°); s. ale.; d. s. eth.-Gives Test 304.-Gives red- brown ppt. on boiling w. x's FeCl3.-CaA-aq. s. in 45 pt. aq. at 18°; Ag2A v. d. s. h. aq.-Warmed w. acetylchloride gives anhy- dride, m. p. 68°. 160-1 Saccharine.-Cf. Genus V, Div. A. 161-6c. 132 f Quinic Ac., (OH)4.C6H7.CO2H.-Monoclinic pr. s. 2-5 pt. aq. at 9°; less s. ale.; alm. i. eth.-Gives Test 302.-Dry distillation gives phenol, salicylic ac. (Test 319), and benzoic ac. (Test 312).- + Gives pungent odor of quinone on boiling in test-tube w. dil. H2SO4 and MnO2!-Br substitutes.-I and KOH give iodoform (Test 801).-Ca and Pb salts e. s. c. aq.-Occurs in cinchona bark, coffee-beans, etc. 162d. 79 Teraconic Ac., Me2.C:C(CO2H).CH2.CO2H.-E. s. c. aq., ale., or eth. -Dist. gives aq. and an anhyd. w. b. p. 270°-80°.-CaCl2 gives pulv. ppt. (best on warming). 166 58-7 Tricarballylic Ac., CO2H._CH.(CH,.CO2H)2.-E. s. aq. or ale.; d. s. eth- -Sbl. w. dec.-Ca3A2.4 aq., d. s. aq.; Pb3A2 pulv. ppt.-FeCls gives floc. ppt. 166-7 Acetoxyl-a-propionic Ac., Me.CH(C2H3O2).CO2H.-Ndl. v. s. aq. or ale. After long keeping becomes i. in ale. and does not melt at 300°.-BaA2 v. s. aq.-Boiled w. NaOH gives acetic and lactic ac. salts. 166-7 72 Methylitaconic Ac., Me.CH: C(CO2H).CH2.CO2H.-Pr. s. aq. or eth. -Ba salt cryst. ppt.-Gives Test 304. 166-7 72-7 Isocamphoronic Ac., C9H]4O6.-Pr. s. c. aq.; e. s. ale., or eth.- Sbl.-Ag3A.-NH40H and BaCl2 give no ppt. 167d. 55 Dicarboxyglutaric Ac., (CO2H)2.CH.CH,.CH.(CO2H)2.-V. s. aq., ale.; d. s. eth.-Test 303 gives CO2 and glutaric ac. (Test 316). Ca, Ba, and Pb salts form ppts. 167-5 164 Prehnitylic Ac., Me3.CGH2.CO2H.-Glassy pr. fr. ale. "Somewhat" s. in aq. 168-70 75 f d-Tartaric Ac., CO2H.(CHOH)2.CO2H.-Monoclinic cryst.-100 pt. aq. dissolve 139 pt. at 20°.-E. s. ale., v. d. s. eth.-Solutions [ + ]. Apply Tests 302 and 314 ! CaCl2 gives volum. ppt. from sol. of neutral K or Na salts, but not from solution of the free acid. The ppt. is sol. in mineral and acetic acids, in cold NaOH, and in an excess of alkaline tartrate. From rather dil. sol. it appears slowly and in cryst. form.-KC2H3O2 gives a ppt. in tartaric acid sols, (facilitated by diluting with an equal vol. of alcohol). Neutral salts must first be acidified with acetic ac.i! -If to an aq. sol. of the acid or a soluble tartrate, 1 drop FeSO4 sol., a few drops H2O2 sol. and an x's NaOH be added, a fine deep violet color is immediately produced, which in cone. sols, is so deep as to be nearly black. (Cf. Allen, I, 515.) This color is not given by citric, malic, succinic, or oxalic acids. 169 188 Naphthol (8)-carbonic Ac., HO.C10H8.CO2H.-E. s. aq., ale., or eth.- CaA2 sol. gives w. FeCl3 a violet ppt. 170 72 trans-Tetramethylenedicarbonic(i, 3) Ac., C4Hc.(CO2H)2.-Sbl. in fine ndl.-S. in 26 pt. aq. at 20°; d. s.eth.-Does not add Br.-Gives an anhyd. w. difficulty, m. p. 50°. 169-71 51-5 f s-Ethanetetracarbonic Ac., C2H,.(CO2H)4.-E. s. aq., ale., or eth. -Gives Test 303, yielding CO2 and succinic ac. (Test 320!). Aq. sol. gives ppt. w. BaCl2. 172d. Oxalacetic Ac., CO2H.CO.CH2.CO2H.-E. s. aq., ale., or eth.-Gives Test 303. Phenylhydrazine hydrochloride gives 1-phenylpyra- zolon (5) carbonic (3) ac. 175 65 Trimethylenedicarbonic (1, 2) Ac. (fumaroid), C3H4.(CO2H)2.-Glassy tbl. s. in 5 pt. c. aq.-Ag,A d. s. h. aq.- B. p. (30 mm.) abt. 210°. GENUS III, DIV. A, SECT. 1. 49 (ORDER I, SUBORDER I.) Melting-point (C.°). Neut. Equiv. SOLID ACIDS.-Colorless and generally soluble (cf. note, p. 38) in 50 parts of cold water. 176 79 Cis-3, 3-Dimethyltrimethylenedicarbonic(i,2) Ac., C7H10O4.-Tbl. rather d. s. c. aq.-Above m. p. gives anhyd., m. p. 56°. Very stable towards KMnO4 and Br. 175d. 175-8 226 d-Mannoheptonic Ac., C7HhOs.-S. in 25 pt. c. aq.-Opt. [ -].-- CaA2 s. h. aq.; BaA2 d. s. c. aq.-Gives Test 302. Glucuronic Anhyd., C6H8O(!.-V. s. aq.; i. ale.-Reduces Fehling's sol.-Ac. syrupy and e. s. ale. 177 78 Diacetylenedicarbonic Ac., CO,H.C • C.C • C.CO2H + aq.-Tbl. fr. ale.-eth. S. aq.; e. s. ale. or eth.-Turns purplish in light. •-Ammon. Cu2Cl2 gives a red ppt. at 30°. 178d. 67 Methyltartronic Ac., Me.COH.(CO,H)2.-Rhombic cryst., s. aq.-■ NH4 salt ppt'd by boiling BaCl2.-Gives Test 303. 178-9 57 Acetylenedicarbonic Ac., CO2H.C • C.CO2H.-(Cryst. w. 2 aq.-■ Cryst. effloresce in air; lose aq. of cryst. over H2SO4).-V. s. aq., ale., or eth.-Gives Test 304 easily. Is reduced to succinic ac. (Test 320) by Na amalgam.-Ag. salt v. unstable. BaA + aq., d. s. c. aq. 180 80 s-Methylethylsuccinic Ac. (fumaroid), CO2H.CHEt.CHMe.CO2H.- Ndl., 3 pt. s. in 100 pt. aq. at 17°; e. s. eth.; d. s. CHC13.- A 5% sol. of Na2A gives w. c. CaCl2 no ppt., but w. h. CaCl2 cubical cryst., CaA, which disappear again on cooling. 181d. 91 Oxyphthalic Ac., CeH3.(OH)(CO,H)2(4 : i :2).-Gives anhyd. on melt" ing.-Rosettes s. in 32 pt. aq. at 10°; s. eth.-Aq. sol. reddish yel" low w. FeCl3.-Fuse for a short time w. some resorcine at 200°- Fusion s. in aq. w. greenish fluorescence; KOH turns to dark yellowish red. 183 • 152 Oxytoluic Ac., C6H3.(OH)(Me)(CO2H)(6 : i : 2).-Ndl. s. c. aq.; v. s. eth.-FeCl3 gives light-brown ppt.-CaA., v. s. aq. 184d. 58 1, 1, 2-Trimethylenetricarbonic Ac., C3H3.(CO2H)3.-Pr. fr. aq.-■ Gives Test 303. 185 59 t Succinic Ac., CO2H.CH2.CH2.CO2H.-Monoclinic pr., s. in 14-57 pt. aq. at 20°, or in 0-826 pt. at 100°; s. ale.; d. s. eth.; i. CHC13 or CS2.-Distils at 235° giving anhydride! Burns w. blue smokeless flame.-CaCl2 gives white cryst. ppt. only in cone, sols, of alkaline salts. Ppt. s. in aq., Ac, HC1, or hot NH4C1 sol.; i. ale.-Although not an n-hydroxy acid, gives a somewhat similar coloration in Test 302.-Apply Test 320! 185 105 Isosaccharic Ac., CGH10Os.-Rhombic cryst., e. s. aq. or ale.; d. s. eth.-Aq. sol. shows birotation.-Dec. on dist.-Ag2A, cryst. ppt. which gives silver mirror on warming w. ammonia. 185-7d. (?) 60 Tartronic Ac., HO.CH.(CO2H)2.-(Cryst. w. | aq.)-Pr. fr. eth., e. s. aq. or ale.; d. s. eth. when not anhyd.-Sbl. at_110°-120°. -Gives Test 303, yielding glycolid (m. p. 220°)_.-BaA (at 100°), floc. ppt. changing to 1ft. v. d. s. h. aq.; Ag2A cryst. ppt. d. s. 186-8d. 61-5 Cyclopentane-tetracarbonic(i, 1, 3, 3) Ac., C9H10O8. - Hygroscopic cryst. mass. Gives Test 303. 189d. 58-5 (^)-3, 4-Dicarboxyl-hexanedioic(i, 6) Ac., C8HI0O8.- Silky ndl. fr. aq.- 100 ph aq. dis. 27-4 pt. at 19°. - In melting gives an anhyd.-Ag4A, amorph. ppt. 189-5 45 f Oxalic Ac. (Anhydrous), CO2H.CO2H.-Octahedra. Takes on water quickly.-S. aq.-For reactions see the hydrated acid on p. 42 of this section 1 191d. 58 f Aconitic Ac., CO2H.CH2.C(CO2H) :CH.CO2H.-Lft. mod. s. c. aq.; v. s. ale.; e. s. eth. (dif. fr. citric ac.).-Sol. boiled w. x's Ca(OH)2 sol. gives no ppt. (dif. fr. citric ac.).-BaA2, s. in 24 pts. aq.; Ba3A2 is ppt.; Zn3A2, i. aq.; Ag3A, floc. ppt. fr. (NH4)3A and AgNO3.-Gives Test 304 (and 901 slowly, hot).-Reduced by Na amalgam to tricarballylic ac. 50 GENUS III, DIV. A, SECT. 1. (ORDER I, SUBORDER I.) Melting-point (C.°). Neut. Equiv. SOLID ACIDS.-Colorless and generally soluble (cf. note, p. 38) in 50 parts of cold water. 192-3d. 66 Dimethylmalonic Ac., (CO2H)2.C.Me2.-4-sided pr. s. in 10 pt. c. aq.; e. s. eth.-Sbl. in ndl. at abt. 120°.-Gives Test 303, yielding COa and isobutyric ac. (cf. Test 311). 195 87 Tetramethylsuccinic Ac.-(Cf. Div. A, Sec. 2.) 198-203d. 58 Tetramethylenetetracarbonic( i, i, 2, 2) Ac., C4H4.(CO2H)4.-V. e. s. aq., ale., or eth. Gives Test 303. 199d. 154 Protocatechuic Ac., (OH)2.C0H3.CO2H.(3 : 4 : 1).-(Loses water of cryst. at 100°.)-S. aq.; v. s. ale.; mod. s. eth.-Aqueous sol.+ FeCl3 becomes blue-green; on adding Na2CO3 changes to dark red!-PbAc gives ppt. s. in dil. Ac.-Reduces ammon. AgNO3, but not Fehling's sol.-On distil., or NaOH fusion, gives pyro- catechin and CO2 (cf. Test 416). 199-200d. 77 Camphenic Ac., C10H14O6.-E. s. aq. or eth.-Ba salt, v. e. s. aq.; Pb3A2 (at 100°). 199-200 154 2, 5-Dioxybenzoic Ac., (HO)2.CeH3.CO2H.-Ndl. or pr., e. s. aq., ale., or eth.-FeCl3 gives deep-blue coloration! On heating w. FeCl3 sol. gives CO2 and odor of quinone.-BaA2, v. s. aq.; PbA2, v. d. s. aq.-Reduces ammon. AgNO3 and Fehling's sol. when warmed. -On distil, dec. to CO2 and hydroquinone. 199-200 76-7 Camphoic Ac., ClfiH14O6.-Cryst. v. s. aq., ale., or eth.-Gives off CO2 at 300°.-Pb3A2 (at 100°) ppt.; BaA cryst., e. s. aq. 201 Camphanic Ac., C9HI3O2.CO,H.-Sbl. fr. 110°.-S. aq.; e. s. ale. or eth. abt. 200 f Tannic Ac., C14H10O9.-Cf. Ill, A, 1, m. p. 210°. 202 65 Mesaconic Ac., Me(CO2H)C:CH.(CO2H).-Ndl. fr. aq. or ale. S. in 37 pt. aq. at 18°; v. s. hot.- Sbl. undec.! Does not give Test 304 easily. Warmed w. acetyl chloride gives citraconic anhyd.-NH4 salt gives brown floe. ppt. w, FeCI3 (i. h. or in x's of reagent).- Ca and Ba salts mod. s. aq.-PbA. and Ag2A ppts. 204 190 2, 3-Dioxybenzoic Ac., C6H3(OH)2.CO,H.2 aq.-S. aq.-Gives blue color w. FeCl3, changing to violet w. Na2CO3.-Ba and Pb salts v. d. s. aq.-Distil, gives CO2 and pyrocatechin. (Cf. Test 416.) 205-6 84 f Racemic Ac., CO2H.(CHOH)2.CO2H.-Triclinic cryst. containing 1 mol. H2O which effloresce in the air!-Hydrated ac. s. in 4 • 84 pt. aq. at 20°, or in 48 pt. c. ale.-Gives Tests 302 and 314! Ppts. CaSO4 sol. (unlike tartaric ac.); ppt. s. in dil. HC1 and reppt'd at once by NH40H (dif. fr. tartaric).-BaA, 2$ aq. alm. i. c. aq.- Ag2A less s. than tartrate. 208 152 5-Oxy-3-toluic Ac., Me.CgHjOH.CO,^-Tbl. fr. h. aq. "Mod. s. c. aq."-Sbl.-PbA2 cryst. ppt.; CaA2.2 aq., pr. e. s. aq.-Dist. w. CaO gives CO2 and m-cresol. 209 73 s-Dimethylsuccinic Ac. (fumaroid), (CHMe)2.(CO2H)2.-Pr. fr. aq.; i. CHC13.-Acetyl chloride gives anhyd. w. m. p. 43°. d.210 t Gallotannic Ac., C]4H10O9 (?).-A light buff-colored powder or scales. Taste very astringent!-S. c. aq.;less s. ale.; i. abs. eth.-1 drop FeCl3 (10% sol.)+ 20 cc. aqueous tannin sol. (1 : 5000) gives a color that is deep blue by transmitted light! Gelatine sol. gives immediate white ppt.!-(The last two reactions distinguish from gallic ac.) Alkaline sol. quickly absorbs O and becomes brown! At 210° gives CO2, pyrogallol, etc.-The salts are amorphous.- Reduces AgNO3 sol. on boiling. 213 79 trans-3, 3-Dimethyltrimethylenedicarbonic(i, 2) Ac., C7H10O4.-Pr.e. s. h. aq.;. d. s. eth.; alm. i. CHC13.-Stable. Heating alone gives no anhyd. 216d. 70 a-Trimellitic Ac., CfiH3.(CO2H)3(i, 2, 4).-S. h. aq. or eth.-Gives an anhyd. on fusion.-Distil and test distillate for phthalic anhyd. by Test 318-1!-Ba3A2. d. s. aq.-Ag3A, ppt. d. s. aq. 218-20d. 65 I, 3, 3-Hexamethylenetetracarbonic Ac., C10H]2Os.-Pr., s. c. aq.; e. s. h. ale.; d. s. eth.-Ag4A gelat. ppt.-Dec. on melting to CO2 and dicarbonic acids. GENUS HI, DIV. A, SECT. 1. 51 Melting-point (C.°). Neut. Equiv. SOLID ACIDS.-Colorless and generally soluble (cf. note, p. 38) in 50 parts of cold water-. 220 58 cis-trans-s-i, 2, 3-Trimethylenetricarbonic Ac., C3H3.(CO2H)3.-S. aq. or ale.-Ba3A2 + aq. ppt.; Ag3A ppt. 232 181 3, 5-Dioxybenzoic Ac., (HO)2.C6H3.CO2H.i| aq.-Pr. mod. s. c. aq.: e. s. ale. or eth.-Gives no color w. FeCl3 and no ppt. w. PbAc.- Fusion w. 8 pts. NaOH gives resorcine (Test 418).-Gives deep- red color on heating at 140° w. 4 pts. cone. H2SO4; ppt'd green by aq. 236 (s. h.) 58-5 a-3, 4-Dicarboxyl-hexanedioic(x, 6) Ac., CsH10O8.-Lft. fr. aq.-100 pt. aq. dissolve 11-8 pt. at 19°; v. s. ale.; d. s. eth. 237d. 63-5 V-Benzenetetracarbonic Ac., C6H2.(CO2H)4.-Cryst. w. 2 aq., which it loses above 100°. E. s. aq.-Aq. sol. not easily extracted by eth. -In melting gives an anhyd.-Crystals resemble prehnite.-• Pb2A, i. aq.; Me4A, m. p. 104°-8°; Me2A, m. p. 176°-7°.-Aq. sol. of acid gives a cryst. ppt. BaA2+ H2O when warmed w. BaCl2 sol. (Dif. fr. 1, 2, 3, 5 acid.) 238d. 63-5 n-i, 2, 3, 5-Benzenetetracarbonic Ac., C6H2.(CO2H)4.- E. s. aq.- Cone. HC1 ppt's fr. aq. sol. in short ndl. On meltin_g forms an anhydride.-Gives floc. ppt. w. PbAc2; floc. pp. w. CaAc2on heat- ing; floc. ppt. w. BaO2H2, but none w. BaCL. 264d. 63-5 s-Benzenetetracarbonic Ac., (Pyromellitic Ac.), C6H2.(CO2H)4.-In melting gives an anhydride.-Triclinic tbl., 100 pt. aq. dissolve 14-2 pt. at 16°; e. s. ale.-Sbl._giving anhyd. m. p. 286°.-Ca, Pb, and Ag salts are ppts.-Me4A, m. p. 138°. 286-8 57 Mellitic Ac., C6.(CO2H)6.-Fine silky ndl., v. e. s. aq.; e. s. ale. 345-50 70 (s)-i, 3, 5-Trimesic Ac., CfiH3.(CO2H)3.-Pr. fr _aq.-"Moderately" s. c. aq.; v. s. ale.-Sbl. below 300°-Ba3A2-aq., lustrous ndl., alm. i. c. aq.; v. d. s. h. aq.: Zn3A2 pr. alm. i. c. aq.; Ag3A, volum. ppt.-Me3A, m. p. 143°. (ORDER I, SUBORDER I.) COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER IJ GENUS III, ACIDS. DIVISION A, SECTION 2,-SOLID ACIDS NOT SOLUBLE IN COLD WATER. Melting-point (0°). Neut. Equiv. SOLID ACIDS.-Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 14 282 t Oleic Ac., C1SH34O2-B. p. 232° (20 mm.).-G. 0-8908lb8/4.-Gives Tests 304 and 901! Absorbs 0 from the air.-Fused in a test- tube w. x's of moist KOH in a bath the temperature of which is gradually raised from 300°-320°, is converted almost quanti- tatively into potassium palmitate, acetate, and H.-Dilute one volume of the nitrosyl-sulphuric ac. reagent described on p. 13 with one vol. of aq., and shake the mixture in a test-tube with an equal volume of the oily acid, keeping it well cooled with run- ning tap-water. Set the tube aside in a beaker containing cold water for 15 minutes. A solid mass of elaidic ac. (m. p. after purification 51°-2°) soon separates. 16-7 298 Ricinoleic Ac., C1SH34O3.-B. p. 250° (15 mm.).-Gives Tests 304 and 901.-Treatment w. nitrosyl-sulphuric acid, as described under oleic ac , gives ricinelai'dic ac., m. p. 50°.-Polymerizes easily. 19-4 166 Ethylethersalicylic Ac., EtO.C6H4.CO2H.-D. s. c., e. s. h. aq.- BaA2 v. s. aq. 21-3 181 Umbellulic Ac., CUH22O2.-Cryst.-B. p. 275°-80° c.-(An ac. fr. fat of Californian Laurel.) 24-4 114 2-Methylpenten(2)-oic(i) Ac., C6H10O2.-B. p. 213° c.-VLd. s. aq.; e. s. eth.-Gives Test 304.-Is volat. w. steam.-AgA, ndl. or 1ft. fr. h. aq. 24-5 184 f Undecylenic Ac., Me.C2H,.C7HI4.CO2H.- B. p. 165°_(15 mm.).- (From distil, of castor-oil i.v.)-G. 0-9072 24/4.-BaA2. ndl. or 1ft. s. in 1073 pt. aq. at 15-5°.-Fuming HN03 oxid. to sebacic ac.-• Gives Tests 304 and 9011 26 344 Anacardic Ac., C22H32O3.- (From Anacardium occidentale.) I. aq.; e. s. ale or eth.-AgA (at 100°) ppt. fr. ale. sol. by AgNO3. 26-7 256 Diheptylacetic Ac., CH(C7H1?)2.COOH.-Cryst., alm. i. aq.; v. e. s. ale., eth., or bz.-BaA2, fine ndl. fr. ale.; i. aq. 28-5 186 Undecylic Ac., CUH22O2.-Scab cryst. mass.-B. p. 212^5° (100 mm.). -Feeble odor like caproic ac.-BaA2, v. d. s.; AgA, i. aq. 29 Triethyl Methanetricarbonate, HC.(CO2Et)3.-B. p. 253°.-Ndl. or pr.-' ' Is saponified at 0° by KOH to alcohol, CO2, and malonic ac." ! S. in NaCO3 sol. 30 Acetylperoxide, (Me.CO)2.O2.-Flat cryst. w. odor like ozone. "Somewhat" s. aq.-Extremely explosive.-NaOH gives Ac. and sodium peroxide. 30 128 Hexahydrobenzoic Ac., C.HjpCOjH.-B. p. 233°.-D. s. aq.; v. s. ale. or eth.--ZnA2 much more s. in c. than in h. aq.-Volat. w. steam. 31 176 Cinnamenylpropionic Ac., _Ph.CH2.CH: CH.CH2.CO2H. - Tbl. fr. Igr. -Gives Test 304.-BaA2, d. s. aq.; AgA ppt. 31-3 172 f Capric Ac., Me.(CH2)R.CO2H.-B. p. 268-4° c.-Feeble odor like perspiration.-Alm. i. c. aq.; v. d. s. h. aq.-Alkali salts alone soluble.-BaA2, 1ft. fr. h. aq.-G. 0-93 at 37°. 52 GENUS III, DIV. A, SECT. 2. 53 (ORDER I, SUBORDER I.) Melting-point (C.°J. Neut. Equiv. SOLID ACIDS.-Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 33 254 Hypogaeic Ac., C10H3„O2.-Ndl. e. s*alc.-B. p. 236° (15 mm.).- Oxidizes in air.-Nitrous acid (cf. oleic ac.) gives gaidic ac., m. p. 39°. Gives Test 304. 33 114 Hexen-2-oic-(i) Ac., C0H10O2.-Ndl. cl. s. aq.-Adds Br2 in CS2 sol. (Test 304).-BaA2+ 1^ aq., 1ft.; e. s. ale.; AgA, ndl. fr. aq. 33-4 338 t Erucic Ac., C2iH41.CO2H.-Long ndl. fr. ale. B. p. 264° (15 mm.). Gives Test 304!-Heated to fusion w. dil. HNO3 and treated w. NaNO2 gives geomet. isomer, brassidic ac., which, after cryst. fr. ale. melts at 60°.-PbA2, e. s. h. eth. or h. bz. 33-4 136 p-Methylenedihydrobenzoic Ac., CH2:C6HK.CO2H.-Ndl. fr. Igr. S. h. aq.; e. s. ale. or eth. Gives Test 304.-AgA silky ndl. 34 270 Oxyhypogaeic Ac., ClcH30O3.-White mass.-Boiling alkalies give dioxypalmitic Ac. 36-7 127 o-Toluic Anhyd., (Me.C6H4.CO)2.O.-B. p. a. 325°.-Cryst. fr. eth. or bz.-Test 307 gives ac. w. m. p. 102°, v. d. s. c. aq.! 37 164 n-Methylhydrocinnamic Ac., Ph.CH2.CHMe.CO2H.-B. p. 272°. Lft. v. d. s. c. aq.-AgA, cryst. ppt. 40-5 214 Tridecylic Ac., Me.(CH2)n.CO2H. 41-5 114 a-Ethylcrotonic Ac.-C6H10O2.-Cryst.-Sbl.-D. s. aq.-Fusion w. KOH gives acetic and butyric acids. (Test 311.) 42 164 Ethylphenylacetic Ac., Ph.CHEt.CO2H. 42 113 j- Benzoic Anhyd., (C7H5O)2O.-B. p. 360° c.-Rhomb, pr. i. and very slowly attacked by c. aq.; s. ale. or eth. For behavior on titration cf. p. 37. Test 307 gives ac. (cf. Test 312) w- m. p; 121°, nearly i. c. aq.! 43-4 166 o-Oxyphenylglyoxylic Ac., HO.CfiH4.CO.CO2H.-Ndl. Dec. on dist. to CO2 and salicylic ac. (Test 319). 43-6 200 t Lauric Ac., CnH23.CO2H.-Ndl. fr. ale.-Dec. by dist. under normal pressure.-Non-alkali salts all v. d. s. h. aq.-BaA2, pearly 1ft. 44 240 Cimicic Ac., C1SH,SO2.-Pr. fr. eth.-BaA2. amorph. ppt.-Unsat. (Test 304). 44-5 282 Isooleic Ac., C15H31.CH:HC.CO2H.-Rhomb, plates fr. eth.-E. s. ale.; less s. eth.-ZnA2 cryst. fr. h. ale. (sep. fr. oleate). PbA2 less s. in eth. than Pb oleate.-Occurs in some commercial '1 stearic ac." 45-5 100 Angelic Ac., Me.CH.MeC.CO2H.-B. p. 185° (th. i.). Long-con- tinued boiling gives isomeric tiglic ac., m. p. 64-5°.-Pr. d. s. c. aq.; e. s. h. aq.-Spicy odor.-CaA2 + 2 aq. alm. i. ale.; s. c. aq.; much less s. at 60°-70°.-BaA2 + 4| aq., e. s. aq.-PbA2 d. s. aq.- Fusion w. KOH gives acetic and propionic acids (Test 311). 46 368 Paraffinic Ac., C24H4SO2.-Lft. fr. ale.-(Fr. action of fuming HNO3 on paraffin.) 46-7 200 Diisoamylacetic Ac., (CflHn)2.CH.CO2H.-Ndl. i. aq.; e. s. eth., ale. or bz. 47 150 m-Ethylbenzoic Ac., Et.C„H4.CO2H.-Ndl. fr. h. aq., alm. i. c. aq.- CaA2 e. s. aq. or ale.-Test 905-1 gives isophthalic ac. 47 252 Palmitolic Ac., C1GH28O2.-B. p. 240° (15 mm.). Silky ndl.; i. aq.; v. s. ale. or eth.-Fuming HN03 oxid. violently.-BaA2, cryst. fr. h. ale.; i. aq.-AgA, ppt., blackens in light.-Gives Test 304. 47-5 164 Benzylpropionic Ac., Ph.(CH2)3.CO2H.-Flat lft. fr. h. aq.; e. s. ale. or eth.-B. p. abt. 290°.-CaA2, v. s. aq.; BaA2, lft., s. aq. 48 280 Stearolic Ac., C,SH32O2.-Long pr. fr. ale.-D. s. c. ale.; e. s. h.- Distils w. little dec.-Gives Test 304.-Oxid. by fuming HNO3. -BaA2, ppt. fr. aq.; s. h. ale. 48-5 156 Diallyloxalic Ac., HO.C(C3H5)2.CO3H.-Ndl. 'Gather d." s. aq.; e. s. ale. or eth.-Gives Test 304.-Dec. on distil.-Ca and Ba salts, e. s. c. aq. 54 GENUS IH, DIV. A, SECT. 2. (ORDER I, SUBORDER I.) Melting-point (C.°k Neut. Equiv. SOLID ACIDS.-Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 48-7 150 Hydrocinnamic Ac., Ph.CH,.CH2.CO2H.-B. p. 279^8° (th. i.).- Ndl. fr. ale. or h. aq.; s. in 168 pt. aq. at 20°.-BaA2, mod. s. ndl. -Boiling with CrO3 mixture (cf. Test 702) gives benzoic ac. (cf. Test 312). 50 298 Ricinelaidic Ac., C1SH34O3.-Ndl.-Oxid. by HN03 gives oenanthic ac. 50 310 Eikosenic Ac., C,0H38O2.-B. p. 267° (15 mm.) (th. i.).-Gives Test 304.-BaA2. Cryst. fr. ale. 51 242 Pentadecylic Ac., C15H30O2.-Dec. on distil.-Pearly scales. 51 244 Oxymyristic Ac., C14H2SO3.-Pearly 1ft., e. s. ale.-Dec. on distil.- Ca and Ba salts, ppts., d. s. h. aq. 51 164 o-Isopropylbenzoic Ac., Pr.CoH4.CO2H.-Pr. s. h. aq.-Ba salt v. s. aq.-Test 905 gives phthalic ac. (cf. Test 318-1). 51 296 Ricinostearolic Ac., C18H32O3.-Ndl. fr. ale.-I. aq.; e. s. ale. or eth. Gives Test_304. Volatile w. very slight dec.-BaA2 1ft. fr. ale.; i. eth.-AgA gran. ppt.; i. eth. 51 258 Oxypentadecylic Ac., C15H30O3.-Ndl. fr. dil. ale. (From convolvulin.) 51-5 282 f Elaidic Ac., HC.(C,4H29) : HC.CH2.CO2H.-Lft.fr. ale.-Solidifies at 44°-45°.-B. p. 234° (15 mm.).-BaA2, PbA2 are ppts.-(Geom. isomer of oleic ac.) 52 178 i-Methoethylphenethanoic(4) Ac., Me,.CH.C0H4.CH2.CO2H.-Ndl. fr. h. aq.-V. s. ale. or eth.-CaA2 heated w. CaO gives cymene. 53 168 ^-Campholenic Ac., C10H,,;O2.-B. p. 247°.-Gives Test 304.-I. aq.; v. s. ale. or bz.-CaA2, ndl., e. s. ale.; d. s. aq. 53-8 228 f Myristic Ac.,_C14H28O2.-Lft. d. s. c. ale. or eth.-B. p._196-5° (15 mm.).-BaA2 cryst. powder; v. d. s. ale. or aq.; PbA2, amorph. powder. 54-6 338 Isoerucic Ac., C22H42O2.-Tbl. fr. ale.; ratherd. s. ale. or eth.-Adds Br2 in glacial Ac. sol. (Test 304.) 54-5 270 Daturic Ac., C17H34O2.-Small ndl. fr. ale.; i. aq.-PbA2, m. p. 104°-5°. 56-7 49 Maleic Anhyd., C4H,O3.-Cryst. melt under h. aq., gradually giving maleic ac.-Ac. obtained by Test 307, v. s. aq., in. p. 130°. 56-7 57 Glutaric Anhyd., CSH6O3.-B. p. 287° c.-Ndl. d. s. h. eth.-Acid obtained by Test 307, s. aq.; m. p. 97-5°. 57 148 Isocinnamic Ac., HCPh : HC.CO,H.-Monoclinic pr. fr. Igr.-V. s. ale., eth., or Igr.-Gives Test 304.-On continued boiling gives cinnamic ac. (Test 313) and styrene.-CaA2, s. in 8 pt. aq. 57-5 336 Behenolic Ac., C22H40O2.- Ndl. e. s. abs. ale.-Gives Test 304.-Zn. dust and acetic ac. reduces to brassidic ac.-BaA2 ppt. i. aq. and 58 164 o-Propylbenzoic Ac., Pr.CcH4.CO2H.-Lft. fr. dil. ale.-Test 905 gives phthalic ac. 58-9 178 cFPhenylvalerianic Ac., Ph.(CH2)4.CO2H.-Lft. fr. h. aq., e. s. ale.- Ba salt d. s. aq. 59-5 182 Undecolic Ac., CnHlgO2.-Lft. e. s. ale.-BaA2 v. d. s. c. aq.-B. p. 177° (15 mm.). Gives Test 304. 59-9 270 Margaric Ac., C]7H34O2.-Cryst. 60 or 65 146 a-Oxycenanthylic Ac., Me.(CH2)4.CHOH.CO2H.-D. s. c. aq.-Sbl. 60 338 Brassidic Ac., C22H42O2.-Lft. fr. ale.-B. p. 160° (0 mm.) -V. d. s. c. ale.-Less s. in ale. or eth. than erucic ac.-PbA2 v. d. s. h. eth.- KOH fusion gives arachidic ac., m. p. 77°-Gives Test 304. 61 150 m-Tolyacetic Ac., Me.C,H4.CH2.CO2H.-Ndl. e. s. h. aq.-AgA, ndl. fr. h. aq.-Amide, m. p. 141° 62-6c 256 f Palmitic Ac., Me.(CH,)14.CO,H.-Ndl. or greasy feeling scales, s. in 10 • 7 pt. ale. at 20°; e. s. h. ale.-B. p. 339°-56° d- G 0 • 8527 62%o. -Nearly odorless and tasteless. Nearly or quite neutral to in- dicators except in ale. sol. GENUS III, DIV. A, SECT. 2. 55 (ORDER I, SUBORDER I.) Melting-point (C.°). Neut. Equiv. SOLID ACIDS.-Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 64 330 Dioxyricinoleic Ac., C1SH34O5.-I. aq.; v. e. s. ale. or eth.-Gives Test 304. 64-5 100 Tiglic Ac., Me.CH:CMe.CO2H.-Gives Test 304; and 901 (slowly hof).-1Cf. Div. A, Sec. 1. 65 162 (a/?)-Phenylcrotonic Ac., Ph.CH2.CH : CH.C0,H.-Ndl fr. h. aq., e. s. ale., eth., and bz.-Gives Test 304.-CaA2 + 3HoO silky ndl. 66-5 298 Nondecylic Ac., C19H38O2.-CaA2, cryst. ppt. 67 284 Palmitoxylic Ac., C10H28O4.-I. aq.; e. s. abs. ale. or eth.-AgA gran, ppt. fr. ale. 68 56 Itaconic Anhyd., C5H4O3.-Dist. in vacuo gives citraconic anhyd., m. p. 7.°-Rhomb, pr. fr. CHC13; v. d. s. eth.-Unites rather easily w. aq to form its acid (cf. Test 307). 68 150 o-Ethylbenzoic Ac., Et.C6H4.CO2H.-Lustrous flat ndl.-Test 905 gives phthalic ac. (cf. Test 318-1). 68 148 Allocinnamic Ac., HCPh : HC.CO2H.-Pr. or tbl. fr. Igr.-Aniline salt ppt'd fr. bz. solution by aniline, m. p. 83° (Dif. fr. hydrocinnamic ac.)-Less s. c. Igr. than isocinnamic ac -Gives Test 304. 69 308 Eikosinic Ac., C20H36O2.-I. aq.-B p. 270° (15 mm.). 69-5 160 a-Oxycaprylic Ac., Me.(CH2)5.CHOH.CO2H.-Large plates, v. d. s. aq.; e. s ale. or eth.-CrO3 mixture oxid. to oenanthol and oenanttuc ac.-Salts generally d. s. 69-3c. 284 t Stearic Ac., Me.(CH2)16.CO2H.-Odorless, tasteless 1ft.-Distils w. dec. at abt. 360°.-I. aq.; s. 40 pt. c. ale.; e. s. c eth., bz., CS2, or CHC13.-Does not dissolve on shaking w c Na2CO3 or deci- normal KOH.-CaCl2 and BaCl2 give gelat. ppt. w solutions of alkali salts. 70 144 Monoethyl Fumarate, CO2H.C2H2.CO2Et.-D s. aq.; e s. ale. or eth. Gives Test 304.-Saponify and identify the fumaric ac. 71-2 180 3-Methtoethylphenol(2)-methanoic(i) Ac., Ci0H]2O3.-Ndl. fr. aq.- V. d. s. aq.; e s. ale. or eth.-Volat. w. steam.-Aq. sol. intense violet-blue w. FeCl3!-AgA mic. ndl. d. s. aq. 72 166 Methoxyphenylacetic Ac., Ph.CH(OMe).CO2H.-Tbl. fr. Igr D. s. aq. or c. Igr.; e. s. ale. or eth.-CaA2, ppt., rather d. s. c. aq. 72-5 Carnaubic Ac., C24H4SO2.-(Combined in Carnauba wax.)-E. s. ale. or eth.-PbA2 (103°), ppt. m. p. 110°-1°; i. eth. 73 142 j-Ethoxy-J'-tetrahydrobenzoic Ac., EtO.C0H8.CO2H.-E s ale.- Gives Test 304.-AgA, ppt. 74 162 a-Benzalpropionic Ac., Ph.CH : CMe.CO2H.-B. p. 288° Cryst. e s ale., eth., or bz.-Gives Test 304.-BaA2, d s. c aq 75 180 Phenyl-1'-oxybutyric Ac., Ph.CHOH.(CH2)2.CO2H.-Pr fr. c CHC13. -S. h. aq.; v. e s. ale , eth., or CHC13.-Aq. + HCl at 80° gives anhvd., m. p. 37°.-BaA2, v s aq.; AgA, ppt , i aq. 75 296 Dioctylmalonic Ac., C19H3tiO4.-Cryst. fr bz -CaA, d. s. aq.-Gives Test 303. 75-6 208 a-Hydropiperic Ac., Cn H12O4. -Ndl.fr h. aq.-V. d s c aq.-e s ale or eth.-KMnO4 oxid. to piperonal (odor like heliotrope!), etc. Gives Test 304 -AgA cryst. ppt 75-6 178 i-Methyl-3-propylbenzoic(4) Ac., (Me)(Pr).CBH3.CO.H.-Ndl fr. aq.- Volat. w steam.-Ba and Ca salts v s aq. or ale. 75-7 214 LanolicAc., C,2H22O3.-Cryst powder.-I. aq. orlgr-BaA2 + aq. ppt. 76-5 136 t Phenylacetic Ac., Ph.CH2.CO?H.-B. p 265-5° c-Thin 1ft e s. h. aq.; d. s c aq.; v s. ale. or eth.-BaA2 + 3H2O, e. s. aq. or ale. BaCl2 gives no ppt Warming w dil. H2SO4 and MnO2 gives benzaldehyde (bitter almond odor, Test 113). 77 312 Arachidic Ac., C20H40O2.-Lustrous 1ft., s in 222 pt 90% ale. at 20°. (Less s. than stearic ac.)-Salts resemble stearates.-Occurs in peanut-oil, etc. 56 GENES III, DIV. A, SECT. 2. (ORDER I, SUBORDER I.) Melting-point (C.°). Neut. Equiv. SOLID ACIDS.-Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 77-8 382 Hyasnic Ac., C25H50O2.-Cryst. grains. 78 396 Cerotic Ac., C20H52O2.-(In beeswax.)-Tasteless and usually granular. -Alm. i. c. ale. (dif. fr. stearic and palmitic ac.).-Stellate mic. ndl. fr. h. ale.-S. bz. or eth.-Does not dissolve in h. dil. NaOH. 78 78-80 312 Ricinstearoxylic Ac., C18H32O4.--Ndl. e. s. ale. or eth.-Gives Test 304.-BaA2, volum. ppt.; AgA, gran. ppt. Pinoylformic Ac., C10H14O5.-Lft. fr. h. aq.; v. s. h. aq.; e. s. eth.-- Gives soluble KHSO3 compound. 80 176 ^-Methylhydrinden-^-Carbonic Ac., CnH12O2.-B. p. 300°-30°.-S. h. aq.; e. s. ale.-BaA2 + 4 aq., ndl., v. s. aq. 80-1 194 o-Ethylethermelilotic Ac., o-EtO.C6H4.C2H4.CO2H.-Silky ndl. fr. aq.; v. d. s. c., d. s. h. aq.; e. s. ale. or eth.-Ba salt, e. s. aq. turns red at 100°. 80-5 368 Lignoceric Ac., C24H4SO2.-D. s. c. ale.; e. s. eth., bz., or CS2.-Pearly 82 82-5 162 a-Benzalpropionic Ac., Ph.CH : CMe.CO2H.-Repeated recryst. gives ac., m. p. 74°. Gives Test 304. Mono-methyl Phthalate, C0H8O4. Examine saponification products. 82-3 272 a-Oxy palmitic Ac., C14H29.CHOII.CO2H.-Scales fr. ale.; e. s. ale. 83 106 Monoethyl Carbopyrotritarate, CsH7O5.Et. -D. s. h. aq.-Lft. e. s. eth.; e. s. ale. Distil, undec.-AgA ppt. 83-5 300 /?-Oxystearic Ac., C1SH36O3.-6-sided tbl. fr. ale. S. in 10-4 pt. ale. at 20°. 84 340 Behenic Ac., C22H14O2.-Solidifies at 78°. 84-5 300 a-Oxystearic Ac., C18H3GO3.-6-sided tbl. fr. eth. S. in 172 pt. ale. at 20°. 84-5 314 Ketostearic Ac., C1SH34O4.-Silky cryst. fr. dil. ale.-AgA, cryst. ppt. 85 176 Ac.-Tetrahydro-n-Naphthoic Ac., C10Hn.CO2H.-Pr. fr. acetic ether. S. in 1052 pt. c. aq.; v. s. ale.-KMnO4 + Na2CO3 sol. decolorizes after 2 min.-AgA ppt. 85-6 218 Dioxyundecylic Ac., CnH22O4.-Ndl. fr. aq.; e. s. h. aq. or ale.; d. s. eth. 86 312 Stearoxylic Ac., C1SH32O4.-Lft. d. s. c. ale.; e. s. h. ale.-BaA, semi- solid ppt., i. ale.; AgA cryst. powder. 86 162 ft-Benzalpropionic Ac., Ph.CH : CH.CH2.CO2H.-B. p. 302° (long-con- tinued boiling gives H2O and a-naphthol. Test 402).-Ndl.fr. h. aq.; d. s, h. aq.; e. s. ale., eth., or CS2.-CaA2 v. s. aq. 86-7 204 Monomethyl Camphorate, CO.,H.CSH14.CO,M .-Long ndl. fr. h. aq.; e. s. ale. or eth.- Saponify and test distillate for methyl alcohol by Test 819. 87 56 Glutaconic Anhyd., C5H4O3.-Ndl. fr. eth., s. in Na2CO3 w. efferves- cence, giving sodium glutaconate (m. p. of acid 138°). 87 240 Dibenzylacetic Ac., (Ph.CH2)2.CH.CO2H.-Pr. fr. Igr.; i. aq.; s. eth.- BaA2 ndl. d. s. h. aq.-Heated w. CaO gives dibenzylmethane. 87 64 s-Dimethylsuccinic Anhyd. (a), CGHgO3.-B. p. 235°.-S. h. aq. giving s.-fumaroid acid, m. p. 124°, and a little less s.-anti acid, m. p. 195°. 87-8 272 Lanopalmitic Ac., C1GH32O3.-(In combination in wool grease.)-I. in . aqueous KOH, s. in ale. 88-9 178 (a) o-Methoxycinnamic Ac., MeO.C,Hl.CH: CH.CO,H. - E. s. ale.-■ Heat gives isomeric (,#) ac., in. p. 182°-3°.-Gives Test 304. 88-9 150 o-Tolylacetic Ac., Me.CGH4.CH2.CO2H.-Silky ndl., e. s. h. aq..-Amide m. p. 161°.-Oxid. to phthalic ac. by KMnO4 (cf. Tests 905-1 and 318). 89 282 Dibenzylacetoacetic Ac., C18HlsO3. 90 452 Melissic Ac., C30H,,nO2.-Silky scales (fr. beeswax).-E. s. CHC13, CS2, and h. ale.; alm. i. c. ale. or eth.-PbA2, amorph. ppt.; may be cryst. fr. toluene. GENUS III, DIV. A, SECT. 2. 57 (ORDER I, SUBORDER I.) Melting-point (C.°). Neut. Equiv. SOLID ACIDS.-Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 91 150 p-Tolylacetic Ac., Me.CGH4.CH2.CO2H.-B. p. 266°.-Ndl., d. s. c. aq.; e. s. h.-AgA ndl., e. s. h. aq.-Amide, 1ft. fr. h. aq.; m. p. 184° 1 91 174 a-Dihydronaphthoic Ac. (labile), CnH10O2.-Tbl. fr. Igr.; s, in 552 pt. c. aq.; e. s. ale. or eth.-Gives Test 304.-Boiling w. dil. NaOH gives stable form, m. p. 125°. 91-2 328 Eikosanol(2)-oic Ac., C20H4()O3.-Silky 1ft. fr. bz. + lgr.; e. s. ale.- BaA2 (at 100°) floc. ppt. 91-2 178 Tolylisobutyric Ac., C7H7.CH2.CHMe.CO2H.-Ndl. fr. Igr.-AgA, ppt v. d. s. aq. 92 180 Methylethermelilotic Ac., o-MeO.CGH4.C2H4.CO2H.-Pr. fr. h. Igr.- D. s. h. aq. 92-3 466 Coceric Ac., C31H02O3.-Cryst. powd. fr. h. ale. 93 226 o-Benzoylbenzoic Ac., Ph.CO.C(iH4.CO2H.-Triclin. ndl. ( + aq.) fr. h. aq.-Ignited w. Zn dust gives anthracene (Test 912).-Oxime melts at 162°. 94 250 Alantolic Ac., HO.C14H20.CO2H.-Ndl. d. s. c. aq.; e. s. ale. or eth.- Loses aq. on fusion giving anhyd., helenine, m. p. 76°. 94 176 /?-Tetrahydronaphthoic Ac., C10Hn.CO2H.-Ndl. fr. dil. ale.; i. c. aq.- Adds Br2 in the cold, but is not immediately oxid. by Na2CO3 + KMnO4. 94 180 4-Methoethylphenol(2)-methanoic(i) Ac., Me2.CH.CGH3OH.CO2H.-■ Lft. fr. aq., v. d. s. c. aq.; s. h. aq.; v. s. ale. or eth.-Red-violet color w. FeCl3.-Distil. gives CO2 and m-propylphenol.-BaAs d. s. aq. 95-7 ' 164 p-Toluylcarbonic Ac., Me.CGH4.CO.CO,H.-I. c. aq.; e. s. ale. or eth.- Unstable.-Cone. H2SO4 + bz gives deep-red sol. changing to blue- violet; red ppt. on dilution.-Oxid. by KMnO4. 95-5 240 Benzyl-o-tolylacetic Ac., (C7H7)2.CH.CO2H.-Large cryst. fr. ale. 96 97 3, 6-Dimethylphthalic(i, 2) Ac., Me2.CGH2.(CO2H)2. - Pr. e. s. eth. or ale. "Moderately" s. aq. 96-5 468 Oxymelissic Ac., C30Hg0O3.-Fine ndl. fr. bz. 96-7 356 a-Oxybehenic Ac., C22H44O3.-E. s. high-boiling petroleum ether. 97-9 150 1, 3-Dimethylbenzoic(2) Ac., Me2.CGH3.CO2H.-Ndl. fr. h. aq. 97 166 Alorcinic Ac., C9H1UO3. + H2O (air-dried).-Ndl. d. s. c. aq.; e. s. ale. or eth. Alkaline sol. becomes cherry-red on standing in air! Reduces Fehling's sol.-Fusion w. 3 pt. KOH gives orcine. Dried over H2SO4 melts at 115°. 98 154 Methyluvinic Ac., C7H9O.CO,H.-Ndl. d. s. aq.; e. s. ale. or eth.- CaA2+4 aq., pearly 1ft. i. ale.-Boiled w. cone. KOH gives potas- sium acetate (Test 311). 98-9 206 Benzyllaevulinic Ac., C]2H14O3.-B. p. 230°-35° (40 mm.). Ndl. fr. dil. ale., v. d. s. aq.-Dec. on dist.-H2SO4 sol. yellow, but after 1 or 2 days blue-green.-Dibrom, derivative fr. Br in Ac., m. p. 153° d. 98-9 372 Isodioxybehenic Ac., C23H44O4.-Tbl. fr. ale., d. s. c. ale. or eth.- AgA ppt. 98-9 184 [ -] Pinonic Ac., Cl0H1BO3.-B. p. (12 mm.), 178°-80°. - 98-5 152 Methylethersalicylic Ac., o-MeO.CGH4.CO2H.-Tbl. or pr. s. in 200 pt. aq. at 30°.-BaA2, v. e. s. aq.-Dec. a. 200° to CO2 and anisol. 99 164 s-Dimethylphenylacetic Ac., Me2.C6H3.CH2.CO2H.-B. p. 274°.-Mod. s. h. aq.-CaA2 + 3 aq., e. s. aq. 99 176 Benzoylacrylic Ac., C,HSO.C2H2.CO2H-Ndl. fr. toluene, d. s. c. aq.; e. s. ale. or eth.-On warming w. alkali gives acetophehone (Test 712).-Heated above m. p. becomes ruby-red.-Gives Test 304. 99 316 Dioxystearic Ac., C1sH3gO4. (from elaidic Ac.).-Alkaline perman- ganate gives azelaic, pelargonic and oxalic acids. 58 GENUS III, DIV. A, SECT. 2. (ORDER I, SUBORDER I.) Melting-point (C.°). Neut. Equiv. SOLID ACIDS.-Colorless and generally not soluble (cf. note, p. 38) in. 50 parts of cold water. 100-5 208 Acetylphenyl-3-lactic Ac., Ph.CH.(MeCO2).CH2.CO2H.-Pearly scales. -Dec. at 200° to acetic and cinnamic ac. (Test 313). 102 164 o-Tolylpropionic Ac., Me.C6H4.C2H4.CO2H.-S. h. aq.-H2SO4 gives o-methylhydrindon. 102 136 o-Toluic Ac., Me.CGH4.CO2H.-B. p. 259° (th. i.).-Ndl., mod. s. h. aq.; v. s. ale.-Test 905-1 or 3 gives phthalic ac. (Test 318).-BaA e. s. aq.-Amide melts at 138°. 102 164 i, 3-Dimethylphenethanoic(4) Ac., Me2.CGH3.CH2.CO2H.-B. p. 265°. -Ndl. e. s. ale. or eth.-AgA + Aq. e. s. h. aq. 102-2-5 194 Meconin, C10Hl0O4 (anhydride of meconic ac.).-Sbl.-Ndl. s. in 700 pt. c. aq. or 22 pt. h. aq.-Contact w. alkalies gives salts of meconic ac. (free ac. unknown); is not soluble in ammonia.-Found in mother liquors from opium alkaloids.-Heated w. dil. H2SO4 and MnO2 gives opianic ac. 103 192 (a), o-Ethoxycinnamic Ac., EtO.CGH4.CH: CH.CO2H.-Tbl. v. d. s. c., d. s. h. aq.; e. s. ale. or eth.-BaA2 + 2 aq. e. s. aq.-Heat gives ^-ac., m. p. 135°.-Gives Test 304. 103-4 184 i-Pinonic Ac., Ci0H1GO3.-Lft. fr. aq. ' ' Rather" d. s. c. aq.; e. s. ale. or eth.-M. p. of oxime 150°. 103-4d. 164 Benzoylacetic Ac., Ph.CO.CH2.CO2H.-D. s. aq.; v. s. ale. or eth.- Ale. sol., colored violet by FeCl3!-Boiled w. KOH sol. gives ben- zoic ac. (Test 312), and acetophenone. Melts w. dec. to CO2 and acetophenone (Test 712) ! Attacked by Br or alk. permanganate. 104 176 Phenylangelic Ac., Ph.CH: CEt.CO2H.-Ndl. v. d. s. c. aq.-CrO3 mixt. oxid. to benzaldehyde and benzoic ac.! Gives Test 304. 104 104-5d. 176 Phenylpenten(4)-oic Ac., Ph.C2H4.CH: CH.CO2H.-Tbl. fr. eth., d. s. aq.; e. s. eth.-Gives Test 304.-CaA + 3H2O, ndl. d. s. aq. Lanoceric Ac., C30H80O4.-Mic. 1ft. fr. ale.; d. s. eth. (In combination in wool fat). 105 174 ^-Dihydronaphthoic Ac., C„H10O2.-Pr. s. in 1734 pt. aq. at 14°.- Oxid. by KMnO4 to phthalic ac. In CS2 sol. changed by Br to bromanhydride m. p. 140° d. 105 170 Campholic Ac., C10H18O2.-B. p. 260°-Lft. fr. eth.-ale.; alm. i. aq. Volat. w. steam.-Ppt'd fr. sol. of alkali salts by CO2.-Fuming HNO3 gives camphoric and camphoronic acids.-CaA2 + H2O, cryst. ppt. 106 94 f Azelaic Ac., CO,H.(CH2)7.CO2H.-B. p. a. 360° (si. d.).-Lft. e. s- h. aq.; s. in 700 pt. aq. at 15°.-S. in 37 pt. c. eth.-CaA, v. d. s. gran. ppt. appearing when the ammoniacal sol. of the acid is boiled w. CaCl2! ZnA, v. d. s. cryst. ppt.-Does not give Test 304. 106 168 i, 3, 3-Trimethylcyclohexene(i)carbonic(2) Ac., C10H1GO2.-B. p. 138° (11 mm.).-Ndl. fr. h. aq.-Unsat. 106-7 148 t Atropic Ac., CH2: CPh.CO2H.-B. p. 267° d.-Monoclin. tbl. s. in 692 pt. aq. at 19°; s. CS2.-Oxid. by CrO3 to benzoic ac. (cf. Tests 702 and 312) !-NaA sol. gives- no ppt. w. MnCl2. (dif. fr. cin- namic c.).-CaA2 + 5H2O s. in 43 pt. aq. at 18°.-Gives Test 304! 106-7 152 m-Methoxybenzoic Ac., MeO.CGH4.CO2H.-Ndl. sbl. undec.-E. s. ale., eth., or h. aq.-Dist. of CaA2 gives phenol (Test 414). 107-8 212 m-Benzylbenzoic Ac., Ph.CH,.CGH4.CO2H.-Ndl. fr. aq.; d. s. c. aq.; e. s. ale. or eth.-CrO3 mixt. oxid. to m-benzoylbenzoic ac.- BaA2 + 4H2O, s. aq.; AgA, ppt., d. s. h. aq. 108 228 Phenylethermandelic Ac., Ph.HC(OPh).CO2H.-Ndl. fr. h. aq., v. d. s. c. aq.--Oxid. by h. dil. HNO3 to benzaldehyde and picric acid. 108-5 168 f Dehydracetic Ac. (Methylacetopyronon), CgH8O4.-B. p. 269-9° c.- S. in 100 pt. aq. at 6°; e. s. h. aq., ale. or eth.-1 drop 10-% FeCl3 gives yellow or orange (YO-OY) ppt. in aqueous solution !-Sol. in NaOH pale yellow.-Boil w. cone. NaOH and test distillate for geetone (Test 711).-Evaporation of the sol. in v. cone, ammonia gives an amide, m. p. abt. 200°. xjENUS III, DIV. A, SECT. 2. 59 (ORDER I, SUBORDER I.) Melting-point (C."). Neut. Equiv. SOLID ACIDS.-Colorless and generally not soluble (of. note, p. 38) in 50 parts of cold water. 108-9 126 2, 5-Methylpyromucic Ac., C4H2O(Me).CO2H.-Ndl. d. s. c. aq.; v. s. h. aq.; e. s. eth.-Sbl easily.-BaA2, octahedra, v. s. c. aq.-Warmed w. cone. H2SO4 + trace of isatin gives chrome-green color! 109 268 Dibenzoylacetic Ac., (Ph.CO)2.CH.CO2H.-D. s. aq.; e. s. eth.-Ale. sol. gives reddish color w. FeCl3. Boiled w. dil. H2SO4 gives benzoic acid and acetophenone (Tests 312 and 712). 109-5 160 Methylphenylpropiolic Ac., Me.CGH4.C • C.CO2H.-Gives Test 304.-Ag salt explosive ppt. 110 106 Ethyl Isocarbopyrotritarate, C10H12Os.-Ndl. fr. h. aq.; v. d. s. c. aq.; e. s. ale. or eth.; e. s. NaOH, Na2CO3 or ammonia, but reppt'd by CO2.-Ale. sol. blue w. FeCl3! Reduces Ag or Cu salts in the cold. 110-11 198 o-Phenylbenzoic Ac., Ph.CGH4.CO2H.-B. p. 343°.-Ndl. d. s. h. aq.; e. s. h. ale.-CaA2 + 2H2O, d. s. aq.; ignited w. CaO gives diphenyl, etc.-Fuming HNO3 at 0° gives nitro deriv., s. ale., m. p. 221°. 110-5 136 m-Toluic Ac., Me.CGH4.CO;.H.-B. p. 263°.-Pr. fr. h. aq. s. in 60 pt. aq. at 100°, e. s. ale. or eth.-Oxid. by CrO3 mixt. to isophthalic ac. (Tests 905-2 and 318). 112 122 Brassylic Ac., CO2H.(CH2)n.CO2H.-100 pt. aq. at 24° dissolve 0.74 pt.; e. s. ale. or eth.-CaA + H,O, pulv. ppt. 112 194 Benzoyllactic Ac., Me.CH(C7H5O2).CO2H.-Cryst. s. ale. or eth., and in 400 pt. c. aq.-Boiled w. dil. HC1 gives benzoic ac. (Test 312) and lactic ac. 112-3 150 p-Ethylbenzoic Ac., Et.CGH4.CO2H.-Lft. s. h. aq.; e. s. ale. or eth.- BaA2 + 2H2O, s. in 45 pt. c. aq.-Oxid. to terephthalic ac. (Test 905 and 318). 112-3 166 Phenoxypropionic Ac., Me.CH(OPh).CO2H.--V. d. s. c. aq.; e. s. h. aq- e. s. eth.-CaA2 + 2H2O, v. d. s. ale.; AgA, small ndl. blackened by light. 112-5d. 192 Ethylbenzoylacetic Ac., Ph.CO.CHEt.CO2H.-Ndl. fr. dil. ale.; e. s. ale- or eth.-Boiling w. cone. ale. KOH gives benzoic ac. (Test 312) and butyric ac!-Oxime m. p. 89°-90°. 113 214 Phenylethersalicylic Ac., o-PhO.C(1H4.CO2H.-B. p. 355° d.-Lft. fr. dil. ale.; v. s. ale. or eth. NH4A, m. p. 130°. 114 212 o-Benzylbenzoic Ac., Ph.CH2.CGH4.CO2H.-Sbl. in ndl.-D. s. c. aq.; e. s. eth.-Warmed w. cone. H2SO4 gives anthranol.-BaA2 + 5|H2O, s. aq. 115 164 o-Acetophenonecarbonic Ac., Me.CO.CGH4.CO,H.-Cryst. s. cone. H2SO4. Sweet taste.-With ale. NH3 at 100° gives comp., m. p. 204°. Sol. in cone. H2SO4 on standing forms isomethylenephtalid, m. p. 215°. 115 288 Dioxypalmitic Ac., C10H32O4.-Lft. s. ale. or eth. 115 162 m-Methylcinnamic Ac., Me.C6H4.CH: CH.C02H.-Silky ndl. fr. h. aq.; e. s. eth. or bz.-FeCl3 gives egg-yellow ppt. w. NH4 salt.-Gives Test 304. 115 178 m-Methoxycinnamic Ac., MeO.C0H4.CH: CH.C02H.-S. h. aq.; e. s. eth. -Gives Test 304. 115 226 p-Phenyltolylacetic Ac., C7H7.CHPh.CO2H.-Lft. fr. aq.; v. d. s. c. aq.; s. h. aq.;_ e. s. ale. or eth.-Oxid. by CrO3 to p-phenyltolylketone, etc.-CaA2 + H2O, d. s. h. aq. 116 178 /?-Benzoylpropionic Ac., Ph.CO.(CH2)2.CO2H. - E. s. aq. at 70°- Heated above m. p. turns orange-yellow. PbA2 + 2H2O, ndl., d. s. c., e. s. h. aq. 116-5 164 Cuminic Ac., p-Me2.CH.CGH4.CO2H.-Triclin. cryst. v. d. s. c. aq.; e. s. eth.-BaA2, lft. s. in 100 pt. aq. at 20°.-Oxid. gives terephthalic • ac. (cf. Tests 905-1 and 318). 117 Pyromeconic Ac., C5H4O3.-Cf. Phenols. FeCl3 gives cherry-red color! 118 180 Salicylic Ac. Acetate, o-C2H3O2.CGH4.CO2H.-Fine ndl. fr. h. aq.- FeCl3 gives violet color w. aq. sol.!-Saponification by hot alkalies gives acetic and salicylic acids! (cf. Tests V, 311 and 319). 60 GENUS III, DIV. A, SECT. 2. (ORDER I, SUBORDER I.) Melting-point Neut. Equiv. SOLID ACIDS.-Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 119-6 261 f Succinic Anhyd., C4H4O2.O.-(For behavior on titration cf. remark on page 37.-Long ndl. fr. ale.; v. d. s. eth.-Test 307 gives ac. s. aq., m. p. 185° (Test 320). 120 152 o-Oxymethylbenzoic Ac., HO.CH2.C6H4.CO2H.-Ndl. s. in 0-428 pt. aq. at 20°; s. eth.-In melting or on prolonged standing w. aq. giv_s phthalid, m. p. 73°.-Salts all soluble. abt. 120 Fellic Ac., C23H40O4.-(In human gall.)--Ndl. fr. dil. ale.; i. aq.; s. ale. or eth.-Taste bitter.-Opt. act.-BaA2 + 4H2O, s. in abt. 800 pt. c. or h. aq.-Color reac. w. sugar and H2SO4 (cf. H. 11. 274). d.120 264 Santonic Ac., C15H20O4.-Cryst. gradually turn yellow.-D. s. c. aq.; e. s. ale.; d. s. eth.-Fusion on boiling w. aq. gives aq. and san- tonin. Opt. active.-Pb.A2 (at 100°) ppt. 120 or 127 192 p-Toluyl-/?-Propionic Ac., C7H7.CO.C2H4.CO2H.-Tbl. fr. Igr., e. s. h. aq., ale., or eth.-Turns red above m. p.-AgA ndl. 121-2c. 122 t Benzoic Ac., Ph.CO,H.-B. p. 249-2° c.-Monoclin. 1ft. or ndl - Sbl. easily, vapor producing coughing.-S. in 344-8 pt. aq. at 20°, or in 17 pt. at 100°; at 15° s. in 2-14 pt. abs. ale., or in 3-19 pt. eth.-Apply Test 312 ! 122 216 Diisoamyloxalic Ac., (C5H11)2.COH.CO,H.-Silky fibres, s. eth.-Sbl.-• BaA2, d. s. c. aq. 122 164 Cetylmalonic Ac., Me.(CH2)15.CH.(CO2H)2.-Rhomb, tbl. d. s. c. ale. : e. s. eth.-alc.-BaA cryst. ppt.; Ag2A powd. ppt.-Gives Test 303. 123 194 o-Thymotic Ac., HO.CGH2(Me)(Pr).CO2H.-V. d s. h. aq.; e. s. eth.- Blue color w. FeCl3.! 123 139 n-Dodecanedicarbonic Ac., CO2H.(CH2)12.CO2H.-Lft. mod. s. c. ale. or eth. 124-5 324 Lichen-stearic Ac., C1SH3IO2.CO2H.-Pearly plates, i. aq.; e._s. h. bz. or CHC13.-Not attacked by Br or permanganate.-NH4A, pr. fr. h. aq. (m. p. 106°). 125 161 m-Tolylpropionic Ac., Me.CGH4.C2H4.CO2H.-Ndl. fr. h. aq.-Oxid. by Test 905-1 gives isophthalic Ac. (Test 318-2). 125 204 Benzallaevulinic Ac., Ph.CH: C(CO.Me).CH,.CO2H.-Cryst. fr CHC13. S. in cone. H2SO4 w. red color!-After boiling w. cone. KOH gives iodoform reac. w. I. (Test 801). 125 179 a-Dihydronaphthoic Ac., CnH10O2.-S. in 3215 pt. c. aq.-Br addition- product m. p. 152°. 125-7 Fluorescine, C19H13O3.CO2H.-Ndl. s. Ac. or eth.-Gentle oxid, gives fluorescein! 126 150 i, 3-Dimethylbenzoic(4) Ac., Me2.C(iH3.CO2H.-Sbl.-B. p. 268°.-D. s. h. aq.; e. s. h. ale.-CaA2 + 2H2O, and BaA.2+xH2O, e. s. aq. 127 164 i, 2, 4-Trimethylbenzoic (6) Ac., Me3.C0H2.CO2H.-Tbl. fr. Igr., y. d. s. c. aq.; s. h. aq.; v. s. ale. or eth.-Volat. w. steam. Distils un- decomposed.-Ignited w. CaO gives pseudocumene. 127 178 m-Isobutylbenzoic Ac., C4H9.CBH4.CO2H.-Ndl. fr. Igr.-Amide, ndl. fr. aq., m. p. 130°. 127 180 m-Acetoxybenzoic Ac., C2H3O2.CGH4.CO2H.-Cryst. s. h. aq.; e. s. ale. or eth. 127-8 166 [ + ] Tropic Ac., Ph.CH(CH,OH).CO,H.-Hard pr. fr. eth. 128 144 Lactide, CGHSO4.-B. p. 255°.-Monoclin. tbl. fr. h. abs. ale., alm. i. c. aq.; v. d. s. ale.-Boil w. aq., and apply Test 302 for lactic ac. to the cold solution.-Dry NH3 gas gives lactamide, s. aq., and ale. M. p. 47°. 128 158 Oxyroccellic Ac., C17H;,O-.-Lft of greasy feel, e. s. eth. or CHC13.-« At 160° gives anhyd. m. p. 82°.-Ag2A floc. ppt. GENUS III, DIV. A, SECT. 2. 61 (ORDER I, SUBORDER 1.) Melting-point Neut. Equiv. SOLID ACIDS.-Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 128 74 j Phthalic Anhyd., o-CGH4.(CO)2.O.-B. p. 284-5c., subliming in fine long ndl.-Alm. i. c. aq.; s. h. aq. or c ale.-Mix a few mgrms. w. an equal quantity of either phenol or resorcin; barely moisten w. cone. H2S()4 and fuse according to Test 402. The fused mass dis- solves in dil. alkalies, in the first case with the deep red color of phenolphthalein, or, in the second case, with the strong green fluorescence characteristic of fluorescein. 128-9 166 p-Hydrocumaric Ac., HO.CGH4.(CH2)2.CO2H.-Monoclin. cryst., e. s. h. aq., ale., or eth.-Cold sat. aq. sol. becomes blue-gray w. l_drop FeCl3 sol.-Reacts like tyrosin w- HgN2OG.-No ppt. w. PL.Ac2 or w. BaCl2-ZnA2 + 2H2O. s 130 pt. c. aq. 128-9d. 196 Camphocarbonic Ac., CnH1G03.-D. s. aq.; e. s. eth. Fusion gives cam- phor and CO2 (Test 715) 1 FeCl3 gradually added to ale- sol. gives first a dark blue and finally a dark green!-Easily oxid.-Br sub- stitutes easily, giving ac. m. p. 109°. 128-9 128-30 170 Pinonic Ac., C9H14O3.-Cryst. fr. CHC13; d. s. c. aq.; v. d. s. Igr.-B. p. (17 mm.), 187°-93°. GlycoIlic Anhyd., C4HGO5.-Powder i. c. aq., ale., or eth.; s. h. aq. giving glycoIlic ac.-Heated above m. p. gives glycollide (m. p. 220°). 128-5 116 /?-Methoxyisocrotonic Ac., Me.C(OMe): CH.CO2H.-S ale. or eth. Gives Test 304. 130 162 Hydrindoncarbonic Ac., C„H4.C3H5.CO2H.-Ndl. s. in 120 pt. aq. at 100°.-BaA2 v. s. aq.-Oxid by alk. KMnO4.-Br substitutes cold. 130-5 139 Cinnamic Anhyd., (C9H7O)2O.-I. aq.; v. d s. c. ale.-Cryst. powd. Test 307 gives acid of Test 313. 130-40d. 220 Acetophenoneacetacetic Ac., (C2H3O)(CSH7O).CH.CO2H.-Heat gives acetophenoneacetone and CO2. 131 186 a-Naphthylacetic Ac., C10H7.CH2.CO2H.-E. s. h. aq.; e. s. eth.- Ignition w. CaO gives a-methylnaphthalin. 132 150 i, 4-Dimethylbenzoic(2) Ac., Me2.CGH3.CO,H.- B. p. 268° (th. i.) - Ndl. v. d. s. h. aq.; v. s. ale.--CaA2 + 2H2O, mod. s. aq.-Amide, ndl. d. s. h. aq ; m. p. 186°- 132 200 a-Ethylnaphthoic Ac., Et.C10HG.CO2H. 132 150 Roccellic Ac., C17H3,O4.-(In certain alga?.)-Cryst., i. h. aq.; e. s. ale. or eth.; s. Na2CO3-Swells up in cone. KOH, dissolving after dilution w. aq.-Ag2A, i. aq ; CaA, i. aq. 133 148 f Cinnamic Ac., Ph.CH: CH.CO2H.-B. p. 300° without dec., but does not sublime.-Monoclin. pr. fr. ale.-Odor faintly aromatic-- S in 1000 pt . aq. at 20°; in 4.3 pt. ale. at 20°; v. s eth.; s. CHC13; d. s. CS2-Warmed w. CrO3 mixt oxid- easily giving strong odor of benzaldehyde.-Identify by Test 313! 133-3-5 101 Sebacic Ac., CO2H.(CH2)8.CO2H.-B. p 243-5° (15 mm.).-Thin 1ft. s. in 1000 pt. aq. at 17°, or in 50 pt. at 100°: e. s. ale. or eth.-Stable toward CrO3 mixture -CaA, ppt --Ignition w. BaO gives octane. Oxid. w. dil. HN03 gives adipic, glutaric, and succinic acids. 133-4 163 /?-Naphthoic Anhyd., (CnH?O)2O.-D. s. c. eth.; s. h. eth. or h. bz. Obtain acid of m. p. 184° c- by Test 307. 133-5 154 Cis- (iso) Campholitic Ac., C9H,4O2.-B. p. 255°-6°.-Pr. fr. dil. ale.- Odor camphor-like.-S. 5000 pt- c aq.; e. s. ale.-Unsat.- CaA2 + 34H2O, ndl., e- s. aq.; ZnA2, s eth.; i aq. 134-5 112 Sorbic Ac., Me.CHrCH.CH: CH.CO2H.-B. p. w. dec. 228°.-Long ndl. fr h. aq.; e. s. ale. or eth.-BaA,, silvery scales scarcely more s. in h. than in c. aq.-Gives Test 304. 135 192 (5) o-Ethoxy cinnamic Ac., CnH]2O3.-Ndl. fr. h. aq.-CaA2 + 2H2O, v. d. s. c. aq.-Gives Test 304. 135 162 Methylatropic Ac., Me.CH: CPh.CO2H.-Gives Test 304. 62 GENUS III, DIV. A, SECT. 2. (ORDER I, SUBORDER I.) Melting-point (C.°). Neut. Equiv. SOLID ACIDS.--Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 135 140 2, 5-Dimethylfurfuranecarf>onic (Uvic) Ac., (Me2).C4HO.CO2H.-Ndl. s. 400 pt. h. aq.; e. s. ale. or eth.-Warmed w. 2 drops fuming HN03 and then treated w. 6 drops cone. H2SO4 gives cherry-red color.- Br substitutes very easily.-With aq. at_160° gives acetyl- acetone.-BaA2 + 4H2O, ndl. d. s. c. aq.; ZnA2 + 8H2O (charac. cryst. aggregates) more s. c. than h. 136-7 146 t Phenylpropiolic Ac., Ph.C:C.CO2H.-V. long hair-like ndl. fr. h. aq.-E. s. ale. or eth.-Melts under h. aq. at 80°.-Boiled w. Zn dust in glacial Ac. gives cinnamic ac. (Test 313).-Reduced by Na amalgam to hydrocinnamic ac.-Salts unstable in h. sol.-Gives Test 304. 136-5 316 Dioxystearic Ac. (from oleic ac.), C18H30O4.-Lft. e. s. h. ale.-BaA2, gran, ppt., i. aq. or ale. 137 166 m-Ethoxybenzoic Ac., EtO.C0H4.CO2H.-Ndl. d. s. h. aq.; s. ale. or eth.-BaA2, e. s. h. aq. 137-5 121 ^-Ethoxyisocrotonic Ac., MeC(OEt): CH.CO2H.-Pr. s. ale. or eth.- Boiled w. dil. H2SO4 gives acetone (Test 711). 139 234 p-Octylbenzoic Ac., CsH17.C0H4.CO2H.-Lft.fr. h. ale.; v. d. s. h. aq.-- Ag.A bulky ppt. 140 164 p-Propylbenzoic Ac., Pr.CnH4.CO2H.-Lft. fr. h. aq. e. s. ale. or eth.- Oxid. by KMnO4 to terephthalic ac. (Tests 925 and 318). 140 87 Suberic Ac., CO2H.(CH2)c.CO2H.-B. p. abt. 300° without dec.-Ndl. or tbl. v. d. s. eth.; alm. i. CHC13; s. in 704 pt. aq. at 15-5°.- CaA + H2O, s. in 161 pts. aq. at 14°.-BaA, s. c. aq., less s. h. aq. Ignition w. BaO gives hexane. 140-1 87 a, s-Dimethyladipic Ac., CO2H.CHMe.(CH2)2.CHMe.CO2H.-B. p. 321°. -D. s. eth. 141 332 Trioxystearic Ac., C17H32(OH)3.CO2H.-Ndl. fr. h. aq. d. s. eth. 141 138 Furfuracrylic Ac., C4H3O.CH:HC.CO2H.-B. p. 255°-65° d.-Thin ndl. s. 500 pt. c. aq.; e. s. eth. or ale.-S. in cone. HOI w. green color!-Ba salt v. s. aq. or ale.-Gives Test 304. 141-3 316 Dioxystearic Ac., C18H3fiO4 (fr. Castor-oil).-I. eth.; d. s. c. ale.-HI reduction gives stearic ac. 141-3 180 4-Methoethylphenol(3)carbonic(i) Ac., C10H12O3.-Boils w. decomp. -Ndl. fr. aq., v. d. s. c. aq.; s. h. aq.; v. s. ale. or eth.-Not ppt'd in dil. sol. by Pb.Ac2; BaA2, e. s. aq.-Long fusion w. KOH gives m-oxybenzoic ac. 142d. 160 Agaricic Ac., C16H3uCh.-Silvery lft. fr. 30% ale. (Cryst. w. 1H2O which is lost at 100°; loses more aq. in melting.)-Gelatinizes w. boiling aq., dissolves, and cryst. out on cooling.-D. s. ale. or eth.- (Obtained fr. Polyporus officinalis.)-BaA, amorph. ppt.; Ag2A (at 90°) gelat. ppt. 142-3 87 t Hydrochelidonic Ac., CO.(CH2.CH2.CO2H)2.-Rhomb, tbl. d. s. aq. or eth.; i. bz.; s. ale.-Above m. p. gives anhydride (lft. fr. dil. ale., m. p. 75°). Oxid. by HNO3 or alk. KMnO4 to oxalic and succinic ac. (Test 320).-BaA + 2H2O, e. s. lft.; ZnA + 2H2O, charac. 6-sided i. lft. 142-4d. 204 Benzoyltetramethylenecarbonic Ac., CI2H12O3.-Pr. fr. eth. v. d. s. c. aq.; e. s. ale. or eth.-AgA cryst. ppt. 144 150 i, 2-Dimethylbenzoic(3) Ac., Me2.C,.H3.CO2H.-Glassy pr. fr. ale.- V. d. s. h. aq.-CaA2 + H,O, mod. s. c. aq.; ignited w. CaO gives o-xylene Test 921. 144d. 90 i-Methylphthalic(2, 3) Ac., C0H3(Me)(CO,H)2. - Anhyd. melts at 109°-10°. 145 163 a-Naphthoic Anhyd., (CnH7O)2O.-V. s. ale.; s. eth. or bz.-Test 307 gives a-Naphthoic ae., m. p. 160°. 145-6 166 p-Methylmandelic Ac., Me.C(iH4.CHOH.CO2H.-Tbl. fr. h. aq.-Gives Test 302 w. FeCl3. GENUS HI, DIV. A, SECT. 2. 63 (ORDER I, SUBORDER I.) Melting-point (C."). Neut. Equiv. SOLID ACIDS.-Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 146 240 p-Toluyl-o-benzoic Ac., Me.Ct,H4.CO.CGH4CO2H.-V. d. s. h. aq.; the milky ppt. that separates on cooling gives 1ft. containing aq. of cryst.-E. s. ale. or eth.-Dec. on dist.-BaA2 + 4H2O., d. s. aq.; Pb:A2, s. eth. NaA melted w. 5-6 pts. KOH gives benzoic ac.+ p-toluic ac. 146 Acetcumaric Ac., C2H3O2.CfiH4.C2H2.CO2H.-Ndl. e. s. h. aq.-Heated gives coumarin (charac. odor of "sweet grass") and acetic ac. 147-8 122 Diisoamylmalonic Ac., (C5Hn)2.C.(CO2H)2.-E. s. ale. or eth.; v. d. s. aq.-At 175° gives CO2 and diisoamylacetic ac. (Test 303). 148 212 Diphenylacetic Ac., Ph,.CH.CO2H.-Ndl. e. s. h. aq., ale , or eth. CrO3 mixt. (cf. Test 905-2) slowly oxidizes to benzophenone (Test 714). -Ba salt ignited w. CaO gives diphenylmethane. 148 sbl. 180 i, 2, 4-Trimethylphenol(6)-Methanoic(5) Ac., C10H12O3.-Ndl. fr. dil. ale.; v. d. s. h. aq.-FeCl3 gives transient blue w. dil. ale. sol.-• CaA2 + 2H,O, glassy pr. s. c. aq. 149-50 164 i, 2, 4-Trimethylbenzoic(5) Ac., Me3.CbH2.CO2H.-Long ndl. fr. bz.; d. s. h. aq.; v. s. eth.-The amide melts at 200°-201°. 150 210 t Opianic Ac., C10H10O5.-Thin pr. s. in 400 pt. c. or 60 pt. h. aq.; s. ale. or eth.-Mix on a porcelain crucible cover 3 mgr. of the acid, an equal bulk of phenol, and 3 drops cone, sulphuric acid. A strong red-orange color (RO-O) is immediately produced.-BaA2 + 2H2O, pr. e. s. aq.-Reduction w. Na amalgam gives meconin.-■ [Does not give Generic Test I.] 150 228 f Benzilic Ac., Ph2.COH.CO2H.-Monoclin. ndl., e. s. h. aq.-Taste slightly bitter.-1 mgr. dissolved in 3 drops cone. H2SO4 on a crucible cover at once gives an intense orange-red [OR.j coloration which soon becomes red-violet [RVTI] about the edges. -Gives Test 302.-Oxid. by CrO3 mixt.-BaA3. e. s. melting under 150 148 Homococaic Ac., C9HSO2-Ndl. e. s. ale. or eth.-Fuming HN03 gives nitro compound, m. p. 226°. 151 152 4-Oxy-m-toluic Ac., HO.C6H3(Me).CO2H.-Ndl. fr. aq.; d. s. c. aq.; v. s. ale. or eth.-Volat. w. st.-FeCl3 gives intense blue violet colo ■! BaA2 + 2H2O, 1ft. v. s. aq. 151-2 254 n-Dltol/lpropionic Ac., (C7H7)2.CMe.CO2H.-Cryst. fr. ale. or eth.; e. s. eth. or h. ale.-Volat. without dec.-Heated w. CaO gives p-ditolyetaanc.-LaA2 pulv. ppt. 152 164 i, 3, S-Trimcthylbenzolc Ac., Me3.C6H2.CO2H.-E. s. ale. or eth.; v. d. s. aq.-Dist. undec.-Ignition w. CaO. gives mesitylene (cf. Test 914).--M. p. of amide, 158°.' 153c. 73 f Adipic Ac., CO2H.(CH2)4.CO2H.-Boils without dec.-Flat ndl. s. in 69 pt. aq. at'15°; v. d. s. eth.; e. s. ale.-May be cryst. without dec. fr. h. cone. HNO,.-CaA + H3O, d. s. h. or c. aq.; BaA, e. s. c. aq., less s. h.; Zn.A-cryst. ppt. less s. in h. than in c. aq. 153-4 288 Abietic Ac., CI9H2SO2.-(Principal constituent of Rosin.)-Cryst. fr. ale., easily s. ale., eth., or CS2.-Salts amorph.-Addition of a little acetic anhyd. and a drop of H2SO4 to a CHC13 sol. gives a purple color, quickly changing to intense blue. 154d. 168 p-Methoxysalicylic Ac., HO.CbH3(OMe).CO2H.-S. in 40 pt. h. aq.; e. s. ale. or eth.--FeCl3 gives sol. intense red-violet color. 154-5 212 p-Benzylbenzoic Ac., Ph.CH2.CbH4.CO,H.-Ndl. fr. h. aq.; e. s. eth.- CaA2, ppt. CrO, gives p-Benzoylbenzoic ac. 154-5 302 p-Tolyldiphenylmethanecarbonic Ac., Me.C0H4.CHPh.C6H..CO,H.- Ndl. fr. ale. 154-5 141 Photosantonic Ac., C15H2203 (dried at 100°).-Pr. fr. ale.; v. d. s. c. aq.; e-. s. ale. or eth.-Ag2A + 3H2O, curdy ppt. 154-5d. 164 Phenylpyruvic Ac., Ph.CH2.CO.CO2H.-Lft. fr. CHC13; v. d. s. h. aq.; e. s. ale. or eth.-Ale. sol. gives intense blue-green color w. FeCl3.- Gives off CO2 in melting.-Na amalgam gives phenyllactic ac. 64 GENUS III, DIV. A, SECT. 2. (ORDER I, SUBORDER I.) Melting-point Neut. Equiv. SOLID ACIDS.-Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 155 125 Stilbenedicarbonic Anhyd., C1GH1GO..-B. p. 236° (15 mm.).-Find ndl.-Sbl. undec.-1. c., v. d.s. h. aq.; i. Na2CO3.-Is oxid. in cold by KMnO4 to benzoic ac. (Test 312).-[The free ac. is unknown.] 155 Isodehydracetic Ac., CSHSO4.-Ndl. fr. c. ale.; d. s. c., v. -s. h. aq;-- At 200°-245° loses CO2.-Warmed w. Ba(0H)2 splits to CO2, mesityl oxide and oxymesitenecarbonic ac. d. abt. 155 74 Dioxymaleic Ac., C02H.C(0H): C(OH).CO2H.-Pearly 1ft., d. s. c. aq. or eth.; e. s. ale.-Heated w. aq. dec. to CO2 and glycolaldehyde.-- FeCl3_gives blackish color, becoming violet upon addition of KOH. -BaA + 2H2O (dried i. v.), cryst. ppt. 155-6 180 p-Oxyisopropylbenzoic Ac., Me2.C(OH).CGH4.CO2H.--Pr.fr. h. aq., e. s. ale. or eth.-Oxid. by CrO3 mixt. (Test 905-^2) gives terephthalic ac. (Test 318).-BaA, + H,O, v. s. aq.; AgA, tbl. d. s. h. aq. 156-7 256 Dibenzylglycollic Ac., (PhCH2)2.C(OH).CO2H.-4-sided pr. fr. ale.; e. s. eth. Boiled w. KOH (G. 1 -2-1 -3) gives oxalic ac. and toluene. 156-7 250 Isatronic Ac., C17HUO2.-Lft. fr. dil. ale.-CaA2, volum. ppt., d. s. h. aq. 156-7 (r. h.) 188 2-Oxynaphthoic(i) Ac., HO.C10Hc.COoH.-V. s. ale.-Ale. sol. gives ((s.h.)124-8d.) blue color w. FeCl3.-Fusion or long boiling w. aq. gives CO2 and ^-naphthol (Test 413). BaA- ppt. (dif. fr. salicylic ac.). 157-8 64 a-Trimellitic Anhyd., C9H4O5.-Cryst. d. s. c., e. s. h. aq.-M. p. of trimellitic ac. (Test 307), 216° d. 158 192 p-Isoamylbenzoic Ac., Me2.CH.(CH7)2.CGH4.CO2H.-Ndl. fr. h. aq.- E. s. ale. or eth.-Oxid. to terephthalic ac. (Test 905-1). 158c. 138 f Salicylic Ac., o-HO.C6H4.CO,H.-Ndl. fr. h. aq., s. in 370 pt. aq. at 20°, v. s. ale. or eth.; e. s. CHC13.-Sol. in aq. (1:10,000) gives purple coloration (RV-VR) w. 1 drop 10% FeCl3 sol. (cf. Test 401) !•-Apply Test 319! 159 224 Stilbene-o-carbonic Ac., Ph.CH:CH.CcH4.CO2H.-E. s. ale. or CHC13.-- Gives Test 304. 159 242 Diphenyllactic Ac., Ph2.CH.CHOH.CO2H.-Ndl. fr. h. aq., e. s. ale. or eth. 159-60 79 trans-Pentamethylene-1, 2-dicarbonic Ac., Cf,Hs.(CO2H)2.-E. s. h. aq.-CaCl2 boiled w. (NH4)2A. sol. gives ppt. 159-5 214 p-Phenoxybenzoic Ac., PhO.CGH4.CO2H.-Coffin-shaped pr. fr. CHC13. -E. s. ale. or eth.-Heated w. baryta gives phenylether. 160 172 a-Naphthoic Ac., C10H7.CO2H.-Ndl. e. s. h. ale.; v. d. s. h. aq.- CaA2 + 2H2O, ndl. s. in 93 pt. aq. at 15°.-Ignition w. CaO gives naphthalene (Test 915). 160-1 198 m-Phenylbenzoic Ac., Ph.CGH4.CO2H.-Lft. e. s. ale. or eth.-BaA2 + 3|H2O, ndl. e. s. aq. (dif. fr. para ac.).-Oxid. by Test 905-1 gives isophthalic ac. (Test 318-2). 160-1 162 p-Propenylbenzoic Ac., CH2:CMe.C,H4.CO2H.-Lft. d. s. h. aq.; v. s. ale. or eth.-BaA2 + H,O, lft. v. s. aq.-Gives Test 304. 161 113 Hemipinic Ac., (MeO)2.C0H3.C,OH.-M. p. varies much according to method of heating. Cryst. fr. h. aq. w. a:H2O.-FeCl3 gives orange color w. aq. sol.-W. KOH at 220° gives protocatechuic ac.-NH4A + H2O at 110° gives hemipinimide, ndl. fr. ale., m. p. 22S°-30°, ale. sol. fluorescing blue. 161 206 /9-Dihydronaphthoic Ac. (stable form), CnH10O2.-Lft. i. c. aq.; e. s. ale. or eth.-Easily oxid. to phthalic ac. (Test 318) by KMnO4. 161 288 p-Triphenylmethanecarbonic Ac., Ph2.CH.C,.H4.CO2H. 161-2 226 m-Benzoylbenzoic Ac., Ph.CO.CcH4.CO2H.-Sbl. in lft.-E. s. ale. or eth.-Fusion w. KOH gives benzoic ac. (Test 312). 162 288 o-Triphenylmethanecarbonic Ac., (CGH5)2.CH.C0H4.CO2H.-I aq.; e. s. ale. or eth.-Ignition w. BaO2H2 gives triphenyl methane.- Dissolve 1 pt. ac. in 3 pt. cone. H2SO4, ppt. sol. w. aq.; wash ppt. w. cold NaOH and recryst. fr. abs. ale. Phenylanthranol is 1 formed, yellow, ndl., m. p. 141°-4° d. GENUS III, DIV. A, SECT. 2. 65 (ORDER I, SUBORDER I.) Melting-point Neut. Equiv. SOLID ACIDS.-Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 162 226 Diphenyleneglycollic Ac., C14H^0O:i.-(Dried at 80°.)-Cryst. w. |H2O. -V. d. s. c., e. s. h. aq.; s. ale. or eth.-Warmed w. cone. H2SO4 gives indigo-blue sol.!-CaA2 + 2H2O, d. s. c. aq. 163 150 i, 2-Dimethylbenzpic (4) Ac., Me2.CoH3.CO2H.-Pr. fr. ale.; v. d. s. h. aq.-CaA2 + 2H2O and BaA2 e. s. aq. 163-4 152 2-Oxy-m-toluic Ac., HO.CcH3(Me).CO2H.-Ndl. e. s. h. aq.-Intense violet-color w. PeCl3.-CaA2 e». s. aq. 164 178 p-Isobutylbenzoic Ac., Me2.CH.CH2.C8H4.CO2H.-Sbl. in ndl.; e. s. ale. or bz.-CaA2 tbl. d. fc. c. aq.-M. p. of amide 171°, ndl. fr. aq. 164 250 Atronic Ac., C17H]4O2.-Alm. i. h. aq.; e-. s. ale.-CaA2 + 6H,O, ppt d. s. h. aq.-Unsat. 164 142 Diphenylglutaric Ac., CO2H.CH(Ph).CH2.(Ph)HC.CO2H.-Ndl. fr. h. aq.; v. d. s. h. aq. 164-5 79 Ethylitaconic Ac., C7H,0O4.-D. s. aq.-Unsat. (cf. Test 304). 165 178 1, 2, 3X 4-Tetramethylbenzoic(5) Ac., Me4.CRH.CO2H.-Ndl. fr. ale.- BaA, e. s. ale. or aq. 165-6 194 o-Hydrocinnamocarbonic Ac., CO2H.C8H4.(CH2)2CO2H.-Ndl. e. s. h. aq.-BaA, v. s. aq. 166 150 Dimethylbenzoic(5) Ac., Me2.CGH3.CO2H.- Pr. v d. s. h. aq.; e. s. ale.-CaA, ignited w. CaO gives p-xylene.-M. p. of amide 133°. 167 80 Phenylsuccinic Ac., CO2H.CHPh.CH2.CO,H.-E. s. h. aq.-(NH4)2A boiled w. CaCl2 sol. gives pulv ppt. 167-5 164 Prehnitilic Ac., Me3.CGH2.CO2H.-Glassy pr. fr. ale. "Somewhat s. in aq." 168 152 Methylphenol(3)-methanoic(2) Ac., HO.C6H-j(Me).CO2H.-Ndl. fr. aq. S. in 700 pt. c. aq.; e. s. h. aq.;. e. s. ale. or eth.-Aq. sol. gives intense blue-violet w. FeCl3.-Ca salt v. e. s. aq. 168-9 194 Ferulic Ac., MeO.C8H3OH.C2H2.CO2H.(3,4, 1).-Ndl. s. h. aq.- After long boiling reduces Fehling's sol.-Floc, yellow, ppt. w. PbAc2. 168-9 94 Cinchoic Ac., C7HSO8.-Tbl. e. s. h. aq.; d s. eth.-BaA + 3H2O, silky ndl., d. s. aq. 169 162 o-Methylcinnamic Ac., Me.CBH4.CH:CH.CO2H.-Ndl. fr. bz.-Unsat. 169-70 80 s-Methylethylsuccinic Ac. (fumaroid), CO,H.CHMe.CHEt.CO2H - S. in 51 pt. aq. at 16°.-BaA + 5H2O, e. s. aq. 171 178 p-Methoxycinnamic Ac., MeO.CGH4.CH: CH.CO2H.-Ndl. s. ale.- Unsat. 171-2 [+ and - ] Isocamphoric Ac., C1QH130,-S. in abt. 300 pt. c. aq. 171-5-2-5 184 Camphenylic Ac., -Opt. inact.-AgA cryst. ppt. 172 224 n-Phenylcinnamic Ac., Ph.CH: CPh.CO2H.-Ndl. e. s. ale. or eth.- Unsat. " (Does not add Br)."-Sbl. 172 152 Oxytoluic Ac., Me.CGH30H.C0,H(i, 4, 2).-Pr. e. s. h. aq.; v. s. ale. or eth.-Brown ppt. w. FeClv 172-3 Oxytoluic Ac., Me.CRH,0H.C02H(i, 6, 3).-(Loses |H,0 of cryst. at 100°.)-Ndl. e. s. h. aq., ale., or eth. CuA2 + |H,O, floc. ppt.; char- acteristic dark-green crystals fr. h. aq.-M. p. of methylester 67°. 172-5-3 79 Ethylmesaconic Ac., C7H]0O4.-Lft. d. s. c. aq.; e. s. h. aq., ale., or eth.-Ca salt separates in ndl. on heating c. sat. sol. 173 226 Methyldiphenylacetic Ac., MeCPh,.CO,H.-B. p. a. 300°.-E. s. eth. or h. ale.-BaA2 + 2H,O, cryst. ppt.-Oxid. by CrO3 mixt. to benzophenone and benzoic ac. (Tests 714 and 312). 173 348 Tetraoxystearic Ac., C,8H32O2.(OH)4.-(Fr. oxid. of linoleic ac.) Silky ndl. or pr. fr. bz.-I. c. aq. or eth.; s. in 2000 pt. h. aq.; d. s. ale.-Alkaline KMnO4 gives azelaic ac.-BaA2, floc. ppt. 173-4 240 Ethyldiphenylacetic Ac., Et.CPh,.CO2H.-Lft. fr. dil. ale. 66 GENUS III, DIV. A, SECT. 2. Melting-point (C.°). Neut. Equiv. SOLID ACIDS.-Colorless and generally not solut e <cf. note, p. 38) in 50 parts of cold water. J 73-5 276 Naphthoyl-o-benzoic Ac., ClcH7.CO.CGH4.CO2H.-Pr. fr. dil. ale.-V. d. s. h. aq.-H2SO4 gives naphthanthraquinom -Ba salt, e. s. aq. or ale. 174 Terebic Ac., C7H10O4.-Large monoclin. cryst. fr. ale.; d. s. c. aq.- Not attacked by fuming HN03.-W. cone. BaO2H2 sol. at 150° gives acetone (Test 711) and succinic ac. (Test 320).-Pb and Ag salts e. s. aq. 175 210 Fluorenecarbonic (4) Ac., C14HiaO2.-Cryst. e. s. ale. or -M. p. of methyl ether 64°. 175 108 1, 2-Naphthalenedicarbonic Ac., C10H6.(CO,H)2.-Cryst. s. h. aq.- Fusion gives anhyd., m. p. 165°.-BaA2 d. s. ndl. 175 90 Homophthalic Ac., CO2H.CGH4.CH,.CO2H.-Fusion w. soda lime gives toluene (cf. Test 918L-BaA, e. s. aq. 175-6 Camphoronic Anhyd., C1SH22O9.-Alm. i. c. ale., eth., or Igr.-S. in alkalies (forming camphoronic ac., e. s. aq.; m. p. 136°). 176d. 170 Orsellinic Ac., Me.CrH2(OH)2.(CO2H)(i, 3, 5, 4).-Cryst. w. 1H.Q. E. s. ale. or eth.-Gives purple-violet color w. FeCl3.-Boil w. aq. and test sol. for orcine (ef. p. 95).-BaA2 + xH20 v. s. aq. 176-7 136 p.-Toluic Ac., Me.CGH4.CO2H.-B. p. 275° c.-V. s. h. aq.; e. s. ale. or . eth.-Oxid. to terephthalic ac. by Test 905-2.-The amide, melts at 156°. Odor of methylester intense and agreeable; m. p. 32°. 177c. 152 Oxytoluic Ac., CGH3(Me)(HO).CO2H(i, 3, 4\-Sbl.-Ndl. fr. h. aq.-- Gives intense violet color w. FeCl3! CaA2 + 3H2O, e. s. aq. 177 308 /?-Triphenylpropionic Ac., Ph3.C.CH2.CO2H.-Pr. e. s. ale. or eth.- BaA,, ppt., d. s. h. aq. 178-9 248 [ + ] Santonous Ac., C1GH20O3.-Ndl. d. s. c. aq.; e. s. eth. or Na2CO. sol.-MeA, m. p. 81°-84°. 179 166 Oxymesitylenic Ac., Me2.C,H2(OH).CO2H(i, 3, 4, 5).-Ndl. d. s. h. aq.: e. s. eth.-Gives intense blue w. FeCl3! CaA2 + zH2O, e. s. h. aq. 179 178 1, 2, 4, 5-Tetramethylbenzoic Ac., Me4.C0H.CO2H.-Lft. v. s. ale.-Sbl. -M. p. of methylester 59°. (r.h.)179-82d. 113 m-Hemipinic Ac., C6H2.(CO2H)2(MeO),(i, 2, 4, 5).-Sometimes cryst. w. 1 or 2 mols. H2O.-Pr. d. s. aq.-FeCl3 gives orange-red ppt. in the aq. sol.! Fusion w. KOH gives protocatechuic ac. 180-1 202 a, a-Methylphenylfuranecarbonic Ac., C12H10O3.-Sbl. in ndl.-E. s. ale. or eth.; d. s. h. Igr.-Very easily oxid. to benzoic ac. (Test 312) by alkaline permanganate. Ka + xH2O ndl. almost i. in x's of alkali. 180-7c. 100 f [ + j Camphoric Ac., ClcH1GO4.-Cryst. s. in 160 pt. aq. at 12° or in 11-12 pt. at 100°; v. s. ale., i. CS2.-Heated in test-tube w. cone. H2SO4 evolves CO,_which burns w. pale-blue flame.-BaA + 4|H2O, s. in 1 pt. aq.; PbA, i. ppt.-Na2A sol. boiled w. sol. of MnSO4 gives ppt. which redissolves as sol. cools.-The properties of the [ -] ac., except the optical ones, are like those of the [ + ] acid. 181 182 Veratric Ac., (MeO)2.CeH3.CO2H(3, 4, 1).-Cryst. w. 1H2O.-Sbl.-D. s. h. aq.; v. s. ale. or eth. Yellow color w. FeCl3.-BaA2 + 6H2O, ndl., d. s. c. aq. 181 180 1, 2, 4-Trimethylphenol(5)-carbonic(6) Ac., CuH.(Me)3(OH)(CO2H).- Ndl. mod. s. eth.; d. s. other solvents.-Sbl.-Ale. sol. blue w. FeCl3!-Hist, gives CO2 and pseudocumene (cf. Test 917). 183 152 Methylphenol(6)-carbonic(2)-Ac., Me.C6Hs(0H).C0,H.-Brown ppt. w. FeCl3.-Cf. Sect. 1. 183 144 s-Diphenylsuccinic Ac., CO,H.(CH.Ph)2.CO,H + H2O.-Solidifies after melting and fuses again at 220°. V. s. ale.-BaA, + 2H,0,v. d. s. c. aq. 184c. 172 /9-or Iso-Naphthoic Ac., C10H7.CO2H.-B. p_. a. 300°.-Silky ndl. v. d. s. h. aq. or c. Igr.; e. s. ale. or eth.-BaA, + 4H,O, ndl. s. in 1400 pt. aq at 15°. CaA2 + 3H2O, ndl. fr. h. aq.; s. in 1800 pt. aq. at 15*. -Methylester, m. p. 77°.-Test 905-f gives trimellitic ac. (ORDER I, SUBORDER I.) GENUS III, DIV. A, SECT. 2. 67 (ORDER I, SUBORDER I.) Melting-point (C."). Neut. Equiv. SOLID ACIDS.-Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 184 105 Phoronic Ac., CnHl805.-Froths in fusing; gives anhyd. at 190° (m. p. 138°).-Lustrous pr. fr. dil. ale.; d. s. h. aq.-CaA, s. h. aq. 184d. 83 f Phthalic Ac., o-C0H4(CO2H)2.-In melting gives the anhyd. which sbl. v. e. and melts at 128°.-Rhomb, cryst. s. in 185 pt. aq. at 14°, or in 5-5 pt at 99°. S. in 146 pt. eth. at 15°; e. s. ale.; i. CHCl,. -Apply Test 318!-[The m. p. given (Lossen, A., 144,76), accord- ing to Ador (A. 164, 230), holds only for acid that has been pre- pared by the usual method of precipitation from a soluble salt. A specially purified acid, made from water and the anhyd., is said to melt, when in the powdered condition, at 203°.] 184-2c. 152 Anisic Ac., p-MeO.C„H4.CO2H.-B. p. 275°-80°.-Monoclin. cryst. alm. i. c. aq.; s. h. aq.: e. s. ale.-BaA7 rhombic tbl. d. s. aq.-In sealed tube w. cone. HC1 at 130°, or fusion w. KOH, gives p-oxy- benzoic ac.-Ignition w. BaO gives anisol. 185 180 p-Acetoxybenzoic Ac., C3H3O2.C6M4.CO2H.-Silvery 1ft fr. CHC13. 185d. 70. i, 2, 3-Hemimellitic Ac., CGH3.(CO2H)3.-Rather d. s. c. aq.-Ba3A,+ 5H2O, e. s. aq. (dif. fr. phthalic ac.).-Above 185° gives sublimate of phthalic anhyd. and benzoic ac.; which hence gives fluorescein in Test 402-1 like phthalic ac. 185-6 188 i-Naphtholcarbonic(2) Ac., HO.C](,H6.CO2H.-Stellate ndl., e. s. eth. or bz.; v. d. s. h. aq.-Sol. of Ka gives blue color w. FeCl3.-BaA2 d. s. aq. Long boiling w. aq. gives CO2 and a-naphthol (Test 412). 185-90 196 Choleic Ac., C24H40O4.-(In ox-gall.)-Ndl. fr. h. ale.-Cryst. fr c. ale. w. 1|H2O, then having m. p. 135°-40°.-S. in 22,000 pt. c. aq.; v. d. s. eth.-At 170°-80° gives an anhyd. Boiled w. HC1 becomes resinous. 186-5 248 Chrysenic Ac., C10H0.(Ph)(CO2H)(2, i).-Lft. fr. bz.; e. s. aic. or eth.- BaA2, e. s. aq. 187-8 274 Podocarpic Ac., CI7H22O3.-V. d. s. bz.; e. s. eth.-Weak ac.-Ca salt ignited gives p-cresol.-(In a resin fr. Podocarpus Cupressina.) 188-9 176 5-Methylcumarilic Ac., C1UHSO3.-Ndl. fr. dil. ale.-Sbl.-Rapid heat- ing gives CO2 and/?-methylcumaron.-BaA2 + 3H2O, cryst. fr. h.aq. 189 114 Tetrinic Ac., CfH6O3.-B. p. 292° d.-Cryst. s. in 66 pt. aq. at 13,-5°; e. s. eth. or h. aq.-BaA2 + 14H2O, e. s. c. aq.-Reacts w. phenyl- hydrazine.-Heated w. KOH at 150° gives much formic (Test 315) and propionic ac. (Test 311).-The residue left upon evaporating w. dil. NaNO-> sol. becomes blue when moistened w. a little cone. HN03. 191 164 m-Cumaric Ac., HO.C6H4.CH:CH.CO2H.-Pr. e. s. h. aq. or eth. 191 i-Isocamphoric Ac., C13H10O4.-100 pt. aq. at 20° dissolve 0-203 pt. 192 162 o-Cumarilic Ac., C9HcO3.-B. p. 310°-15°.-S. h. aq.; v. s. ale.-KOH fusion gives salicylic acid (Test 319).-Ba salt d. s. aq. 192 87 s-Diethylsuccinic Ac. (fumaroid), CO2H.(CHEt)2.CO2H.-Sbl.-V. d. s. c. aq.; e. s. eth.-ZnA + 2H2O, more s. c. than h. 192 86 cis-Hexahydrophthalic Ac. (mahnoid), CGH10.(CO2H)2.-4-sided pr. fr. aq. d. s. aq.-Ba salt less s. in h. than c. aq. 194 72 Ethylfumaric Ac., CO2H.CEt:HC.CO2H.-D. s. aq.; e. s. eth. p-Benzoylbenzoic_Ac., Ph.CO.C0H4.CO2H.-Sbl. in 1ft.-D. s. h. aq ; e. s. eth.-BaA2 + 2H2O, d. s. c. aq. 194 226 195 166 p-Ethoxybenzoic Ac., EtO.C.H4.CO2H.-Ndl. alm. i. h. aq.-CaA2, ndl fr. h. aq. 195 72 3-Hexenedioic Ac., CO2H.CH2.CH: CH.CH2.CO2H.-Pr. d. s. c. aq. or eth.-Na amalgam reduces to adipic ac. 195 73 s-Dimethylsuccinic Ac. (fumaroid), CH(Me)(CO2H).CH(Me)CO2H.- Ndl. d. s. c. aq.; e. s. eth.-Dist. gives anhyd., m. p. 87°. 68 GENUS IH, DIV. A, SECT. 2. (ORDER I. SUBORDER I.) Melting-point (C.°). Neut. Equiv. SOLID ACIDS.-Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 195 409 Cholic Ac., (CH2OH)2.C20H31.CH(OH).CO2H.-Cryst. w. 1 aq.-I. c. aq.; v. d. s. h. aq.; d. s. eth.-Warming w. a little sugar sol. and cone. H2SO4 gives a violet-red color! BaA2T7H2O, s. c. aq.-Aq. sol. dec. by CO2.-Oxid. by KMnO4.-To 0 • 02 grm. ac. in 0 ■ 5 grm. ale., add 1 cc. normal sol. of I in KI, and gradually dilute w. aq.; ndl. w. yellow metallic lustre, blue by transmitted light, separate. (Dif. fr. other gall acids.) d. 195 96 Benzalmalonic Ac., Ph.CH: C.(CO2H)2.-V. s. h. aq.; "d. s." c. aq.; s. eth.-Na2A + BaCl2 gives ppt., sm. ndl. on boiling (no ppt. cold). Test 303, at 195°-200° gives CO2 and cinnamic ac. (Test 313). 195d. 87 Tetramethylsuccinic Ac., CO2H.(CMe2)2.CO,H.-100 pt. aq. at 13•5° dissolve 0-48 pt.; s. eth.-Fusion gives anhyd. w. camphor-like odor, m. p. 147°. d. 195-200 170 Pyrogallocarbonic Ac., C,.H2(OH)3.CO2H(2, 3, 4, 1).-Silky ndl. fr. h. aq.; s. 767 pt. c. aq.; v. s. eth.-Colored violet by v. dil. FeCl3.- Reduces ammon. AgNO3 sol. in the cold.-(Cryst. w. JH2O.) 196-7d. 108 Cineolic Ac., C10H1(iO5.-Cryst. s. in 70 pt. c. aq.; e. s. eth.--Dec. by heat to CO2 and an ac. C9H10O3.-(An oxid. product of cineol.) 197 162 p-Methylcinnamic Ac., Me.CGH4.CH: CH.CO,H.-Mod. s. h. aq.-Ndl. fr. bz. 199 199 154 Protocatechuic Ac.-Cf. Ac. of Sect. 1. Lithobilic Ac., C30H68Oa.-Mic. cryst. e. s. ale.; i. aq.; s. eth. Warm cone. HC1 colors intense red-violet.-Gives Pettenkofer's reaction. -BaA2 + 6H2O, i. aq. 199 166 1, 2-Dimethylphenol(5)carbonic(4) Ac., Me2.CGH2(OH).CO2H.-Ndl. d. s. h. aq.; e. s. ale. or eth.-Gives intense blue-violet color w. FeCl3! BaA2, d. s. c. aq. 200 304 Triphenylcarbinol-p-carbonic Ac., Ph2.COH.CGH4.CO,H.-I. aq.; e. s. eth.-Ba salt v. d. c. s. aq. 200 174 ;--Methylindene-/?-carbonic Ac., C]1Hl0O2.-Ndl. fr. ale.-Warmed w. MnO2 and cone. KOH gives a blue solution. Sbl. w. m. 200 58 t Fumaric Ac., CO2H.CH: CH.CO2H.-M. p. in closed capillary (cf. foot- note, r>. 219) 286°-7°.-Cryst. s. 148-7 pt. aq. at 16-5°.-BaA + 1|H2O, s. 100 pt. c. aq.-Ag2A, alm. i. c aq.; e. s. h.-Above m. p. gives maleic anhyd. w. some carbonization.-M. p. of Me2A, 102°. -Unsat., but adds Br2 w. some difficulty. 200 138 f m-Oxybenzoic Ac., HO.CGH4.CO2H.-Dist. undec. Tastes faintly sweet (dif. from para acid).-S. 108 pt. aq. at 18°.-No color w. FeCl3.-CaA2 + 3H2O, s. aq.-0-02 grm. boiled w. 5 cc cone. H2SO4 gives orange-red (OR) sol. (Dif. fr. 0- and p-ac , the o-acid giv- ing only pale-yellow, and the p-acid giving orange-yellow (OYTI) when treated in this way.) 200 164 p-Acetylbenzoic Ac., Me.CO.C,H4.CO2H.-Sbl.--Ndl. rather d s. h. aq.; e. s. eth.-BaA2 + |H2O, s. h. aq. 201 201 298 Picenic Ac., CI0H7.C1uH0.CO2H.-Flocks fr. ale.; s. ale. or CHC13.- Heated w. Ca(OH)2 (i. v.) gives /?-binaphthyl. [-] Camphanic Ac., C10HhO4.-Rhombohedra fr. eth.-Volat. w. st.- Sbl. easily fr. 110°.-W. aq. at 180° gives CO2 and a hydrocarbon CsH]4, b. p. 119°. 203 302 4-Methyltriphenylmethane-2-carbonic Ac., C2IH1SO2.-Dist. undec.- Ignition w. Ba(OH)2 gives p-methyltriphenylmethane. 204 204-5 212 m-Tolylbenzoic Ac., Me.CGH4.C(;H4.CO2H. Lithofellic Ac., C2oH3a04.-(Cryst. w. 1H2O fr. 33% ale.)-S. h. ale. or h. eth. Gives intense red color w. cone. HC1.-(Found in ben- zoars.) 204-5 92 Methylfurfurancarbonacetic Ac., C4HO.(Me)(CO2H)(CH2.CO2H).-Sbl. undec.-Short ndl., v. d. s. c. aq.; e. s. ale.; s. eth.-NH4 salt heated gives pyrrol-red.-CaA, cryst. ppt. i. h. aq. GENUS III, DIV. A, SECT. 2. 69 Corder i, suborder i.) Melting-point (C.°). Neut. Equiv. SOLID ACIDS.-Colorless and generally not soluble (of. note, p. 38) in 50 parts of cold water. 204-6d. 154 2, 4-Dioxybenzoic Ac., (OH)2.CGH3.CO2H.-Cryst. w. 3H2O.-S. 381 pt. aq. at 17°.-Aq. sol. colored violet by little Ca(OCl)2 sol.-BaA2 e. s. aq.-PbAc2 gives no ppt. 205d. 91 Furalmalonic Ac., C4H3O.CH: C.(CO,H)2.-Pr. alm. i. c. aq.; s. ale. or eth.-AgA; curdy ppt.-Loses CO2 on fusion, giving furfurol acrylic ac. 205-10d. Coumalic Ac., C5H3O2.CO2H.-Sm. pr. d. s. c. aq.; s. ale. or eth.-Re- duces ammon. AgNO3 or Fehling's sol. on warming.-Boiled w. dil. H2SO4 gives crotonic aid.-Boiling aq. sols, of salts gives carbonates. 206 198 /?-Isoatropic Ac., CISH1c04.-Tbl. fr. h. aq.-Cryst. ppt. w. BaCl2.-Con- tinued heating at 225° gives «-ac., m. p. 237° 206 164 p-Cumaric Ac., HO.CoH4.CH: CH.CO2H.-V d. s. c., e. s. h. aq.; v. s. eth. or ale.-Ale. sol. becomes golden brown w. FeCl3.-Fusion w. KOH gives p-oxvbenzoic ac. 206 97 2, 6-Dimethylterephthalic Ac., Me2.CGH2.(CO2H)2.-Ndl. fr. ale ; e. s. eth.-Sbl undec.-BaA + 3H2O, pearly 1ft. 206d. (s. Ii.) f Mucic Ac., CO2H.(CHOH)4.CO2H.-Sandy cryst. powder s. in 300 pts. aq. at 14°; i. ale -t Mix 0-01 grm. acid w. 5 drops cone, ammonia in 5-in. test-tube. Evaporate to dryness. Hold soft pine splinter that has been soaked in cone. HC1 for several min. in upper part of tube, and ignite residue strongly. Pyrrol vapors evolved develop bright-red color in splinter ! (' ' Pyrrol reaction,"-a simple test, but also given by some other substances )-(M. p. higher w. rapid heating.) 206d. 222 a-Anthracenecarbonic Ac., C15H10O2.-Silky pale-yellow ndl, d. s. h. aq.-Br subst. easily. Oxid. by CrO3 in Ac sol. gives anthraquinone. -Dist w. soda lime gives anthracene (Test 912). 206-7c. 152 2-Oxy-p-toluic Ac., HO.CcH3Me.CO2H.-Ei s h. aq ; s. eth.; i. CHC13. -Sbl.-Gives no color w. FeCl3.-Ignited w CaO gives o-cresol. 207 168 t Vanillic Ac., C6H3.'(MeO)(OH)CO2H.(3, 4, 1).-Ndl. fr. h. aq.; s. 850 pt aq. at 14°; e s eth -Odorless if pure.-Gives no color w. FeCl31-Salts w. exception of those of Pb and Ag generally soluble. -AgA blackens in h. aq.-Dist of Ca salt w. slacked lime gives pure guiacol (cf. p 91) 208 164 o-Coumaric Ac., HO.CGH4.CH: CH.CO2H.-D. s. c. aq ; d. s. eth ; e. s. ale.-Sbl.-Dec on dist into CO, and phenol. (Test 414.)-- Fusion w. KOH gives salicylic and acetic acids-Dil. ammonia gives a yellow sol . pale green by reflected light.-FeCl3 gives a yellow-red ppt-BaA3 + H2O, e s. aq. 208 100 i. Camphoric Ac., C10H10O4 -Difficult to cryst-100 pt c. aq. dissolve 0-239 pt.; v s eth.-Ba salt ndl. s. in 10 pt aq. 210 138 f p-Oxybenzoic Ac., H0.C6H4.C04H.-Pr w 1H2O fr h aq, S. in 126 pt. aq. at 15° -Gives amorph. yellow ppt w FeCl3.-Dist. dec to phenol (Test 414) and CO,-Taste not sweet like that of meta ac. abt. 210 198 a-Naphthylacrylic Ac., CinH7.CH:CH.COJL-I h. aq. 210-1 188 <r-Oxy-/?-Naphthoic Ac., HO.Cl0H(.CO,H.-Ndl s h. aq.-Gives dirty- red ppt. w. FeCl3, becoming black on boiling. 210-5 192 Pentamethylbenzoic Ac., Mefl.C0.CO2II.-Cryst. fr h. aq-Sbl.- Methylester m. p 67 5°. 215 86 r trans-Hexahydrophthalic Ac. (fumaroid), C,;H10.(CO2H)2.-Lfts. s. in 434 pt. c. aq.-C. alk. permanganate does not attack -Ca salt d. s. aq. 215 85 d2-Tetrahydrophthalic Ac., CsH10O4.-S. in 114 pt. aq. (10°). Decol- orizes alkaline permanganate sol. at once in the cold, forming oxalic ac and succinic ac. 215 164 1,2,3-Trimethylbenzoic(s) Ac., Me3.CBH2.CO2H.-Cryst. v. d. s. h aq.; s. eth.^Ca salt d. s. c. aq.-Ignited w. CaO gives 1, 2, 3- Me3.C6H3. 70 GENUS III, DIV. A, SECT. 2. (ORDER I, SUBORDER I.) Melting-point (C.°). Neut. Equiv. SOLID ACIDS.-Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 215 84 J2,6-Dihydrophthalic Ac., CGHG.(CO2H)2.-Pr. v. d. s. c. aq.; e. s. h.-13aA, s. c. -aq., less s. h. aq. 215-6d. 247 Santononic Ac., C30H3sOG.-Pearly 1ft. fr. ale.; i. aq.; e. s. ale.; d. s. eth.-Ag2A, ppt. 216 188 Oxynaphthoic Ac., C10H6.(OH).CO2H(2, 3).-E. s. ale., eth.-Rhomb. 1ft. fr. h. aq.; e. s. eth.-Sol. becomes blue w. FeCl3! 216-7 206 Piperic Ac.-Pale-yellowish ndl.-Cf. Suborder 2. 217 302 3-Methyltriphenylmethane(6)carbonic Ac., Ph2.CH.CGH3(Me).CO2H. -- Tbl. fr. eth. or ale., i. aq.; e. s. ale. or eth.-Dist. undec.-Ignited w. Ba(OH)2 gives m-methyltriphenylmethane.-BaA2 + H2O, i. ppt. 218-9 198 p-Phenylbenzoic Ac., Ph.CGH4.CO2H.--Sbl. in ndl.-V. d. s. h. aq.; e. s. ale. or eth.-BaA2, L t. v. d. s. h. aq. 219d. 100 Diphenylmethanetricarbonic Ac., (CO2H.CGH4)2.CH.CO2H.-S. h. aq.- M. p. of trimethylester 145°. 220-1 91 Camphoric Anhyd., C10H14O3.-B. p. a. 270° (undec.). Long rhomb, pr. fr. ale.-V. d. s. aq.-Boiling aq. slowly gives camphoric ac., v. d. s. aq. m. p. 187°.-Opt. inact. 221 210 Diphenyleneacetic Ac., (C6H4)2CH.CO2.H.-Alm. i.aq.; e. s. ale. or eth.- Ignition w. CaO gives fluorene. 223 166 1, 3-Dimethylphenol(2)benzoic(5) Ac., Me2.CBH2OH.CO2H. - Sbl. - Hair-like ndl. fr. h. aq.; e. s. eth.-BaA2 mod. s. c. aq. 227-5-28 166 Piperonylic Ac., CH2.O2.C,.H3.CO2H.-Sbl. in pr.; ndl. fr. ale.; d. s. h. aq., c. ale. or eth.-CaA2 + 3H2O, s. in 161 pt. aq. at 15°.-:AgA cryst. ppt. s. h. aq. 228 194 Isoferulic Ac., CGH3.(C2H2.CO2H).(OH)(MeO).(r, 3, 4).-Ndl. d. s. c. aq.; e. s. ale. or eth.-CaA2 + 2H2O, d. s. ndl. 228 148 f-Truxillic Ac., C1SH1GO4.-V. d. s. aq.; e. s. eth.-Dist. gives cinnamic ac. (cf. Test 313). Alkaline permanganate gives benzoic ac. (Test 312).-Ag2A ppt. 229 121 Biphenyl-i, 1 o-dicarbonic Ac., (Diphenic Ac.). CO2H.CGH4.CGH4.CO2H. -Sbl. in ndl. S. h. aq.; e. s. eth.-BaA. + 4H2O, e. s. aq.- Heated w. Zn dust gives diphenyl. abt. 230 160 Indenecarbonic Ac., Ci0HsO2.-Sbl.-V. s. eth. 230-1 90 2, 5-Dimethylfurandicarbonic(3, 4) (Carbopyrotritaric) Ac., Me2.C4O.(CO2H)2.-Sm. ndl. fr. h. aq., alm. i. c. aq.; e. s. ale.; s. eth.; v. d. s. CS2.--Fusion w. KOH gives succinic ac._(Test 320) and acetic ac.-CaA + BaA, cryst. ppts. fr. h. aq.; Ag2A, ppt. 222-40d. t Gallic Ac., (IJO)3.C6H2.CO2H(3, 4, 5, 1).-Cryst. w. 1H2O (lost at 120°) in silky ndl. S. 130 pt. aq. at 12 • 5°.-Aq. sol. absorbs O from air and turns brown during titration; gives no ppt. w. sol. of gelatine (dif. fr. tannic ac.). 234-7 188 a, a-Oxynaphthoic Ac., HO.C10H6.CO2H.-Sbl.-S. h. aq.; e. s. ale.- Fusion w. CaO gives a-naphthol (Test 412).-Aq. sol. gives dirty- violet ppt. w. FeCl3. 237 148 a-Isoatropic Ac., C1SH]GO4.-V. d. s h. aq.; alm. i. eth.-CaA2 + 2H2O, alm. i. ppt.-Warm cone. H2SO4 gives CO. CrO3 gives anthraqui- none (Test 1011). 237-8 90 Homoterephthalic Ac., p-CO2H.CGH4.CH2.CO2H.-S. h. aq.; alm. i. eth. -Ag2A, cryst. ppt. 238 154 2, 5-Diphenylfurandicarbonic("3, 4) Ac., C4O(Ph)2.(CO2H)2.-D. s. aq.; e. s. ale. or eth.-Sol. in cone. H2SO4 becomes blue on warming!- Ignition w. soda-lime gives acetophenone (Test 712). 243 212 p-Phenyltolylcarbonic Ac., Me.CGH4.CBH4.CO2H.-D. s. h. aq. 243 91 2-Oxyisophthalic(i, 3) Ac., HO.CGH3.(CO2H)2. - Cryst. w. 1H2O.- S. h. aq.; v. d. s. c. aq.; e. s. eth.-Aq. sol. cherry red w. FeCl31 Solutions fluoresce blue-violet; color destroyed by alkali.-Dist. gives CO2 and salicylic ac. (Test 319). GENUS 111, DIV. A. SECT A 71 (ORDER I, SUBORDER I.) Melting-point (.C.'j. Neut. Equiv. SOLID ACIDS.-Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 245 210 Fiuorenic Ac., C]4H10O2.-Sbl. undec.-Alm. i. h. aq.; e. s. h. ale.- BaA2 + 3H2O, 1ft. d. s. c. aq.-Ignition w. CaO gives fluorene. 247 150 Isocholanic Ac., C2SH38O7.-Pearly scales alm. i. aq. or eth.; e. s. ale.- Ba3A2 d. s. h. aq., not pptd. by CO2. 250 168 Isovanillic Ac., C6H3.(MeO)(OH)CO2H(4, 3, 1).-Sbl. undec.; alm. i. c. aq.; d. s. h. aq.-Gives yellow color w. FeCl3. 250d. 140 Comanic Ac., C5H3O,.CO2H.-D. s. aq.-No color w. FeCl3.-BaA2, e. s. aq.-Boiled w. baryta water gives acetone (Test 711), oxalic (Test 317) and formic (1'est 315) acids. 251 222 /?-Phenanthrenecarbonic Ac., C14H9.CO2H.-Sbl.-Alm. i. aq.; s. eth. -BaA2 + 6H2O, v. d. s. c. aq.-Ignition w. soda-lime gives phenan- threne (cf. Test 916).-Oxid. w. CrO3 gives phenanthrene quinone (cf. Test 1013). (r. h.) 252d. 135 /?-Bibenzyldicarbonic Ac., C]4H12.(CO2H)2.-Ndl. fr. ale.; i. aq.; s. in 89 pt. abs. ale.-CrO3 oxid. to benzoic ac. (Tests 905-2 and 3).- Ba salt e. s. aq. 250-60 Lactic Anhyd., C3H9O3,CO2H.-Yellowish amorph. mass alm. i. aq.; e. s. ale. or eth.-Alkalies immediately give lactic-acid salts.- Heated, dec. to CO, CO2, lactide and citraconic ac. 256d. 292 ^?-o-Oxynaphthoylbenzoic Ac., HO.C10H6.CO.C0H4.CO2H.-V. d. s. h. * aq.; e. s. ale. or eth.-Fusion w. KOH gives /?-naphthol and phthalic ac. (Tests 413 and 318). 255-60 162 p-Isopropenylbenzoic Ac., CH2:CMe.C0H4.CO2H.-Ndl. d. s. c. ale.- BaA2 + H2O, amorph. ppt.-Br2 adds very slowly. d. 260 180 Umbellic Ac., C6H3.(OH)2(CH:CH.CO2H)(2, 4, 1).-S. h. aq.; i. eth.- Browns at 240°.-Reduces ammon. AgNO3 on warming.--BaA2 s. aq.-AgA becomes resinous on boiling.-FeCl3 gives dirty-brown coloration. d.a. 260 Comenic Ac., HO.C5H2O2.CO2H.-S. 16pt. h. aq.; i. abs. ale.-Pale-yel- lowish crusts.-Dec. by heat gives CO2 and pyromeconic ac.-Br sub- stitutes readily.-Red color w. FeCl3.-Ag2A yellow ppt. fr. NH4 salt. 261d. 211 Tetraphenylsuccinic Ac., CO2H.(CPh2)2.CO2H.-E. s. eth. 262d. 92 2, 6-Pyrondicarbonic [Ch°lidonic] Ac., C7H4O6.-Silky ndl. w. 1H2O fr. h. aq.; d. s. c. ale.-Many salts yellowish.-Boiling w. milk of lime gives acetone (Test 711) and oxalic ac. (Test 317). 264d. 294 Triphenylacetic Ac., Ph3.C.CO2H.-Softens at 230°.-Ignition w. CaO gives triphenylmethane. 266 222 a-Phenanthrenecarbonic Ac., C14H9.CO2H.-Lft. fr. h. Ac.-Reactions like /?-ac. (m. p. 251°). 267 237 Pyrenecarbonic Ac., CjgHg.COjH.-Sbl.-Yellowish warty mass, s. h. ale. or eth.-Heated w. CaO gives CO2 and pyrene. 270 230 Biphenyldiol(3, 8)-carbonic(i) Ac., HO.C6H4.C0H3(OH).CO2H.-Gives green color w. Ca(OCl)2 sol.-Gives chocolate ppt. w. FeCl3. abt. 270 108 Naphthalic Ac., C10Ho.(CO2H)2(i, 8).-The anhyd. is formed at 150° without melting.-Silky ndl. fr. ale.; alm. i. aq.; d. s. eth.-Igni- tion w. CaO gives naphthalene (Test 915).-The anhyd. dissolves in cone. H2SO4 w. blue fluorescence, and boiled w. cone. NH3 gives the imide of m. p. 300°. (m.p. of anhyd.) 274 148 2, 4-Diphenylcyclobutanedicarbonic(i, 3), (a-Truxillic) Ac., CI8HieO4. -Ndl. s. eth. or h. ale.-Dist. gives cinnamic ac. (Test 313). 276 99 a-Resodicarbonic Ac., (HO)2.C6H2.(CO2H)2.-Cryst. v. d. s. h. aq.; s. eth.; gives blood-red color w. FeCl3 sol. 277 97 Hydrocinnamic-p-carbonic Ac., CO2H.C6H4.(CH,)2.CO2H.-Sbl.-S. h. aq. or ale.-Gives nitro-deriv., m. p. 191°-2°. 278c. 196 Cantharic Ac., CgHpO.CO.COjH.-Cryst., s. 120 pt. c., or 12 pt. h. aq.; v. s. ale.; alm. i. eth.-AgA ppt.-The imide, by heating w. 56 pt. ale. NH3 at 150°, forms tbl. fr. ale., m. p. 187°.-Ignited w. CaO gives CO2 and cantharene (C8H]2). 72 GENUS III, DIV. A, SECT. 2. (ORDER I, SUBORDER I.) Melting-point (C.°). Neut. Equiv. SOLID ACIDS.-Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 278 166 Triphenylmethanedicarbonic(2, 4) Ac., Ph2.CH.CGH3.(CO2H)2. -Ig- nited w. Ba(0H)2 gives triphenylmethane.-CaA + 2H2O, ppt. 280-3 90 Methyltcrephthalic Ac., C0H3.(Me)(CO2H)2(i, 2, 5).-Sbl. below 280°. -BaA v. e. s. aq. 283 252 /?-Anthraquinonecarbonic Ac.-Cf. Suborder 2. 285d. Cholanic Ac., C20H2sO6 (?).-Pr. fr. ale., s. in_4000 pt. h. aq.-Sol. in cone. H2SO4 fluorescent. Opt. act.-AgA, curdy ppt., Ba salt s. aq. 287-8 90 s-Uvitic Ac., C6H3.(Me)(CO2H)2(i, 3, 5).-Sbl.-Ndl. fr. h. aq., e. s. eth.-BaA + H2O, e. s. aq.-Ignition w. CaO gives toluene (Test 918) ! 288c. 91 5-Oxyisophthalic(i, 3) Ac., H0.CGH,.(C02H)2.-(Cryst. w. 2H2O.)- Sbl.-E. s. eth. or h. aq.-Gives yellowish-brown color w. FeCl3.- Ignition w. CaO gives phenol (Test 414). 290 128 Diphenylmethanedicarbonic Ac., CH2.(CgH4.CO2H)2(i :4)2. 290d. 151 m-Oxyuvitic Ac., HO.CGH2(Me)(CO,H)_2.--E. s. eth. or h. aq.-Gives reddish-violet color w. FeCl3.-BaA, e. s. aq. 305 91 4-Oxyisophthalic(x, 3) Ac., HO.CGH3.(CO2H)2.-D. s. h. aq.; e. s. eth. -Aq sol. becomes cherry-red w. FeCl3.-Destructive dist. gives phenol and salicylic ac. (Test 319). d. abt. 320 71 Muconic Ac., CO2H.CH: CH.CH: CH.CO2H.-S. 5000 pt. c. aq.- Me2A, m. p. 154°. 320-30 90 i-Methylisophthalic(2, 4) Ac., Me.CGH3.(CO2H)2.-Sbl. in thick glassy cryst-D. s. h. aq.; s. h. ale.-Gives no anhyd.- BaA + 2H2O, e. s. aq. or ale. a. 300 83 f Isophthalic Ac., m-CGH4(CO2H)2.--Sbl. undec, without forming an anhyd.-Hair-like ndl. fr. h. aq.-S. in 7800 pt. aq. at 25°, or 460 pt. h. aq.; s. ale.-BaA + 6H2O, triclinic cryst., v'. s. aq. and efflo- rescent !-Ag,A amorph. ppt., alm. i. h. aq.; swells like a zeolite on heating.-Apply Test 318-2 ! a. 300 108 /?-Naphthalenedicarbonic Ac., C10HG.(CO2H)2.-Alm. i. h. bz. or Ac.- Ca salt v. d. s. cryst. ppt. much a. 300 108 a-Naphthalenedicarbonic Ac., C10HG.(CO2H)2.-Closely resembles /?-acid (above).-Salts somewhat more soluble. Sb. w. m. 83 •(•Terephthalic Ac., p-CGH4.(CO,H)2.--Powder.-S. in 67,000 pt. c. aq.; alm. i. ale. or h. aq.!--Alm. i. eth. or CHC13.-BaA + 4H2O, tbl. v. d. s. (1:355-4 at 5°)!-Ag2A ppt.; CaA + 3H2O, alm. i. c. aq.- Apply Test 318-3! 345-50 70 s-Trimesic Ac., CGH3.(CO.,H)3.-Solubility in aq. at 22-5°, 2-69%; at 16°, 0-38%; v. s. ale.-Sbl. at 300°.-BaA2 + H2O (at 150°); alm. i. c. aq.; v. d. s. h. aq. (dif. fr. iso- and tere-phthalic acids).-■ Me3A (fr. Ag3A and CH3I), m. p. 143°. Sb. w. m. 68 Furfuranedicarbonic (Dehydromucic) Ac., CGH4O5.-Ndl. fr. h. aq. (dif. fr. terephthalic ac.). V. d. s. ale.; d. s. eth.-Aq. sol. warmed w. FeCl3 in absence of mineral acids gives a transparent jelly.-BaA.+ 2|H2O, s. h. aq.!-Dry dist. gives pyromucic ac. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I] GENUS III, ACIDS. DIVISION B, SECTION 1-LIQUID ACIDS SOLUBLE IN COLD WATER. Boiling-point (C.°). Neut. Equiv. LIQUID ACIDS.-Colorless and generally soluble (cf. note, p. 38) in 50 parts of cold water. 32-3 60 f Methyl Formate, H.C0,Me.-G. 0 • 9984%.--S. aq.-Saponified very easily and may be slowly titrated like a monobasic ac.-Test for methyl ale. by Test 819-1, and for formic ac. by boiling the neutral solution resulting from the titration for neut. eq. with AgNO- sol. Ag will be ppt'd. 100-8 46 t Formic Ac., H.C02H.-G. 1-2448%.--M. p. +8-6°.-Mise. w. aq.- Neutral salts all s. in aq.-Odor very charp.-Gives Test 304.- Apply Test 315! 118-lc. 60 f Acetic Ac., Me.CO2H.--G. l-0512%0.-Solidifies at 16-7°. Mise. w. aq.; neutral salts all s. in aq.-Sharp odor.-Does not give Test 304. Apply Test 311! 137 51 f Acetic Anhyd., (Me.CO)2.O.-G. 1-0969 at 0°.-Sharp and irritating odor. S. c. aq. and v. slowly decomposed by it.-For behavior on titration cf. p. 37! Identify by Tests 307 and 311! 139-6 Acetylacetone, CH3.CO.CH2.CO.CH3.-Cf. IV, B. (A weak acid.) 140 36 Acrylic Ac., CH,: CH.C02H.-G. 1-062118/4.-M. p. +8°.-Sharp odor like Ac.-Gives Test 304.-PbA2 lustrous ndl. s. in ale.-KOH fusion gives formic and acetic ac. (Tests 315 and 311). 140-7c. 74 t Propionic Ac., C2H5.CO2H.--G- 0 • 99619/19.-M. p. - 22°.-Odor like Ac. -Salts all soluble.-Does not give Test 304.-Apply Test 311! 144d. 70 Propiolic Ac., CH.:C.C0,H.-M. p. +6°.--S. aq.,alc., oreth.-Strong acetic-acid odor.-Dec. by sunlight.-Gives Test 304. Addition product w. Br2 has m. p. 85°.-Explosive brown ppt. w. ammon. CuCl sol. (Test 906)!-Reduces AgNO3 sol.-Salts v. s. aq., but the solutions are dec. by boiling. 144-8 Methyl Lactate, C4HSO3.--G. 1 • 118 at 0°.-Sapon. gives lactic acid (cf. p. 39), and methyl ale. (Test 819-1). 154-5 Ethyl Lactate, C5H10O3.-G. l-055at0°.--Sapon. gives lactic acid (cf. p. 39) and ethyl ale. (Test 814). 155 88 t Isobutyric Ac., Me2.CH.CO2H.-G. 0-948719'74--S. in 5 pt. aq. at 20°.-Unpleasant odor like rancid butter.-Aq. sol. of the v. s. Ca salt does not become turbid on boiling (dif. fr. normal Ca salt). -Salts are ail more soluble than those of the normal acid.-May be oxid. by alkaline permanganate to acetonic ac. (a reaction used by V. Meyer to detect it in presence of much normal acid).- Identify by Test 311! 162-3 86 Methacrylic Ac., CH2:CMe.C02H.-G. l-01532%.-M. p. + 14°.- S. aq.-Gives Test 304.-Heated for some time in tube at 130° polymerizes to a porcelain-like mass which dec. above 300° --CaA2, e. s. aq.-Na amalgam gives odor of isobutyric ac. 162-5 88 f n-Butyric Ac., C3H7.CO,H.-G. 0 ■ 959919' %.-Miscible w. aq. (dif. fr. isobutyric ac.), ale., or eth.-M. p. -7-9°. Unpleasant and per- sistent odor of rancid butter.-Prepare a clear sat. sol. of the e. s. Ca salt by neutralizing a solution of the acid w. an x s of CaCO3, concentrating, allowing to stand for some time in the cold, and filtering. The cold saturated sol. gives a white ppt. when warmed (dif. fr. isobutyric ac.).-Identify by Test 311! 73 74 GENUS UI, DIV. B, SECT. 1. (ORDER I, SUBORDER I.) Boiling-point (C.°). Neut. Equiv. LIQUID ACIDS.-Colorless and generally soluble (cf. note, p. 38) in 50 parts of cold water. 165 s. d. 88 f Pyruvic Ac., Me.C0.C02H.-G. 1-288 at 18°.-Mise. w. aq., ale., or eth.-Sharp odor like Ac.-Readily attacked by Br or KMnO4.- Mixed w. equivalent quantity of phenylhydrazine dissolved in 5 pt. ether gives a hydrazone, cryst. fr. ale., m. p. 192° (r. h.).-• Mirror w. ammon. silver sol.-Salts fr. boiling solutions are gummy.-For color reaction w. sodium nitroprusside and ammonia, cf. Compt. rend. 125, 534. 168 86 Buten(i)oic(4) Ac., C,H5.CO2H.-CaA, + H,O, 1ft. fr. h. aq.: cryst. fr. c. aq. w. 2H2O.-Gives Test 304. 169-9-3 86 t Isocrotonic Ac., Me.CH:HC.CO,H.-G. 1-031215/,.-S. in 2-5 pt. aq.-Odor sharp! Gives Test 304.-CaA2, s. aq.; AgA, curdy, ppt.-f Heat 0'5 cc. of the acid w. 5 mgr. iodine for 1 hour in a dry test-tube whose lower end is immersed in an oil-bath at 150°. Dissolve product in 1 cc. hot ligroin. Cool w. ice-water. Drain crystals which separate on porous tile. Washw. a few drops cold ligroin, and dry. The crystals are crotonic acid, and melt at 72° (uncor.) ! 176c. 102 Isovalerianic Ac., Me2.CH.CH2.CO,H.-G. 0 • 9467 at 0°.-M. p. -51°.- S. 23-6 pt. aq. at 20°; misc. w. ale. or eth.-Odor offensive like decayed cheese!-Alkali salts give no ppt. w. CaCl2; gelat. ppt. w. ZnSO4 in the cold, or scales if hot; v. d. s. cryst. ppt. w. AgNO3. 177 (th. i.) 102 Methylethylacetic Ac., Et.CHMe.CO2H.-G. O-9382%o.-Feeble_odor of isovalerianic ac.-Not solid at -80°.-CaA2, s. aq.-ZnA2 more s. c. than h. 182 86 Trimethylenecarbonic Ac., C3H5.CO2H.-G. l-08792%-M. p. 17°.- "Somewhat" s. in aq. 186-6-4c. 102 n-Valerianic Ac., Me.(CH2)3.CO2H.-G. 0-9577 at 0°.-M. p. -58-5°. -Odor and solubilities of ac. and its salts nearly the same as for isovalerianic ac. (cf. above). 186-lc. 146 f Diethyl Oxalate, C,O4.Et2.-G. 1-0815 at 18-2°.-Titrates w. deci- normal NaOH like monobasic ac.-Shaken w. cone, ammonia gives an immediate heavy cryst. ppt. of insol. oxamide !-Saponify (Test V), and test for ethyl alcohol (Test 814), and oxalic ac. (Test 317). 190 116 Methylisopropylacetic Ac., Me.CHPr.CO2H.-G. 0-928 at 15°.-CaA2 less s. in h. than in c. aq. 190 (th. i.) 116 Diethylacetic Ac., Et2.CH.CO2H.-G. 0-9355 at 0°.-CaA2, e. s.; ZnA2 more s. c. than h. 191 (th. i.) 103 i-Methyltrimethylenecarbonic(2) Ac., C4H7.CO2H.-G. l-01518/4.-S. in 12 pt. aq. at 15°?-BaA2 + 2H2O, ndl. v. s. c. aq. 193 116 Methylpropylacetic Ac., Me.CHPr.CO2H.-G. 0-9414 at 0°.-CaA2, s. aq.; FeA3 flesh-red ppt. s. in x's FeCl3. 194 100 Pentene(2)-oic(i) Ac., Me.CH2.CH:CH.CO2H.-G. 0-992 at 15°.-M. p. 9-5°-10-5°.-S. in 16 pt. c. aq.-Gives Test 304.-CaA2 + H2O, e. s. aq., ale., or eth.; AgA voluminous ppt. 195-8d. 118 a-Ethoxypropionic Ac., Me.CH(OEt).CO2H.-E. s. aq., ale., or eth.-• CaA2 + 2H2O, e. s. aq.; AgA fine silky ndl. mod. s. c. aq.; v. e. s. h. aq. 200-1 100 Penten(2)oic(i) Ac., C4H7.CO2H.-G. 1-0074 at 0°.-Lft., m. p. 10°.-• Sharp odor.-Gives Test 304.-S. in 16 pt. aq.-Ba salt v. s. aq. 203 90 Methoxyacetic Ac., MeO.CH2.CO2H.-G. 1 • 18.-Misc. w. aq.-PbA2, s. aq. and ale. 206-7 104 Ethoxyacetic Ac., EtO.CH2.CO2H.-S. aq.-CaA2 + 2H2O v. s. aq. or 213-20 132 ^-Ethoxybutyric Ac., Me.CH(OEt).CH2.CO2H. 239 (si. d.) 116 f Laevulinic Ac., Me.CO.(CH2)2.CO2H.-M. p. 33°.-Gives iodoform in the cold in Test 801.-Cf. Div. A, Sect. 1. 275 (si. d.) 130 /--Acetylbutyric Ac., Me.CO.(CH2)3.CO2H.-Deliquesces to hydrate w. m. p. 35°-36°. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER 1} GENUS III, ACIDS. DIVISION B, SECTION 2,-LIQUID ACIDS NOT SOLUBLE IN COLD WATER. Boiling-point (C.°). Neut. Equiv. LIQUID ACIDS.-Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 168-6 65 j Propionic Anhyd., (Et.CO)2O.-G. 1-0169 at 0°.-Sharp and irritat- ing odor.-For behavior on titration cf. p. 37.-D. s. c. aq. and v. slowly dec. by it.-Identify by conversion into propion-p-toluide (cf. p. 81) either by heating w. p-tohudine directly or by methods of Tests 307 and 311! 181 132 a-Ethoxyisobutyric_ Ac., Me2.C(OEt).CO2H.-G. 1-0211 at 0°.-D. s. c., e. s. h. aq.-BaA2 + H2O, s. ale. or h. aq.-ZnA2, 1ft., e. s. ale. or eth. 182-5 79 Isobutyric Anhyd., (Me2.CH2.CO)2.O.-G. 0-9574 at 16-5°.-For be- havior on titration cf. p. 37.-Convert into isobutyr-p-toluide (cf. p. 81) either by heating directly w. p-toluidine or by methods of Tests 307 and 311! 187 116 Dimethylethylacetic Ac., Me2.CEt.CO2H.-V. d. s. aq.-BaA2 + 5H2O, e. s. tbl.; AgA ndl. fr. h. aq.; ZnA2, d. s. aq. 188 (th. i.) 100 Allylacetic Ac., CH2: CH.(CH2),.CO2H.- G. 0-9842 at 15°.-Unpleasant valerianic odor.-D. s. aq.; e. s. ale. or eth.-Gives Test 304.-No ppt. w. CaCl2.-AgA, ndl. fr. h. aq. 189-91 116 Methylisopropylacetic Ac., Me.CHPr.CO2H.-Cf. Div. B, Sect. 1. 191-3 79 n-Butyric Anhyd., (Pr.CO)2.O.-G. 0-978 at 15-5°.-For behavior on titration cf. p. 37. Identify by conversion into butyr-p-toluide (cf. p. 81) by methods indicated under anhydride of Iso-acid above I 195 100 Tetramethylenecarbonic Ac., C4H7.CO2H.-G. l-053830/4.-D. s. aq.; misc. ale.-Odor penetrating, unpleasant.-Oxid. by alk. KMnO4; Br2 does not add.-CaA2 + 5H2O, v. e. s.; AgA ppt 197 (th. i.) 116 [ + ]-Caproic Ac., Me.CHEt.CH2.CO2H.-G. 0-930 at 15°. 200-5 Ethyl Diacetoacetate, C6H7O4.Et.-G. 1 • 101 at 15°.-D. s. aq.-FeCl3 gives bright-red color to sol. !-' ' Expels acetic ac. fr. its salts."- CuA2 + 2H,O, sky-blue ppt. w. copper acetate. 202-4 114 Hexen(r)oic(6) Ac., C0H10O2.-Ba salt, 1ft., e. s. aq. or ale. 205-7c. 116 t n-Caproic Ac., Me.(CH2)4.CO2H.-G. 0-9449 at 0°.-M. p. -5-2°.- Unpleasant odor, like valerianic acid, but fainter.-V. d._s. aq.- CaA2 + H2O, 1ft. s. in 37 pt. aq. at 18-5°; AgA ppt.; ZnA2 + H2O cryst. ppt. formed when ac. is poured into ZnAc2 sol. 206-5 (th. i.) 114 Hexen(2)oic(6) Ac., C0H10O2.-Still liquid at -10°.-Ba salt alm. i. 207-8 130 Methyldiethylacetic Ac., Me.CEt2.CO2H.-Oil, alm. i. c. aq.; still liquid at -20°.-BaA2 + 5H2O, ndl. e. s. aq. 207-7c. 116 Isobutylacetic Aca Me2.CH.(CH2)2.CO2H.-G. 0-925 at 20°.-Odor un- pleasant.-CaA2 + 5H2O, s. aq. 209 130 Isoamylacetic Ac., Me2.CH.(CH2)3.CO2H.-G. 0-9122 at 19°.-CaA2, d. s. h. aq. 209-2c. 130 Ethylpropylacetic Ac., Me.(CH2)2.CHEt.CO2H.-CaA2, more s. in c. than in h. aq. 210 130 2-Methylhexanoic(i) Ac., C6Hn.CHMe.CO4H.-Alm. i. aq.-CaA2 + 6H2O, ndl., quickly efflorescing; c. saturated sol. becomes turbid on warming. 75 76 GENUS III, DIV. B, SECT. 2. (ORDER I, SUBORDER I.) Boiling-point (0°). Neut. Equiv. LIQUID ACIDS.-Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 211-2 114 2-Methylpenten(3)-oic(s) Ac., C6H10O2.-Oil of unpleasant odor. 213c. 114 2-Methylpenten(2)-oic(i) Ac.-Cf. m. p. 24-4°, Div. A, Sect. 2. 213-4c. 56 Citraconic Anhyd., C5H4O3.-G. 1-262 at 4°.-M. p. +7° (tends to remain liq.).-(Citraconic ac. is v. s. aq., m. p. 80°.) 214-15 114 Pentamethylenecarbonic Ac., C5H9.CO2H.-G. 1-0385 at 25°.-M. p. - 4° to -3°.-Odor like perspiration. 215 93 Valerianic Anhyd., (C5H9O)2.O.-(Prepared fr. fusel oil.)-G. 0.92927/.. -Cf. Test 307. 218 (th. i.) 130 Teracryhc Ac., C7HI2O2.-Unpleasant valerianic odor.-Adds Br2 easily. 219-5 144 Dipropylacetic Ac., Pr2.CH.CO2H.-G. 0-9215%.-D. s. aq.-CaA2 + 2H2O, s. aq. 221 130 Act. Amylacetic Ac., (Me)(Et).CH.(CH2)2.CO2H.-G. 0-9149 at 20°. 223 130 n-Heptylic (CEnanthylic) Ac., Me.(CH2)5.CO2H.-G. 0-9313 at 0°.-- "Faint tallow-like odor."-CaA2 + H2O, s. 110 pt. aq. at 8-5°.-■ PbA2, ppt. (1ft. fr. h. aq.); ZnA2 easily cryst. fr. h. abs. ale., giv- ing prisms (dried) w. m. p. 132°; AgA, ppt., ndl. fr. h. aq. 227c. 140 Diallylacetic Ac., (C3HS)2.CH.CO2H.-G. 0-9555 at 15°.-Unpleasant odor.-Alm. i. aq.-Gives Test 304.-CaA2 + 2H2O, less s. h. than c. 227 (th. i.) 128 Hepten(3)oic(i) Ac., Pr.CH: CH.CH2.CO2H. - Gives Test 304.- BaA2, 1ft. 230 107 Diethylacetic Anhyd., (Et2.CH.CO)2.O.-Cf. Test 307. 235 144 2-Methylhexamethylenecarbonic(i) Ac., C7H13.CO2H.-G. 1-0079 at 4°.-Odor unpleasant. 237-5c. 144 t n-Caprylic Ac., Me.(CH2)6.CO2H.-G. 0 • 91002%.-Lft., m. p. +16-5°. •-S. in 400 pt. aq. at 100°; alm. i. c. aq.-CaA2 + H2O, ndl. v. d. s. c. aq.; ZnA2, scales (m. p. 136°); AgA. curdy ppt. 238-40 Diethyl Acetylmalonate, Me.CO.CH(CO2Et)2.-Ale. sol. colored dark red by FeCl3!-Cf. Genus IV. 240-2 154 Cis-trans-Campholytic Ac., C9H14O2.-G. l-01715/4.-Unsat.-ZnA2, ppt. e. s. eth. 245-6 78 s-Diethylsuccinic Anhyd., [CO.(CHEt)?.CO].O.-G. 1-O8616'5/o.-W. aq. gives mixture of para and anti acids which are d. s. aq.; former melts at 192°, latter at 129°. 245-6 116 f Laevulinic Ac.-Cf. Div. A, Sec. 1, M. p. 33°. (If slightly impure usually remains liquid at ordinary temperature after fusion.) 245-8 144 Cycloheptanecarbonic Ac^, C7H13.CO2H.-Sharp-smelling oil, remain- ing liq. at -20°.-CaA2 (at 140°), silky ndl. fr. dil. ale. 353-4 (th. i.) 158 f Nonylic (Pelargonic) Ac., Me.(CH2)7.CO2H.-G. 0 • 9O6817'%.- Odor faintly rancid but not very unpleasant.-Leafy cryst., m. p. 12-5°.-BaA2, 1ft. v. d. s. c. aq.-AgA, ppt., v. d. s. h. aq. 257 [ + ]-Citronellic Ac., C10H18O2.-Opt. active.-Odor like capric ac.- Unsat. 264-5 150 n-Phenylpropionic (Hydratropic) Ac., Me.CHPh.CO2H.-Heavier than aq. and v. d. s.-BaA2 + 2H2O, ndl. s. aq.-AgA, scales, e. s. h. aq.-Amide, m. p. 92°. 265-5c. 168 a-Campholenic Ac., C]0H1GO2.-G. 1-0092 at 0°.-I. aq.; e. s. ale. or eth.-Yellow viscous oil w. turpentine odor! Gives Test 304. 266-9 Phenylacetylacetone, Ph.CH2.CO.CH2.CO.Me.-Cf. IV, B. 268-71 121 (Enanthylic Anhyd., (C7H,3O)2.O.-G. 0-932 at 21°.-Cf. Test 307. 272 178 Ethylbenzylacetic Ac., Et.CH.C7H7.CO2H.-BaA2, s. aq.; AgA curdy ppt. 275-80 184 Umbelulic Ac., CUH„O2.-M. p. 21°-23°.-Ag salt cryst. fr. h. aq.- Faint tallowy odor. (From California laurel.) 292 si. d. 176 2, 6-Dimethyloctanon(3)-oic(8)Ac., CWH1SO3.-Yellow oil, v. d. s. aq.; e. s. ale. or eth.-Br (in CHC13) gives oily substitution product.- Ba salt, e. s. ale. 300-10 228 Amylheptylacetic Ac., C5Hn.CH(C7H18).CO2H.-Still liq. at -10°. NUMBERED SPECIFIC AND SEMI-SPECIFIC TESTS FOR ACIDS. [TESTS 301-400.] 301. Neutralization Equivalent (Neut. Eq.). The neutralization equivalent of an acid is the number expressing in grams the quan- tity of the compound required for the neutralization of one liter of normal alkali. For monobasic acids it is identical with the number representing the molecular weight; for polybasic acids a simple submultiple of this number. In the tables the neutralization equivalent always follows the melting- or boiling-point of an acid in the next vertical column to the right. Its value in this genus ranges from 45 to above 400, and is a numerical constant of great analytical importance. The determination of neutralization equivalent should be made with a portion of the acid which has been dried to constant weight at 105°-110°, in order to remove hygro- scopic moisture or water of crystallization, - the equivalents in the tables having been calculated for the anhydrous acids whenever these are easily obtainable. The titration should be performed with a pure decinormal sodium hydroxide or baryta solution, using phenolphthalein as the indicator, and observing all the precautions noted in the observa- tions on Generic Test III (p. 35). If the supply of the substance permits, it will, how- ever, be better to weigh out 0.200 grm. of the acid instead of 0.100 grm., and also to double the quantities of phenolphthalein and water or alcohol prescribed. These changes in quantities will not affect the "sharpness limit" demanded in Test III, but will raise the minimum limit of decinormal alkali consumption set for all species of the genus from 2 cc. to 4 cc. To calculate a neutralization equivalent from the results of a titration, it is only neces- sary to substitute the experimental data into the following formula: 1000 X grams of acid taken " ' cc. of alkali consumed X normal strength of alkali If 0.200 grm. of benzoic acid, for example, neutralized 16.41 cc. of a 0.0999 baryta solution, the neutralization equivalent of benzoic acid would be 1000X0.200 16.41X0.0999 Titrations with decinormal acid and alkali are made with such frequency in organic analysis that it is almost imperative that every organic laboratory should have these solu- tions, each with its special burette, always ready for immediate use. One of the simplest and most satisfactory arrangements for this purpose is shown in Fig. 2. The bottles, even in small private laboratories, should have a capacity of not less than three liters, and the labels should be inscribed with the dates of standardization as well as the titres of the solutions. The bottle figured in the cut is fitted for use with caustic alkali, and its contents are protected from carbon dioxide by the small guard-tubes A and B, which are packed with granulated soda-lime. The arm C supporting the burette is a 77 78 NUMBERED SEMI-SPECIFIC TESTS FOR ACIDS. strip of wood two inches wide and an inch thick, through which three circular holes have been bored to admit the passage of the neck of the bottle, the tube D, and the burette. After boring the holes the strip is sawed longitudinally through the middle, and the two halves are then tightly clamped in position by the long screws whose heads are visible in the cut. Strips of rubber, leather, or canvas should be wrapped around the glass surfaces at the points of contact to ensure a firm hold on the bottle-neck and burette without risk of crushing them when the screws are tightened. The burette is filled by suction at E, or, if it is preferred, by the action of a pressure-bulb attached at F. 302. a-Hydroxy-acids. Dissolve 0.1 grm. of the acid in 100 cc. of cold water. Place 20 cc. of this solution in a test-tube of about 20 mm. diameter; add one drop of a ten-per- cent aqueous solution of crystallized ferric chloride, and mix quickly. Hold the tube over a sheet of white paper side by side with another of like size, containing 20 cc. of a cold aqueous tartaric-acid solution of exactly the same concentration as that of the unknown acid, and with which one drop of the same ferric-chloride solution has also just been mixed. Compare the "hues" and "tints" of the colors in the two tubes with each other, and with the color standard (cf. p. 232), observing the color from above. After a few seconds the color of the tartaric-acid solution will be a clear yellow (Y-YT1). If the hue of the solution of the unknown acid is nearly the same, while the intensity of its color equals or exceeds that of the standard, the substance is very likely to be an a-hydroxy-acid. If, on the other hand, the color is distinctly paler than the standard (i.e. lighter than YT1), or is a tint of yellow-orange or orange-yellow, the test has little significance. This test can be used only with cold solutions; for heat alone develops a yellowish coloration in ferric- chloride solutions of the concentration employed. Nearly all hydroxyl derivatives, when in sufficiently concentrated solution, will give a slight coloration with dilute neutral ferric chloride. The test is therefore valuable only when made comparatively. While it is not impossible that the hydroxyl group may produce identical color-effects in the case of some acids in which it does not occupy the alpha position with reference to carboxyl, in absence of any direct evidence that such acids exist, it may be assumed that the phenomena of this test are characteristic of the a-hydroxy-acids. Yellow colors approaching Tint 2 are likely to be given by almost any soluble acid. The colors given by the polybasic and keto-acids are much the most intense. Oxalic acid gives YT2-1- GYT2-1. Succinic and glutaric acids give slightly brownish colors, OYT1-2. Malonic acid gives no color. Pyruvic acid gives a Y-YO, and might almost be mistaken for an a-hydroxy-acid. Acetic acid and its homologues give a color that is YT2 or paler. 303. Acids Losing Carbon Dioxide at 2000. Place 0.1 grm. of the acid in a piece of glass tubing 8 cm. long and 5 mm. in internal diameter, sealed at one end. Connect the open end by a bit of rubber tubing with a narrow Fig. 2. NUMBERED SEMI-SPECIFIC TESTS FOR ACIDS. 79 gas delivery-tube that leads into a three-inch test-tube ("weighing-tube") containing clear baryta solution. Immerse the tube holding the acid for half its length in a bath of melted paraffin, or the sulphuric-acid mixture of page 219, contained in a small beaker. The bath must have been previously heated to 200° and be held constant at this temperature during the experiment. Continue the heating for two minutes.' Acids that lose one or more molecules of carbon dioxide below 200° will give a heavy precipitate of barium carbonate. This test is given by all acids having two or more carboxyl groups attached to the same carbon atom. Other acids, excepting only a few of unusual instability, do not give it. It is not given, for example, by oxalic, tartaric, citric, lactic, salicylic, tannic, or gallic acids, although none of these compounds are particularly stable substances. Whenever the reac- tion does take place with a polybasic acid, one product is an acid of lower basicity. Thus, malonic acid gives carbon dioxide and acetic acid: CH2.(CO2H)2 = CO2+CH3.CO2H. By repeating the experiment on a somewhat larger scale, and continuing the heating as long as carbonic acid is given off, the organic acid formed may generally be isolated and identified. 304. Unsaturated Acids. Dissolve 0.1 grm. of the acid in 3 cc. of sodium-carbonate solution (the ordinary laboratory reagent, about 1 : 10). Then add, drop by drop, a one-per-cent solution of potassium permanganate. If the purple color of more than 1 cc. of the permanganate is instantly destroyed, and a brown precipitate of oxides of manganese appears, the acid may be unsaturated. The essential phenomena in this test are very uniform, and easily observed. Several cubic centimeters of the permanganate are usually reduced, and the reaction is practically instantaneous. It is unsafe, however, to draw the conclusion that every acid which shows this behavior must be unsaturated. Formic acid, and most phenol acids like oxybenzoic acid and gallic acid, behave like the unsaturated compounds; but saturated acids are, as a rule, very slowly attacked, if at all. As a confirmatory test for unsaturation in acids, Test 901 is often very useful. But aS the addition of bromine at the multiple bonding, on which this reaction depends, takes place very slowly id the case of some of the double-bonded dibasic acids, the results (e.g. with fumaric acid) are occasionally a little difficult to interpret. Other cases in which unsaturated acids do^not add bromine easily are discussed by Bauer (Ber. 37, 3317), and Sudborough and Thomas (Soc. 97, 715). 305. Use of Esters with Characteristic Odors. The odors of many volatile esters are highly characteristic, though an adequate verbal description of their peculiarities can seldom be given. Ethyl cinnamate and ethyl ben- zoate may both be said to have an agreeable, sweet, aromatic odor; yet no one who is in the least familiar with these compounds would be in any danger of mistaking one for the other. The following procedure is occasionally referred to in the tables as a simple means for distinguishing between acids by differences in the odors of their esters. It is most satis- factory when it can be followed by a duplicate comparative experiment in which the organic acid used is known. The result requires confirmation by other more exact methods. To a few centigrams of the dry acid in a test-tube, add 0.5 cc. of a mixture of one part of concentrated sulphuric acid and two parts of methyl or ethyl alcohol. Heat the mixture several minutes at about 100°, keeping the tube loosely stoppered and the upper portion cool. Pour off into 3-5 cc. of cold water in a watch-glass. Warm gently and note the odor. An odor is much more easily observed in the open watch-glass than in a test-tube, and the dilution with water removes the sharp smell of sulphurous acid or alcohol that might otherwise mask the more delicate odor of the ester. 80 NUMBERED SPECIFIC TESTS FOR ACIDS. 306. Precipitation of Metallic Salts. The statement in the description of any acid, that its calcium salt is insoluble in water, does not justify the unqualified conclusion that it will appear as a precipitate when an aqueous solution of the acid is mixed with one of calcium chloride; for the salt will often be held in solution by the hydrochloric acid, which is the second product of the reaction. But a precipitate may usually be expected, whenever the neutral sodium salt of an organic acid is mixed with an equivalent quantity of any other neutral metallic salt which by a metathesis could yield a compound described in the tables as " insoluble." In attempting to prepare an insoluble salt of an acid for analytical purposes, it is therefore a good general rule to start from an exactly neutral solution of its sodium salt, rather than from the free acid itself. To obtain such a solution quickly, a small quantity of the acid may be dissolved or suspended in about twenty parts of water, a trace of phe- nolphthalein added, and caustic-soda solution then dropped in until the first appearance of a pink color; or, when the acid is difficult to obtain in quantity, the solution left over from the determination of neutralization equivalent in Test 301 may be used, after being somewhat concentrated by evaporation. When engaged in experiments of this kind, it is well to remember that some precipitates which, when once separated from solution, are very insoluble, do not appear immediately upon mixing the reagents; also, that some of the most characteristic salts of certain acids with the alkali earths, manganese, and zinc are more soluble in cold than in hot water, and hence do not begin to precipitate until the solutions containing them are heated or boiled. 307. Acid Anhydrides of Genus III. All these anhydrides are soluble in dilute aqueous alkali to salts of the corresponding acids, though in many cases solution proceeds slowly. A general method for the identifi- cation of such compounds is, therefore, to exactly neutralize and dissolve them, while sus- pended in water, by the addition of an equivalent quantity of caustic-soda solution; to decompose the soluble sodium salts with an exactly equivalent quantity of normal sulphuric or hydrochloric acid; and then, finally, to isolate and examine the liberated organic acid. A second important method is conversion into anilides or p-toluides. The anhydride is treated-heating above 100° for some minutes is occasionally necessary-with some- what more than an "equivalent" weight of aniline or p-toluidine. The reaction product is crushed; washed with a little cold dilute acid, to remove the excess of base; and then purified by crystallization from hot water, dilute alcohol, or ligroin. The anilides and toluides are distinguished for the ease with which they can be crystallized and purified. The melting-points for a very large number have been determined and will be given a .place in Vol. II of this work. 311. Acetic, Propionic, Butyric, and Isobutyric Acids. Whenever these acids have to be identified in an aqueous solution-and this is the problem which in actual practice will have to be solved more frequently than any other- the first step should always be to exactly neutralize with caustic soda, and then evaporate to dryness on a water-bath. The dry residue of sodium salt, from which it is not necessary that the water of crystallization should be removed, is then ready for use in the following tests. In very careful work, the result from the " Preliminary Test 1 " should be accepted as final only when it is negative. If, on the contrary, it points to the probable presence of one of these acids, Test 2, which is trustworthy and specific, should be applied. 1. [Preliminary Test.]-Place 0.05 grm. of the dry salt in a three-inch test-tube. Add 0.1 cc. of concentrated sulphuric acid, and warm over a very small flame until the odor NUMBERED SPECIFIC TESTS FOR ACIDS. 81 of the vapors of the liberated organic acid can be easily recognized at the mouth of the tube. After noting whether the odor is simply sharp like acetic or propionic acid, or sharp and rancid like the butyric acids, cool; add 0.1-0.2 cc. of strong ethyl alcohol, and warm until vapors again begin to come off freely. Then pour into a watch-glass containing 5 cc. of cold water and carefully observe the odor of the ester that has been formed. (Cf. Test 305.) This is sensibly different for the different acids; but the differences are not great and the odors may all be described as ethereal and fruity. That given by acetic acid, and closely resembled by the ester from propionic acid, is often spoken of as " refresh- ing and agreeable." The test is rather delicate, and, if made comparatively, may suggest which of the four acids is present. More than this should not be expected from it. 2. [Identification as Toluides.]-Mix in a dry six-inch test-tube 1.0-1.2 grms. of para- toluidine, and 0.3-0.4 cc. of concentrated hydrochloric acid. Add 0.4 grm. of the powdered sodium salt of the fatty acid. Rest the lower end of the test-tube in a circular hole 1 cm. in diameter cut, by a cork-borer, in a piece of thick asbestos-paper or thin asbestos felt, to screen the side walls from overheating; and support the tube in a vertical position by a clamp on a lamp-stand. Boil gently over a very small gas-flame for one hour. During the first fifteen minutes steam should be allowed to escape slowly. After about twenty minutes, the water having all been removed by evaporation, the vapors of the condensing toluidine should be seen wetting the glass in a ring showing a clearly outlined upper margin and extending half way up the tube. Regulate the heat so that this appearance will continue unchanged to the end of the hour. [The following treatment of the fused mixture is designed to separate the acid-toluide, the desired product of the reaction (RCO.NH.C7H7), from the excess of toluidine, and from a dark oily resinous substance, by which it is always accompanied. Resinous residues filtered off in the course of this treatment should never be thrown away until it is found that the yield of acid-toluide will be sufficient for the purpose of identification; for unless properly extracted, small quantities of the resin will hold back the greater part of the toluide. The sep- aration depends on the solubility of the toluides and the insolubility of the resin in boiling water, and on the volatility of toluidine with steam. If the directions given are carefully followed, the yield of pure acid-toluide will be entirely satisfactory, although never large.] Boil the cooled reaction product with 5 cc. of strong alcohol until nothing but white sodium chloride remains undissolved. Pour the solution, with stirring, into 50 cc. of hot water in a small beaker, and boil down quickly to 10-12 cc. Filter the boiling hot solution through a very small wet filter supported in a funnel that has been warmed by rapid rota- tion in a flame. Wash the filter with 2 cc. of boiling water. Unless the resin left on the filter forms only an exceedingly thin film, boil out filter and resin with 5 cc. of water, and filter hot into the first filtrate. Boil down the combined filtrates to a volume of about 10 cc. Cool well with running water; shake vigorously and filter. Dissolve the pre- cipitate in 5 cc. of boiling water; or, if it will not dissolve in this volume of water, increase the quantity by successive additions of 1 cc. until all does dissolve. Filter hot through a very small wet filter in a hot funnel 2.5 cm. in diameter. Wash with 2 cc. of hot water. Cool well in running water. Shake and filter. This precipitate should be white and free from resin. If yellowish, another crystallization from 5 cc. of boiling water followed by hot filtration will be necessary. Dry the precipitate at 100°, if the odor of the acid was not rancid,-otherwise at a lower temperature,-and determine its melting-point. Acetic Acid (properties tabulated on p. 73) gives acet-p-toluide, melting-point 146°-7° (uncor.). The corrected melting-point of the pure compound is 148.2°. Propionic Acid (properties tabulated on p. 73) gives propion-p-toluide, melting- point 123.5°-124.5° (uncor.). Isobutyric Acid (properties tabulated on p. 73) gives isobutyr-p-toluide, melting- point 104°-5° (uncor.). 82 NUMBERED SPECIFIC TESTS FOR ACIDS. n-Butyric Acid (properties tabulated on p. 73) gives butyr-p-toluide, melting-point 72.5°-73.5° (uncor.). By diminishing the quantities of reagents and solvents used, heating for two hours instead of one, and working very carefully, Test 2 may be carried out with one quarter of the weight of sodium salt recommended; but the yield is then so small that failures will sometimes occur. The quantity of hydrochloric acid used in a test ought never to exceed greatly the quantity theoretically required to combine with the sodium of the organic salt, toluidine hydrochloride reacting upon the toluides at high temperatures. Hence, if the quantity of salt taken for any experiment is less than has been directed, the hydrochloric acid must be diminished proportionally. A moderate excess of para-toluidine will, however, do no harm, and the quantity should under no circumstances be reduced to less than 0.5 grm. Test 2 may be used for the identification of acids containing slight admixtures of homo- logues. In the case of acetic acid it is still applicable when the impurity is quite con- siderable, if the first crop of impure acet-toluide crystals is recrystallized from hot ben- zene. The benzene gives at the same time a good separation both from the resin and from homologues. The other toluides are too soluble in benzene to be crystallized from it with advantage, but they may be recrystallized from a few cubic centimeters of hot petroelum ether, in which the resin will remain dissolved on cooling. Whenever it is desired to separate the acids under consideration from a dilute aqueous solution containing salts, neutral compounds of any description, or non-volatile acids, proceed as follows: Distil over into a dish containing 3 cc. of normal caustic-soda solution, or 0.12 to 0.14 grm. of solid caustic soda dissolved in a little water, the solution being colored by the addition of a little phenolphthalein. As soon as enough acid has distilled over to discharge the pink color, evaporate to dryness, scrape together the residue of dry sodium salt, and use the whole of it for Test 2. 312. Benzoic Acid. (Properties tabulated on p. 60.) 1. To 0.1 grm. of the acid in a dry test-tube add 0.17-0.20 grm. of phosphorus pen- tachloride, and warm, stirring with a glass rod until a clear solution is obtained. Cool, and add, drop by drop, cooling, 1 cc. of cold water to destroy the excess of chlorides of phosphorus. Then add slowly 0.4-0.5 cc. of aniline. Dissolve the reaction product in 2 to 5 cc. boiling dilute alcohol (1:1). Cool. Filter off the white crystalline precipitate; dry at 100°, and determine the melting-point. The benzanilide obtained from benzoic acid in this test is in the form of pearly-white scales melting at 159.5°-160.5° (uncor.). 2. Heat in a six-inch test-tube for one-half hour 0.1 grm. of the acid, 0.5-0.7 grm. of para-toluidine, and two or three drops of concentrated hydrochloric acid. The tube must be supported by a clamp, and its bottom made to rest in a circular hole 1 cm. in diameter, cut by a cork-borer in a piece of thick asbestos-paper which has been laid upon the small iron ring of a lamp-stand. Heat with a very small flame whose height is so regu- lated that the vapor of the boiling toluidine shall condense upon the walls of the tube for a distance of two to three inches from the lower end. Dissolve the reaction product in 10 cc. of dilute alcohol (1 : 1). Filter hot. Cool and filter. Wash the crystalline precipi- tate with 5 cc. of cold water. Repeat the crystallization with the same quantity of solvent, and wash as before with 5 cc. of water. Dry at 100°-105° and determine the melting-point. p-Benztoluide, the product in this test, crystallizes in white or slightly yellowish plates melting at 155.5°-156.5° (uncor.). 313. Cinnamic Acid. (Properties tabulated on p. 61.) 1. Stir 0.05 grm. of the acid into 3 cc. of a cold ten-per-cent solution of potassium NUMBERED SPECIFIC TESTS FOR ACIDS. 83 permanganate on a watch-glass or in a small round-bottomed glass dish. A strong odor of bitter almonds (benzaldehyde) will immediately develop. 2. Stir 0.1 grm. of the powdered acid into 3 cc. of fuming nitric acid (sp. gr. 1.48- 1.60), contained in a small round-bottomed dish. The substance will at first dissolve, but within two or three minutes a considerable light-colored precipitate will separate. Allow to stand for 7-10 minutes. Then mix with 30 cc. of .cold water and stir for a minute. Filter off the bulky precipitate of nitro acids and wash with 10 cc. of cold water. Transfer the precipitate to a test-tube and boil with 5 cc. of strong alcohol. Cool well. Shake, and allow to stand a few minutes to insure complete precipitation. Filter, and wash with 5 cc. of cold alcohol. Boil up the precipitate in a test-tube with 5 cc. of ether. Cool. Shake and filter. Wash the rather scanty precipitate with 5 cc. of cold ether. Dry at 100°, and make a melting-point determination. The final product in this test is para-nitrocinnamic acid. It is more or less distinctly crystalline, nearly white, and melts to a dark-brown liquid at 286°-287° (uncor.), after turning brown and beginning to soften at about 265°-270°. [Ortho-nitrocinnamic acid, and possibly a little nitrobenzoic acid, are also formed during the nitration, but they are completely removed by the treatment with alcohol and ether.] 314. Color Reactions for Citric, Malic, and Tartaric Acids. To 0.05 grm. of the finely powdered acid in a small porcelain evaporating-dish add 10-15 drops of a freshly prepared solution of 0.1 grm. 2-naphthol in 5 cc. of pure concen- trated sulphuric acid. Place the dish on a boiling water-bath and remove it at intervals of thirty seconds to one minute for the observation of the color changes which follow one another in quite rapid succession. When the maximum color intensity has been reached, dilute cautiously with four to five volumes of water and again note all the changes that occur. Citric Acid (cf. p. 47) gives at first a pale greenish blue, soon turning to blue-green (BG), and finally, rather slowly on continued heating, to an impure green of very slight intensity and permanence. The color after dilution with water is similar in quality to that from tartaric acid, only very much paler. Tartaric Acid (cf. p. 48), after exhibiting a momentary pale blue-green color changes very rapidly to pure intense green (G), which is rather persistent, even when heated on the water-bath. The dilution with water causes a change to a very distinct orange-yellow (YO-OY). Malic Acid (cf. p. 43) at first gives a momentary greenish yellow (GY-Y) that changes rapidly to an intense yellow (Y) which is quite permanent. Dilution gives a yellow- orange (YO), which is distinctly more intense than the corresponding color from the two other acids. These tests were first described by Pinerua (Compt. rend. 124, 291). While not con- clusive unless supported by other specific tests, they are useful reactions. They are most satisfactory when used as "comparative tests." 315. Formic Acid. (Properties tabulated on p. 73.) Formic acid has a very sharp penetrating odor much like that of acetic acid, but more irritating. Like other acids of its series, aqueous solutions of its neutral sodium salt show reddish or orange colorations with ferric chloride. Unlike its homologues it reduces alkaline permanganate in the cold in Test 304. 1. To 5 cc. of a 1-3 per cent aqueous solution of the acid, add one gram, or an excess, of powdered mercuric oxide. Warm to a temperature of 40°-50°. Close the mouth of the tube with the thumb and shake vigorously for about one minute. Filter off the 84 NUMBERED SPECIFIC TESTS FOR ACIDS. undissolved oxide, and boil the clear filtrate for at least half a minute. A dark gray pre- cipitate of finely divided mercury will appear suddenly within a few seconds after boiling begins. HgO + CH2O2=Hg + CO2+H2O. 2. Place at least two drops of strong acid, or 0.1 grm. of the dry sodium salt in a small "weighing-tube" (a narrow three-inch test-tube). Add five drops of concentrated sul- phuric acid and heat over a very small flame until a brisk effervescence begins. Ignite the escaping gas. [H2CO2 = H2O + CO.] The carbon monoxide will burn at the mouth of the tube with a pale-blue flame for some seconds, if the heating is continued. 316. Glutaric Acid. (Properties tabulated on p. 42.) In a dry test-tube fitted with a cork stopper and a 25 cm. length of glass tubing, to act as a return condenser, heat 0.1 grm. of the acid with 0.4-0.6 cc. of aniline at 175°- 190° for one hour. Boil with 10 cc. dilute alcohol (1 : 1). Cool and filter. Wash with 2 cc. cold dilute alcohol (1:1). Crystallize from 5 cc. boiling strong alcohol. Cool, shaking if no precipitate appears at once. Filter. Wash with 1 cc. cold strong alcohol. Recrystallize from 4 cc. boiling strong alcohol. Filter. Wash with 1 cc. cold alcohol. Dry at 100°, and determine the melting-point. The product, glutar anilide, crystallizes in white needles and melts at 221°-222°. It begins to sublime slightly at 214°-218°. 317. Oxalic Acid. (Properties tabulated on p. 42.) 1. Dissolve a few centigrams of the acid in water. Add ammonia in excess, and then a few drops of calcium-chloride solution. A white pulverulent precipitate of calcium oxalate will at once make its appearance. The precipitate is insoluble in ammonia or acetic acid, but dissolves readily in dilute hydrochloric acid. 2. In a dry three-inch test-tube (small "weighing-tube") place 0.1 grm. of the acid and five drops of concentrated sulphuric acid. Heat over a very small flame so as to obtain a brisk effervescence. Ignite the gas that issues from the tube-(a mixture of carbon monoxide and dioxide). The carbon monoxide will burn with a pale-blue flame for several seconds, if the application of heat is continued. 3. Heat in a six-inch test-tube for fifteen minutes 0.1 grm. of the acid and 0.5-0.7 grm. of para-toluidine. The bottom of the test-tube should be made to rest in a circular hole 1 cm. in diameter cut by a cork-borer through a piece of heavy asbestos-paper. The tube should be supported in an upright position by a clamp, and the asbestos-screen rested upon the small iron ring of a lamp-stand. Heat with a very small flame protected from drafts, and so regulated that the toluidine vapors shall be seen to condense and flow back along the walls of the lower third or half of the tube. Boil out the reaction product with 10 cc. of dilute alcohol (1 : 1). Cool and filter. Wash the residue of oxaltoluide on the filter with 5 cc. of cold water. Transfer to a test-tube and boil up with 10 cc. of strong alcohol. Cool and filter. Wash with 2 cc. of strong alcohol. Dry at 100°-110°, and determine the melting-point. Oxal-para-toluide crystallizes in white plates melting at 266.5°-267.5° (uncor.). 318. The Phthalic Acids. The different behavior of these isomers towards heat is an important distinguishing characteristic. Phthalic acid melts with loss of water at 184°, giving a sublimate of thin flat needles of its anhydride. Isophthalic acid also melts and then sublimes; but this occurs above 300°, and the sublimate is the unchanged acid. Terephthalic acid sublimes unchanged above 300°, but without previously melting. Phthalic Acid. (Properties tabulated on p. 67.) 1. Mix 0.05 grm. of the powdered acid with an equal quantity of resorcin. Place in a drv test-tube and moisten with one drop of concentrated sulphuric acid. Stand the NUMBERED SPECIFIC TESTS FOR ACIDS. 85 test-tube in a small beaker containing a liquid bath (cf. p. 152), that is, at a temperature of 160°, and heat for three minutes. Cool. Treat the fused mass with 2 cc. dilute sodium- hydroxide solution. Pour off into 500 cc. of cold water. The water will show a very intense yellow-green fluorescence due to' fluorescein (cf. Test 402). The isomers of phthalic acid do not give this reaction, though similar colorations are given by some other dibasic acids, like succinic and glutaric. The test is extremely delicate. 2. Heat in a six-inch test-tube for fifteen minutes 0.1 grm. of the acid and 0.4-0.6 cc. of aniline. The tube must be supported by a clamp, and its lower end rest in a circular hole 1 cm. in diameter cut by a cork-borer through a square piece of thick asbestos-paper that is supported on the iron ring of a lamp-stand. Heat with a very small flame whose height is so regulated that the boiling aniline vapor shall be seen to condense upon the walls of the tube for a distance of two or three inches from its bottom. Boil the reaction product with 10 cc. dilute alcohol (1 : 1). Cool and filter. Wash the precipitate with 5 cc. of cold water. Recrystallize from 10 cc. of boiling strong alcohol. Cool and filter. Dry at 100°, and determine the melting-point. o-Phthalanil, the product in this test, crystallizes in white plates which melt at 204°-205°. Isophthalic Acid. (Properties tabulated on p. 72.) Mix in a dry test-tube 0.1 grm. of the acid and 0.3 grm. of phosphorus pentachloride. Heat cautiously over a very small flame until the mixture fuses to a clear liquid. Cool. Dissolve in 2 cc. of pure methyl alcohol. Precipitate out the dimethyl isophthalate formed, by adding 5 cc. of cold water, cool- ing and shaking. Filter. Wash the flocculent crystalline precipitate with 2 cc. of cold water. Recrystallize from 4 cc. of boiling dilute methyl alcohol (1 : 1). Cool well. Shake. Filter, and wash with 2 cc. of cold water. Press the precipitate between dry filter-paper. Dry at a temperature not exceeding 50°, and determine the melting-point. Dimethyl isophthalate melts at 64° (uncor.). It is very much more soluble in dilute methyl alcohol than the corresponding terephthalate. Terephthalic Acid. (Properties tabulated on p. 72.) Follow the direction given in the test for isophthalic acid, as far as the close of the first paragraph. Then precipitate the dimethyl ester from the methyl-alcohol solution by the addition of 10 cc. of cold water. Filter, and wash the precipitate with 5 cc. of water. Recrystallize from a boiling mixture of 4 cc. strong methyl alcohol and 1 cc. of water. Filter off the heavy precipitate of thin, white, lustrous crystals that separates when the solution cools, and wash with 3 cc. of dilute methyl alcohol (1 : 1).-[Dimethyl terephthalate melts at 140°. This test might be successfully conducted, if it were necessary, with much smaller quantities of acid and reagents than are here recommended.] 319. Salicylic Acid. (Properties tabulated on p. 64.) (1) Prepare the methyl ester from methyl alcohol and 0.05 grm. of the acid or one of its salts by the method of Test 305. Methyl salicylate has the agreeable odor of oil of wintergreen. There are a few rare phenol-acids that are said to have a somewhat similar odor; but it is one that is not given by the isomers of salicylic acid, or by any acid of commercial importance. (2) Dissolve 0.1 grm. of the acid in 5 cc. of boiling water. Add 1 cc. of nitric acid (sp. gr. 1.2) and boil gently for five minutes. Pour into 20 cc. of cold water. Filter off the precipitate. Wash with 2 cc. of cold water. Recrystallize twice-the first time from 5 cc. of boiling water; the second time from 3 cc. Dry, and determine the melting-point. 5-Nitrosalicylic acid, the product in this test, crystallizes in white needles which begin to sinter together at 220°-222°, and then melt sharply to a brown liquid at 226°- 227° (uncor.). 86 NUMBERED SPECIFIC TESTS FOR ACIDS. [The purple coloration (RV-VR), which will be observed in a 1 : 10000 aqueous solu- tion of the acid while applying Generic Test IV with ferric chloride, is a simple and favorite reaction. It is said to be sufficiently delicate to show the presence of the acid in solutions containing only one part in 500,000 parts of water. It is also given by neutral solutions of salicylates of the alkalies, but is prevented by the presence of free acids, alkalies, or salts of strongly alkaline reaction, like the alkaline carbonates or borax. The isomers of salicylic acid do not give it. Calcium and barium chlorides do not give a precipitate in neutral solutions of sodium salicylate, even after dilution w'ith an equal volume of alcohol, or after adding ammonia and warming. Sharply ignited above its melting-point, salicylic acid emits a faint odor of phenol.] 320. Succinic Acid. (Properties tabulated on p. 49.) Place in a dry test-tube 0.1 grm. of the acid and 0.5 grm. of para-toluidine. Immerse the lower part of the tube in a small beaker containing one of the liquid baths mentioned on page 152. Insert a cork stopper fitted with a 25 cm. length of glass tubing to serve as a return cooler, and heat for one half hour at 200°-220°. After the tube has been removed from the bath and allowed to partially cool, add 10 cc. of dilute alcohol (1 : 1), and boil. Cool well and filter off the crystalline precipitate of succintoluide. Wash with 2 cc. cold dilute alcohol (1 : 1). Crystallize from 5 cc. of boiling strong alcohol. Filter. Wash the crystals with 1 cc. cold strong alcohol. Dry at 100°, and take the melting-point. The succintoluide thus obtained forms white needles melting at 254.5°-255.5° (uncor.). CHAPTER VL GENUS IV. PHENOLIC COMPOUNDS OF SUBORDER I, ORDER I. (Colorless Compounds of Carbon, Hydrogen, and Oxygen.) To this genus belong all the true phenols of the suborder not included in the fore- going genera, and many non-aromatic " enols." GENERIC TEST IV. APPLY PROCEDURE 1 OF THIS TEST FIRST TO EVERY COMPOUND, SOLID OR LIQUID. APPLY PROCEDURE 2 TO EVERY SOLID COMPOUND THAT FAILS TO GIVE A COLORATION IN PROCEDURE 1; BUT NOT TO LIQUIDS. COMPOUNDS THAT SHOW A PHENOLIC BEHAVIOR IN THE FIRST PART OF THE TEST ARE CLASSI- FIED AS PHENOLS IRRESPECTIVE OF THEIR BEHAVIOR IN PROCEDURE 2. PROCEDURE 1. (The Test with Ferric Chloride.) Dissolve about 0.05 grm. of the substance in 1 cc. of cold water; or, if this should be found impossible prepare a hot saturated aqueous solution; cool; filter, and use 1 cc. of the cold saturated filtrate. To this solution, in a narrow three- inch test-tube (small weighing-tube), held in front of a sheet of white paper, add three drops of the ferric-chloride reagent described below,* pausing for a few seconds after the addition of each drop to note whether any color change occurs. If no coloration is noticed, repeat the test in the same way as before, except that alcohol is substituted for water as the solvent. If any coloration, transient or permanent, other than a tone of yellow or orange-yellow (Y or OY), is observed, the substance is probably a phenol or an enol. PROCEDURE 2. (The Test with Alkali.) a. Place 0.10 grm. of the finely powdered substance in a narrow three-inch test- tube with 1 cc. of cold water, and ascertain by shaking and stirring whether it will dissolve. If it dissolves completely in the cold, and gave no color with ferric chloride in Procedure 1, it is not a phenol. * The Ferric-chloride Reagent.-Prepare the reagent as required for use by diluting three drops of the 10 per cent stock solution of ferric chloride with 1 cc. of water. 87 88 PHENOLIC COMPOUNDS. b. If the substance did not dissolve appreciably in experiment a, add 1 cc. of a cold aqueous sodium-hydroxide solution (1 :10) to the mixture. Shake or stir well for about one minute, and notice whether solution is effected, and whether any strong coloration is produced. If the compound now dissolves completely, or if it dissolves completely after diluting the alkaline mixture with an additional cubic centimeter of cold water, the compound should be sought among the phenols. The appearance of any pronounced coloration in the alkaline solution, also shows the compound to be a phenol, though most of the phenols give colorless solutions in alkali. If a considerable part of the substance, though not all, dissolves in experi- ment a, add a little more of it to the solution, so that an undissolved residue of about 0.10 grm. shall remain. Treat this mixture with sodium hydroxide just as directed in the last paragraph, except that the subsequent dilution with water should be omitted in this case, unless a change in the appearance of the powder should indicate strongly that the formation of a sodium salt insoluble in concentrated alkali has taken place. The phenomena observed are to be interpreted as in the last paragraph. Observations on Generic Test IV. In "the test with ferric chloride" yellow and orange-yellow colorations have to be disregarded, because tones of these hues are produced by many polyatomic alcohols belonging to subsequent genera. A strong yellow also appears whenever alcohol is substituted for water as the solvent. Fortunately the colorations given by phenols, although varying widely in hue, intensity, and permanence, are not very often yellow, or either of the two adjacent hues in the color standard. The colorations characteristic of some phenols appear in extremely dilute solutions; others only in concentrated solutions. Some remain unchanged in quality for many hours; others appear and disappear within a second. A trifling excess of the reagent is sometimes sufficient to destroy the color; in other cases it is beneficial or necessary. It is for this reason, that it is desirable to observe the color after the addition of each drop of the chloride. The ferric-chloride test is applicable to cold solutions only. For further information concerning this reaction see numbered Tests 302 and 401. In "the test with alkali " several distinct principles are involved. The first and most important of these is, that, with the exception of some polyatomic phenols like resorcin and pyrogallol, the species of this genus as a class are not ' ' easily soluble" in cold water, although they do dissolve readily in cold sodium-hydroxide solutions of certain concentrations. For the larger number of species a " normal" concentration of the alkali has been found to be the best. But since the sodium salts of some phenols (e.g. sodium-methyl salicylate) are much less soluble in strong caustic soda than in water, they occasionally appear as precipitates even when the alkali used is only normal. It is to provide for this contingency that it is directed to dilute with about one volume of water whenever a precipitate (an insoluble sodium phenolate) is found to form. The use of a weaker alkali at the start is not advisable, because the salts of many phenols are so completely hydrolyzed in solution, unless a considerable excess of alkali is present, that their solubility in decinormal soda may appear to be no greater than in pure water. Finally, it should be men- PHENOLIC COMPOUNDS. 89 tioned that a few compounds having phenolic structure will not dissolve unless the alkali is much stronger than normal. But their number is so small that it has been considered better to treat them as exceptions than to complicate the test for the sake of assuring them a position with the other phenols. The production of a colored solution in the test with alkali is not a general reaction of the phenols, but whenever a coloration does appear at this point, or in the titration in Test III, in the examination of an unknown substance, it is a very significant phenomenon, and is alone sufficient to indicate that the body should be sought among the phenols. The colors are sometimes very brilliant, as with the phthaleins, but often yellow, and sometimes dark brown, appearing gradually on stirring. Brown colorations are characteristic of phenols like pyrogallol, whose alkaline solutions are rapidly oxidized by the absorption of atmospheric oxygen. It is necessary to restrict "the test with alkali" to solid phenols, because it has been found that a considerable number of liquid species in Genus V and VI (e.g. diethyl succinate), which react neutral in Test III with very dilute alkali, are saponified by short shaking with a 1 :20 aqueous soda solution. Since the liquid phenols, so far as is certainly known, all give colorations with ferric chloride, this limitation placed on the application of the alkali test is accompanied by no serious disadvantages. General Physical and Chemical Characteristics of the Phenols and Enols. Many of the phenols, like ordinary phenol, eugenol, and methyl salicylate, possess intense and characteristic odors and tastes; but many solid species are odorless and taste- less. All except a few of the simpler phenols, such as ordinary phenol, resorcin, and pyrogallol, are nearly insoluble in cold water, though soluble in solutions of the caustic alkalies. All the water-soluble species either give colorations in the test with ferric chlo- ride, or else solutions in dilute sodium hydroxide that rapidly turn brown through oxida- tion upon exposure to the air. In alkaline solution many phenols reduce potassium per- manganate in the cold in Test 304, and a smaller number, including many of the polyatomic phenols, reduce metallic silver, from Tollen's reagent in Test 101. The phenols are as a rule readily soluble in cold concentrated sulphuric acid, being very easily sulphonated, and are not reprecipitated upon dilution with water. In Test VIII they evolve hydrogen when treated with sodium, and are sometimes acetylated in the treatment with acetic anhydride. The color reactions of the phenols are numerous. Those depending upon fusion with phthalic anhydride (cf. Test 402), treatment with sulphuric acid containing oxides of nitrogen, or with aromatic diazonium salts, all have analytical application. Colorations obtained with ferric chloride, as in Test IV, have been described for about half the solid species mentioned in this volume, and for nearly every liquid species. These color- ations are ascribed to the formation of unstable iron salts. Some phenols, like a-naphthol, whose dilute aqueous solutions are little or not at all colored by ferric chloride, are oxidized by it, and then separate from the solutions as precipitates of insoluble condensation prod- ucts (like dinaphthol). A portion of the aromatic hydrogen in phenols is very easily substituted by halogens or by nitro groups, poly-halogen, or poly-nitro derivatives being formed. Even very dilute aqueous phenol solutions consequently give precipitates upon treatment with an excess of bromine water (cf. Test 414-3). Test 901 may also be applied when evidence as to ease of substitution by bromine is desired. The nitro derivatives are readily prepared on the small scale, and are very often useful in completing identifications (cf. Tests 414-(2), 415, 418-(2), and 419). A few phenols, like guiacol (cf. p. 91), give characteristic crystalline derivatives with picric acid. 90 PHENOLIC COMPOUNDS. One of the most important reactions of the enols is their behavior upon saponifica- tion. The saponification may be conducted, and the saponification products identified, by the method of Part 2 of Test V, as described on pp. 113 et seq. The following are examples of such reactions: CHs.CO.CH2.CO.CH.„ (or, CH3.C(OH): CH.CH3)+KOH = CH3.CO.CH3 + CH3.CO2K. (Acetyl acetone) (Acetone) (Potassium acetate) CH3.CO.CH,.CO,Et, (or, CH3.C(OH): CH.CO3Et) + 2KOH = K2CO3 + CH3.CO.CH3+EtOH. (Acetoacetic ether) (Acetone) (Alcohol) The names usually applied to the enols in the tables of this volume, and in the illus- trations here given, are those properly belonging to the ketones with the corresponding desmotropic formulae. This keto nomenclature, while open to criticism, is used, because, besides being probably the one in more general use at the time of writing, it also more quickly suggests the names of the saponification products that are to be expected. The enols, like the phenols, are soluble in cold dilute alkalies, give colorations with ferric chloride, and are attacked by sodium or bromine. When shaken with a saturated solution of copper acetate in water or dilute alcohol, some enols give precipitates of stable and characteristic blue or green copper salts. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I]. GENUS IV, PHENOLIC COMPOUNDS. DIVISION A-SOLID PHENOLIC COMPOUNDS. Melting-point (C.D- Boiling-point (C.D- PHENOLIC COMPOUNDS.-Colorless and Solid. 26 211-5c. t i, 3-Xylenol(4), Me2.C(iH3.OH.- V. d. s. aq.; miscible w. ale. or eth.-In Test 401 w. FeCl3, the 1% ale. sol. gives a GB color, very quickly fading through G to YT2, while the aq. sol. (1:100) gives a BV color, which fades in 2 min. to a white turbidity. 26 228 m-Propylphenol, Pr.C6H4.OH.-V. d. s. aq.-Aq. sol. pale blue w. FeCls; ale. sol. green. 30 190-8 t o-Cresol, Me.C0H4.OH.-1% aq. sol. w. FeCl3 in Test 401 gives a VB color on mixing, changing to Y in 5 min. and later to a turbid brown -The picrate, prepared by mixing a sol. of the cresol in a little 50% ale. with a concentrated solution of picric acid in 50% ale., forms orange-yellow ndl. w. m. p. 88° (m- and p-cresols give no picrates).- Unlike phenol, not dissolved by 5 pt. cone. NH40H! 31-2 205 j- Guiacol, o-MeO.CcH4.OH.-S. in 60 vols. aq. at 15°.-The 1% aq. sol. gives w. FeCl3 in Test 401 a ROR color which slowly fades, the sol. becoming turbid. The 1% ale. sol. gives a GB w. FeCl3, which very rapidly fades to a YT2.- The alkaline sol. fr. the fusion w. phthalic anhydride in Test 402 has a VB-BV color, and an absorption spectrum not easily distinguishable from that of thymol (IV, A, m. p 49-6°).-f To a mixture of 0-1 grm. guiacol and 1 cc. aq., add a hot sol. of 0-2 grm. picric acid in 5 cc. aq.; shake well and allow to cool slowly. A brilliant O-YO cryst. ppt. of the picrate compound, w. m. p. 86°, appears within a minute or two! 35 Diacetylbenzoyl Methane, Ph.CO.CH.(COMe)2.-E. s. ale.; s. w. yellow color in Na2CO3.-Ale. sol. blood-red w. FeCl3.- Cu salt dark blue tbl. w. m. p. 224°-5°, s. CHC13.-Saponi- fication by Test V-2 gives acetophenone and acetic ac. (Tests 712 and 311). 36 201-8 f p-Cresol, Me.C6H4.OH.-Is not dissolved by 5 pt. cone. NH4OH.-Aq. sol. (1:100) in Test 401a gives BVT1-BT1-2 on mixing; the sol. then finally becomes turbid. 40-1 250 (560 mm.) o-Oxybenzophenone, Ph.CO.C()H4.OH.-M. p. oxime 133°-4°. 42-5 172-3 (12 mm.) f Phenyl Salicylate (Salol), o-HO.CGH4.CO,Ph.-Odor faintly aromatic.-Alm. i. h. aq. (dif. fr. phenol); e. s. ale. or eth.- Dil. ale. sol. colored violet-red w. FeCl3.-Saponification by Test V-2 gives salicylic acid and phenol (Tests 319 and 414). 42-5-3 183 f Phenol, CcH5.0H.-S. in 15 pt. aq. at 16°; alm. i. Na2CO3; miscible w. ale. or eth. Is dissolved by less than 5 pt. cone, ammonia (dif. fr. cresols).-An aq. sol. (1:100) w. FeCl3 (Test 401) gives a violet color (V), permanent for more than 15 min.-Identify by Test 414 ! 43 Ethyl Benzoylpyruvate, Ph.CO.CH,.CO.CO2Et.-Dec. on dist.- Pr. fr. Igr., e. s. ale.-Ale. sol. blood-red w. FeCl3.-Saponifi- cation by Test V-2 gives acetophenone (Test 712), sodium oxalate, and ethyl alcohol. 91 92 GENUS IV, DIV. A. (ORDER I, SUBORDER I.) Melting-point (C.°). Boiling-point (C.°). PHENOLIC COMPOUNDS.-Colorless and Solid. 46 218-5 p-Ethylphenol, Et.CBH4.OH -V. s. ale. or eth.-Aq. sol. gray- blue w. FeCl3.-Warmed w. P2OS gives phenol and ethylene. 47 239d. Isohomopyrocatechin, Me.CBH3.(OH)2(i, 2, 3). - E. s. aq., ale., or eth.-Aq. sol. gives a transient green w. FeCl3. 49 211-2 1, 3-Xylenol(2), Me2.CBH3.OH.-S. h. aq.-Tribrom-derivative, m. p. 175°. 49 Diacetylacetone, CO.(CH2.COMe)2.-Decomposes spontaneously. -Lustrous 1ft. e. s. eth. or h. ale.; sol. in alkalies w. yellow color! Gives dark-red color w. FeCl3.-Gives a leaf-green Cu salt and light-yellow Ba salt i. aq.--With NH3 gives lutidone. 49-6 231-8 f Thymol, Me.CBH3.(Me2CH)(OH)(r, 4, 3).- Strong odor of thyme!-S. at 15° in 1200 pt. aq., or in 900 pt. at 100°.- Gives no color w. FeCl3 except in cone. ale. sol. (1:2), when a trace of the very dil. reagent gives a transient green color (G). (Dif. fr. guiacol.)-Test 402 w. phthalic anhyd. is very striking though similar to that given by guiacol. The fused mass, which has a very intense VR-R color, dissolves to an intense blue (B) in dilute NaOH. This sol. shows an absorption band, when viewed through the spectroscope, extending fr. E to the orange. It narrows on cautious dilution until it finally appears as a thick line almost exactly at D!-Identify by Test 419! 50 Paonol, Me.CO.CBH3OH.OMe.-Ndl. e s. ale. or eth.; vol. w. st.-Ale. sol. colored dark red-violet by FeCl3.-Oxime, ndl., e. s. ale.; d. s. aq. 51 251-2 Homopyrocatechin, Me.C6H3.(OH)2(i, 3, 4).-V. s. aq. ale. or eth.-W. FeCl3 gives green color, which changes to red- violet w. Na2CO3.-Reduces AgNO3 or Fehling's sol. 51-2 253 Pyrogalloldimethylether, HO.CBH3.(OMe)2.-FeCl3 gives ebru- lignon (s. in cone. H2SO4 w. intense corn-flower color).- Cone. HC1 at 100° gives pyrogallol. 53 243 Hydroquinone Methyl Ether, p-HO.CBHrOMe.-Not vol. w. st.-E. s. c. bz.-Reduces h. ammon. Ag. sol. 57 239 Iridol, Me.C0H,.(OMe)2(OH)(3, 4, 5, 1).-E. s. ale., eth., or bz. 59-60 330-40d. Dioxybenzophenone, (CBH4OH)2.CO.--Pale-yellow pr. fr. Igr.; alm. i. aq.; v. s. ale. or eth.; s. in K2CO3 sol., but ppt'd by CO2.-Dil. ale. sol. colored brown-red by FeCl3.-Warming w. cone. H2SO4 or boiling w. KOH sol. gives carbonyldi- phenyleneoxide, i. aq., m. p. 173°-4°. 60 1,2 (a/?)-Hydronaphthoquinone, C10H6.(OH)2. - Silvery 1ft., s. in NaOH w. yellow color, which changes to an intense green.-Diacetate melts at 105°. 60-1 260-2 Benzoylacetone, Ph.CO.CH2.COMe.-D. s. c. aq.; v. s. ale. or eth.; e. s. NaOH; d. s. Na,CO3; i. NaHCO3.-Intense red color w. FeCl3!-Saponification by Test V-2 gives acetophenone (Test 712).-Cu salt, pale-green ppt. by CuAc2 fr. dil. ale. sol.! Ag salt i. ppt. 61 229c p-Isopropylphenol, Me2.CH.C6H4.OH.-Aq. sol. becomes pale blue w. FeCl3; ale. sol. green. 63-6 Dioxytoluene, Me.CBH3.(OH)2(i, 2, 6). - E. s. aq. or ale.-W. Ca(OCl)2 quickly turns to a fuchsine-red color that changes to yellowish brown. 65 225c. f 1, 2-Xylenol(4), Me2.CBH3.OH.-Long ndl. fr. h. aq.-Odor like phenol. Cold saturated aq. sol. becomes B on mixing with FeCl3 (Test 401); the color rapidly fades, however, and is replaced by a white turbidity.-Tribrom-derivative melts at 169°. GENUS IV, DIV. A. 93 (ORDER I, SUBORDER I.) Melting-point (C.°). Boiling-point (C.°). PHENOLIC COMPOUNDS.-Colorless and Solid. 66 246-7 Hydroquinone Ethyl Ether, p-HO.C0H4.OEt.-Thin 1ft. e. s. h. aq. or eth.; d. s. c. aq. 64 or 68 219-5 i, 3-Xylenol(5), Me2.C6H3.OH.-V. d. s. c. NaOH.-No color w. FeCl3.-M. p. of tribrom-derivative 162-5°. 67 m-Oxybenzyl Ale., HO.C0H4.CH2OH.-Cryst., e. s. ale., eth., or h. aq.; d. s. CHC13.-Aq. sol. gives violet-blue color w. a little FeCl3. 68-9 219-5c. Mesitol, Me3.C6H2.OH(i, 3, 5, 2).-V. s. ale. or eth.; i. NH40H or Na2CO3.-No color w. FeCl3. 71-2 234-5 Pseudocumenol, CBH2.(Me3)(OH)(i, 2, 4, 5).-Alm. i. c. aq.; v. s. ale. or eth.-No color w. FeCl3.-Very vol. w. st.-Acetic ac. sol. with Br gives Br deriv. m. p. 35°. 73-4 Coniferyl Ale., MeO.C?H3: (OH)(C3H4.OH).(3, 4,1).-D. s. h. aq.; e. s. eth.; s. alkalies.-Dil. mineral acids change quickly to amorphous isomer, alm. i. eth.-Na amalgam reduces to eugenol, Div. B, b. p. 247°.-CrO3 mixture oxid. to vanil- line, etc. 74-5 211-5 (th. i.) 1, 4-Xylenol(2), Me2.CbH3.OH.-Odor like phenol.-Gives no pronounced color reac. w. FeCl3 in aq. or ale.! 75 218c. 1, 2-Xylenol(3), Me2.C6H,.OH.-Odor like phenol.-Aq. sol. blue w. FeCl3!-M. p. of tribrom-derivative 184° (ndl.fr.ale.). 76-5 Diethyl Ketipate, EtCO2.CH2.CO.CH2.CO2Et.-Flat pr. fr. ale.- I. c. aq., e. s. eth.-Gives intense-red color w. FeCl3.-Boil- ing w. dil. H2SO4 gives diacetyl!-Substitutes Br2 easily.- The free acid is unstable. 79 262 Pyrogalloldiethylether, HO.C6H3.(OEt)2.-V. s. c. bz.; d. s. c. dil. ale.-Vol. w. st. 79-80 Propylpyrogallol, Pr.CfiH2.(OH)3(i, 3, 4, 5)--V. s. aq., ale. or eth.-Aq. sol. indigo-blue w. FeSO4. 81 1, 2, 3-Trimethylphenol(5), Me3.C6H2.OH.-No color w. FeCl3. 81 a. 200 Dibenzoylmethane, CH2.(COPh)2.-Tbl. fr. methyl ale.; e. s. ale. or eth.; i. Na2CO3; v. e. s. NaOH.-Ale. sol. intense red- violet w. FeCl3!-Monobrom-derivative formed fr. 1-8 grm. Br and 2 • 24 grm. substance, each dissolved in 3 pt. CHC13 at 0°, (silky ndl., m. p. 93°). 80-5 (a)-Dibenzoylacetone, (PhCO)2.C: COH.Me.-Pr. fr. Igr.; dec. at 270°.-Sol. in Na2CO3 w. yellow color.-Ale. sol. blood-red w. FeCl3.-Quite a strong acid.-Heated for 1 hour at 85° gives (/?)-dibenzoyl acetone of m. p. 107°-10°, i. in Na2CO3 sol., and giving no color in ale. sol. w. FeCl3. 84 Dipyrocatechin, [C (iH3. (OH) 2]2.-Ndl.-Sbl.-Unstable.-Aq. sol. pale green w. FeCl3, becoming dark blue w. a little Na2CO3. 84 abt. 325 p-Benzylphenol, Ph.CH2.C!.H4.OH.-Cryst. fr. ale.-S. in NaOH, but not in NH40H.-Dist. w. P2O5 gives benzene, anthracene, and phenol. (Tests 913, 912, and 414.)-Dibrom-derivative, fr. excess of Br in CS2 sol., m. p. 175°. 86 f Saligenin, o-HO.C0H4.CH,.OH.-Rhombic tbl.-Sbl. fr. 100° -E. s. c. aq.; v. s. h. aq.; v. s. ale. or eth.-Test 401 w. a 0-5% ale. sol. and FeCl3 gives a RV color, soon changing to YOT2.-The powder stirred w. a little cone. H2SO4 gives a red color (RT1-VRT1).-Boiled for a short time w. 5 pts. aniline gives oxybenzyl-aniline, m. p. 108°; ndl. fr. ale. 86 266 (th. i.) i, 2, 3-Tetramethylphenol (4), Me4.C6H.OH.-E. s. ale. or eth.- Gives no color w. FeCl3. 94 GENUS IV, DIV. A. (ORDER I, SUBORDER I.) Melting-point Boiling-point PHENOLIC COMPOUNDS.-Colorless and Solid. 88 f Diethyl Diacetylsuccinate, CgHgO^E^.-Tbl., e. s. ale. or eth. -Sat. aq. sol. w. FeCl3 gives, in Test 401, a very pale but rather permanent violet-red (VRT2).-f To 5 cgrms. ester in a test-tube add 1 cc. cone. NH40H, 1 cc. glacial acetic acid and 10 cc. dilute H2SO4. Place a pine splinter in the mixture and boil for 2 min.-The splinter becomes colored deep red (pyrrol reaction)!-Saponification gives acetonyl- acetone, C2H6OH, and CO2. 89 2-Methylnaphthol(i), Me.C10H6.OH.-Ndl. fr. aq.-Gives white ppt. w. FeCl3; green ppt. w. Ca(OCl)2.-Ignition w. Zn dust gives /3-methylnaphthalene. 92 2-Methylnaphthol(4), Me.C10H6.OH.-Gives same reactions as preceding, except that Zn dust gives a-methylnaphthalene. 92-3 255 p-Isoamylphenol, C5Hn.C(.H4.OH.-Ndl. fr. h. aq. 93 250d. p-Anol, Me.CH: CH.C6H4.OH.-S. in alkalies.-Exposure to air or h. dil. acids gives a brown oil. 94 278-80 t a-Naphthol, C10H7.OH.-Monoclinic.-Odor phenolic.-D. s. h. aq.; i. c. aq.; e. s. ale., eth., bz., or alkalies.-Aq. sol. gives scanty white ppt. w. FeCl3. Identify by Test 412! 95 Pyrogallol Ethyl Ether, (OH)2.CfiH3.OEt.-Ndl. vol. w. st.-S. c. aq.; e. s. h. aq.; v. d. s. c. bz.-Gives blue-violet color w. FeSO4. 95 230-1 (th. i.) Trimethylphenol, C6H2.(Me3)(OH)(i, 2, 4, 6). 95-7 Ethyl Oxalylacetate, CO2H.CO.CH2.CO2Et.-FeCl3 + aq. sol. gives deep-red color. 96-7 /?-Hydrojuglon, C10H5.(OH)3.-Silvery 6-sided ndl. fr. ale.-S. 1000 pt. c. aq.; d. s. ale. or eth.; e. s. CHC13 and bz.-Gives an intense-yellow color w. NaOH, changing to red.-Boiled w. FeCl3 gives jugion. 98 Benzocotoin, CI5HI4O4.-Pale-yellow ndl., e. s. eth. or dil. NaOH. -FeCl3 gives dark-brown color.-Ammon, sol. gives amor- phous yellow ppt. w. PbAc2. 99 237 p-tert.-Butylphenol, Me3.C.C0H4.OH.-Ndl. fr. aq.-Heated w. P2O5 gives isobutylene and phenol. 99 o-Oxyhydroanthranol, C14H12O2.-Yellowish 1ft. fr. ale.-S. ale. or eth.-The ale. sol. is colored green by FeCl3.-Solutions show a pronounced green-yellow fluorescence. 103 325 si. d. Methyl Oxynaphthyl Ketone, Me.CO.C10H(,.OH.-6-sided pale- green pr. fr. bz.; i. aq., d. s. ale.; s. alkalies, but ppt'd by CO2.-Oxime, m. p. 168°-9°. 103-4 267-70 1, 2-Dioxytoluene(4), (OH)2.CGH3.Me.-E. s. aq., ale., or eth.; d. s. bz.-Aq. sol. colored green-blue by FeCl3; gives ppts. w. Br or PbAc2; gives yellow color w. Ca(OCl)2 sol.-Phthalic anhyd. fusion (Test 402) gives a fluorescein. 104 240-5 f Pyrocatechin, o-C8H4.(OH)2.-Lft. fr. bz.; e. s. aq., ale., or eth.; s. c. bz. (Separation fr. hydroquinone.)-Aq. sol. (1:250) gives w. FeCl3 a green (G) color, which, on addition of Na2CO3, changes to R, becoming OR within 15 min.!-■ Alkaline sol. browns in the air.-PbAc2 gives white ppt. (dif. fr. hydroquinone).-Easily reduces sol. of noble metals and Fehling's sol. on warming.-Apply Test 416 I 105 Homosaligenin, Me.CGH3.(CH,0H)(0H)(i, 2, 4).-Lft. s. 15 pt. c. aq.-Sol. gives deep-blue color w. FeCl3.-Dec. by heat- ing w. dil. HC1 to i. homosaliretin, m. p. 200°-5°. 104-6 Dihydroresorcin, CGHSO2.-Pr. e. s. aq. or ale.; v. d. s. abs. eth. -Aq. sol., reacts strongly acid.-Aq. sol gives intense violet color with FeCl3. Reduces Ag sol.'-Gives a phenyl- hydrazone w. m. p. 176°. GENUS IV, DIV. A. 95 (ORDER I, SUBORDER I.) Melting-point (C.°). Boiling-point (C.°y PHENOLIC COMPOUNDS.-Colorless and Solid. 105-6 298 Dlmethylapionol, CGH2.(OH)2(OMe)2(i, 2, 3, 4).-S. h. aq., ale., eth., bz., and alkalies. 106-5-108 287-90 t Orcin, Me.C0H3.(OH)2(i, 3, 5).-Cryst. w. 1H2O (m. p. 58°).-■ Sweet taste.--E. s aq., ale., or eth.; d. s. CHC13.-A 1% aq. sol. gives a VBT1-BVT1 color w. FeCl3 in Test 401, which slowly fades to a light tint of the same hue.-Reduces am- nion. Ag sol.-Sol. in ammonia absorbs O from air, becoming red.-Br aq. ppts. tribrom-derivative (ndl. fr. dil. ale., m. p. 98°).-t Bring to a boil a sol. of 5 cgrm. orcin in 5 cc. of a 1% NaOH sol. to which 5 drops of CHC1S have been added. An O-OR color is produced. Dilute the solution to 50 cc. and view with a black background. An intense YG fluorescence appears!-The phthalic anhyd. fusion (Test 402) gives a pure OR solution. 108 1, 2, 3-Tetramethylphenol(5), Me4 C6H.0H.-Ale. sol. becomes yellow-green w. FeCl3. 108-9 Phloridzin.-Cf. m. p. abt. 170°, at which temp, it remelts after losing aq. 110 Ethyl Tsocarbopyrotritarate.-Ale. sol. blue w. FeCL.- Cf. Genus III (A., 2). 110 p-Oxybenzyl Ale., HO.C6H4.CH2.OH.-Fine ndl., e. s. aq., ale., or eth.-Sol. in cone. H2SO4 is red-violet. 112 Phenanthrol, C14H8.OH.-Lft. w. blue fluorescence.-D. s. aq.; e. s. ale. or eth 114 255 Pentamethylphloroglucin, CnH16O3.-E. s. in sol. of NaOH or Na2CO3.-Reduces KMnO4 immediately. Abs. methyl ale. sol. with Br gives Br deriv., ndl., m. p. 75°-6°. 115 d. Vanillyl Ale., C6H3.(MeO)(OH)(CH2OH),(3:4:1).- Ndl. E. s. ale., eth., or warm aq.-S. in cone. H2SO4 w. red-violet color. -Gentle oxidation w. a little CrO3 mixture gives vanillins (odor like vanilla) ! 115 295-300 Acetovanillon, MeO.C0H3.OH.COMe.-Pr. s. in 200 pt. c. aq.- Cu salt a yellowish-green ppt.-Oxime melts at 95°. 116 276-5 f Resorcin, m-CGH4.(OH)2.-Tbl. fr. aq., ale., or eth.-Taste sweet.-V. s. c. aq., ale., or eth.; i. CHC13 or CS2.-A 1% aq. sol. gives a strong clear BV with FeCl3 (Test 401), permanent for more than 15 min.-Identify by Test 418 1 116 297-8 Ethyl p-Oxybenzoate, HO.CGH4.CO2Et.-Saponification by Test V-2 gives p-oxybenzoic ac. and C2H5OH. 116 m-Oxybenzophenone, Ph.CO.CGH4.OH.-Lft. e. s. ale. or eth.- Gives two oximes w. m. p. 76° and 126°; fusion of first gives second. 117 227-8 (th. i.) Pyromeconic Ac., C,H4O3.-Sbl. at 100°.-4-sided pr. fr. h. aq. -V. s. ale., CHC13, and h. aq.-Gives a cherry-red color w. FeCl3.-Boiling w. alkalies gives formic ac and CO2. -Salts very unstable. 117 249-50c. 1, 2, 4-Tetramethylphenol(5), Me4.C0H.OH.-Flat pr. fr. ale.- E. vol. w. st. 120 2, 6-Dioxy-i, 3-xylnl, Me2.CGH2.(OH)2.-S. aq.; v. s. ale. or eth. -Aq. sol. reddish w. FeCl3. 120-1 1, 3-Trioxynaphthalene, C10H5.(OH)3.-Sbl. in scales.-V. s. eth., CHC13, or bz. 120-1 Oxalyldiacetone, C2H3O.CH,.CO.CO.CH2.COMe.-Cryst. d. s. aq.; s ale., eth., or NaOH(Na comp, yellow).-Ale. sol. is col- ored dark brownish-red by FeCl3. 96 GENUS IV, DIV. A. (ORDER I, SUBORDER I.) Melting-point (C.°). Boiling-point PHENOLIC COMPOUNDS.-Colorless and Solid. 122 122 285-6 p-Diphenolethane, Me.CH.(CGH4OH)2.-Cryst. fr. bz.; i. Igr.- Aq. sol. gives yellow-brown ppt. w. FeCl3.-Gives Ag mirror w. h. dil. ammon. AgNO3 sol., evolving aldehyde. j- /?-Naphthol, C1pH7.OH.-D. s. h. aq.; e. s. ale., eth., or bz.- FeCl3 gives a white opalescence w. the c. aq. sol.-Identify by Test 4131 2, 5-Dioxytoluene(i), Me.CGH3.(OH)2.-Sbl. partially. - V. s. aq., ale., or eth.; less s. bz.; s. alkalies.-Aq. sol. w. FeCl3 gives brownish-red color.-Sol. in NaOH is blue-green, soon turning brown.-Boiled w. aniline gives compound (1ft. fr. aq.) w. m. p. 82°-85°. m-Xylorcin, C6H2.(Me2)(OH)2(i, 3, 4, 6).-Tbl. e. s. aq. or eth. 124 125 276-9 125 126-7 128 129 129-5 129-31 133 293 (si. d.) Cubebin, CH2.O2.CGH3.C3H4OH.-Ndl., alm. i. aq.; d. s. ale.; s. eth.-Cone. H2SO4 quickly produces a purple-red color.- HNO3 gives picric and oxalic acids. Diethyl Succinylosuccinate, C8H6O6.Et2.-Pale-greenish cryst. w. bluish fluorescence fr. eth.; v. d. s. h. aq.-FeCls colors ale. sol. deep cherry-red.-The sol. in NaOH is deep yellow. -The ale. sol. shows intense light-blue fluorescence. Ethylsuccinylosuccinic Ac., CGHSO3.-Ndl. or tbl.-Sbl.-S. c. aq.; e. s. ale.-FeCl3 gives cherry-red color w. aq. sol.- Fusion w. KOH gives formic and butyric acids.-BaA + 2H2O, or 4H2O, pale rose-colored crystals. Methylpyrogallol, CH3.C0H2(OH)3.-Sbl. in ndl.-W. FeSO4 gives same bluish color as pyrogallol. 9, io-Dihydroanthrol(2), CGH4: (CH2)2:CeH3OH.-E. s. ale. w. blue fluorescence. Diketohydrinden, CGH4:(CO)2:CH2.-Cryst. fr. Igr.; v. d. s. c. aq.; e. s. h. ale. or bz. S. w. intense yellow color in dil. NaOH or Na2CO3!-Boiled w. aq. or alkali gives an acidic body, m. p. 206°-8°, whose alkaline salts are intensely red- violet, and whose Ag salt is dark red! f Pyrogallol, CGH3.(OH)3(i, 2, 3).-V. s. c. aq.; s. ale. or eth.- Taste bitter (poisonous).-Alkaline sol. absorbs 0 rapidlv, turning brown.-A 1% aq. sol. gives w. FeCl3 an OYS1 color, changing within 15 min. to OYS2.-V. dil. FeCl3 gives bluish color.-Reduces AgNO3 sol. in the cold.-Apply Test 417! Diethyl Hydroquinonedicarbonate, C8H4Of,.Et2. - Sbl. in flat greenish 1ft. w. bluish fluorescence.-D. s. c. ale.; sol. fluo- resces blue in reflected light, pale greenish yellow by trans- mitted light.-S. in dil. NaOH w. deep-yellow color.-With a trace of FeCl3 gives a blue-green color. p-Benzoylphenyl, Ci3Hio02.-Dist.-Lft. d. s. c.aq., more s. h. aq.; e. s. ale., eth., and Ac.; s. in alkalies, but reppt'd by acids.- Dec. by cone. H4SO4 at 200°, giving phenol and benzoic acid. 1, 6-Dioxynaphthalene, Ci0H6.(OH)2.-D. s. c. ale.; e. s. eth.- FeCl3 gives a transient blue color, then a copper-red ppr. t Furoin, C4H3O.CO.CH(OH).C4H3O.-Nearly colorless (about YT3) cryst., d. c. ale.; i. aq.-Sol. in c. cone. H2SO4 is deep blue-green!-FeCl3 gives no coloration.-E. s. c. NaOH to deep bluish-green sol., very deep violet-red by transmitted light; color discharged on dilution, after first changing to green! The violet-red sol. diluted as much as practicable shows heavy absorption bands between D and C in orange, and between D and DJE!-The m. p. of oxime is 160°-l°; of the phenylhydrazone 79°-80°. 1, 4-Dimethylnaphthol(2), Me2.C10H5.OH.-Sbl. fr. 100°.-D. s. aq.; s. ale.; e. s. eth.-Zn dust ignition gives dimethyl- naphthalene.-Acetate, m. p. 77°-78°. 133-3-5 134 134-5 135 135-6 GENUS IV, DIV. A. 97 Melting-point (C°). Boiling-point (C.°). PHENOLIC COMPOUNDS.-Colorless and Solid. 135-6 139 139-5 140 abt. 140 140-5 141-2 142 143 144 145 144-6 146 149 149-50 151-2 152 - o-Oxystilbene, HO.CcH4.CH:CH.Ph.-Alm. i. h. aq.; d. s. c. ale.; e. s. h. ale. Butenylonphenol(2), C10H10O2.-Ndl. d. s. aq.; e. s. ale.-• Aq. sol. deep blue-violet w. FeCl3.-M. p. of oxime 84°-5°. Oxythymol, Me.C6H2.(Me2.CH)(OH)2(i, 4, 2, 5).-B. p. 290°. --Sbl. undecomposed.-V. d. s. c. aq.; s. h. aq.; e. s. ale. or eth.-Oxid. gives thymoquinone.-Occurs in oil fr. root of Arnica Montana. 1, 8-Dioxynaphthalene, C10H6.(OH)2.-D. s. h. aq.; e. s. eth. or bz.-Dust provokes sneezing.-Aq. sol. w. FeCl3 gives flocculent white ppt. which soon becomes dark green.- Easily oxidized.-Diacetate, silvery Ifts. fr. ale. (m. p. 147°-8°). t Hematoxylin.-Sol. in alkalies intense purple-red.-Cf. Suborder II, A, 1, p. 207. Oxyhydroquinone, C6H3.(OH)3(i, 2, 4).-V. s. aq., ale., or eth.; alm. i. CHC13, CS2, or bz.-Aq. sol. exposed to air soon browns.-Aq. sol. w. v. dil. FeCl3 gives transient green which changes w. Na2CO3, first to dark blue and then to wine-red.-A cone. aq. sol. gives dark floc. ppt. w. FeCl3. --M. p. of triacetate 96-5°. Protocotoin, C16H14Oo.-Pr. fr. ale.-Gives blue-green color w. c. cone. HNO3.-Dibrom-deriv. fr. Br in CS2 sol., scales, m. p. 170°. Resacetophenone, Me.CO.C6H3.(OH)2(r, 2, 4).-Cryst. d. s. aq. •-Aq. sol. colored wine-red by FeCl3.-M. p. of oxime, 198°-200° d. Dioxyphenanthrene, C14H8.(OH)2.-E. s. NaOH w. green color, quickly changing to red.-S. in cone. H2SO4 +trace of HN03 w. red color.-V. e. oxidized.-Diacetate, m. p. 159°. Benzoresorcin, Ph.CO.O6H3.(OH)2.-Ndl. fr. h. aq.; d. s. c. aq. ; e. s. ale. or eth.-Ale. sol. becomes brown-red w. FeCl3. -M. p. of dibenzoate 141°. Benzopyrocatechin, Ph.CO.C0H3.(OH)2.-V. d. s. c. aq.-Ale. sol. w. FeCl3 gives rich green coloration, changing to red on addition of a drop of ammonium carbonate.-Re- duces Tollen's reagent (cf. Test 101). Arbutin, C25H34O14 (?) (substance dried in vacuo at ioo°).- (Statements concerning symbol and m. p. are conflicting; m. p. 165° and 170° are also recorded.)-Taste bitter.- Lustrous ndl e. s. h. aq. or ale.; i. eth.; more s. in dil. NaOH than in aq.-A 1% aq. sol. gives a transient VB-BV color w. FeCl3.-Boiled w. x's of FeCl3 sol. gives pungent odor of quinone!-(A glucoside hydrolyzed by dil. H2SO4 to dextrose and hydroquinone.) Orcacetophenone, (Me)(OH)2.C,H2.CO.Me.-Silky ndl. v. s. ale. or eth.; e. s. NaOH or NH40H.-Aq. sol. black w. FeCl3. Dioxyxylene, CoH2.(Me2)(OH)2(i, 3, 2,4).-Sbl. in ndl.; v. s. aq., ale., or eth.-Gives intense violet color w. FeCl3. 1, 3? 5-Trimethylphendiol, Me3.C6H.(OH)2. - B. p. 275° c.- Sbl. in 1ft.-D. s. c. aq.; e. s. ale. or eth.-Aq. sol. gives transient green color and gray ppt. w. FeCl3.-Reduces ammon. AgNO3 sol. p-Diphenylol-dimethyl-methane, (C6H4.OH)2.C.Me2.-I. c. aq.; d. s. h. aq.; e. s. ale. or eth. Dimethyl Succinylosuccinate, CsH6O6.Me2.-FeCl3 gives red color w. ale. sol.-The free acid is unstable. (ORDER I, SUBORDER I.) 98 GENUS IV, DIV. A. (ORDER I, SUBORDER I.) Melting-point (C.°). Boiling-point PHENOLIC COMPOUNDS.-Colorless and Solid. 154 Bicarvacrol, C,0H2GO2.-Silky ndl.; i. aq.; e. s. ale., eth., or bz. 156 i, 2, 4-Trimethylphendiol(3, 5), Me3.C6H.(OH)2. 156 Anemonin, C10HsO4.-Vol. w. st.-Lustrous ndl. fr. ale., or plates fr. CHC13.-D. s. h. aq. orc. ale.; i. eth.-Ale. sol. reacts neutral.-E. s. alkalies w. yellow-red to blood-red color.-A few degrees above m. p. solidifies to yellow com- pound which decomposes at 290°.-Combines w. phenyl- hydrazine. 158 p-Dioxydiphenylmethane, CH2.(CGH4OH)2.-Sbl.-Not vol. w. st.-E. s. ale.; v. s. eth.; s. CHC13; i. CS2; s. in NaOH and ppt'd by CO2.-Aq. sol. colored brown-yellow by FeCl3.-Aq. sol. of disodium salt is green.-Fusion w. KOH gives p-oxybenzoic ac. and phenol (Test 414). 158 f Convolvulin, C32H62O16 (?).-Amorphous.--Alm. i. aq. or eth.; e. s. ale.-Mix a few mgr. w. a drop of c. cone. H2SO4 After 5 min. a VR color appears, changing after 4 hr. to R.- Warm a little w. x's of cone. H2SO4; disagreeable odor of rancid butter, changing to sharp odor if temp, is increased. -S. NaOH w. dec.-A glucoside fr. jalap root (Convol- vulus purga), yielding dextrose, etc., on hydrolysis by h. baryta water. 159 Maltol, C6H4O.(OH)2.-Sbl. in 1ft.-D. s. bz. or c. aq.; v. s CHCI3 or h. aq.; s. NaOH, but reppt'd by CO2.-Aq. sol. colored an intense violet by FeCl3.-Reduces amnion., Ag sol. c., or Fehling's sol. when hot 159 2, 3-Dioxynaphthalene, C10HG.(OH)2.-Rhombic 1ft. fr. aq.-• S. h. aq.; e. s. ale. or eth.--Gives intense dark-blue color w. FeCl3. 160 t TEsculin, C15H1GO9.-White lustrous odorless ndl , slightly bitter taste.-Loses cryst. aq. at 120°-130°-S in 600 pt. c., or 12-5 pt. h. aq.; d. s. c. ale. or eth.; e s NaOH - The cold supersaturated aq. sol. gives blue-green color (BG) w. FeCl3.-V. dil. aq. sol., especially in presence of a trace of alkali, shows a magnificent light-blue (BT2) fluo- rescence! Shaken w. little HNO3 gives yellow sol., which becomes deep blood-red upon addition of NH40H!- Hydrolysis by h. dil. HC1 gives dextrose and Eesculetin - Gives the Molisch color reaction in Test 11 w. n-naphthol - (In bark of the horse-chestnut) 161 4, 4-Dioxytriphenylmethane, Ph.CH.(CGH4OH)2.-Ndl. fr dil. ale.; i. c., d. s. h. aq.; e s ale. or eth.-Diacetate melts at 109°-lll°. 161 0-Bicresol, (Me.CGH3.OH)2.-D. s. h. aq;; e. s. ale. or eth - Diacetate m. p. 131°. 161 Benzyhydroxylphenol, Ph.CHOH.CGH4.OH.-D. s. c aq.; e. s. ale. or eth.; s. alkalies -Aq. sol colored red by FeCl3. 161 d-Biphenol, (C0H4.OH)2.-B p 342° Ndl, v. d s h aq.; v. s. ale. or eth.-Aq. sol. gives ppt w PbAc2 -Diacetate melts at 94°. 162-3 3, 3'-Dioxybenzophenone, (C6H4OH)2-CO.-E s KOH but re- precipitated by CO2.-Fusion w. KOH gives phenol and oxybenzoic ac. 163 ^-Orcin, C6H2.(Me2)(OH)2(i, 4,3,5).-B. p. 277°-80° -Much less s. aq. than orcin -NH4OH sol w Ca(OCl)2 gives clear carmine-red color.-Boiled w. dil. NaOH and CHC13 gives deep-red sol. w. green fluorescence like orcin!-Tetra- brom-derivative, ppt'd by Br aq., cryst fr Igr. w.. m. p. 101°.-Phthalic anhyd. fusion gives no color. GENUS IV, DIV. A. 99 (ORDER I, SUBORDER I.) Melting-point (C.D. Boiling-point (C.°). PHENOLIC COMPOUNDS.-Colorless and Solid. 160-70d. t Anthranol, C8H4: C2H(OH): C6H4.-Lustrous v. pale-yellow (about YT3) ndl.-E. s. h. bz. Does not dissolve fully in c. alkali, but becomes bright yellow and gives a yellow filtrate; reppt'd by CO2.-The alkaline sol. when boiled in presence of air absorbs 0, giving much anthraquinone! -Dissolve a small quantity in cold fuming HN03; dilute w. aq. and dissolve orange ppt. in ale. containing 1 drop NaOH sol.; an intense violet-red color is produced!- Ignition w. Zn dust gives anthracene (Test 912). 165-5 Bithymol, C„0H26O2 + H2O.-I. aq.; e. s. ale., eth., or bz.; s. in alkalies w. orange color. 168 Arbutin, cf. IV, A, m. p. 144°-6°. 168 Trioxyacetophenone (Gallacetophenone), (HO)3.CfiH2.CO.Me.-■ Pearly 1ft., e. s. h. aq.-S. in NaOH w. brownish color; in cone. H2SO4 w. clear yellow color.-Picrate, yellow ndl., w. m. p. 133°.-Oxime, ndl. fr. toluene w. m. p. 162°-3°. 168-70 a-Hydrojuglon, CI0H5.(OH)3(i, 4, 5) (fr. the walnut-tree, Ju- glans regia).-Cryst., s. in 200 pt. aq. at 25°; v. s. ale. or eth.; i. CHC13 or bz.; e. s. alkalies w. intense yellow color which changes in air to red.-Br or FeCl3 gives jugion. 169 f Hydroquinone, p-C6Hr(OH)2.-Sbl. in 1ft.-Taste slightly sweetish.-S. in 17 pts. aq. at 15°; e. s. ale. or eth.-The cold saturated aq. sol. gives a YO colored sol. w. FeCl3 in Test 401.-Boiled w. excess FeCl3 gives pungent odor of quinone.-Alkaline sol. browns in air.-Reduces AgNO3 on warming, and Fehling's sol. in the cold.-Identify by Test 411! 169 1, 2, 4-Trimethylphendiol(3, 6), Me3.C0H.(OH)2.-D. s. c. aq.; e. s. h. aq., ale., eth., or bz. Diacetate, m. p. 112°. abt. 170 Phloridzin, C,iH24O10.-Taste bitter!-Silky ndl. wh. first melt at 108°-9°, losing 2H2O of cryst., and then solidifying at 130°. -S. in 1000 pt. c. aq.; e. s. h. aq. or ale.; alm. i. eth.; sol. in NaOH absorbs O, becoming red-brown.-Sol. dark violet w. FeCl3.-A glucoside readily hydrolyzed by boiling w. dil. H2SO4 to phloretin and dextrose. 171 Tetraoxytriphenylmethane, Ph.CH.[CcH3.(OH),]2.-D. s. aq.; e. s. ale. or eth.-Easily oxid. to resorcinbenzein. 173-4 2-Acetylnaphthol(4), Me.CO.C10Hfi.OH.-Ndl. e. s. ale.-FeCl3 gives floc. ppt. w. aq. sol.-Ppt'd fr. sol. in alkali by CO2.- KMnO4 oxid to phthalic ac. (Test 318). 175 1, 4-Hydronaphthoquinone, CjHgdOH)^-Long ndl. s. h. aq.; e. s. h. ale. or eth.; alm. i. CS2.-CrO3 oxid. to a-naphtho- quinone.-Diacetate melts at 128°-30°. 176 Phenyl p-Oxybenzoate, HO.C6H4.CO2Ph.-Saponification by Test V very easilv gives p-oxybenzoic ac. and phenol (Test 414). 178 1, 7-Dioxynaphthalene, C10HG.(OH)2.-S. aq.; e. s. ale. or eth.-• Aq. sol. gives deep-blue ppt. w. FeCl3.-Alkaline sol. blackens in the air.-Diacetate melts at 108°. 180 Benzoylsalicin (Populin), C20H22O8.-Cryst. w. 2H2O (lost at 100°).-Taste sweetish.-S. in abt. 2000 pt. c. aq.; s. cone. KOH.-Cone. H2SO4 colors amethyst-red.-Saponified by h. Ba(OH)2 to salicin and benzoic ac. (Test 412). 184 1, 3, 5-Trimethylphloroglucin, Me3.CG.(OH)3.-S. alkali carbon- ates.-Br gives derivative w. m. p. 90°. 184-5 Filixic Ac., C14H1RO5 (fr. Aspidium Filix mas.).-Mic. 1ft. fr. eth.-I. aq.; alm. i. ale.; s. eth.-Reduces ammon. AgNO3. -Fusion w. KOH gives phloroglucin (cf. Test 415). 100 GENUS IV, DIV. A. (ORDER I, SUBORDER I.) Melting-point (0.°). Boiling-point PHENOLIC COMPOUNDS.-Colorless and Solid. 185 Dithymolethane, Me.CH.(C10H12OH)2.-Dist. undecomposed.- Ndl. fr. bz., plates fr. ale.-Oxid. by MnO2 and dil. H2SO4. gives thymoquinone (Suborder 2, m. p. 45-5°). 185 f Coniferine, C16 H22OS + 2H2O.-I. c. aq.; v. s. h. aq. or dil. alka- lies.-Warmed with cone. HC1 turns cobalt-blue.-Warmed w. cone. H2SO4 gives violet sol. changing to violet-red.-■ Gives no ppt. w. PbAc2.-Gives no color w. FeCl3. 186 Iretol, CGH2.(MeO)(OH)3(2, i, 3, 5).-Ndl. e. s. aq., ale., or eth. ■-Br aq. gives hexabromacetone.-HNO3 oxid. to oxalic ac. (Test 317). 186 Irigenin, C1SH1GO8.-Rhombohedra fr. dil. ale.; d. s. aq.; i. eth. or Igr.-Aq. sol. deep violet w. FeCl3. 190 Phenolphthalol, (HO.CGH4)2.CH.C,H4.CH2OH.-Pr. d. s. h. aq.; e. s. ale. or eth.; i. bz. or CHC1S,-Becomes red w. cone. H2SO4.-Alkaline potassium ferricyanide oxid. to deep-red solution of phenolphthalein. 190 2, 7-Dioxynaphthalene, C10HG(OH)2.-Ndl., sbl. w. dec.-E. s. h. aq., ale., or eth.; alm. i. CS2.-Transient dark-red color- tv. Ca(OCl)2.-Alkaline sol. darkened by air.-M. p. of diacetate 129°-30°. 190 Hydroccerulignon, (MeO)4.C12O4.(OH)2.-Monoclinic pr. fr. ale.- V. d. s. aq. or eth.; s. h. ale. or bz.-Reduces c. ammon. Ag sol.-FeCl3 on exposure to air causes separation of coeru- lignon. 194d. Methylene-di-/?-Naphthol, CH2.(C,0H6OH)2.-Mic. ndl., e. s. ale.; alm. i. CS2.-M. p. of diacetate 211° (i. ale.; e. s. bz.).- Picrate melts at 178°-9°. 198-200 Diethyl-p-diphenol-methane, Et2.C.(CGH4.OH)2.-Pr. fr. ale.; i. h. aq.; e. s. ale. or eth. 200 Resorcinphthalein.-Yellowish crystals.-Cf. Suborder 2. 200 f Picrotoxin, C:j0H34O13 (from Menispermum Cocculus).-- Cryst. s. 300-400 pt. c. aq.; e. s. ale. or h. aq.; e. s. in NaOH, the sol. soon becoming golden yellow.-The color of a sol. obtained by dissolving a few crystals in cone. H2SO4 on cruci- ble cover is a strong orange-yellow (OY) !-Taste of aq. sol. (1:10,000) intensely bitter !-No pronounced color w. FeCl3. -Gives ppt. w. Br aq.-Reduces AgNO3 sol. when warmed. (Very poisonous.) 200d. Daphnin, C15H1GO9.-(Loses 2H2O of cryst at 100°.)-Colorless; pr. w. bitter astringent taste !-D. s. c. aq.; e. s. h. aq. or h. ale.; i. eth.; s. NaOH or Na2CO3 w. yellow color.-FeCl3 colors the solution bluish.-HNO3 gives red color in the cold. -Hydrolyzed by dil. acids to dextrose and daphnetin. (In bark of Daphne Mezereum.) 200 or 210d. Tannic Ac., C14H10O9.-See III, A, 1, m. p. 210°. Taste astringent_ 200-5 Phenoglucin, C6HGO3 + 2H2O.-Taste very sweet.-Pr. fr. aq.- Gives pale-violet color w. FeCl3. 201 t Salicin, C13H1SO7.-Taste bitter.-A glucoside.-Hydrolyzed by h. dil. H2SO4 gives dextrose and saliretin; by emulsin gives dextrose and saligenin.-Cryst. s. 28 pt. aq. (15°); more s. in NaOH; i. eth.-Gives no color w. FeCl3.-The powder stirred into cone. H2SO4 on crucible cover gives bright scarlet (OR) color! 202-3 Hydroquinonphthalin, C20HI4O6.-Oxid. agents give hydro- quinonphthalein. 200-9 (s. h.) Phloroglucin.-See m. p. 217°-19°. GENUS IV, DIV. A. 101 (ORDER I, SUBORDER I.) Melting-point (C.°). Boiling-point (C/). PHENOLIC COMPOUNDS.-Colorless and Solid. - 206 4-4'-p-(or a)-Dioxybenzophenone, CO.(C6H4OH)2.-Dist. unde- composed.-Cryst. fr. h. aq., e. s. ale., eth., or alkalies.- Ppt'd fr. Ba(OH)2 sol. by CO2.-No color w. FeCl3.-Fusion w. KOH gives CO2 and phenol.-Tetrabrom substitution product fr. ale. sol. of compound w. Ac sol. of Br in cold, m. p. 213°-14°. 206-8d Anhydrobisdiketohydrindene, C,8H10O3.-Sol. in alkalies intense red to violet; ppt'd by CO2.-Oxime d. at 210° without melting. 212 Phenolphthalidein, C^H^O^.-S. ale. or eth.; s. alk. w. pale yellow and in cone. H2SO4 w. intense violet color. 212 Hydrophloron, C6H2.(Me2)(OH)2(i, 4, 2, 5).-Sbl. in 1ft., s. h. aq.; v. s. ale. or eth.; d. s. CS2.-Boiled w. FeCl3 or dil. HNO3 gives phloron.-Reduces Ag sol. 212-13 Acetonresorcin, Me.CO.(CoH4OH)2 + H2O.-I. aq., CHC13, bz., or abs. eth.; s. NaOH.-Resorcin and acetone are among the products of decomposition by heat. 210-20 a-Tribenzoylmethane, (Ph.CO)2.C: (HO)C.(Ph).-S. in CHC13 or aq.-Freshly prepared gives pale-yellow sol. in 1% Na2CO3, and a deep-red color w. FeCl3. After fusion or keeping goes over to neutral ^-modification, w. m. p. 225°-6°. 215-16 2, 6-Dioxynaphthalene, C10H6.(OH)2.-Sbl. in pearly 1ft.-D. s. c. aq.; e. s. ale. or eth.-Aq. sol. gives yellowish-white color w. FeCl3.-AI. p. of diacetate 175°. 215-20 1, 2, 4, 5-Tetroxybenzene, C0H2.(OH)4.-Silvery 1ft. fr. Ac.-E. s. aq., eth., or ale.-Quickly oxid. by FeCl3 or by air in alka- line sol. to dioxyquinone. 217-19 (r. h.) f Phloroglucin, C6H3.(OH)3.(i, 3, 5).-Loses 2H2O cryst. on heating to 100°.-Sbl. w. si. decomposition.-Taste sweet- ish.-E. s. aq., ale., or eth.-A 1% aq. sol. in Test 401 w. FeCl3 gives BV-V coloration, which fades rapidly.-Sol. in NaOH absorbs O, but less rapidly than pyrogallol.-A pine splinter first well soaked w. cone. HC1 assumes a deep-red coloration (R-VR) when dipped in a- dilute aqueous sol. of phloroglucin!-The aq. sol. gives a heavy ppt. of tribrom- phloroglucin, which when purified melts at 151°.-Identify by Test 415! 218c. /?-Binaphthol, (HO.C10H0)2.-Distillation gives ^-naphthol (Test 413).-Flat ndl. fr. ale.; i. aq.; s. ale.; e. s. eth. Gives greenish color w. FeCl3, becoming bright red on heating.- Picrate, e. s. ale., has m. p. 174°. 218-19d. Fustin, C5sH46O23 (?).-White lustrous ndl., e. s. h. aq. or c. dil. NaOH; d. s. eth.-FeCl3 gives green coloration changed to blue-violet and red by Na2CO3!-PbAc2 gives yellow ppt.- (A glucoside; hydrolyzed by dil. H2SO4 giving fisetin and a carbohydrate.) 220d. Methylenedipyrocatechin, CH2.[C6H3.(OH)2]2.-D. s. ale. or eth. 222 Di-p-Oxyhydrobenzoin, C14H14O4.-Cryst., e. s. h. aq.; lesss. ale.; i. eth.-(Forms a Na salt.) 223-4 Umbelliferon, C9HGO3.-I. c. aq.; s. ale. and h. aq.-S. w. in- tense blue fluorescence in cone. H2SO4.-When warmed has odor like coumarin.-S. in cold KOH, but on heating the sol. to 60° gives umbelliferic ac. 224 4-Oxyxanthone, C13HgO3.-Sbl. easily.-White ndl. fr. ale.- Acetyl derivative, mic. cryst. fr. dil. ale., m. p. 137°-8°. 223-6 (r. h.) /?-Tribenzoylmethane, (CGH5.CO)3CH.-Small ndl.; d. s. ale. CHC13 or bz.; i. NaOH. 226-7 Hydroquinonephthalein, C20H10O3.(OH)2.-Ndl. fr. eth.-S. in alkalies w. deep-violet color. 102 GENUS IV, DIV. A. (ORDER I, SUBORDER I.) Melting point (C.°). Boiling-point PHENOLIC COMPOUNDS.-Colorless and Solid. 222-40d. d. 230 231 235d. 237 si. d. 241d. 242 d. w. m. 245 f Gallic Ac., (HO)3.CgH2.CO2H(3, 4, 5, 1).-Cryst. w. 1H2O (lost at 120°) in silky ndl.; s. 130 pts. aq. at 12 -5°.-Aq. sol. absorbs O from air and turns brown during titration; gives no ppt. w. sol. of gelatine (dif. fr. tannic ac.). Orcinphthalein, C22H14O3.(OH)2.-Pr. i. aq.; e. s. ale. or eth. S. in alkalies w. intense dark-red color without fluorescence. 2-Oxyxanthone, C13H8O3.-Lustrous yellowish ndl. fr. ale.- Acetyl derivative, ndl. fr. dil. ale., m. p. 161°. /?-Quinovin, C3sHo2On (?). - (A glucoside of quinovic ac. and quinovase-ethylether found in Cuprea bark.)-Cryst. scales fr. dil. ale.; alm. i. aq. or abs. eth.; s. alkalies.-Sol. in cone. H2SO4 is yellow, becoming cherry-red on exposure to air. Bihydroquinone, [C6H3.(OH)2]2.-Taste very sweet.-Lft. e. s. aq.; v. s. ale. or eth.-Aq. s. w. little FeCl3 gives red colorj x's of reagent gives biquinone. Methylenedipyrogallol, CH,.[C0H2(OH)3]2.-Cryst. powd. 3, (/?)-Oxyxanthone, C13H8O3.-Colorless ndl., e. s. NaOH sol.- FeCl3 added to ale. sol. gives brown color. Diresorcinphthalein, C,0H12O0+3|H2O.-Silvery 1ft. fr. aq.-S. 248 abt. 250 250 d. w. m. 250 251d. 250-3 252d. 252-4 in alkalies w. indigo-blue color. Tetraoxytetraphenyl-ethane, C20H18.(OH)4.-Scales i. aq.; e. s. ale. or eth. f Brazilin, C16HWO5.-Cryst. in colorless ndl. w. 1|H2O, soon assuming a broken orange-red color on exposure.--Taste at first faintly bitter, then very sweet!-Sol. in NaOH intense carmine-red (R); in cone. H2SO4 YO.-f Boil gently in a test-tube resting on a perforated asbestos screen, as de- scribed in Test 311-2, for 15 min., 0-1 grm. brazilin, 0-15 grm. fused sodium acetate, and 2-0 cc. acetic anhydride. Cool. Add 10 cc. water to residue, and boil. Cool. Filter. Dissolve cryst. in 10 cc. boiling dil. ale. (1:1). Cool. Filter. Repeat cryst. and filtration twice more as above directed. Dry crystals at 100° and determine melting- point. - The product, tetraacetylbrazilin, melts at 149° (uncor). 1, 5-Dioxynaphthalene, C10H0.(OH)2.-D. s. aq.; e. s. eth.-Re- duces Fehling's or ammon. Ag sol.-CrO3 oxid. to the quin- one.-Diacetyl compound has m. p. 159°-60°. Methylenediresorcin, CH2.[C6H3.(OH)2]2.-The alkaline sol. ab- sorbs O from the air and reddens. Hesperidin, C22H2(iO12 (?).-Odorless, tasteless cryst. powder, s. 5000 pt. b. aq.; i. eth.; d. s. ale.; s. NaOH but reppt'd by CO2.-The sol. in NaOH on evaporating to dryness and treat- ing w. x's H2SO4 and warming gives red to violet color!- [A glucoside hydrolyzed by boiling w. dil. acids to glucose and hesperitin (latter melts at 224°-6°, and is s. in alkalies and colored brown-red by FeCl3).] f Phenolphthalein, C20HI4O4.-When amorphous e. s. eth.; when cryst. d. s. eth.; s. ale.; i. aq.-S. in NaOH or Na2CO3 w. intense red color, approximately RV, but much purer than color of the standard. The color is discharged by large x's of NaOH or by warming w. Zn dust. Tetraoxydinaphthylmethane, CH2.[C10H5.(OH)2]2.-E. s. ale. or eth.-S. in cone. H2SO4 w. yellow color, changing to deep red. Thymolphthalein, C2RH3(1O4.-Ndl., e. s. ale.; s. eth.; alm. i. aq. -NaOH gives intense blue sol. (purple by transmitted light). GENUS IV, DIV. A. 103 (ORDER I, SUBORDER I.) Melting-point Boiling-point (C.°). PHENOLIC COMPOUNDS.-Colorless and Solid. 253-5d. Phloretin, Cj5H14O5.-Lft. v. d. s. h. aq. or eth.; v. s. ale.-Sol. in alkalies absorbs 0 fr. air.-Boiled w. KOH gives phloretic ac. and phloroglucin.-Heated w. aniline at 170° gives scarlet sol.-Anilide, alm. i. aq. or eth., but s. in ale. w. deep-orange color. 253-6 f Daphnetin, C9H,O2.(OH)2.-Yellowish ndl. w. coumarin-like odor when warmed!-Sbl.-S. h. aq.; v. d. s. eth.; s. Na2CO3 w. orange color.-Aq. sol. gives green color w. FeCl3, becoming red w. Na2CO3.-Gives yellow ppt. w. PbAc2.-Diacetyl deriv., m. p. 129°-30°. a. 270d. f TEsculetin, C9H4O2.(OH)2 + H2O.-(After loss of cryst. aq. be- comes yellow.)-Lustrous ndl. v. d. s. c. aq.; s. h. aq.; alm. i. eth.; s. in NaOH w. yellow color.-FeCl3 gives intense green color w. aq. sol.!-PbAc2 gives yellow ppt. fr. sol.! 272 7-(p)-Biphenol, [CaH4.OH]2.-Sbl. in scales.-D. s. aq.; e. s. ale. or eth.-Aq. sol. gives no color w. FeCl3 and very transient violet w. Ca(OCl)2.-Sol. in H2SO4 and trace of HN03 be- comes blue.-Ignition w. Zn dust gives biphenyl.-Diacetate, m. p. 159°-160°. d. w. m. 275 Arabinose-resorcin, CnH14O(i.-Amorph. powder, v. s. aq.; v. d. s. ale. or eth.-Aq. sol. blue-violet w. FeCl3; intense red- violet w. Fehling's sol. 280d. p-Dioxystilbene, (HO.C0H4.CH:)2.-E. s. eth.-Diacetate, d. s. h. ale.; m. p. 213°. 300 a-Binaphthol, [C10Ha.OH]2.-Sbl.-I. aq.; s. ale.; more s. eth.- Ale. sol. gives violet-red color w. FeCl3 and ppt. of same color. 310 Biresorcin, C12H10O4 + 2H2O.-Cryst. s. h. aq.-FeCl3 gives pale- blue color.--Heated at 100° for 10 min. w. 1 cc. H2SO4 +1 cc. acetic anhyd. gives blue-violet sol.-M. p. of tetraacetate 158°. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I] GENUS IV, PHENOLIC COMPOUNDS. DIVISION B -LIQUID PHENOLIC COMPOUNDS. Boiling-point (C.°)- Specific Gravity. PHENOLIC COMPOUNDS.-Colorless and Liquid. 139-6 0-987 (15°) f Acetylacetone, Me.CO.CH2.CO.Me.-Odor like acetone and acetic acid.-S. in 8 pt. aq.-The color of aq. sol. (1:100) w. FeCl3 (Test 401) is a very permanent OR-RO.-Dis- tinctly acid!-The aq. sol. gives heavy light-blue ppt. w. sol. of CuAc2.-Saponification by Test V gives acetone and acetic ac. (Tests 711 and 311). 158 0-954 (15°) Hexanedione(2, 4), Me.CO.CH2.CO.Et.-Has acid properties.- Cu salt obtained by ppt'n of sol. in dil. ale. w. CuAc2 sol., blue ndl. fr. ale., m. p. 197°-8°. 167-70 3-Methylhexanedione(2, 4), Me.CO.CHMe.CO.Et.-Blue ppt. w. ammon. CuCl sol., m. p. 192°. 169 0-994 (4°) 3-Methylpentanedione(2, 4), Me.CO.CHMe.CO.Me. 169-70c. 1-037 (9°) Methyl Acetoacetate, Me.CO.CH2.CO2Me.-E. s. aq!-Sol. dark cherry-red w. FeCl3!-Saponification by Test V-2 gives acetone and CH3OH. 174-5 0-941 (15°) 2, 4-Heptanedione, Me.CO.CH2.CO.Pr.-Gives a Cu salt, m. p. 160°-l°. 180-5 1-046% f Ethyl Acetoacetate, Me.CO.CH2.CO2Et.-An aq. sol. (1:100) gives a clear and very permanent RT1 color w. FeCl3 (Test 401).-Saponification by Test V-2 gives acetone, C2H5OH and CO2 (cf. Tests 711 and 814). 183 f Phenol (cf. IV, A, m. p. 42-5°). 186-8 1-009 (6°) Ethyl Methylacetoacetate, Me.CO.CHMe.CO2Et.-Sol. colored blue by FeCl3.-Saponification by Test V gives methyl ethyl ketone, C2H5OH and CO2. 189-7c. 0-995 (14°) Methyl Ethylacetoacetate, Me.CO.CHEt.CO2Me. - Violet-red color w. FeCl3.-Saponification by Test V gives methyl propyl ketone and CO2. 191 o-Cresol (cf. Genus IV, A, m. p. 30°). 196 Caffeol, HO.CoH4.CH2.O.Me.--Odor like coffee.-D. s. h. aq.; e s. ale. or eth.-Aq. sol. colored red by FeCl3.-Fusion w. KOH gives salicylic ac. (Test 319). 198c. 0-998 (12°) Ethyl Ethylacetoacetate, Me.CO.CHEt.CO2Et.-Sol. colored blue by FeCl3.-Saponification by Test V gives methyl propyl ketone, C2H5OH, and CO2. 201 0-981 (0°) Ethyl Isopropylacetoacetate, Me.CO.CHPr.CO2Et.-Sol. colored pale red-violet by FeCl3.-Saponification by Test V gives methyl isobutyl ketone, C2H5OH, and CO2. 201-8 t p-Cresol (cf. IV, A, m. p. 36°). 202-8 1-050 (0°) + m-Cresol, Me.C,;H4.0H.-Does not solidify at 0°.-The color w. a 1% aq. sol. and FeCl3 (cf. Test 401) is BV-BVT1 (on mixing).-Odor like phenol.-Not sol. in 5 pt. cone, ammo- nia.-f Nitrate and purify the product, 2, 4, 6-trinitrocresol, by the procedure given in Test 414-2 for phenol. This tri- nitrocresol is a cryst. compound resembling picric acid in most of its properties, but melting at 106-5° (uncor.). 104 GENUS IV, DIV. B. 105 (ORDER I, SUBORDER I.) Boiling-point Specific Gravity. PHENOLIC COMPOUNDS.-Colorless and Liquid. 204-6 Acetylmesityloxide, Me.CO.CH2.CO.C4H7.-S. in alkalies.-Ale. sol. is colored intensely red by FeCl3.-Olive-green Cu salt, m. p. 123°. 205 t Guiacol (cf. IV, A, m. p. 31°-2°). 205-6 1-086 (15°) Veratrol, o-C6H4(OMe)2.-Solid at +15°. 206 0-9822% Ethyl Allylacetoacetate, Me.CO.CHC3Hs.CO2Et.-Sol. colored carmine-red by FeCl3.-Saponification by Test V gives allyl- acetone, C2H5OH, and CO2. 207c. 1-037 (0°) Phlorol, o-Et.CcH4.OH.-Not solid at -18°.-Violet color w. little FeCl3.-Fusion w. KOH gives salicylic ac. (Test 319). 2C8-5 0-981% Ethyl Propylacetoacetate, Me.CO.CHPr.CO2Et.-Saponification by Test V gives methyl butyl ketone, C2H5OH, and CO2. 211-5 i, 3-Xylenol(i) (cf. IV, A, m. p. 26°). o-Isopropylphenol, Me2.CH.C0H4OH.-M. p. 15°.-Aq. sol. violet and then green w. FeCl3. 213c. 1-012% 214 1-025 (0°) m-Ethylphenol, Et.C6H4OH.-M. p. abt. -4°.-Violet w. FeCl3. 217-5 0-951 (17-5°) Ethyl Isobutylacetoacetate, Me.CO.CH(C4H9).CO2Et.-Saponifi- cation by Test V gives isobutylacetone, C2H5OH, and CO2. 221-2 1-111 (0°) Homopyrocatechinmethylether, Kreosol, C6H3.(Me)(MeO)(OH)(i, 3, 4).-Miscible w. ale. or eth.-• Ale. sol. emerald-green w. FeCL.-M. p. of picrate 96°. 224c. 1-197 (0°) f Methyl Salicylate, o-HO.C6H4.CO2Me.-Odor of oil of winter- green.-The color of the cold saturated aq. sol. w. FeCl3 (Test 401) is RV, permanent for more than 15 minutes.- Saponification by Test V gives salicylic ac. and CH3OH (Tests 319 and 819). 225c. 1-015 (0°) o-Propylphenol, HO.C6H4.Pr. 227-5 Ethyl Isoamylacetoacetate, Me.CO.CH(C5Hn).CO2Et.-Saponi- fication by Test V-2 gives isoamylacetone, C2H5OH, and CO2. 231c. 1-009 (0°) p-Propylphenol, HO.C6H4.Pr. 231 Isocymophenol, C6H3.(Me)(Pr)(OH)(r, 3, 6).-Not solid at -25°. -S. aq.-Aq. sol. pale-violet w. FeCl3.-Vapor induces coughing. 231-5 f Ethyl Salicylate, o-HO.C6H4.CO2Et.-Odor of oil of wintergreen. -The color of the cold saturated aq. sol. w. FeCl3 (Test 401) is RV (on mixing); VRT2-RVT1 after 15 minutes.-Saponi- fication by Test V-2 gives salicylic ac. and C2H5OH (Tests 319 and 814). 236-5-7 0-986 (15°) f Carvacrol, Me.CcH3.(Pr)(OH)(i, 4, 2).-Viscous oil which solidifies at -20°.-FeCl3 gives a coloration, but only in very cone. ale. sol.; the color is then an impure green, which changes and fades rapidly.-M. p. of the phenylcarbamate 140°.-(Cf. Ber. 26, 2086.) 238-40d. 1-098 (15°) Diethyl Acetylmalonate, C2H3O.CH.(CO2Et)2.-Has a strong ac. reaction! Ale. sol. dark red w. FeCl3.-Phenylhydrazine derivative melts at 120°.-Saponification by Test V-2 gives acetone, acetic ac., and C2H5OH (Tests 711, 311). 238-40 1-098 (15°) Propyl Salicylate, PrCO2.C,H4.OH.-Saponification by Test V-2 gives salicylic ac. and C3H7OH (Tests 319 and 820). 240-41C. 1-056 (15°) Ccerulignol, HO.C9H10.OMe.-Odor like creosote.-V. d. s. c. aq.; miscible w. ale. or eth.-Aq. sol. gives carmine ppt. w. FeCl3. -Ale. sol. green w. FeCl3 and blue w. Ba(QH)2. 242 1 • 144 (23°) Methyl 4-Oxy-m-toluate, HO.C6H3(Me).CO2Me.-Oil of winter- green odor.-Saponification by Test V gives 4-oxy-m-toluic ac. and CH3OH (Test 819-1). 243 1-140 (23°) Methyl 3-Oxy-p-toluate, HO.C0H3Me.CO2Me.-Saponification by Test V-2 gives 3-oxy-p-toluic ac. and CH30H (Test 819-1). 106 GENUS IV, DIV. B. (ORDER I, SUBORDER I.) Boiling-point (C.°J. Specific Gravity. PHENOLIC COMPOUNDS.-Colorless and Liquid. 243-4 Methylresorcin Ether, m-H0.CGH4.0Me.-S. c. aq.; miscible w. ale. or eth.-Aq. sol. pale violet w. FeCls. 247-5 si. d. 1-063 (18-5°) t Eugenol, CGH3.(CH2.CH: CH2)(OH)2(i, 3, 4)--Odor of cloves. -V. d. s. aq.; e. s. ale., etn., or Ac.-Cold saturated aq. sol. gives a turbid YGT2 color in Test 401, w. FeCl3; the ale. sol. (1:50) gives a B color fading in 15 min. to GYT2. 248 1 • 102 (23°) Ethyl i-Methyl-2-oxybenzoate(3), Me.CGH3(OH).CO2Et.-Sapon equiv. 178.-The corresponding ac. gives violet color w FeCl3.-Saponification by Test V-2 gives l-methyl-2-oxy- benzoic ac. and C2H6OH (Test 814). 254 1-097 (23°) Ethyl 3-Oxy-p-toluate, HO.CGH3(Me).CO2Et.-Saponification by Test V-2 gives 3-oxy-p-toluic ac. and C2H5OH (Test 814). 254-5 1-067 (15°) Betelphenol, (CH2.CH:CH2).C6H3.(OH)2(OMe)(i, 3, 4).-Ale. sol. intense blue-green w. ale. FeCls. (In ethereal oil from Piper betle.) 254-6 1-088 (15°) Diethyl Acetylsuccinate, C10H1GO5.-Red-violet color w. FeCl3.-- Saponification by Test V-2 gives acetic and succinic acids and C2H5OH (Tests 311, 320, and 814). 258-62 1-080 (16°) Isoeugenol, (CH: CH.Me).CGH3.(OH)2(r, 3, 4). - Solidifies in freezing mixture.-Ale. sol. green w. FeCl3. 265-70d. 1-122 (15°) f Ethyl Benzoylacetate, C6H5.CO.CH2.CO2Et.-S. without de- composition in c. dil. NaOH.-Ale. sol. gives red-violet color w. FeCl3.-Saponification by Test V-2 gives acetophenone, C2H5OH and CO2 (Tests 712 and 814). 266-9 Phenylacetylacetone, Ph.CH2.CO.CH2.CO.Me.-D. s. c. aq.; e. s. dil. alkalies.-AgCuH^Oj, flocculent ppt. 270 Isoamyl Salicylate, o-HO.C^.COjCgH,,.-Saponification by Test V gives salicylic ac. and C5HnOH (Test 319). 273 Methyl Orcinyl Ether, MeO.C7HB.OH.- D. s. aq.; e. s. ale. or eth.-Browns on exposure to air. 283-4 1- 03615/ie Ethyl Benzylacetoacetate, C2H3O.CH(C7H7).CO2Et.-Saponifica- tion by Test V-2 gives Me.CO.(CH2)2.Ph, C2Hfi0H, and CO2. NUMBERED SPECIFIC AND SEMI-SPECIFIC TESTS FOR PHENOLIC COMPOUNDS. [TESTS 401-500.] 4oi. Ferric-chloride Colorations. The test with ferric chloride, forming the first part of Generic Test IV, is designed rather to favor the development of a maximum color effect in the largest possible number of cases than to secure the most characteristic results for individual species. To obtain the ferric-chloride coloration attributed to any phenol in the description given in the tables, it is necessary to pay attention both to certain principles that will be now stated, and to the special supplementary directions concerning dilution, etc., that form part of many of the individual specific descriptions. The most desirable concentration for the phenol solution is one that will give a color of such quality and intensity that, when viewed horizontally in a six-inch test-tube, it will nearly match a spectrum color or "tint", rather than a "shade" or a "broken color" of the color standard. This concentration varies greatly with the phenol, but in aqueous solu- tions is often met in a 1 per cent solution. Alcohol is usually a much less satisfactory solvent in these tests than water, but is sometimes to be preferred. The same phenol often gives different colorations in the two solvents. Hot solutions must never be used with either solvent. The colors from some phenols are permanent for hours; but more often are very transitory, the first coloration sometimes undergoing a complete change in hue, or entirely fading away within a few seconds or minutes. The coloration is occasionally accompanied by a precipitate. The appearance of a color is prevented by the presence of either free acid or alkali, or else its character is essentially modified (cf. pyrocatechin). An excess of ferric chloride may destroy the coloring matter that is first formed, or obscure the proper coloration by blending it with yellow. The usual procedure in the specific test with ferric chloride is as follows: Place 5 cc. of the clear, cold solution of the phenol, which has the concentration speci- fied in the tables, in a six-inch test-tube. Add one or more drops of a ferric-chloride solu- tion (1 : 40) prepared by diluting one volume of the 10 per cent stock solution of the salt with three volumes of water. Use no more of the reagent than is required to produce a color suitable for comparison. Shake; and then, without delay, make a careful com- parison of the color produced with the color standard. Repeat the comparison after the mixture has stood for five and for fifteen minutes. Comparisons should be made in clear diffused daylight, looking horizontally through the tube towards a white wall or card imme- diately behind it (cf. p. 232). 402. The Phthalein Fusion. Mix about 0.05 grm. of the phenol with an equal bulk of powdered phthalic anhydride in a dry test-tube. Moisten with one drop of concentrated sulphuric acid. Stand the tube in a small beaker containing an inch or two of sulphuric acid, oil, or molten paraffin, which has been heated up to a nearly constant temperature of 160°. Heat for three minutes. Cool. Add 2 cc. of cold water, and 1-2 cc. of sodium-hydroxide solution (1 : 10); i.e. 107 108 SPECIFIC TESTS FOR PHENOLIC COMPOUNDS. enough to give the solution quite a strong permanent alkaline reaction. Stir the fused mass at the bottom of the tube until most of it has dissolved. Dilute with an equal vol- ume of water and filter. Compare the color of the filtrate with the color standard (cf. p. 232\ using such a dilution that the comparison can be conveniently made in a six-inch test-tube held before a white background. If the solution shows a fluorescence, examine its color with a black background. The colors observed in this test are frequently intense and characteristic. When the coloration given by a phenol has been compared with the color standard, it will usually be found mentioned among the tabulated properties and reactions of the species. 411. Hydroquinone. (Properties tabulated on p. 99.) 1. Dissolve 0.1 grm. of the substance in 3 cc. of warm water. Cool, and slowly add 2-3 cc. of a 10 per cent ferric-chloride solution. Shake. Filter off the precipitate of green-black glistening quinhydrone. Collect the filtrate in a small graduate and wash with cold water until the total filtrate measures 10 cc. Rinse the precipitate into a test-tube, using 6 cc. of water. Warm to just 40°, so as to partly dissolve the crystals. (Boiling would decom- pose the quinhydrone to quinone.) Cool to below 20°. Filter into a small graduate, and wash with cold water until the filtrate measures 10 cc. Dry the precipitate on a piece of porous tile supported over a drying-oven where the temperature will be 35° to 40° for twenty minutes, and determine its melting-point. Quinhydrone is obtained in this test in slender needles of a peculiar greenish-black color and beautiful metallic luster. Rapidly heated it begins to sublime at 145°-50°; gradually softens; and, finally, not far from 170° (uncor.) melts completely to a dark orange-red liquid. Even when cold it emits a faint pungent odor of quinone. 412. n-Naphthol. (Properties tabulated on p. 94.) 1. Dissolve 0.05 grm. of the naphthol in 10 cc. of a 1 per cent caustic-soda solution. Add five drops of chloroform, and boil 20 seconds. Compare the color immediately with the standard (cf. p. 232). a-Naphthol gives at first a clear blue (B). In 15 minutes the color changes to a bluish- green (GB-BG); in 4| hours to yellow-green (YG). 2. Dissolve 0.10 grm. of the substance, and 0.15 grm. of picric acid, in 10 cc. of boiling dilute alcohol (1 : 1). Allow to cool slowly. Filter off the orange (O) needles of picrate, which separate after short standing and shaking, and wash with 2 cc. of dilute alcohol (1 : 1). Dry in a warm place on a bit of porous tile. Determine the melting-point in a bath whose temperature is rising somewhat rapidly. The picrate, (C10HsO.C8H3(NO2)3O), melts at 188.5°-189.5° (uncor.). 413. /3-Naphthol. (Properties tabulated on p. 96.) 1. Apply Test 412,1.-The first coloration is blue (B); but unlike that from a-naphthol it fades rapidly, passing through GB and YT2 of the color standard to colorlessness in 10 minutes. 2. Dissolve 0.10 grm. of the substance, and 0.15 grm. of picric acid, in 6 cc. of boiling dilute alcohol (1 : 1). Then proceed as in Test 412, 2. The picrate, (C10HsO.C8H3(NO2')3O), crystallizes in long thin needles of an orange- yellow color (YO) which melt, when somewhat rapidly heated, at 155.5°-156.8° (uncor.). 414. Phenol. (Properties tabulated on p. 91.) 1. The "phthalein fusion" (Test 402) gives a bright violet-red (VR) solution after adding alkali due to formation of phenolphthalein. 2. Dissolve 0.05 grm. of the substance in 1 cc. of concentrated sulphuric acid. Pour with stirring into a mixture of 1 cc. of concentrated sulphuric acid and 1 cc. of concen- trated nitric acid. Heat on a water-bath for 5 to 10 minutes. Pour slowly into 10 cc. SPECIFIC TESTS FOR PHENOLIC COMPOUNDS. 109 of cold water. Cool thoroughly. Filter. Wash the precipitate with a cold mixture of 2 cc. of water and 0.5 cc. concentrated hydrochloric acid. Recrystallize from a boiling mixture of 4 cc. of water and 1 cc. of concentrated hydrochloric acid. Cool well and filter. Wash as before with a cold mixture of 2 cc. of water and 0.5 cc. concentrated hydrochloric acid. Dry at 100°, and determine the melting-point. The product in this test is picric acid (trinitrophenol) melting at 122.5° (cor.). Picric acid crystallizes from the dilute hydrochloric acid in plates, that are at first nearly color- less, but which gradually become yellow on exposure to the air. It deflagrates when heated on platinum foil. A dilute aqueous solution of the compound stains the skin and dyes wool an intense yellow; and its taste is very bitter. The test is simple, and very satis- factory when the result is corroborated by other evidence; but it should be remembered that picric acid is also formed, though usually not with the same ease, by the nitration of some other compounds. Since picric acid can be dried at 100°, this test may be com- pleted more quickly than Test 3. It is, nevertheless, at least equally reliable. 3. Dissolve 0.05 grm. of the substance in 2 cc. of water, and add a saturated aqueous solution of bromine until the reagent is present in excess, the color of the liquid then re- maining permanently yellow. Filter off the bulky, curdy yellowish-white precipitate. Transfer to a small beaker. Cover the precipitate with water, and add acid sodium-sul- phite solution gradually until a strong odor of sulphur dioxide remains after stirring and warming to 40°. Filter. Wash well with cold water. Dissolve in 15 cc. of boiling 40 per cent alcohol. Filter off the precipitate which separates on cooling. Transfer to a piece of porous tile; allow to become thoroughly air dry, and determine the melting-point. The white, crystalline 2, 4, Sdribromphenol obtained as the final product by this pro- cedure is very insoluble in cold water and melts at 92.5°-93.5° (uncor.). The precipitate with bromine water contains at first an excess of bromine, and consists of the compound C6H2Br4O, which loses one atom of bromine and is converted into the tribrom-derivative during the treatment with the sulphite solution. Salicylic acid also gives tribromphenol when treated with bromine water. The bromine-water test is most useful when phenol is present in small quantity in a dilute aqueous solution. 415. Phloroglucin. (Properties tabulated on p. 101.) Dissolve 0.1 grm in. 1 cc. of concentrated sulphuric acid by stirring. Pour the clear solution into a mixture of 1 cc. of concentrated sulphuric, and 1 cc. of concentrated nitric acids, cooling with cold water, and stirring until a precipitate appears. Allow to stand for five or six minutes; then pour into 10 cc. of cold water. Cool well and filter. Wash the precipitate with 2 cc. of water containing 0.5 cc. of concentrated hydrochloric acid. Recrystallize from a boiling mixture of 3 cc. of water and 1 cc. of concentrated hydrochloric acid. Cool and filter. Wash with 2 cc. of water containing 0.5 cc. of con- centrated hydrochloric acid. Dry at 100°-105°. The product, trinitrophloroglucin, crystallizes easily in pale-yellow needles melting at 165°-166° (uncor.). It stains the skin yellow, and deflagrates when heated on platinum foil like picric acid. 416. Pyrocatechin. (Properties tabulated on p. 94.) 1. Always apply the ferric-chloride color reaction as directed in the tables, adding 1 co. of the ordinary laboratory sodium-carbonate solution in the latter part of the test. This test requires very little substance, and is one of the most satisfactory of its class. 2. Dissolve 0.05 grm. of the substance in 2.5 cc. of warm chloroform. Add 0.4 cc. of bromine. Evaporate to dryness on a water-bath. Dissolve the residue in 5 cc. of cold alcohol. Add 20 cc. of cold water. Shake, and then filter. Wash the precipitate with a little cold water. Redissolve in 5 cc. of alcohol, and reprecipitate with 20 cc. of cold water. Allow the precipitate to become air dry on a piece of porous tile, and determine its melting- point. 110 SPECIFIC TESTS FOR PHENOLIC COMPOUNDS. The product, tetrabrompyrocatechin, crystallizes in white needles. As obtained in this test, the crystals are often tinged with violet, and melt (not very sharply) at about 192°-3° (uncor.) after beginning to shrink and soften at 185°-187°. 417. Pyrogallol. (Properties tabulated on p. 96.) 1. To 2 cc. of water in a 6-inch test-tube add 1 drop of glycerine and 5 drops of a solution of 0.01 grm. of the substance in 1 cc. of water. Next add 2 cc. of concentrated sulphuric acid and boil for 20-25 seconds. Then, without delay, compare the color of the hot solution with the color standard (cf. p. 232). Use a white background behind the tube. The color given by pyrogallol in this test is a clear tint of violet-red (VRT 1-2). On continued boiling or standing, the color intensifies rapidly, but soon becomes impure and unsuited for purposes of comparison. 2. In a dry test-tube place 0.1 grm. of pyrogallol, 0.5 grm. of powdered anhydrous sodium acetate, and 1.0 cc. of acetic anhydride. Boil for one and one-half to two minutes. Add 10 cc. of water, and boil for fifteen or twenty seconds till the oily liquid solidifies. Cool. Filter, and wash with 10 cc. of cold water. Dry at 100°-105°. The product obtained in this test, pyrogallol triacetate, is in the form of white crys- tals which soften at about 155° and melt at 160.5°-161.5° (uncor.) when heated rathei rapidly. Recrystallization from 4 cc. of strong alcohol raises the melting-point about 0.5°. 418. Resorcin. (Properties tabulated on p. 95.) 1. One of the simplest, most delicate, and rapid of the tests for resorcin is the fluoresceih fusion, which is fully described under Test 318-1. If more convenient, substitute phthalir anhydride for the phthalic acid. Color reaction 114 with formic aldehyde furnishes another simple resorcin test. 2. Dissolve 0.1 grm. in 1 cc. concentrated sulphuric acid. Pour slowly with constant stirring into a cold mixture of 1 cc. concentrated nitric acid and 1 cc. concentrated sul- phuric acid. (It is well to place the mixed acids in a small round-bottomed dish resting on the top of a small beaker filled to the brim with very cold tap water.) Do not run in the resorcin solution fast enough to cause a permanent brown coloration in the acid. When all has been added, remove the dish from the cold water and allow to stand on the table for two or three minutes. Then pour the mixture of liquid and yellow crystals that have sepa- rated slowly into 10 cc. of cold water, keeping well cooled with running water. Filter. Wash with 5 cc. of cold water. Recrystallize from a boiling mixture of 10 cc. of cold water, 4 cc. strong alcohol, and 0.4 cc. concentrated hydrochloric acid. Cool well and shake. Filter. Wash with 5 cc. of cold water and dry at 100°. The product in this test, trinitroresorcin, consists of slightly yellowish crystals of melting-point 175° (uncor.). It stains the skin yellow like picric acid. The yield is good. 41g. Thymol. (Properties tabulated on p. 92.) 1. The colors obtained in the phthalein fusion (Test 402), and described in the tables, are quite characteristic. This test should always be applied. 2. Dissolve 0.1 grm. of the powdered substance in 1 cc. of concentrated sulphuric acid. Add with stirring to a mixture of 1 cc. of concentrated nitric, and 1 cc. of concen- trated sulphuric acids contained in a very small dish. Allow to stand on the cover of a boil- ing water-bath for three or four minutes. Pour into 20 cc. of cold water. Cool well and shake vigorously. Filter. Wash the precipitate with 10 cc. of cold water. Crystallize from a boiling mixture of 10 cc. water, 4 cc. alcohol, and 0.4-0.6 cc. concentrated hydro- chloric acid. Filter. Wash with 5 cc. of cold water. Dry on a piece of porous tile in the air, or in a drying-oven below 50°. The product in this test is trinitrothymol, melting at 109°-110° (uncor.). The crys- tals, which are at first nearly colorless, like those of many other nitrophenols, turn lemon- yellow after a few hours' exposure to the air. CHAPTER VIL GENUS V. ESTERS OF SUBORDER I, ORDER I. (Colorless Compounds of Carbon, Hydrogen, and Oxygen.] The tables of this genus contain only the most important esters derived from the well- known volatile alcoholic compounds enumerated in the table on p. 116. Other esters are to be identified through their alcoholic and acidic saponification products by a method which will be given in connection with " Procedure 2 " of the generic test. Esters that are rapidly saponified by cold alkali, the ester-acids, ester-phenols, and the enolic esters, show a behavior with reagents which places them in Genus III or IV with the acids or phenols. Finally, a few esters like those of the aromatic diortho-substituted carbonic acids, which offer extraordinary resistance to the action of hot alkali, fall in later genera. GENERIC TEST V. APPLY PROCEDURE 1.-IF THE RESULT IS NEGATIVE, THE COMPOUND DOES NOT BELONG TO EITHER GENUS V OR VI. IF IT SHOWS THAT THE COMPOUND MAY BE AN ESTER OR ACID ANHYDRIDE, BUT FAILS TO POSITIVELY IDEN- TIFY IT WITH ANY SPECIES DESCRIBED IN GENUS V OR VI, PROCEDURE 2 SHOULD, IF POSSIBLE, THEN BE APPLIED.-[PROCEDURE 2 MAY LEAD TO THE IDENTIFICATION OF ANY ESTER THAT SAPONIFIES TO AN ALCOHOL AND ACID DESCRIBED IN THESE TABLES, WHETHER THE ESTER IS ITSELF MEN- TIONED OR NOT, BUT IS LONGER THAN PROCEDURE 1.] PROCEDURE 1. Weigh out very carefully in a 3-inch lipped weighing tube about 0.1 grm. of the substance. Add 2 cc. of a nearly colorless and approximately normal solution of sodium or potassium hydroxide in pure strong alcohol from a thin-stemmed pipette. The pipette need not be accurately calibrated, but must be used with such precautions to ensure uniformity in delivery that the volume of liquid dis- charged by it in two successive experiments shall not differ by more than about 0.005 cc. Stopper the weighing tube tightly with a sound soft cork, which must be wired down with a thin copper wire in the manner shown in Figure 3. [The wire, after being first doubled, is twisted so as to form a small eye at A. It is then drawn tightly around the tube by twisting with pliers at B, and the free ends passed over the cork and through the eye. The ends are then seized with the pliers and drawn back with sufficient force to slightly imbed the wire at the edges of the cork. If the wire is now bent sharply back upon itself, as is shown at C, the stopper will be securely held during the subsequent heating.] Place 2 cc. of the same normal alkali that was added to the substance in a second tube stoppered like the first. 111 112 ESTERS. Hang the two tubes from a glass rod by their wires, side by side, in a beaker of boiling water, and heat for thirty minutes. Or, better still, thrust the tubes through perforated cork stoppers, and heat half an hour at 100° in a bath of the kind described on p. 152 and shown in Figure 4. Then wash the contents of each tube into a separate small beaker, and titrate carefully with decinormal acid and phe- nolphthalein. From the results of the titrations calculate the 1 ' saponification equivalent" * of the compound by use of the following formula, in which the Fig. 3. number of cubic centimeters of standard acid consumed in neutralizing the alkali used for the blank experiment is represented by a', and the quantity consumed by the alkali after being heated with the substance, by 6. Then- „ P _ 1000 Xgrm. of ester taken 1 (a-6)Xnormal strength of the standard acid' If this equivalent is found to have a value greater than 500, pass on to Genus VII; for in this case the compound can not be a species described in either Genus V or VI. If, on the contrary, the equivalent has a value less than 500, a search must be made through the proper divisions of the tables of Genera V and VI for a species whose physical constants and saponification equivalent correspond to those found for the substance. If this search leads to the discovery of an apparently corre- sponding species, the identification may sometimes be satisfactorily completed by the application of special tests suggested in the text. In all other cases, provided the supply of substance remaining permits, it is best to saponify a larger quantity, * By " saponification equivalent " is here meant the number expressing how many grams of a compound would be required to just neutralize 1000 cc. of normal sodium hydroxide solution in a saponification experiment. ESTERS. 113 and isolate and identify its acid,* or alcohol, or both, by the methods given under Procedure 2. PROCEDURE 2. Saponify with aqueous alkali as directed below under A. Identify any neutral saponification products (alcohols, phenols, or ketones) as directed under B, below, and any acid saponification products according to C, p. 116. A (Saponification). Fit a 250-cc. round-bottomed flask with a clean, sound cork stopper perforated to receive the lower end of a return-flow condenser that has been mounted verti- cally on a heavy iron stand. Introduce about 2 grm. of the substance, accurately weighed, into the flask; and then, from a pipette, exactly 50 cc. of an aqueous normal solution of pure sodium hydroxide. Next drop in an ebullator-tube to prevent bumping (cf. p. 223) and boil briskly for about two hours, or even longer if the odor or appearance of the mixture gives indication that, while the substance has been attacked by the treatment, a portion of it remains unchanged. The flask should rest lightly on a square of iron gauze during the boiling, and the burner flame should be shielded from drafts of air; for any pause in the boiling that is more than momentary will cause the ebullator capillary to fill, after which such violent bumping may occur as to shatter the flask. The saponification completed, cool; add two drops of phenolphthalein solution, and titrate with normal sulphuric acid without removing from the flask. The saponification equivalent may now be calculated from the experimental data by substituting in the equation- 1000Xno. grm. ester saponified * ' no.cc. alkali neutralized in saponific. X normal strength of alkali* B (Examination of the Neutral Saponification Products). Drop a fresh ebullator-tube into the flask whose contents have been neutralized in the titration mentioned in the last paragraph, and rapidly distil off 40 cc. of liquid through an inclined condenser, collecting the distillate in a tall narrow graduated cylinder or test-tube. During the first part of the distillation, observe whether the distillate is turbid, separating into two layers in the recipient, or is clear and apparently homogeneous. At the same time make careful note of the odor. (The greater part of the volatile alcohols, phenols, and ketones will be contained in the first few cubic centimeters of the distillate.) After the distillate has all been collected, if two layers are still * The quantity of acid present as sodium salt in the neutral solution after the titration in Procedure 1 is so small that its direct identification is only occasionally possible. In such cases the procedure, after evaporating the solution to a very small volume and filtering, is identical with that described in Section C (p. 116) of Procedure 2. 114 ESTERS. present, close the mouth of the test-tube with the thumb and shake, in order to ascertain whether the smaller layer, which will usually have a volume con- siderably less than 1.0 cc., can be dissolved in the water present. If a clear solution is not obtained, separate the two layers by the aid of a long and very thin-stemmed pipette. The aqueous solution is at once used for the lettered tests (a) to (i) which follow. The smaller layer, consisting of compounds not readily soluble in cold water, is dried, and its boiling-point later determined by the procedure given towards the end of paragraph (i). '(a) Phenol.-If the odor of the distillate suggests the presence of phenol, remove 1 cc. of the clear aqueous solution to a 3-inch test-tube and add bromine water in excess. If a voluminous white precipitate appears, add to a second 1 cc. portion of the distillate one drop of a ferric-chloride solution (1:200). Then, if a violet coloration is obtained, phenol is probably present. If more conclusive evidence is wished for, apply Specific Test 414-3 to the remaining portion of the distillate. (b) Allyl Alcohol.-If the odor of the distillate is purely pungent, like horse- radish or mustard-oil, allyl alcohol may be present. In this case 1 cc. of the distillate will instantly decolorize two or three drops of a saturated aqueous solution of bromine. (Allyl alcohol is miscible with water.) (c) Isobutyl and the Amyl Alcohols.-If the vapors from the first part of the distillate are disagreeable and suffocating, tending to produce coughing when deeply inhaled, isobutyl alcohol or an amyl alcohol is likely to be present. These alcohols always rise to the surface of the distillate as distinct layers during the first part of the distillation, but are miscible on shaking,-isobutyl alcohol easily, the amyl alcohols with more or less difficulty. Isolate, dry, and determine the boiling-point of the alcohol in the distillate by the method described under test (i). (d) Benzyl Alcohol.-If the odor of the distillate is faintly aromatic, and some of the oily drops that separate from it sink to the bottom of the recipient but dissolve later upon being shaken, benzyl alcohol may be present. Separate from the solution by the method of paragraph (i). Determine the boiling-point and finally apply Test 812. (e) Higher Volatile Fatty Alcohols.-If the distillate contains an upper layer whose odor is milder, less suffocating, and more aromatic than that of amyl alcohol, and does not dissolve in the aqueous layer after shaking, one of the volatile fatty alcohols higher in the homologous series than amyl alcohol should be looked for. In this case ' ' salt out " the organic compound directly, by adding 40 grm. of dry potas- sium carbonate; mix it with the smaller insoluble layer which separated from the original distillate; and then dry and determine the boiling-point as in paragraph (i). (f) Methyl Alcohol and other Lower Fatty Alcohols and Ketones.-If the dis- tillate is a clear solution without layers, and is odorless, or has a mild alcoholic odor, remove 2 cc., oxidize with a hot copper spiral, and examine for methyl alcohol by Specific Test 819. If no colored ring whatever appears in this test, the distillate does not contain any volatile alcohol provided for in this method, or acetone; and unless some non-volatile alcohol can be separated from the salts remaining in the distilling-flask, the compound under examination must next be sought among the species of Genus VI. ESTERS. 115 (g) Acetone and Isopropyl Alcohol.-If no satisfactory reaction for methyl alcohol was obtained in (f), but a reddish, yellowish, or brownish ring was noticed, remove 1 cc. of the original distillate to a 3-inch test-tube and add; first, two drops of the iodine solution (described in Test 801); and then barely enough sodium hydroxide (1 : 10) to just destroy the brown color of the iodine. The immediate appearance of a yellowish-white precipitate of iodoform will indicate the possible presence of acetone or isopropyl alcohol.* In case such a precipitate does appear, separate out the alcohol or acetone contained in the remaining portion of the distillate by the method of paragraph (i), and determine its boiling-point. (h) Ethyl Alcohol.-If no iodoform was obtained in (g), heat the same portion of solution used in the test to 60°, and add another drop of caustic soda and just enough more iodine to give a very faint permanent coloration. If a good precipitate of iodoform appears within one minute, and the colored ring in test (f) was a deep impure greenish or amber yellow, ethyl alcohol is very probably present. If no iodoform separates within a minute, normal propyl and butyl alcohols remain to be looked for. In any case, proceed as directed in the following paragraph. (i) Identification of n-Propyl and n-Butyl, or other Soluble Alcohols, by Boil- ing-point Determination.-Transfer the remainder of the distillate, which will now measure at least 30 cc., to a 100-cc. distilling-flask containing 30 grm. of dry potassium carbonate. Connect with a condenser, and, when the carbonate has dissolved, drop in a fresh ebullator-tube and distil over 15 cc. of liquid, collecting in a narrow graduated cylinder or test-tube. Dissolve 15 grm. of dry potassium carbonate in the distillate by stirring, cooling with running water to prevent loss of alcohol by heating and evaporation. Stopper, and allow to stand for at least ten minutes. Insert a thin-stemmed pipette of about 25 cc. capacity into the liquid, so that its almost capillary point shall rest lightly on the bottom of the tube. Suck the solution, to the last drop, into the pipette. After waiting a few seconds for all the small globules of alcohol to rise to the surface and unite, allow the lower layer, consisting of carbonate solution, to run out slowly into a beaker. Collect the upper layer of alcohol, which may measure less than 0.5 cc., by itself, in a narrow weighing-tube just wide enough to admit the stem of the pipette. Drop in a granule of dry potassium carbonate having a bulk one- third as great as that of the liquid. Stopper, and allow to stand for half an hour or more. Then incline the tube; remove the clear alcohol by a thin capillary pipette, and determine the boiling-point by Siwoloboff's method, following the directions for manipulation given on p. 222. Do not neglect the precaution to boil off half the liquid before allowing it to recede into the capillary for the final observation of temperature. This method requires no complicated apparatus, and gives useful results with as little as 0.1 cc. of an alcohol. Enough alcohol will often be left after the boiling-point determination to permit its identification by other special confirmatory tests. The accompanying table contains a list of all the neutral volatile products that are formed from the saponification of the ester species described in the tables of Genus V. With the exception of phenol, they are all liquids at the ordinary tempera- ture; and with the exception of phenol and acetone, all are alcohols. * See Test SOI, p. 166. 116 ESTERS. Neutral Saponification Product. Boiling-point (C.°). Number of Specific Test. Neutral Saponification Product. Boiling-point (C.°). Number of Specific Test. Acetone Methyl Alcohol Ethyl Alcohol Isopropyl Alcohol Tert. Butyl Alcohol. . .. Allyl Alcohol Propyl Alcohol Sec. Butyl Alcohol Isobutyl Alcohol n-Putyl Alcohol 56-5c. 66 78-4 82-8 82-9c. 96-6 97-4c. 99-8 106-5 117c. 711 819 814 818 811 820 817 813 Act. Amyl Alcohol. . Isoamyl Alcohol. . . . n-Amyl Alcohol. . . . n-Hexyl Alcohol. . .. n-Heptyl Alcohol. . . n-Octyl Alcohol. . . . Phenol Benzyl Alcohol Glycerine 128-7 130 137-8 (th. i.) 157c. 175-8 (th. i.) 195-5 (th. i.) 183 204-7c. 290 (very lit- tle volatile with steam) 414 812 816 (j) Non-volatile Alcohols.-Esters of alcohols not volatile with steam form- ing, with the exception of the natural fats, a comparatively unimportant class, are omitted from the tables. The alcohols from such esters remain behind in the flask with the neutral sodium salts after the distillation in B. They may usually be separated from these salts by extraction with ether or other organic solvent, and identified, after purification, by application of the usual systematic procedure used for the species of Genera IV, VII, and VIII. But unless the alcohol in such cases is very easily purified, a much larger quantity of substance will have to be used in the saponification than would otherwise be necessary. For the identification of glycerine, after saponification, evaporate the neutral salt solution to dryness on the water-bath, extract with ether-alcohol, and then proceed as directed in Test 816. C (Examination of the Acid Saponification Products). The acid radicals of esters are identified through an examination of the sodium salts remaining in the neutral solution obtained from the saponification equivalent determination of A (p. 113) after the alcoholic saponification products have been removed by the methods described under B (p. 113). This neutral saline solution, if not clear, must first be filtered. Then add to it, in the cold, a quantity of normal sulphuric or hydrochloric acid exactly equivalent * to the alkali consumed during the saponification; i.e. just enough to unite with that portion of the sodium present which is in combination with the organic acid. Shake vigorously, and then proceed as directed in paragraphs (a), (b), and (c) below. (a) Insoluble Acids.-If a precipitate of an insoluble acid appears upon acidifi- cation and shaking, filter it off; purify it by recrystallization or other means; and identify it by reference to the tables of Genus III. (b) Soluble Acids Volatile with Steam.-If no precipitate appears upon acidi- fication, place the solution in a distilling-flask, drop in an ebullator capillary (cf. page 223), to prevent bumping, and rapidly distil over all but about 20 cc. (It may be necessary to add more water to the flask and to again distil, if the acid should be one that is only slowly volatile with steam.) Examine the distillate for soluble volatile acids. To identify acetic acid or any of its immediate higher homologues in the same * If the mineral acid added at this point, and the alkali used for the saponification, both have the same normality, the volume of the standard acid here required will be identical with the ' ' cc-alkali neutralized " which appears as a term in the denominator of the equation for the cal- culation of the saponification equivalent on p. 113. ESTERS. 117 series, neutralize the distillate exactly with caustic soda, evaporate to dryness, and apply Test 311 to the residue. The presence of formic acid in the distillate may be established by Test 315. (c) Soluble Acids not Volatile with Steam.-Pour the mixture remaining in the distilling-flask after the removal of the volatile acids in (b) into an evaporating- dish, and evaporate to dryness on the water-bath. Extract the residue with ether or other volatile organic solvent. Purify the extracted acid, and identify it by the tables of Genus III. Observations on Generic Test V. The ease with which esters are saponified differs with the species and the method of saponification. Species soluble in water are all readily saponified by either Procedure 1 or 2; and some of them, like methyl formate, so rapidly that they may be slowly titrated, and are therefore described in Genus III instead of V. Among the liquid esters there are some slightly soluble species, like diethyl succinate, which appear perfectly neutral in the titration test for acids, but which are dissolved with saponification when shaken with cold aqueous normal alkali. Compounds of this class escape being classified with the phenols only because of the provision that Test IV-2, with alkali, shall not be applied to liquid species. With increasing insolubility of the ester in water, saponification by Procedure 2 becomes slower and more difficult; but as most esters are quite soluble in hot alcohol, the rate of saponification of different species by Procedure 1 is comparatively uniform, so that the reaction is usually completed within half an hour. Procedure 1 is on this account an indispensable preliminary generic test for difficultly soluble esters. Some insoluble esters of high molecular weight would escape recognition as species of Genus V if examined by Procedure 2 only. As regards really " non-saponifiable esters," there is no positive evidence that such species exist in Order I; and it has been shown by Mr. J. R. Odell, in the writer's laboratory, that even the esters of diortho-substituted aromatic acids, which V. Meyer has pointed out are exceptionally alkali resistant, are measurably attacked by the treatment of Procedure 1. Methyl 2, 4, 6-Trimethylbenzoate, for example, is 7 per cent saponified in the procedure at the end of half an hour, or 18 per cent when the salting-out effect * of the .normal alkali is counteracted by previous dilution with an equal volume of alcohol. The velocity of saponification with esters of this class is not great enough, however, to bring them into Genus V. The most serious limitation of Procedure 1 as a complete generic test is, that the use of ethyl alcohol as a solvent renders the direct identification of the lower boiling alcohols, when they are formed as saponification products, impracticable. The possibilities for experimental error in the determination of a " saponification equivalent " by either of these procedures are more numerous than in the deter- mination of the " neutralization equivalent " for acids. Differences of 5 per cent between the values found by these methods, and calculated from the theory, should not be considered serious discrepancies. The main object of the saponification is to ascertain quickly whether a compound really belongs to Genus V or VI or not. * Caustic soda appears to produce a "salting-out" effect upon some esters in alcoholic solu- tion even when its concentration is only normal. In such cases the addition of one or two vol- umes of alconol will give a clear solution and accelerate the saponification. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I] GENUS V, ESTERS. DIVISION A-SOLID ESTERS WHOSE NEUTRAL SAPONIFICATION PRODUCTS, METHYL, ETHYL, PROPYL, BUTYL, AND ISOBUTYL ALCOHOLS, AND PHENOL, ARE SOLUBLE IN COLD WATER AND READILY VOLATILE WITH STEAM. Melt- ing- point (C.°). Sapon. Equiv. Boiling-point ESTERS.-Solid Esters whose Neutral Saponification Products are Soluble in Cold Water and Readily Volatile with Steam. Generic Position and Properties of the Acidic Saponification Products. 20 150 211c Phenyl Propionate, C9H10O2.- (III, B, l),b.p. 140-7°; Test 311. 22 350 Methyl Behenolate, C23n42O2.- (III, A, 2), m. p. 57-5°. 24-2 284 Ethyl Palmitate, C1SH3GO2.- " " 62-6°c. 27-8 176° d, (13 mm.) " Benzoylacetoacetate, Ci; H14O4. 28 270 Methyl Palmitate, C17H34O,.-- (III, A, 2), " 62-6° c. 29 253° Triethyl Methanetricarbonate, C10HI6Oo. - Cf. Genus III, A, 2, m. p. 29°. 29-30 30 32 366 a. 360 Ethyl Brassidate, C24H4GO2.- (III, A, 2), m. p. 60°. " Tetrinate, C7H10O3.- " " 189°. Diethyl Benzalmalonate, C14H1GO4.-" " 195°; also cin- namic and malonic acids. 33-7 312 224d. Ethyl Stearate, C20H40O,.- " " 69-3°c. 34 180 254 " Mandelate, C10H12O3.- (III, A, 1), " 118°. 34 194 273 " o-Hydrocoumarate, Cnlf14O3.-(III, A, 1), m. p. 82°-3°. 34 ' 256 " Benzilate, C16H16O3.- (III, A, 2), m. p. 150°. 34 140 197c. " Pyromucate, C7HsO3.- (III, A, 1), " 132°-4°. 36 162 260c. Methyl Cinnamate, C10H10O2.- (III, A, 2), " 133°; Test 313. 38 38 115 288d Dimethyl Sebacate, C12H22O4.- (III, A, 1), " 133°. Methyl Stearate, C19H3bO2.- (III, A, 2), " 69-3° c. 42 149 Diethyl Diphenate, ClgH]8O4.- " " 229°. 43-4 210 295° Ethyl Veratrate, CnH14O4.- " " 181°. 44 196 292 " Vanillate, C10H12O4.- " " 207°. 44 111 Diethyl Terephthalate,C12H14O4.- " sbl. a. 300°; Test 318. 45-5 166 255° Methyl Anisate, C8H10O3.- " m. p. 184-2°. 48 89 280 Dimethyl Tartrate, C6H10OG.- (III, A, 1), " 168°; Test 314. 51 204 290 Ethyl /3-Methylcoumarilate, C12H12O3.-(III, A, 2), m. p. 188°-9°. 52 166 Methyl Mandelate, C9H10O3.- (III, A, 1), m. p. 118°. 52 119 Diethyl 4-Oxyisophthalate, C12H14O5.- (Ill, A, 2), m. p. 305° 54 59 163-3c. f Dimethyl Oxalate, C4HGO4.- Belongs to Genus III, A, 1. 57 57 96 abt. 200 Diethyl Mesoxalate, C7H12O6.- (III, A, 1), m. p. 119°-20°. Ethyl Dibenzylacetoacetate, C20H22O3.-(III, A, 2), m. p. 89°. 56-8 325-8d. Tetraethyl Ethylenetetracarbonate C14H20O8.-Acid unstable. 59 228 Phenyl Methylethersalicylate, C]4H12O3.-(Ill, A, 2), m. p. 98-5°. 59 196 283 Methyl Veratrate, C10H12O4.- " " 181°. 59-5 295-297d. Ethyl Benzalacetoacetate, C13H14O3. - Benzoic, acetic, and acetone. 118 GENUS V, DIV. A. 119 (ORDER I, SUBORDER I.) Melt- ing- point (C.°). Sapon. Equiv. Boiling-point ESTERS.-Solid Esters whose Neutral Saponification Products are Soluble in Cold Water and Readily Volatile with Steam. 61-5 127 207 (16-5 mm.) Generic Position and Properties of the Acidic Saponification Products. Dimethyl Hemipinate, C12H14O6.-(III, A, 2), m. p. 161°. 62-5 182 285-7 Methyl Vanillate, C9H10O4.- " " 207°. 68 131 324 Diisobutyl Tartrate, C12H22O6.- (III, A, 1), " 168°; Test 314. 64-5 97 Dimethyl Isophthalate, Ci0H.0O4.-(III, A, 2), m. p. a. 300°: Test 68-9 198 314c. 318-2. Phenyl Benzoate, C13H10O2.- (Ill, A, 2), m. p. 121°; Test 312- 70 159 Diphenyl Phthalate, C20H14O4.-• " " 184°; Test 318-1 72 166 282 Ethyl m-Oxybenzoate, C9H10O3.-• " " 200°. 72-5 224 Phenyl Cinnamate, C15H12O2.- " " 133°; Test 313. 73 480 Ethyl Melissate, C32H64O2.- " " 90°. 73 85 Hexaethyl Mellitate, C24HS0O12.-(III, A, 1), " 286°(clos'd tube) 74-5 242 Methyl Benzilate, C1SH14O3.- (III, A, 1), " 150°. 75 182 Ethyl 2, 5-Dioxybenzoate, C9H19O4.-(III, A, 2), m. p. 199°. 73-8 290 Phenyl p-Phenoxybenzoate, C19H14O3.-(III, A, 2), " 159-5°. 76 305d. Tetraethyl s-Ethanetetracarbonate, C14H22O8.-(III, A, 1), m. p- 77 186 290 169°. Methyl 5-Naphthoate, C12H10O2.-(HI, A, 2), m. p. 184°. 77-5 246 Ethyl Piperate, C14H14O4.- " " 216°. 78 301-2 Diphenyl Carbonate, C13H10O3. 79 78 285 Trimethyl Citrate, C9H14O7.-(III, A, 1), m. p. 153°; Test 314. 79-5 85 89 282 Ethyl Benzosalicylate, C16H14O4. Dimethyl Racemate, C6H10O6.-(HI, A, 1), m. p. 205°; Test 314. 85 178 Methyl m-Coumarate, C10Hj0O3.-(Ill, A, 2), " 191°. 96 95 Dimethyl 4-Oxyisophthalate, C10H10Os.-(III, A, 2), m. p. 305°. 102 72 192 (th. i.) " Fumarate. C6H8O4.- " sbl. 200°. 102 105 " 4-Oxyphthalate, C10H10O6.- (III, A, 1), m. p. 181°. 109 290 Phenyl Phenylethersalicylate, C19H14O3.- (III, A, 2), " 113°. 109 258 f Peucedanin, C14HnO3.OCH3.-Tasteless, odorless, ndl. from 111 198 270-80d. Peucedanum officinale.-I. aq.; e. s. h. ale. or eth.-f Mix a warm saturated ale. sol. w. an equal vol. cone. HC1 and boil half a minute. Cool. Wash the white cryst. ppt. w. c. ale. Recryst. fr. h. ale. The product of these operations, oreoselon, melts at 173° (uncor.). Methyl n-Anthracenecarbonate, C]0H12O2.-(HI, A, 2), m. p. 206°. 118 135 330 Diphenyl Succinate, C16H14O4.-(HI, A, 1), m. p. 185°; Test 320. 130d. 121 " Oxalate, C14H10O4.- " " 99°; Test 317 131 152 Methyl p-Oxybenzoate, C8H8O3.-(HI, A, 2), m. p. 210°. 138 65-5 Tetramethyl s-Ethanetetracarbonate, C10H14O8.-(HI, A, 1), m. p. 140 97 169°. Dimethyl Terephthalate, C10H10O4.-(HI, A, 2), sbl. a. 300°; Test 158d. 183 318-3. Diethyl Mucate, C10H1SOs.- " m. p. 213°. 146 164 abt. 330° ' ' a-Truxillate, C22H24O4.- " " 274°. 187 71 Hexamethyl Mellitate, C18H18O12.- (HI, A, 1), " 286° (closed 192d. 238 tube). Methyl Gallate+ 3H2O,CsH14O8.- (HI, A, 2), " 222°-40°. 260-70 Ethyl p-Toluylcarbonate, CnH12O3.-- " " 95°-7°. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I] GENUS V, ESTERS. DIVISION B - LIQUID ESTERS WHOSE NEUTRAL SAPONIFICATION PRODUCTS, ETHYL, PROPYL, ISOPROPYL, ALLYL, AMYL AND ISOAMYL, BUTYL AND ISOBUTYL, HEXYL, HEPTYL, OCTYL AND BENZYL ALCOHOLS, ACETONE, AND PHENOL, ARE READILY VOLATILE WITH STEAM. Boiling- point (C.°). Sapon. Equiv. ESTERS.-Liquid Esters whose Neutral Saponification Products are Readily Volatile with Steam. Generic Position and Properties of the Acidic Saponification Products. 32-3 60 f Methyl Formate, C2H4O2.-G. 0-998%.-Acid (III, B, 1), b. p. 100-8°; Test 315. (Belongs with Acids, Gen. Ill, B, 1.) 54-4 74 Ethyl Formate, C3H6O2.-G. 0-938%.-Acid (HI, B, 1), b. p. 100-8°; Test 315. 57-5 74 f Methyl Acetate, C3H6O2.-G. 0-958%.-Acid (III, B, 1), b. p. 118c; Test 311. 68-71 88 Isopropyl Formate, C4H8O2.-G. 0-883(0).-Acid (III, B, 1), b. p. 100-8°; Test 315. 77 88 Ethyl Acetate, C4H8O2.-G. 0-924%.-Acid (III, B, 1), b. p. 118°; Test 311. 79-9 88 Methyl Propionate, C4HSO,.-G. 0-937%.-Acid (HI, B, 1), b. p. 140-7°; Test 311. 80-3 86 Methyl Acrylate, C4H6O2.-G. 0-973(0).-Acid (HI, B, 1), b. p. 140°. 81 88 Propyl Formate, C4HSO2.-G. 0-918%.-Acid (HI, B, 1), b. p. 100-8°; Test 315. 82-5 86 Allyl Formate, C4H6O2.-G. 0-932(17-5).-Acid (HI, B, 1), b. p. 100-8°; Test 315. 90-3 102 Isopropyl Acetate, C6H10O2.-G. 0-917(0).-Acid (HI, B, 1), b. p. 118°; Test 311. 90-6c. Dimethyl Carbonate, C3H6O3.-G. 1-065(17).-Acid carbonic. 92-3 102 Methyl Isobutyrate, C6H10O2.-G. 0-912%.-Acid (HI, B, 1), b. p. 155°; Test 311. 98-3 102 Ethyl Propionate, C5H10O2.-G. 0-912(0).-Acid (HI, B, 1), b, p. 140-7°; Test 311. 98-5 102 Isobutyl Formate, C5H10O„-G. 0-905%.-Acid (HI, B, 1), b p. 100-8°; Test 315. 98-5c. 100 Ethyl Acrylate, C5H8O2.-G. 0-939(0).-Acid (HI, B, 1), b. p. 140°. 101 116 Methyl Trimethylacetate, C6H12O2.-Acid (HI, A, 1), m. p. 35-5°. 102 102 Propyl Acetate, CflH10O2.-G. 0-909%.-Acid (HI, B, 1), b. p. 118°; Test 311. 102-3 102 Methyl Butyrate, CfiH10O2.-G. 0-919%.-Acid (HI, B, 1), b. p. 162-5°; Test 311. 103-5 100 Allyl Acetate, C5H8O2.-G. 0-938(0).-Acid (HI, B, l),b.p. 118°; Test 311. 106-9 102 Butyl Formate, C5H10O2.-G. 0-911(0)/-Acid (HI, B, 1), b. p. 100-8°; Test 315. 109-2c. Methyl Ethyl Carbonate, C4HSO3.-G. 1-002(27).-Acid carbonic. 110-1 116 / f Ethyl Isobutyrate, C6H12O2.-G. 0-890%.-Acid (III, B, 1), b. p. 155°; Test 311. 120 GENUS V, DIV. B. 121 (ORDER I, SUBORDER I.) Boiling- point (C.°). Sapon. Equiv. ESTERS.-Liquid Esters whose Neutral Saponification Products are Readily Volatile with Steam. 116-3 116 Generic Position and Properties of the Acidic Saponification Products, fIsobutyl Acetate, C6H12O2.-G. 0• 892%.-Acid (III, B, 1), b. p. 118°; 116-7 116 Test 311. Methyl Isovalerianate, C6H12O2.-G. 0-901%.-Acid (1H, B, 1), b. p. 176°. 115-20 114 Ethyl Methacrylate, CGH10O,.-Acid (III, B, 1), b. p. 162°. 118-5 (th. i.) 130 " Trimethylacetate, C7H14O2.-G. 0-875(0).-Acid (III, A, 1), m. p. 35 • 5°. 119 98 Ethyl Propiolate, C5HGO2.-Acid (III, B, 1), b. p. 144°. 119-9 116 " Butyrate, CfiH12O2.-G. 0-900%.-Acid (III, B, 1), b. p. 162-5°; 120-7 100 Test 311. Methyl a-Crotonate, C5HSO2.-G. 0-981(4).-Acid (III, A, 1), m. p. 72°. 123-3 116 t Isoamyl Formate, CGH12O2.-G. 0-894%.-Acid (III, B, 1), b. p. 100-8°; 124-5 98 Test 315. Propargyl Acetate, C6HGO2.-G. l-0052%.-Acid (III, B, 1), b. p. 118°; 125 116 Test 311. Butyl Acetate, C6H12O2.-G. 0 • 902(0).-Acid (III, B, 1), b. p. 118°; Test 311. 126 127-3 116 Diethyl Carbonate, C5H10O3.-G. 0-9762%.-Acid carbonic. Methyl Valerianate, C6H12O2.-G. 0-910(0).-Acid (III, B, 1), b. p. 186°. 127c. 104 Methyl Methoxyacetate, C4HSO3.-G. 1-089(0).-Acid (III, B, 1), b. p. 203°. 128-5 130-4 116 Ethyl Isoacetoacetate, CGH10O3.-CO2 and acetone; Test 711. Amyl Formate, CGH12O2.-G. 0-902(0).-Acid (III, B, 1), b p. 100-8°; Test 131 (th. i.) 118 315. Ethyl Methoxyacetate, C5H10O3.-G. 1-074(0).-Acid (III, B, 1), b. p. 203°. 133-5 128 Allyl Isobutyrate, C7HI2O2.-Acid (III, B, 1), b. p. 155°; Test 311. 134 (th. i.) 130 Ethyl Methylethylacetate, C7H14O2.-G. 0 - 87 0 22/17.5.-Acid (III, B, 1), 134-3 130 b. p. 177°. f Ethyl Isovalerianate, C7H14O2.-G. 0-885%.-Acid (IIIVB, 1), b. p. 176°. 134-7 102 Methyl Pyruvate, C4H6O3.--G. 1-154(0).-Acid (III, B, 1), b. p. 165°. 136 114 Ethyl Isocrotonate, C0H10O2.-G. 0-927(19).-Acid (III, B, 1), b. p. 169°. 139 130 f Isoamyl Acetate, C7H14O2.-G. 0-884(0).-Acid (III, B, 1), b. p. 118°; 141-5 128 Test 311. Ethyl Angelate, C7H12O2.-G. 0-935(0).-Acid (III, A, 2), m. p. 45°. 142 128 Allyl Butyrate, C7H12O2.-Acid (III, B, 1), b. p. 162-5°; Test 311. 142-3 114 Ethyl a-Crotonate, C6H10O2.-G. 0-9212%.-Acid (III, A, 1), m. p. 72°. 143 128 " Allylacetate, C7H12O2.-Acid (III, B, 2), b. p. 188°. 144-5 130 " Valerianate, C7H14O2.-G. 0-894(0).-Acid (III, B, 1), b. p. 186°. 148 130 Amyl Acetate, C7II14O2.-G. 0-896(0).-Acid (III, B, 1), b. p. 118°; Test 311. 148 118 Methyl Ethoxy acetate, C5H10O3.-G. 1-015(0).-Acid (III, B, 1), b. p. 206°. 149-6 130 " Caproate, C7H14O .-G. 0-904(0).-Acid (III, B, 2), b. p. 205-7°. 150 (th. i.) 118 Ethyl Oxyisobutyrate, CGH12O3.-Acid (III, A, 1), m. p. 79°. 150 151 144 Methyl Isobutylacetate, C7H14O2.-G. 0' 898(18).-Acid (III, B, 1), b. p. 207-7°c. Ethyl Diethylacetate, CSH1GO2.-G. 0-883(0).-Acid (III, B, 1), b. p. 190°. 151-2 (th. i.) 90 Methyl Glycollate, C3H,O3. -G. 1-187(0).-Acid (III, A, 1), m p. 78° 152 132 Ethyl Ethoxyacetate, C8H12O3.-G. 1-000(0).-Acid (III, B, 1), b. p. 206°. 153 (th. i.) 144 " Methylpropylacetate, C8H1BO2.-G. 0-882(0).-Acid (III, B, 1), b. p. 153-6 130 193°. Hexyl Formate, C7H14O2.-G. 0-898(0).-Acid (III, B, 1), b. p. 100-8°: 154-5 142 Test 315. Allyl Isovalerianate, CgH 4O2.-Acid (III, B, 1), b. p. 176°. 155 (th. i.) 146 Ethyl a-Ethoxypropionate, C7H14O3.-G. 0-950(0). Acid (III, B, 1), b. p. 195°-8°. 122 GENUS V, DIV. B. (ORDER I, SUBORDER I.) Boiling- point (C.°). Sapon. Equiv. ESTERS.-Liquid Ester? whose Neutral Saponification Products are Readily Volatile with Steam. 156c. 128 Generic Position and Properties of the Acidic Saponification Products. Ethyl Tiglate, C7H12O2.-G. 0-926(21).-Acid (III, A, 1), m. p. 64-5°. 156-9 144 Isobutyl Butyrate, C8H10O2.-G. 0-888%--Acid (III, B, 1), b. p. 162-5°: 158-9 160c. 104 Test 311. Ethyl Orthocarbonate, C9H20O4.-G. 0-925. " Glycollate, C4HgO3.-G. 1-108(0).-Acid (III, A, 1), m. p. 78° 160-2 144 Isoamyl Propionate, CgH16O2.-G. 0-888%.-Acid (III, B, 1), b. p. 140-7°; 161 130 Test 311. Ethyl Isobutylacetate, CgH16O2.-G. 0-887(0).--Acid (III, B, 2), b. p. 207-7°. 159-62 128 " Tetramethylenecarbonate, C7H12O2.-Acid (III, B, 2), b. p. 195°. 165 146 Methyl Oxydiethylacetate, C7H14O3.-G. 0-990(16-5).-Acid (III, A, 1), 165 142 b. p. 80°. Ethyl u-Ethylcrotonate, CgH14O2.-G. 0-920(13).-Acid (III, A, 2), m. p. 165 144 41-5°. Butyl Butyrate, CsHlc02.-G. 0-888(0).-Acid (III, B, 1), b. p. 162-5°; 165 132 Test 311. Ethyl a-Oxybutyrate, C6H]2O3.-G. 1-004(0).-Acid (III, A, 1), m. p. 43°. 166-6 144 " Caproate, CgH1GO2.-G. 0-889(0).-Acid (III, B, 2), b. p 205-7°. 168-2c. 168-5c. 160 Dipropyl Carbonate, C7H14O3.-G. 0-949(17)'-Acid, carbonic. Ethyl a-Ethoxybutyrate, C8H16O3.-G. 0-903(0). 168-8 158 Isoamyl Isobutyrate, C9H18O2.-G. 0-876%.-Acid (III, B, 1), b. p. 155°; 169-2 144 Test 311. n-Hexyl Acetate C8H10O2.-G. 0-890(0).-Acid (III, B, 1), b. p. 118°; Test 170-5c. 118 311. Propyl Glycollate, C6H10O3.-G. 1-064(0).-Acid (III, A, 1), m. p. 78°. 173 144 Methyl Oenanthylate, C8H16O2.-G. 0-887(0) -Acid (III, B, 2), b. p. 223°. 173-7c. 132 " Ethyl Oxalate, C5HSO4.-G. 1-156(0).-Acid (III, A, 1), m. p. 99°; 175 160 Test 317. Ethyl Oxydiethylacetate, C8H16O3. - G. 0-961(18-7). -Acid (III, B, 2), 175 146 b. p. 80°. ' Ethyl a-Oxyisovalerianate, C7H14O3.-Acid (III, A, 1), m. p. 83°-6° 176-7 144 Heptyl Formate, CSH16O2.-G. 0-894(0).-Acid (III, B, 1), b. p. 100-8°; 177 158 Test 315. Ethyl Isoamylacetate, C9HlgO2.-Acid (HI, B, 2), b. p. 209°. 177-5 156 Isobutyl Angelate, C9H16O2.-Acid (III, A, 2), m. p. 45°. 178 80 Dimethyl Dimethylmalonate, C7H19O4.-G. 1-071(15).-Acid (III, A, 2), 178 160 m. p. 192°. Ethyl Acetoxyl-a-propionate, C7H12O4.-G. 1-046(17).-Acid (III, A, 1), 178-4c. 130 m. p. 166°. Ethyl /?-Methoxyisocrotonate, C7H12O3.-G. 1-039(15).-Acid (III, A, 2), 178-6 158 m. p. 128-5°. f Isoamyl Butyrate, C9H1SO2.-G. 0-882%.-Acid (HI, B, 1), b. p. 162-5°; 179 73 Test 311. Methyl Isosuccinate, C6H10O4.-G. 1-107(15).-Acid (HI, A, l),m.p. 135°. 181-5c. 66 " Malonate, C5H8O4.-G. 1-160(15).-Acid (HI, A, 1), m. p. 132°. 183 172 Ethyl Dipropylacetate, C10H20O2.-Acid (HI, B, 2), b. p. 219-5°. 184 186• 1c. 73 " Dimethylacetoacetate, CSH14O3.-G. 0-991(16).-CO2 and isopropyl acetone. f Diethyl Oxalate, CBH10O4.-G. 1-082(18-2).-For reactions of ester cf. page 74. (Belongs in Genus HI, B.) Diisobutyl Carbonate, C9H1SO3.-G. 0-919(15).-Acid, carbonic. Ethyl a-Oxy valerian ate, C7H14O3.--Acid (HI, A, 1), m. p. 31°. 190 190 146 GENUS V, DIV. B. 123 (ORDER I, SUBORDER I.) Boiling- point (C.°). Sapon. Equiv. ESTERS.-Liquid Esters whose Neutral Saponification Products are Readily Volatile with Steam. 190 158 Generic Position and Properties of the Aci ic Saponification Products. Heptyl Acetate, C9H1SO2.-G. 0-874(16).-Acid (III, B, 1), b. p. 118°: Test 193 158 311. Methyl Caprylate, C9H18O2.-G. 0-894(0).-Acid (III, B, 2), b. p. 237-5°. 194 172 f Isoamyl Isovalerianate, C10H,0O2.-G. 0-87(0).--Acid (III, B, 1), b. p,176°. 195 168 Ethyl Diallylacetate, C10H16O2.-Acid (III, B, 2), b. p. 227° c. 195-2 (th. i.) 73 Methyl Succinate, CcH10O,.-G. L 126(15).-Acid (III, A, 1), m. p. 185°; 195-5 140 Test 320. Ethyl Sorbate, C8H12O2.-Acid (III, A, 2), m. p. 134-5°. 196 (si. d.) 63 Dimethyl Acetylenedicarbonate, C6H6O4.-Acid (III, A, 1), m. p. 178°-9°. 196 136 Phenyl Acetate, C8H8O2.-G. 1-093%--Acid (III, B, 1), b. p. 118°; Test 311. 196 196-5 94 Ethyl Ethyleneacetoacetate, CSH12O3.-G. 1-048(15).-CO2 and acetopro- pyl ale. Diethyl Dimethylmalonate, C9H1GO4.- G. 1-002(15). - Acid (III, A, 1), 198 87 m. p. 192°. Diethyl Isosuccinate, C8H14O4.-G. 1-021(15).-Acid (III, A, 1), m. p. 135°. 198c. 80 f " Malonate, C7H12O4.-G. 1-077(0).-Acid (III, A, 1), m. p. 132°. 198 158 Octyl Formate, C9H18O2.-G. 0-893.-Acid (III, B, 1), b. p. 100-8°; Test 315. 199c. 136 f Methyl Benzoate, C8HgO2.-G. 1-103(0).-Acid (III, A, 2), m. p. 121°; 199 200-5 (th. i.) 203-7 172 Test 312. Ethyl n-Propionylpropionate, C8H14O3.-G. 0-995(0).--CO2 and diethyl ketone. Ethyl Methylethylacetoacetate, C9H1GO3.-G. 0 • 94 722/17.5.-CO2 and sec. butyl acetone. n-Amyl Valerianate, C10H2uO2.-G. 0-881(0).-Acid (III, B, 1), b. p. 186°. 200-5 204-5 170 Diethylacetylacetone, Me.CO.C.Et2.CO.Me.-Acid (III, B, l),b.p. 118° and diethylacetone. Isoamyl Tiglate, C10HlgO2.-Acid (III, A, 2), m. p. 64-5°. 205c. 144 Ethyl Laevulinate, C7H12O3.-G. 1-033(0).-Acid (HI, B, 1), b. p. 239°. 205 (th. i.) 72 Dimethyl Maleate, C0H8O4.-G. 1 • 153(14).-Acid (III, A, 1), m. p. 130°. 205-1 172 Hexyl Butyrate, C, 0H,0O2.-G. 0-883(0).-Acid (III, B, 1), b. p. 162-5°; 206c. 79 Test 311. Dimethyl Mesaconate, C7H10O4.-G. 1-136(4).-Acid (HI, A, l),m.p.202°. 206 150 Benzyl Acetate, C9H10O2.-G. 1-057(16-5).-Acid (HI, B, 1), b. p. 118°; 207 94 Test 311. Diethyl Ethylmalonate, C9H16C4.-G. l-00818/15.-Acid (HI, A. 1), m. p. 207-5 101 111-5°. Diethyl Methylethylmalonate, Ci0H18O4.-G. 0-994(15).-Acid (HI, A, 1), 207-5 172 m. p. 118°. Ethyl Caprylate, C10H23O2.-G. 0 • 887(0).-Acid (HI, B, 2), b. p. 237-5°. 207-7c. 208-2c. 80 Dibutyl Carbonate, C9H1SO3.-G. 0-941(0).-Acid, carbonic. Methyl Ethyl Succinate, C7H12O4.-G. 1-093(0).-Acid (HI, A, 1), m. p. 208 210 172 185°; Test 320. Ethyl a-Butyrylpropionate, C9H16O3.-G. 0-988(0). " Mesitonate, C9H1GO3.-Acid (III, A, 1), m. p. 74°. 210 172 n-Octyl Acetate, C10H,0O2.-G. 0-885(0).-Acid (HI, B, 1), b. p. 118°; 210-5 79 Test 311. Dimethyl Citraconate, C7H1(>04.-G. 1 • 121(15).-Acid (HI, A, 1), m. p.80°. 211c 150 Phenyl Propionate, C9H]0O2.-G. 1-054(15).-Acid (HI, B, 1), b. p. 140-7°; 210-2-5 212c. 150 Test 311. MethylItaconate, C7H10O4.-G. 1-140(14.7).-Acid (III, B, 1), b. p. 161°. f Ethyl Benzoate, C9H10O2.-Acid (HI, A, 2), m. p. 121°; Test 312. * 124 GENUS V, DIV. B. Boiling- point (C.°). Sapon. Equiv. ESTERS.-Liquid Esters whose Neutral Saponification Products are Readily Volatile with Steam. 213-5 (th. i.) 172 Generic Position and Properties of the Acidic Saponification Products. Methyl Pelargonate, C10H20O2.-G. 0-892(0).-Acid (III, B, 2), b. p. 253°-4°. 213 93 Diethyl Ethylenemalonate, C9H. O-G. 1-065(15).-Acid (III, A 1), m. p. 140°. 213-4 101 Diethyl Isopropylmalonate, C19H1SO4.-G 0-9972%5.-Acid (III, A, 1), m. p. 213-5c. 82 Dipropyl Oxalate, CSH14O4.-G. 1-038(0).-Acid (III, A. 1), m. p. 99°; 214 Test 317. Ethyl Methylpropylacetoacetate, C10H18O3.-G. 0-959(15).-CO2 and methyl 214 (th. i.) 150 propyl acetone. p-Cresyl Acetate, C9H10O2.-G. 1-066%.-Acid (III, B, 1), b. p. 118°: Test 214 (th. i.) 168 311. Ethyl Pyrotritarate (Uvate), C9H12O3.-Acid (III, A, 2), m. p. 135°. 216 85 Diallyl Oxalate, CgH10O4.-G. 1-055(15-5).-Acid (III, A, 1), m. p. 99°: 216-5c. 87 Test 317. f Diethyl Succinate, CSH14O4.-G. 1-072(0).-Acid (III, A, 1), m. p. 185°: 215-20 186 Test 320. Isoamyl Isobutylacetate, CjjH^O^-Acid (III, B, 2), b. p. 207-7° c. 217-5 Ethyl Isobutylacetoacetate, C10H18O3.-G. 0-951(17-5).-Cf. Genus IV, B. 218 " Diethylacetoacetate, C10HlsO3.-G. 0-974(20).-CO2 and diethyl ace- 218-5c. 86 tone. Diethyl Fumarate, CgH12O4.-G. 1-063(10).-Acid (III, A, 2), sbl. 200°. 220 150 Methyl Phenylacetate, C9H10O9.-G. 1-044(16).-Acid (III, A, 2), m. p. 221 101 76-5-°. Diethyl Propylmalonate, C10HlsO4.-G. 0-993(15).--Acid (III, A, 1), m. p. 96° 221 176 Methyl a-Phenylpropionate, C10H12O2.-Acid (III, B, 2), b. p. 264°. 221 (th. i.) 108 Diethyl Methylisopropylmalonate, ChH2()O4.-G. 0-990(15).-Acid (III, A, 221 164 1), m. p. 124°. Ethyl o-Toluate, C10H12O2.-Acid (III, A, 2), m. p. 102°. 221-5 101 Diethyl(mal.)s-Dimethylsuccinate, C10HlsO4.-G. 1-022(0).-Acid (III, A, 220-3 108 l),m. p. 129°. Diethyl Methylpropylmalonate, C11H20O4.-Acid (III, A, 1), m. p. 106°. 222-5c. 100 " Allylmalonate, C10Hl0O4.-G. 1-014(15).-Acid (III, A, 1), m. p. 223 108 103°. Diethyl Diethylmalonate, CnH20O4.-G. 0-992(15).-Acid (III, A, 1), m. p. 223-5 186 121°. Methyl Caprate, CUH22O2.-Acid (III, A, 2), m. p. 31-3°. 222-5 88 Diethyl Tartronate, C7H12O5.-Acid (III, A, 1), m. p. 185°-7°. 223-6 101 " Etnylsuccinate, C1OH1SO4.-G. 1-030(21).-Acid (III, A, 1), m. p. 98° 225 (th. i.) 86 Diethyl Maleate, CSH12O4.-G. 1-074(15).-Acid (III, A, 1), m. p. 130°. 225 108 " Isobutylmalonate, CnH,0O4.-G. 0-983(17).-Acid (III, A, 1), m. 225-6d. 100 p. 107°. Diisopropyl Fumarate, C10HlcO4.-Acid (III, A, 2), sbl. 200°. 226-5 Ethyl Trimethyleneacetoacetate, CfiH14O3.-G. 1-070(15).-M. p. 4-9°.- 226-8 164 Acid (III, A, 2), m. p. 119°. Ethyl m-Toluate, C10H12O2.-Acid (III, A, 2), m. p. 110-5°. 225-30d. 148 " a/?-Dioxybutyrate, C6H12O4.-Acid (III, A, 1), m. p. 74°-5°. 227-5 (th. i.) 186 " Pelargonate, CUH2,O2.-G. 0-866(17-5). Acid (III, B, 1), b. p. 253°. 227-5 " Isoamylacetoacetate.-Cf. Genus IV, A. 227-8c. 93 Diethyl Itaconate, C9H14O4.-G. 1-050(15).-Acid (III, A, 1), m. p. 161°. (ORDER I, SUBORDER I.) GENUS 7, DIV. B. 125 (ORDER I, SUBORDER I.) Boiling- point (C.°). Sapon. Equiv. ESTERS.-Liquid Esters whose Neutral Saponification Products are Readily Volatile witn Steam. Generic Position and Properties of the Acidic Saponification Products. 228 178 Methyl Ethylphenylacetate, CnH14O2.-Acid (III, A, 2), m. p. 42°. 228 164 Ethyl p-Toluate, C10H12O2.-Acid (III, A, 2), m. p. 176°-7°. 228 166 Methyl Methylethersalicylate, C9H10O3.-Acid (III, A, 2), m. p. 98-5°. 228-3c. 228-7c. 94 Dipropyl Malonate, C9H16O4.-G. 1-027(0).-Acid (III, A, 1), m. p. 132°. Diisoamyl Carbonate, CnH22O5.-G. 0-912(15).-Acid, carbonic. 229 (th. i.) 93 Diethyl Mesaconate, C9HI4O4.-G. 1-060(4). Acid (III, A, 1), m. p. 202°. 229 101 Diisobutyl Oxalate, C10H18O4.-G. 1-002(14).-Acid (III, A, 1), m. p. 99°; Test 317. 229c. 164 Ethyl Phenylacetate, C10H12O2.-G. 1-086(16).-Acid (III, A, 2), m. p. 76-5°. 229-5c. 150 Propyl Benzoate, C10H12O2.-G. 1-032(16).-Acid (III, A, 2), m. p. 121°; Test 312. 230 162 Allyl Benzoate, C10H10O2.-Acid (III, A, 2), m. p. 121°; Test 312. 230 178 Ethyl a-Phenylpropionate, CnHuO2.-Acid (III, B, 2), b. p. 264°. 231 93 Diethyl Citraconate, C9Hl4O4.-G. 1-047(15).-Acid (III, A, 1), m. p. 80°. 231 188 Ethyl a-Oxycaprylate, C10H,0O3.-Acid (III, A, 2), m. p. 69-5°. 230-5 101 Diethyl (fum.)s-Dimethylsuccinate, C10H18O4.-G. 1-013(0).-Acid (III, A, 2), m. p. 195°. 232 190 Methyl a-Methylhydrocinnamate, CnH14O2.-Acid (III, A, 2), m. p. 37°. 233-5 (th. i.) 108 Diethyl Butylmalonate, CnH20O4.-G. 0-988(15).-Acid(III, A, 1), m. p.76°. 235 235-6 180 Ethyl Methylethersalicylate, C10H12O3.-Acid (III, A, 2), m. p. 98-5°. " Dipropylacetoacetate, CrH22O3.-G. 0-959%.-CO2 and dipropyl- acetone. 237 178 f Isobutyl Benzoate, CnH14O2.-G. 1-002(15).-Acid (III, A, 2), m. p. 121°; Test 312. 237c. 94 Diethyl Glutarate, C9H16O4.-G. 1-025(21).-Acid (III, A, 1), m. p. 97-5°. 236-8 93 " Glutaconate, C9H14O4.-Acid (III, A, 1), m. p. 132°. 237-8 178 Ethyl m-Toly lac etate, CnH14O2.-G. 1-018(17-5).-Acid (III, A,2),m. p.61°. 236-40 108 Diethyl Isopropylsuccinate, CnH20O4.-Acid (III, A, 1), m. p. 117°. 238-5 176 Methyl Hydrocinnamate, C10H1,O2.-G. 1-047(0).-Acid (III, A, 2), m. p. 48-7°. 240 178 Ethyl p-Tolylacetate, CUH14O2.-Acid (III, A, 2), m. p. 91°. • 240 MO si. d. 168 " Cuminate, C12H10O2. -Acid (III, A, 2), m. p. 116-5°. Diethyl Diglycollate, CKHUO6.-Acid (III, A, 1), m. p. 148°. 240 239-41 120 " Diallylmalonate, C]3H29O4.-G. 0-99614/15.- Acid (III, A, 1), m. p. 133°. Ethyl Diallylacetoacetate, CUH18O3.-G. 0-9482%r6.-CO2 and diallyl ace- tone. 241 178 Ethyl I 3-Dimethylbenzoate, C11H14O2.-Acid (III, A, 2), m. p. 166°. 241 115 Diethyl Isoamylmalonate, C12HMO4.-Acid (III, A, 1), m. p. 93°. 243-4c. 101 Dibutyl Oxalate, C10H1BO4.-G. 1-010(0).-Acid (III, A, 1), m. p. 99°; Test 317 244 200 Ethyl Caprate, C12H24O2.-G. 0-862.-Acid (III, A, 2), m. p. 31-3°. 245 180 Methyl Ethylethersalicylate, C10H12O3.-Acid (III, A, 2), m. p. 19-4°. 245 101 Diethyl Adipate, C10H18O4.-Acid (III, A, 2), m. p. 153° c. 247 • 1c. 101 Diisopropyl Succinate, C10H18O4.-G. 1-019(0).-Acid (III, A, 1), m. p. 185°; Test 320. 247-3c. 178 Butyl Benzoate, CUH14O2.-G. 1-000(20).-Acid (III, A, 2), m. p. 121°; Test 312. 247-9c. 178 Ethyl Hydrocinnamate, CUH14O2.-G. 1-034(0).-Acid (III, A, 2), m. p. 48 • 7°. 126 GENUS V, DIV. B. (ORDER I, SUBORDER I.) Boiling- point (C°) Sapon. Equiv. ESTERS.-Liquid Esters whose Neutral Saponification Products are Readily Volatile with Steam. Generic Position and Properties of the Acidic Saponification Products. 248 210 Methyl Undecylenate, C12H22O2.-Acid (III, A, 2), m. p. 24-5°. 249-5 99 Diallyl Succinate, C10H14O4.-Acid (III, A, 1), m. p. 185°; Test 320. 250-8c. 101 Dipropyl Succinate, Ci0H18O4.-G. 1-016(4).-Acid (III, A, 1), m. p. 185°; Test 320. 249-52 107 Diethyl Pentamethylenedicarbonate, C11H18O4.-Acid (III, A, 2), m. p. 159°-60°. 251 194 Ethyl Ethylethersalicylate, Ci,H14O3.-G. 1-101.-Acid (III, A, 2), m. p. 19-4°. 250-3 Ethyl Diisobutylacetoacetate, C14H20O3.-G. 0-947(10).-CO2 and diisobutyl acetone. 251-5c. 108 Dibutyl Malonate, CnH20O4.-G. 1-005(0).-Acid (III, A, 1), m. p. 132°. 255 85 Diethyl i-Malate, C8H14O5.-G. 1 • 12421/4.-Acid (III, A, 1), m. p. 133°: Test 314. 256-7 178 Ethyl Benzoylformate, C10H10O3.-G. 1-121(17-5).-Acid (III, A, 1), m. p. 65°-6°. 259 212 Ethyl Undecylenate, C13H24O2.-G. 0-883(15).-Acid (III, A, 2), m. p. 24-5°. 261 192 Isoamyl Benzoate, C12H16O2.-G. 1-004(0).-Acid (III, A, 2), m. p. 121°; Test 312. 263 194 Ethyl m-Ethoxybenzoate, CUH14O3.-G. 1-088(0).-Acid (III, A, 2), m. p. 137°. 263 115 Diisoamyl Oxalate, C12H22O4.-G. 0-968(11).-Acid (III, A, 1), m. p. 99°; Test 317. 265 120 Dimethyl Camphorate, C12H20O4.-G. l-0752%.-Acid (III, A, 2), m. p. 180-7° c. 265c. 115 Diisobutyl Succinate, C12H22O4.-G. 0-974(15).-Acid (III, A, 1), m. p. 185°; Test 320. 265-7 226 Isoamyl Orthoformate, C16H34O3.-G. 0-864(23).-Acid (III, B, 1), b. p. 100-8°; Test 315. 269 228 Ethyl Laurate, C14H28O2.-G. 0-867(19).-Acid (III, A, 2), m. p. 43-6°. " Anisate, C10H12O3.-Acid (III, A, 2), m. p. 184-2°. 269-5c. 180 270 208 Isoamyl Salicylate, C12H16O3.-Cf. Genus IV, B; Test 319. 270-5 72 Trimethyl Aconitate, C9H13O„.-Acid (III, A, 1), m. p. 191°. 271 176 f Ethyl Cinnamate, CnH12O2.-G. 1-066(0).-Acid (III, A, 2), m. p. 133°; Test 313. 272 206 n-Hexyl Benzoate, C13H18O2.-G. 0-999(17).-Acid (III, A, 2), m. p. 121°; Test 312. 275 117 Diisopropyl Tartrate, C10H18OG.-G. 1-13(20).-Acid (III, A, 1), m, p. 168°; Test 314. 275 86 Triethyl Aconitate, Ct2HlsO6.-G. 1-074(14).-Acid (III, A, 1), m. p. 191°. 276d. 224 Ethyl Camphocarbonate, C13H20O3.-G. l-O562%.-Acid (III, A, 2), m. p. 128°. 278-3d. 82 Triethyl Ethenyltricarbonate, CUH18O6.-G. l-0952%.-Acid (III, A, 1), m. p. 159° d. 280 103 Diethyl[ + ]Tartrate, C8H14O0.-G, 1-206(20).-Acid (III, A, 1), m. p. 168°; Test 314. 282 97 Dimethyl Phthalate, C10H10O4.-Acid (III, A, 2), m. p. 184°; Test 318-1. 282-6 115 Diethyl Suberate, C12H22O4.-G. 0-985(15).-Acid (III, A, 2), m. p. 140°. 284 (th. i.) 175 " Carbopyrotritarate, C12HieO6.-Acid (III, A, 2), m. p. 230°-l°. 285 111 " Isophthalate, C12H14O4.-Acid (III, A, 2), m. p. a. 300°; Test 318-2. 285-5 128 Diethyl Camphorate, C14H,4O4.-G. 1-029(16).-Acid (III, A, 2), m. p. 180° c. GENUS V, DIV. B. 127 (ORDER I, SUBORDER I.) Boiling- point Sapon Equiv. ESTERS.-Liquid Esters whose Neutral Saponification Products are Readily Volatile with Steam. Generic Position and Properties of the Acidic Saponification Products. 290 Methyl Benzoylpropionate, CnH12O3.-Acid (III, A, 2), m. p. 116°. 291-2 122 Diethyl Azelate, C13H24O4.-G. 0-991%.-Acid (III, A, 2), m. p. 106°. 294 92 Triethyl Citrate, C12H20O7.-G. 1 • 13 720/4.-Acid (III, A, 1), m. p. 153°; Test 314 295c. 111 t Diethyl Phthalate, C12H14O4.-G. l-11820/4.-Acid (III, A, 2), m. p. 184°; Test 318-1. 295 256 Ethyl Myristate, C16H32O2.-Acid (III, A, 2), m. p. 53-8°. 298-5 258 Diisoamyl Succinate, C14H2o04.-G. 0-961(13).-Acid (III, A, 1), m. p. 185°; Test 320. 295-305 86-7 Triethyl Tricarballylate, C12H20O6.-Acid (III, A, 1), m. p. 166°. 305 234 Octyl Benzoate, C15H22O2.-Acid (III, A, 2), m. p. 121°; Test 312. 307-8 129 t Diethyl Sebacate, C^H^O,.-G. 0-965(16).-Acid (III, A, 2), m. p. 133°. 308 212 Methyl o-Phenylbenzoate, C14H12O2.-Acid (III, A, 2), m. p. 110°-l°. 308-9 200 Ethyl /?-Naphthoate, C13H12O2.-Acid (III, A, 2), m. p. 184° c. 309c. 200 " a-Naphthoate, C13H12O2.-Acid (III, A, 2), m. p. 160°. 308-5-11 284 " Diheptylacetate, C18H36O2.-Acid (III, A, 2), m. p. 26°-7°- 310 (th. i.) 166 Methyl p-Oxyphenylacetate, C9H10O3.-G. 1 • 195°/4.-Acid (III, A, 1), m. p. 148°. 314 226 Etbvl o-Phenylbenzoate, CI5H14O2.-Acid (III, A, 2), m. p. 110°-l°. 323-4c. 212 Benzyl Benzoate, C14H12O2.-G. 1 • 114(18-5°).-Acid (III, A, 2), m. p. 121°; Test 312. a. 360 228 Methyl Phenylethersalicylate, C14H]2O3.-Acid (III, A, 2). m. p. 113° CHAPTER VEI. GENUS VI. ACID ANHYDRIDES AND LACTONES OF SUBORDER I, ORDER I. (Colorless Compounds of Carbon, Hydrogen, and Oxygen.) To this genus belong all species of the suborder, which, while not attacked rapidly enough by cold alkali to give Tests III or IV, yield a saponification equiva- lent of less than 500 in Test V, and form the sodium salt of an acid as their sole organic saponification product. No independent Generic Test VI exists, the claim of any species to membership in the genus being settled by the outcome of the exam- ination of the reaction products obtained in Test V (p. 111). The number of important species described under Genus VI is smaller than for any other genus in Order 1. It has already been mentioned elsewhere that many of the simpler and more important anhydrides; like acetic, benzoic, and succinic, and phthalid, are sufficiently reactive towards either cold decinormal or normal alkali to be entitled to positions with the acids or phenols. The number of species which might otherwise have established a valid claim for admission to the genus has been still further diminished by the difficulties that lay in the way of procuring pure preparations of representative types for direct examination, and the utter impossibility of drawing safe conclusions, a priori, as to the behavior of many of them towards alkali from the vague or conflicting statements that may be gleaned from a study of their literature. These unavoidable omissions, which can only be remedied by later investigations, consist almost exclusively of rare and unim- portant compounds. The fact that Genus VI is a skeleton genus to a greater extent than most others, has, therefore, little practical significance, except to the investigator in a few special fields. 128 COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I]. GENUS VI, ACID ANHYDRIDES AND LACTONES DIVISION A,-SOLID ACID ANHYDRIDES AND LACTONES WHICH DO NOT NEUTRALIZE COLD SODIUM HYDROXIDE SOLUTIONS READILY ENOUGH TO GIVE TESTS HI OR IV, 2. Melting-point (C.°). ACID ANHYDRIDES AND LACTONES.-Colorless and Solid. 25 Melilotic Anhyd., o-O.(.CGH4.C2H4.CO.).-B. p. 272°.-Odor like vanilla grass or Tonka bean!-S. c. aq.; d. s. h. aq.; e. s. CHC13.-Boiled w. alkali gives melilotic ac., m. p. 82°-3°.-Br2 substitutes in CS2 sol. giving compound w. m. p. 106° (pr. fr. CHC13). 63-4 3-Methoethylol(3')-heptanon(6)-olid(i, 3'),C10H1GO3.-B. p. 330°. - (An oxid. product of pinene, etc.).-Cryst. v. e. fr. h. aq.; s. aq.; v. s. CHC13; much less s. eth.-Sodium hydroxide and Br added to aq. sol. give CBr4.-Neut. equiv. 184. 64 Palmitic Anhyd., (C1GH31O)2.O. 67 f Coumarin, o-O(.CGH4.C2H2.CO.).-Fragrant odor like vanilla grass or Tonka bean!-B. p. 290°-0-5°.-Alm. i. c. aq.; s. h. aq.; e. s. ale. or eth.-Does not give Test III or IV.-Test V gives coumaric ac.!-The solution in alkali has a peculiar greenish-yellow color!-Adds Br2 in CS2 sol. (Cryst. fr. ale., m. p. 105°.) 71-7 Stearic Anhyd., (Ci8H35O)2.O. 73 tPhthalid. o-O(.CH2.CrH4.CO.).-B. p. .290° (th. i.).-Ndl. fr. h. aq.; v. d. s. c. aq.; e. s. ale.-Alkaline KMnO4 gives phthalic acid (Test 318-1) easily.- Test V gives o-Oxymethylbenzoic ac. (HI, A, 2), m. p. 120°.-[Finely powdered dissolves after shaking 1-2 min. in Test IV-2, and so properly belongs in Genus IV.]! 86-7 Glycolid, C4H4O4.-Lft. fr. ale., d. s. c. ale. or eth.; v. s. acetone.-Protracted boiling w. aq. gives glycoIlic ac. 102-5 Meconine, C10HI0O4. (from mother-liquors of opium alkaloids).-Sbl. in lus- trous ndl.- (Cf. Genus III, A, 2.) 103-5 Benzoylperoxide, (PhCO)2.O2.-Rhomb, cryst., e. s. eth. or bz.-Explodes on heating!-Boiled w. KOH sol. gives benzoic ac. (Test 312) and oxygen. 128 Lactid, CGHSO4.-Cryst. fr. h. ale., alm. i. c. aq.-Boiled w. aq. gives lactic ac.- (Cf. Genus HI, A, 2.) 128-30 GlycoIlic Anhyd.-Powd. i. aq.-(Cf. Genus HI, A, 2.) 134 Benzoin.-Slightly attacked in Test V.-(Cf. Ketones, VII, A.) 160-61 Saccharin, C6H10Os.-Pr. of bitter taste. 100 pt. aq. at 15° dissolve 13 pt.-Opt. act. [ + ]; salts however [ - ].-Ether extracts fr. strongly alk. sol. in Na2CO3.- Aq. sol. boiled w. CaCO3 gives soluble uncryst. Ca saccharate.-Gives Test 801! 169-70 Santonin, C15H1SO3.-Cryst., s. in 5000 pt. c., or 250 pt. h. aq.; s. c. ale.; d. s. c. eth.; e. s. CHC13.-Opt. act.-Cryst. rapidly turn yellow in air!-Does not redden litmus.-Alcoholic KOH colors red!-Warming w. alkali gives santonic ac. 218c. f Cantharidin, C10H12O4.-Well-formed cryst., alm. i. c. or h. aq.; v. d. s. ale. or eth.-Ale. sol. placed on skin quickly produces painless blisters!-2 pt. heated at 100° for 15 min. w. 3 pt. phenylhydrazine hydrochloride, 4-5 pt. NaAc, and 30 pt. aq. gives a hydrazonehydrate cryst. fr. ale. w. m. p. 194° c. -t Test V gives sodium cantharidate. The cantharidin may be recovered unchanged by boiling the cantharidate sol. for a few minutes after acidifi- cation w. dil. H2SO4; the cantharidic ac. in the heating loses water and gives i. cantharidin, which precipitates out. 129 130 GENUS VI, DIV. A. Melting-point (C.u). ACID ANHYDRIDES AND LACTONES.-Colorless and Solid. 220 Polyglycolid, (C2H2O2)X.-White powder, v. d. s. h. aq.-Reacts neutral, but by persistent boiling w. aq. or KOH gives glycoIlic ac.-Prepare aniline derivative, Bl., 30, 102. 220-1 Camphoric Anhyd.-B. p. 91°.-(Cf. Genus III, A, 2.) 223-4 Umbelliferone, C9HGO3.-(Cf. Genus IV, A).-Odor when warm, fragrant, like coumarin. 334-5 Biphthalyl, C1GHSO4.-Sbl. in ndl.; i. aq.; alm. i. ale. or eth., s. h. glacial acetic ac. or cone. H2SO4.-The sol. in cone. H2SO4 shows blue fluorescence, but becomes transiently emerald-green if a trace of nitric acid is added.-Warmed w. KOH sol. gives diphthalylaldehydic ac. (ORDER I, SUBORDER I.) COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I.] GENUS VI, ACID ANHYDRIDES AND LACTONES. DIVISION B,-LIQUID ACID ANHYDRIDES AND LACTONES WHICH DO NOT NEUTRALIZE COLD DECINORMAL SODIUM HYDROX- IDE READILY ENOUGH TO TITRATE LIKE SPECIES OF GENUS TH. Boiling-point (C.°y ACID ANHYDRIDES AND LACTONES.-Colorless and Liquid. 167 si. d. a-Lsevulinic Anhyd., C5H6O2.-M. p. 18°-18-5°.-E. volatile in air.-S. in 21 pt. aq. at 15°, but ppt. by K2CO3.-"5 hours' boiling w. aq. gives Isevulinic ac." 204 /?-Methyl-/-butyrolactone, O(.CH2.CHMe.CH2CO.).-G. 1-077%.-S. in l|-2 pt- aq.-BaA3 ndl.; v. s. aq.-Pure ac. unknown. 206c. /-Butyrolactone, O(.(CH2)3.CO.).-G. 1 • 12915/0.-Mise. w. aq.; separated fr. cone. sol. by K2CO3.-Volat. w. st.-Reduces ammon. AgNO3.-"Boiled 5 min. w. n/200 NaOH is only | converted into salt of acid."-Oxid. by CrO3 to succinic ac. (Test 320). 206 <x-Methyl-/-valerolactone, O(.CHMe.(CH2)3.CO.).-S. 20-25 pt. aq.; sat. sol. becomes turbid on warming, but clears at 80°.-Acid v. unstable. 207c. /-Isocaprolactone, O(.CMe2.C,H4.CO.).-M. p. 7°-8°.-G. 1-01516'2/4.-S. in 2 pt. c. aq.; sat. sol. becomes turbid on warming, but clears at 80°.-K2CO3 separates lactone fr. cone. aq. sol.-Free ac. cryst. but unstable, especially on warming.-Ag salt ppt. cryst. in flat ndl. fr. h. aq. 206-9 Coumalin, O(.(CH)4.CO.).-G. l-20018'5/4.--Agreeable coumarine-like odor!-• M. p. +5°.-Mise. w. aq. but separated fr. sol. by K2CO3.-Aq. sol. neutral, even after warming.-Neutralizes n/10 NaOH very slowly, giving yellow sol.-Neutralized and then boiled w. x's alkali gives crotonic aldehyde (odor). 207-8c. f/-Valerolactone, O(.(CH,)4.CO.).-G. l-057I8/4.-Sapon. Eq. 100.-Mise. w. aq.-Ppt'd from the cone, neutral aq. sol. by K2CO3.-Half converted into salt of acid after 7 min. boiling w. equivalent quantity n/2oo NaOH; pro- tracted boiling w. aq. gives only 6-6% acid.-Ac. very unstable. Its Ag salt (AgC5H8O3), large triclin. ndl. fr. h. aq. 208-9 /9-Laevulinic Anhyd., C5H6O2.-G. 1-108(0°).-V. s. aq.-Hydrolyzed v. slowly and incompletely by h. aq.-Dec. by c. Ba(OH)2 sol. to Isevulinic ac. in 12 hours. 215 Valerianic Anhyd., (C5H9O)2.O.-G. 0-92926'7/4.-"Slowly hydrolyzed by boil- ing aq."--Vapor produces coughing. When fresh has apple-like odor.- Sapon. equiv. 93.-Of. Genus III, B, 2. 215 n-Ethyl-/-butyrolactone, O(.CH2.CH,.CHEt.CO.).-G. 1-035(16°).-S. in 10-11 pt. c. aq., sol. becoming cloudy on heating; e. s. ale. or eth.-Separated fr. aq. sol. by K2COS.-Boiling w. alkali gives salt of sirupy soluble ac. 219-5 n-Ethylvalerolactone, O(.HCMe.CH,.CHEt.CU.).-G. 0-992(16°).-Rather d. s. aq.; aq. sol. sat. at 0° becomes turbid at 90°.-Ac. unknown.-Still liq. at -18°. 220 /-Caprolactone, O(.HCEt.CH2.CH,.CO.).-S. in 5-6 pt. aq. at 0°; K2CO3 sepa- rates fr. sol.-Becomes turbid at 30°~50°, clearing again at 80°.-Still liq. at -18°. 235 (th. i.) /-CEnantholactone, O(.HCPr.CH2.CH2.CO.). - V. d. s. aq. - Ac. unknown. - Still liq. at -18°. 254-5 /-Ethyl-d-Caprolactone, O(.HCMe.HCEt.CH2.CH2.CO.).-G. 1 -0802%.-Still liquid at -20°.-Mise. ale. or eth.; s. 28 pt. aq.-Feeble aromatic odor.- Aq. sol. at first neutral, but a little acid forms after 24 hours in cold w. aq. -Ac. unstable liq. 131 132 GENUS VI, DIV. B. (ORDER I, SUBORDER I.) Boiling-point (C.°). ACID ANHYDRIDES AND LACTONES.-Colorless and Liquid. 268-71 CEnanthylic Anhyd., (C7HI3O)2O.-G. 0-932(21°).-Neutral reaction.-W. cone. NH4OH solidifies at once to imide, which recryst. fr. h. aq. melts at 95°.- Saponification gives acid, b. p. 223°, neut. equiv. 121. 272 Melilotic Anhyd., o-O(.C6H4.C2H4.CO.).-Odor like sweet grass or Tonka bean! -M. p. 25°.-Cf. V, A. 280-90 Caprylic Anhyd., (CsH15O)2O. - Odor very disagreeable. - Neutral.-Not at- tacked by boiling or distilling w. aq.; though a little acid forms upon long exposure to moisture.-Test V gives caprylic ac. (cf. Ill, B, 2), b. p. 237-5°. CHAPTER IX. GENUS VII. KETONES OF SUBORDER I, ORDER I. (Colorless Compounds of Carbon, Hydrogen, and Oxygen.) This genus includes all species of' the Suborder containing the carbonyl radical that have not been described in the earlier genera. These species, with some exceptions, are recognized by their behavior towards phenylhydrazine or hydroxylamine in Test VII. The few that escape recognition by this test will at first appear to belong to Genus IX, in which they receive mention in connection with a reference to the position in Genus VII where they are described. IF THE COMPOUND TO BE EXAMINED IS A SOLID HAVING A MELTING-POINT ABOVE 30°, EMPLOY PROCEDURE 1 OF THE TEST ONLY. IF IT IS A LIQUID, OR A SOLID WITH A MELTING-POINT NOT HIGHER THAN 30°, USE PROCEDURE 2 ONLY. GENERIC TEST VII. PROCEDURE 1. (The Test with Hydroxylamine.) Fit two dry six-inch test-tubes with perforated rubber stoppers, through each of which a meter length of glass gas delivery-tubing 7-8 mm. in internal diameter has been inserted. In the first tube place 0.04-0.06 grm. of the powdered sub- stance, 0.5 cc. of a hydroxylamine hydrochloride solution,* and 2 cc. of the alcoholic sodium hydroxide solution described below. Charge the second tube, which is to be used for a blank experiment, in the same manner, except that 0.5 cc. of 25 per cent alcohol is to be substituted for the hydroxylamine solution. Support both tubes by clamps in vertical positions so that their lower extremities may be heated by immersion in the bath represented in Fig. 4 on page 152, which is at a temperature of 100°, or in a beaker nearly filled with water already boiling. Allow the solutions to boil up briskly for at least five minutes. Then cool; dilute each with 10 cc. of cold water, and shake vigorously to precipitate out any substances insoluble in dilute aqueous alkali. Filter through double wetted filters, repeating if necessary until clear filtrates are obtained. Add one drop of phenolphthalein to each filtrate, and then dilute hydrochloric acid, drop by drop, until the red color is just discharged. Again close the mouth of each tube and shake vigorously. Note whether the solutions remain clear, become turbid or opaque, or give pre- cipitates. * The Reagents for Test VII (i).-The hydroxylamine hydrochloride solution is made by dissolving 7.25 grms. of the purest commercial salt in 9 cc. of water, and diluting to 35 cc. with strong alcohol. The soda solution is made by dissolving 10 grms. of the purest sodium hydroxide in 20 cc. of hot distilled water, and then diluting to 140 cc. with strong or absolute alcohol. Small quantities of both solutions should be kept in stock in laboratories where tests are often made. The hydroxylamine solution may be preserved for some months, at least, without seriously deteriorating in strength. The soda solution will soon become strongly colored on keeping unless it is prepared with unusually pure alcohol. 133 134 KETONES. If the solution from the tube to which hydroxylamine was added gives a pre- cipitate, or becomes opaque after neutralization with acid and shaking, while the solution in the blank experiment remains clear, or only becomes opalescent or slightly turbid, the compound under examination is to be sought in the tables of Genus VII. The precipitate in this case consists of an oxime which is soluble in alkali, but not in a neutral aqueous solution. A majority of the oximes which are precipitated in this test-though there are many exceptions to the rule-dissolve in an excess of cold dilute hydrochloric acid to clear solutions, from which they may be again precipitated by neutralization and shaking. (The Test with Phenylhydrazine.) PROCEDURE 2. If the unknown compound is readily soluble in water, dissolve one drop in 2 co. of cold water in a dry six-inch test-tube 18-20 mm. in diameter, and add four drops of a phenylhydrazine solution prepared by the method described below.* If the compound is not soluble in water, substitute for the latter 2 cc. of dilute alcohol (one volume of strong alcohol to two volumes of water). It is not necessary in this case that the substance should dissolve visibly. Suspending the test-tube by its lip between the thumb and forefinger, sway it from side to side with a slow pendulum motion (one or two swings a second) for at least a minute. Vigorous shaking might spoil the test by breaking up a difficultly soluble substance into minute droplets and forming an opaque emulsion. If the solution remains clear, stopper the tube very loosely with a clean cork, and stand it upright in a beaker containing a layer of water 2-3 cm. deep. Have the water gently boiling at the moment when the tube is introduced, and continue to heat at 100° for five minutes. The water in the beaker should not boil actively during this period, for the steam arising then heats the side walls of the test-tube to such an extent that the loss of alcohol by evaporation may become too impor- tant a factor in the final result, and violent bumping of the mixture may cause emul- sification of the original mixture. Whenever this test in hot solution has to be applied, a blank experiment must be made at the same time, using the same quan- tities of the substance and solvent, but omitting the phenylhydrazine. If the solution still remains clear after five minutes' heating, remove it from the water-bath, and, after allowing it to stand twenty-five to thirty seconds, care- fully observe its degree of transparency and its color. (The delay in making this observation is mainly to permit suspended drops of unchanged substance to settle out. The appearance of a precipitate or opacity after thirty seconds may be caused by the separation of the original substance from its supersaturated solution, and is without significance.) To test for opacity, hold the test-tube in front of, and in actual contact with, a piece of white paper on which a small cross has been drawn in lines 1 mm. in width in black ink. If the cross can not be seen through the solution when the position of the test-tube is slightly changed, the solution is to be considered "opaque." * [The Phenylhydrazine Reagent for Test VII (2).-Mix 0.3 cc. of glacial acetic acid with 7.0 cc. of cold water. To the mixture add 2 cc. of light-colored phenylhydrazine. The clear solution, if not exposed to direct sunlight, will remain in good condition for four or five days but then becomes strongly colored and should be thrown awav.l KETONES. 135 Any compound to which Test VI1-2 has been applied is probably a ketone: (a) If an "opaque" solution is obtained on treating it with phenylhydrazine in the cold by the method of the first paragraph. (b) If an "opaque" solution is obtained during the five minutes' heating described in the second paragraph, or within thirty seconds after its removal from the bath, provided the solution in the corresponding blank experiment remains clear, or nearly so. (c) If both solutions mentioned in (b) become "opaque" after heating, but the solution of the blank test remains unchanged in color, while the suspended matter in the solution containing phenylhydrazine assumes a much deeper yellow color. Observations on Generic Test VII. In using Procedure 2 of this test the analyst should never lose sight of the danger that exists of mistaking an alcohol or hydrocarbon containing traces of aldehydic impurities for a ketone; for aldehydes yield insoluble phenylhydrazones, and give opaque solutions under the test conditions, quite as easily and uniformly as the species of Genus VII. A contamination with aldehyde that is barely sufficient to produce a very faint pink coloration with the fuchsine reagent in Test I, may cause a pronounced tur- bidity in the test with phenylhydrazine. Conclusions as to the ketonic character of a substance of doubtful homogeneity which reacts slightly with the fuchsinfe reagent, can not, therefore, be safely drawn from Test VII-2. It is necessary that such bodies shall first be purified with every possible .care. Of the two procedures 1 and 2, neither one can be trusted for the recognition of ketones belonging to the group for which its alternative is prescribed in the "generic test; " though it is true that most solid species do show a ketonic behavior in Procedure 2, and that very many liquid ketones, which it is directed shall be examined by Procedure 2, would also react as ketones when tested by Procedure 1. Both reactions, in the form recommended, fail in certain special cases. Thus they are not given by aromatic ketones having two alkyl radicals substituting in the ortho position to the carbonyl group; or by the fatty ketones (CnH2n+1)2CO., in which "n" is 9 or a higher number, though still given by caprone (C5Hn)2CO.* The liquid aliphatic ketones which are soluble in water are, in general, readily rec- ognized by Procedure 2, but not by Procedure 1. In explanation of the numerous rather arbitrary conditions imposed in these procedures, it should be said that the tests as they stand are the result of informa- tion obtained from a study of the behavior of about one hundred purified and typical species of Genera VII, VIII, and IX towards hydroxylamine and phenylhydrazine under a great variety of carefully controlled conditions. By lengthening the period of heating with the reagents, and by other devices, the number of ketones calling for mention in the tables of Genus IX might have been somewhat reduced, and a slight gain made in the direction of simplicity of classification; but this advantage would have been more than offset by the increased length or experimental difficulty of the operations necessitated. * The oximes of the higher fatty ketones are formed in the test with hydroxylamine, but they are not soluble enough in alkali to give a precipitate or opaque solution in the neutraliza- tion with acid. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I] GENUS VII, KETONES. DIVISION A-SOLID KETONES. Melting-point (C.°). Boiling-point (C.°). KETONES.-Colorless and Solid. 20-5 202 f Acetophenone, Me.CO.Ph.-Odor aromatic !-Alm. i. aq.- (When melted, often refuses to solidify unless a crystal is added.)-Sol. in Test VII-2 becomes opaque and gives yellowish-white ppt. after 30 seconds in the cold. Color- reaction 701 is quite characteristic.-Identify by Test 712! 26-6-5 306 Allotropic Benzophenone, CI3H,J)O(?).-Eth. sol. on evapo- ration leaves an oil that solidifies to benzophenone (m. p. 48°-9°) upon contact w. a crystal of the latter substance. 27 215 Methyl Benzyl Ketone, Me.CO.CH.Ph.-Combines easily w. NaHSO3.-Mixed w. phenylhydrazine, reacts at once w. evolution of heat and separation of aq., giving a hydra- zone, 1ft. fr. Igr., m. p. 83°. 27 273-5 p-Propionylanisol, Et.CO.C6H4.OMe.-KMnO4 oxid. to anisic ac. -M. p. of oxime, 67°. 28 198-5 t Phoron, C9H14O.-Slightly yellow cryst.-Adds Br4 in- stantly in the cold in CS2 sol.; the addition product cryst. fr. ale. w. m. p. 88°-9°.-Sol. in Test VII-2 becomes opaque and yellow after 3 min. heating. 28 263 Methyl Undecyl Ketone, Me.CO.CnH23.-G. 0-829 (28°). 30 p-Propionylphenetol, Et.CO.C6H4.OEt.-Oxime, m. p. 97°. 30 264c. Dihexyl Ketone, (C0H13)2.CO.-G. 0.825 (30°).-V. s. ale. or eth. 33-9 330-6c. Dibenzyl Ketone, (C7H7)2.CO.-Test 702 gives benzoic ac.- M. p. oxime, 119-5°. 33-4 205-6(100 mm.) Tetradecanone(2), Me.CO.C12H25.-Test 702 gives lauric and acetic ac. 36 318c. Phenyl p-Xylyl Ketone, Ph.CO.CGH3.Me2.-V. s. ale. or eth.- Stable towards oxid. agents.-Warming w. cone. H2SO4 splits off benzoic ac. (Test 312.) 38 196 Camphenylon, C8H14:CO.- Strong camphor odor. - Forms oxime, ndl. fr. eth., m. p. 105°-6°. 39 294 Methyl Tridecyl Ketone, Me.CO.C13H27.-G. 0-818 (39°). Gives an oxime. 39 229d. Furfuralacetone, C4H3O.CH: CH.CO.Me.-Sol. in acetylchlo- ride is light red, becoming emerald-green on warming. 40 178 Diheptyl Ketone, (C7H15)2.CO.-Ndl. fr. ale.-Probably does not give a very satisfactory ketone reaction in Test VII-1. 40 244 a-Hydrindone, C0HsO.-Rhombic tbl. v. s. ale.-Oxid. bv Test 905-3, gives phthalic ac. (Test 318-1).-M. p. of oxime 146°. 41-2 260-2 (th. i.) Benzalacetone, Me.CO.CH:CH.Ph.-Thick tbl. e. s. ale. or eth.-S. in cone. H2SO4 w. orange color.-Dibromide melts at 124°-5°.-Oxime melts at 115°.-Forms NaHSO3 comp, easily. 42 Vinyl Phenyl Ketone, C,H3.CO.Ph.-Ndl. v. s. ale. or eth.- NaHSO3 comp, forms slowly. 42-3 p-Tolyl Hexyl Ketone, C7H7.CO.CGH13.-Oxime is an oil. 136 GENUS VII, DIV. A. 137 Melting-point (c»y. Boiling-point (C.°). KETONES.-Colorless and Solid. 43-3-5 230-1 Hexadecanone(2), Me.CO.CuH^.-Test 702 gives myristic and acetic acids. 46 310c. Diacetylmesitylene, Me3.C6H.(CO.Me)2.-Pr. fr. Igr. 48 319-20 Methyl Quindecyl Ketone, Me.CO.C15H31. 48-8-5 306c. f Benzophenone, Ph2.CO.-Rhombic pr., i. aq.; e. s. ale. or eth - Sodium gives an intensely dark blue compound when gently heated w. the fused ketone ! Identify by Test 714 I 50-1 323 Propyl Naphthyl Ketone, Pr.CO.C10H7.-S. ale.-Oxime m. p. 89°.-M. p. picrate 68°-9°. 51-2 251-2(100 mm.) Octadecanone(2), CjaH33.CO.Me.-Gives oxime. 51-2 300-1 ^-Methyl Naphthyl Ketone, Me.CO.C10H7.-Ndl. fr. Igr.- Oxime, m. p. 142°-3°.-Dibrom.-derivative, fr. CS2, m. p. 101°. abt. 56 266 (110 mm.) Methyl Heptadecyl Ketone, Me.CO.C17H35.-Gives oxime. 57 Benzyl Naphthyl Ketone, C7H7.CO.C10H7.-Tbl. fr. ale., e. s. ale. or eth. 57-8 345-8 f Benzylideneacetophenone, Ph.CH:CH.CO.Ph.-Pale yellow- ish rhombic pr., s. ale., e. s. eth.-Gives isomeric solid oximes.-Heated w. HC1 (sp. gr. 1 • 12) at 200° gives benz- aldehyde and acetophenone. 58 a.350 f Dinonyl Ketone, (C9H19)2.CO. - Pearly 1ft. fr. ale.-[This, and the other symmetrical aliphatic ketones higher in the series, do not give Test VII-1 satisfactorily, because their oximes are not readily soluble in alkali.] 59 m-Methylhydrindone, Cj0H10O.-Long ndl. fr. Igr. 59 251 (15 mm.) Phenyl Pentadecyl Ketone, C22H36O.-V. d. s. c. ale.; s. eth. 59-60 326 (th. i.) f p-Phenyl Tolyl Ketone, Ph.CO.C7H7.-(M. p. of dimorphous hexagonal form is 55°.)-S. c. ale.; e. s. eth.-Oxid. by CrO3 mixture to p-benzoyl-benzoic ac.-Gives isomeric solid oximes, m. p. 153°-4° and 115°-6°.-Heated w. soda-lime at 300° gives benzene (Test 913), and p-toluic ac. 60 262 (15 mm.) p-Tolyl Pentadecyl Ketone, C23H3gO. 60 320-2c. Desoxybenzoin, Ph.CO.CH2.Ph.-Tbl. d. s. h. aq.; e. s. c. ale. or eth.-Easily attacked by HNO3 or bz.-Oxime, ndl. fr. ale., m. p. 98°. 61 220-5d. /?-Hydrindone, C9H8O.-E. s. ale. or eth.-Oxime, ndl. fr. dil. ale., m. p. 155°.-M. p. of phenylhydrazone 120°.- Oxid. by KMnO4 gives homophthalic ac. 63 2, 5-Dimethyl-3, 4-diacetylfurfuran, Cj0H12O3.-Fine silky ndl. fr. h. aq., w. peculiar faint aromatic odor when warmed.- S. in cone. H2SO4 and ppt'd unchanged by aq. 63 p-Methylhydrindone, C10H10O.-Ndl. fr. Igr., e. s. ale. or eth. 67 278 (15 mm.) p-Tolyl Heptadecyl Ketone, C7H7.CO.Cj7H35.-V. d. s. c. ale. -Oxid. by Test 905-3 gives p-toluic ac. 68 dec. Methyl Cinnamenylvinyl Ketone, C12Hi2O.-Rhombic plates fr. eth.; e. s. ale. Color soon changes to light yellow.- Oxime, m. p. 153°.-Adds Br2 easily in ethereal sol., giving dibromide of m. p. 173-5°. 69 Laurone, (CnH23)2.CO.-I. c. ale.-Probably does not give Test VII-1, oxime not being sol. in alkali. 72-3 a.360 Benzylacetophenone, C7H7.CH2.CO.Ph.-V. s. ale. or eth.-Oxid. by Test 905-1 gives benzoic ac. (Test 312).-Br substitutes easily.-Oxime, m. p. 87°, v. s. ale. 73 255-60 Methyl s-Duryl Ketone, MerC0H.CO.Me.-Pearly 1ft. 75-5 385 a-Phenyl Naphthyl Ketone, Ph.CO.C1()H7.-S. 41 pt. ale. at 12°.- Heating w. soda-lime at 350° gives naphthalene (Test 915) and benzoic ac.-Oxime, m. p. 140°-2°. (ORDER I, SUBORDER I.) 138 GENUS VII, DIV. A. (ORDER I, SUBORDER I.) Melting-point (C.°). Boiling-point (C.°). KETONES.-Colorless and Solid. 76 3 78 81-5-2-5 82 82-8 83 83-5-4 85 85-5-86 87-8 92 93-4 94 95 95 99 99-5-100 102-3 104-5 106 107-10 109-10 112-2-5 115 117 t Myristone, (C13H27)2.CO.-Scales fr. abs. ale.-Oxime being v. d. s. in alkali does not give Test VII-1. 6-Phenylindanone(7), C15H12O.-B. p. 344° d.-E. s. ale. or eth. -Reduces ammon. AgNO3 sol. on warming.-Oxime, m. p. 141°.-Oxid. by Test 905-3 gives benzoic and phthalic ac. (Tests 312 and 318-1). Lactarone, (C14H29)2.CO.-Pearly 1ft. fr. clc. ^-Phenyl Naphthyl Ketone, Ph.CO.C10H7.-Ndl. s. 49 pt. C. ale. -Picrate fr. sat. sol. of picric ac. in bz., m. p. 112°-13°.- Heating w. soda-lime gives naphthalene (Test 915) and ben- zoic ac. (Test 312). Palmitone, (CifH31)2.CO.-Lft. fr. ale.-Oxime being v. d. s. alk., probably does not give Test VII-1.-Gives no NaHSO3 comp. Isodiphenylene Ketone, C]3HSO.-D. s. ale.--Stable toward oxid. agents.-Not changed by fusion w. KOH. Diphenylene Ketone, (C0H4)2.CO.-Large yellow tbl.-See Sub- order II. Methyl Pentamethylphenyl Ketone, C.,H,„O.-E. s. ale. or eth.-- Oxid. by c. KMnO4. Oxyacetophenone, Ph.CO.CH2OH.-V. s. ale. or eth.; s. h. aq.-• Decomposed by heat alone, or by heating w. NaOH, giving benzaldehyde (Test 113).-Reduces Tollen's reagent giving benzaldehyde.-Gives Test 702. f Stearone, (C17H35)2.CO.- Lft. d. s. h. ale. or eth. - Dibrom- derivative, m. p. 72°.--Because of insolubility of oxime in alkali does not give Test VII-1. s-(p)-Dimethylbenzophenone, (C0H4.Me)2.CO.-B. p. 335°-7°.- V. s. ale. or eth.-HNO3 (sp. gr. 1-51) gives dinitro-comp., s. bz.; m. p. 144°.-Oxime, pr. fr. ale., m. p. 163°.-Boiled w. solid KOH gives p-toluic ac. 9, 9-Dimethyldihydroanthrenone(ro), C1GH14O.-Cryst. e. s. eth. or bz.-Oxid. by CrO3 to acetic ac. and anthraquinone. Phenyl-p-Xylyl Ketone, Ph.CO.CH2.C0H4.Me.-4-sided pr.- Oxime, m. p. 109°. Benzoinethylether, Ph.CH(OEt).CO.Ph.-Pr. e. s. ale. or eth. o-Methylhydrindone, C10H10O.-Ndl. fr. Igr.-Oxid. by Test 905-3 to methyl-phthalic ac. Benzoylveratol, (MeO)2.CcH3.CO.Ph.-Ndl. fr. ale. m-Phenylene Diphenyl Ketone, C6H4.(CO.Ph)2.-Dist. undec.- Oxime, m. p. 201°.-Fusion w. KOH gives only benzoic ac. (Test 312). Cinnamyleneacetophenone, C17H14O.-Cf. Suborder II. Ledum Camphor, C15H2GO (fr. leaves of Ledum palustre, wild rosemary).-Sbl. v. e. in long ndl.-Sol. in cone. H2S64 be- comes violet w. a drop of HNO3.-Gentle heating w. 50% H2SO4 gives a sesquiterpene, b. p. 255°. Cinnamylenebenzylideneacetone, C19H10O.-Cf. Suborder II. /?-Dibenzoylacetone, C17H14O3.-Ndl., d. s. eth., CHC13 and Igr.; s. in 100 pt. bz.-(Alcoholic sol. gives no color w. FeCl3.) Anisoin, C16H1G04.-Ndl. d. s. c. ale. or eth.-S. in cone. H2SO4 w. pale-green color changing to yellow and purple-red on warming!-Reduces Fehling's sol. f Dibenzylideneacetone, (Ph.CH:CH)2.CO.-See Suborder II. Methylhydrocotoi'ne, (MeO)3.CGH2.CO.Ph.-Br substitutes.- Fusion w. KOH gives benzoic ac., etc. Dibenzoylmesitylene, (Ph.CO)2.C0H.Me3.-B. p. abt. 300°. GENUS VII, DIV. A. 139 (ORDER I, SUBORDER I.) Melting-point (C.°). Boiling-point KETONES.-Colorless and Solid. 119-20 Phenyldibenzoylmethane, (Ph.CO)2.CH.Ph.-B. p. 300°-5° (15 mm.). 120 Piperonyloine, C1GH12OG.-Oxid. by dil. HNO3 (Test 905-3) gives oxalic ac. (Test 317). 121 m-Acetylbiphenyl, Me.CO.CGH4.Ph.-B. p. 325°-7°.-E. s. ale. or acetone.-Oxid. by CrO3 in Ac. to m-phenylbenzol. ac. 121c. Acenaphthenone, Ci2HsO.-Ndl. v. s. ale.-Gives substitution product_w. Br in CS2 sol., m. p. 112°.-Boiled w. Zn dust and glacial ac gives acenaphthylene.-Oxime, 1ft. fr. ale., m p 175°- 126 1,2, 4-Triphenylbutanedione(i,4), Ph.CO.CH(Ph).CH,.CO.Ph.- Upon sol. in c. cone. H2SO4 and addition of aq. gives ppt. of triphenylfurfurane -Oxime, m. p. 151°. 129 1,2, 4-Triphenylbutenedione(i, 4), Ph.CO.C(Ph): CH.CO.Ph.- Yellowish ndl., v. d. s. ale. or eth.-Dry, adds Br2 cold; moist, Br substitutes. abt. 133 t Benzoin, Ph.CH(OH).CO.Ph.-B. p. 343°-4°.-6-sided pr. (often pale sulphur-yellow).-I. c. aq.; v. d. s. h. aq.; s. h. ale.-Gives Test VII-1.-Ale. sol. reduces Tollen's reagent (Test 101)!-Strongly heated above b. p. gives faint odor of benzaldehyde.-Boiled w. normal NaOH sol. in porcelain dish while air is blown through the solution the liquid soon assumes a RVT1 color.-Apply Test 713. 135 a/?-Dinaphthyl Ketone, (C10H7)2.CO.-S. in 77 pt. ale. at 14°; e. s. eth.-Heated w. soda-lime at 350° gives naphthalene and a- and /?-naphthoic ac. 144-5 Diphenylbutanedione(i, 4), Ph.CO.CH2.CH2.CO.Ph.-Ndl. d. s. ale. or eth.-Sol. in cone. H2SO4 is green, becoming red- brown w. blue-green fluorescence on warming.-Dioxime, m. p. 203°-4°. 159 s(-p)-Ditoluylethane, C7H7.CO.CH2.CH2.CO.C7H7.-Ndl., v. d. s. c. ale.; e. s. bz.-Boiling w. ammonium acetate and glacial Ac gives p-ditolylpyrrol. 159-60 Terephthalophenone, CGH4.(CO.Ph)2.-Ndl. or 1ft., d. s. c. ale. or eth.-Oxime, m. p. 212°-13°; dioxime, fr. dil. ale., m. p. 235°. 162-3 Triacetylbenzene, CGH3.(CO.Me)3.-Small ndl. d. s. aq., ale., or eth.-Oxid. by HNO3 gives trimesic ac. 173-5 Diacetyldibenzylethane, C20HlsO4.-Ndl. fr. ale.-I. aq. or dil. alkalies. 176-4 f [ + ] Camphor, C10H16O. - ("Camphor.") - B. p. 205-3°.- Tough, white cryst., translucent, slightly unctuous mass, w. peculiar, penetrating, fragrant odor, and bitter, pungent taste ! Small fragments thrown upon pure water, float and assume singular circulatory movements, which immediately cease upon the addition of a drop of oil.-Very volatile, sub- liming crystalline on sides of vessels in which it'is contained at ordinary temperatures, and in the saponification test soon passing out of flask and depositing in condenser!-V. d. s. aq.; v. s. ale ; e. s. eth.-Identify by Test 715! (The oxime forms so slowly that camphor does not give an appre- ciable ppt. in Test VII-1.)-''Synthetic Camphor" is opt. i. 198 f a-Dibenzaltriacetophenone, C38HS2O3.-Cryst. fr. bz.; v. d. s. ale.-Ppt. in Test VII-1 rather scanty.-Dist. splits to acetophenone (Test 712) and diphenylpropenone.-Warmed w. ale. NaOH gives (/?) isomer, m. p. 256°. 208 Phenyloxanthranol, C20H14O2.-Rhombic tbl., i. alkalies; e. s. ale.; s. cone. H2SO4 w. intense purple-red color.-Warmed w. glacial Ac and Zn dust gives phenylanthranol. 232 " Octahedral " Oxylepidine, C28H20O2.-Cf. Suborder II. 140 GENUS VII, DIV. A. (ORDER I, SUBORDER I.) Melting-point (C.°). Boiling-point KETONES.-Colorless and Solid. 256 f (/?)-Dibenzaltriacetophenone, C38H32O3.-Thin lustrous pr. d. s. ale.-Does not give Test VII-2.-On dist. splits to aceto- phenone (Test 712) and diphenylpropenone. 269-70 Duryldibenzoyl, Me4.C6.(CO.Ph)2.-Small pr. s. bz.; alm. i. h. ale.-Sbl.-Fusion w. KOH gives benzoic ac. and durene. 289 Truxone, (C9H6O)X.-Sbl. in ndl.-Cryst. fr. HNO3 (sp. gr. 1-38) in long lustrous ndl. COLORLESS COMPOUNDS CONTAINING G, H, AND O [SUBORDER I OF ORDER I], GENUS VII, KETONES. DIVISION B-LIQUID KETONES. Boiling-point (C.°). Specific Gravity. KETONES.-Colorless and Liquid. 56-5c. 0-819% t Acetone, Me.CO.Me.-Mise. w. aq., ale., or eth.-Odor alco- holic-ethereal.-Identify by Test 711! 80-6 0-805(19-8) t Methyl Ethyl Ketone, Me.CO.Et.--Odor like acetone.-Oxid, by Test 702 gives acetic ac. only! 87-5-8 0-973(22) t Diacetyl, Me.CO.CO.Me.-Yellow liquid w. peculiar sweetish- pungent odor. (Belongs to Div. B of Suborder II.) 95 0-822% Methyl Isopropyl Ketone, Me.CO.Pr.-Oxid. by Test 702 gives Ac and CO2. 98-102 2-Methylbutenon(i, 3), Me.CO.CMe: CH2. 102c. 0-812(15) t Methyl Propyl Ketone, Me.CO.Pr.-Test 702 gives acetic and propionic acids. 102-7c. 0-834% t Diethyl Ketone, Et.CO.Et.-CrO3 oxid. to acetic and propionic acids (cf. Test 702).-Gives NaHSO3 comp. w. difficulty. 106 (th. i.) 0-800(16) f Pinacoline, Me.CO.C.Me3.-Alm. i. aq.-Peppermint-like odor. -No NaHSO3 comp.-Test 702 oxid. to trimethylacetic ac. -Treated w. Cl cold gives C6H10Cl2O, m. p. 51°; b. p. 178°.- Becomes opaque and yellow in 10 sec., cold, in Test VII-2. 114 Acetyltrimethylene, Me.CO.C3H5. - Polymerized by mineral acids.-KMnO4 gives trimethylenecarbonic ac. 114-5 0-830% Ethyl Isopropyl Ketone, Et.CO.Pr. 116 O-8O319/o Methyl Isobutyl Ketone, Me.CO.Bu.-Strong camphor-like odor. -Test 702 oxid. to isobutyric, isovalerianic, and acetic acids (disagreeable odor).-Gives a NaHSO3 comp. 118c. 0-81814-% Methylethylacetone, Me.CO.CH(Me)Et.-Peppermint-like odor. -Test 702 gives acetic ac. (Test 311). 122 0-861(15) Ethylideneacetone, Me.CH:CH.CO.Me.-S. aq. 122-4 0-818(17-5) Ethyl Propyl Ketone, Et.CO.Pr.-Test 702 oxid. to Ac, pro- pionic and butyric acids. 123-7 0 • 8062% Diiosopropyl Ketone, (Me2.CH)2.CO.-No comp. w. NaHSO3.- CrO3 gives acetic and isobutyric acids (Test 702). 126 0-810(21) 2, 2-Dimethylpentanone(3), Et.CO.C.Me,.- Camphor odor.- Test 702 gives Ac and trimethylacetic ac. 127 0-830(0) Methyl Butyl Ketone, Me.CO.Bu. 128 0-920(21-7) Acetylcarbinolethylether, Me.CO.CH2.OEt.-Mise. w. aq.-Re- duces Tollen's AgNO3 reagent-In HC1 sol. gives acetone and ethyl ale. w. Na amalgam. 128-30 0-8342%7.s Allylacetone, Me.CO.(CH2)2.CH: CH2.-Unpleasant odor.-Test 702 oxid. to acetic and oxalic ac. (Tests 311 and 317). 129-5-30c. 0 - 8583% f Mesityl Oxide, Me,.C:CH.CO.Me.-Peppermint odor.-I. aq.; v. s. ale.-Boiled w. v. dil. H2SO4 yields acetone (Test 711). •-Gives no NaHSO3comp.-Shaken w. phenylhydrazine re- acts w. evolution of heat (product oily). Solution opaque and yellow in 5 sec. in cold, in Test VII-2. 130c. 0-9422b% Cyclopentanone, C4HSCO.-Peppermint odor-Dil. HN03 gives glutaric and succinic ac.-Semicarbazon, m. p. 200°-5° d. 132 0-825(21) 3,3-Dimethylpentanone(2), Me.CO.C(Me2)Et.-Test 702 oxid. to dimethylethylacetic ac. 141 142 GENUS VII, DIV. B. (ORDER I, SUBORDER I.) Boiling-point (C.°). Specific Gravity. KETONES.-Colorless and Liquid. 135 0-907(15) Methyl Tetramethylene Ketone, Me.CO.C4H7.-Peppermint odor. -Gives a NaHSO3 comp. 136 O-81517/o Ethyl Isobutyl Ketone, Et.CO. Bu.--Test 702 oxid. to acetic and isovalerianic ac. 135-40 0-815(20) 2, 3-Dimethylpentanone(4), Me.CO.CHMe.CHMe2. 137-5-9 0-817(22) 3-Ethylpentanone(4), Me.CO.CHEt2.-Gives a bisulphite comp. 141-3 0-91420/0 i-Methylcyclopentanone(3), Me.C4H7.CO.-Opt. active [ + ]. 144c. 0-818 (17-2) Methyl Isoamyl Ketone, Me.CO.C5Hn.-Test 702 oxid. to acetic, isovalerianic and isocaproic ac. 144 0-8202%0 Dipropyl Ketone, Pr.CO.Pr.-I. aq.-Test 702 oxid. to pro- pionic and butyric acids.-Gives no NaHSO3 comp. 147d. Acetylcarbinol (Acetol), Me.CO.CH,OH.-Mise, w aq., ale., or eth.-"Faint, sickly odor"!-Reduces Fehling's sol. cold.-Combines w. 2 mols. phenylhydrazine at 100° forming methylglyoxalosazone, m. p. 145°.-Phenyl- hydrazone oily.-' ' Soon acquires acid reaction." Posi- tion in tables in -doubt. 149-50 0-914(0) 2-Hexinone(5), Me.CO.CH2.C • C.Me. 151 0-829(21) 3, 3-Dimethylhexanone(4), Et.CO.C.(Me2)Et. 151-2 0-837(0) Methyl Amyl Ketone, Me.CO.C5Hir-Oxid. by Test 702 to acetic and valerianic acids.-Gives a NaHSO3 comp. 155 0-831(0) Propyl Isobutyl Ketone, Pr.CO.Bu.-Gives no NaHSO3 comp. 155-6 0.900(15) Propionylcyclobutane, Et.CO.C4H7.-Gives a NaHSO3 comp. 155 0-9472% Cyclohexanone, (CH2)5:CO.-Odor like acetone.-E. s. aq.- Dil. HN03 oxid. to adipic ac.-Gives comp. w. NaHSO3. 163-5-4-5 0-931(25) Diacetone Ale., Me.CO.CH2.CMe2.OH.-Mise. w. aq. or ale.- Sol. in cone. H2SO4 gives mesityl oxide. 169 0-909(20) [ + ] i-Methylcyclohexanone(3), Me.C6H9O. 170 0-850(0) Ethyl Amyl Ketone, Et.CO.C5Hn.-Gives no comp. w. NaHSO3. 170-1 0-817(19) 2-Methylheptanone(6), Me.CO.(CH2)3.CHMe2. 172-5 0-8192% Methyl Hexyl Ketone, Me.C0.C(iH13.-Oxid. by HNO3 gives cenanthic and acetic acids.-Gives comp. w. NaHSO3. 173-4 Dipropylacetone, Pr2.CH.CO.Me. 173-4 0-860(20) 2-Methylheptene(2)-one(6), C7H14-CO.-KMnO4 oxid. to ace- tone and laevulinic ac.-Gives purple-red color to pine splinter moistened w. HC1. 174-5 as.-Diallylacetone, C3H5)2.CH.CO.Me. 176-7 1-000(15) Hydracetylacetone, Me.CH(OH).CH,.CO.Me.-S. aq., ale., eth., or CHC13.-Gives phenylhydrazone, m. p. 85°-7°. 179-81C. 0-969(0) Suberone, C0H12:CO.-Peppermint odor.-Adds Br easily. 180 0-827(16) Methylbutyrone, CsH10O.-Cone. HNO3 oxid. to cenanthic ac. 181-2 0-833(20) 2, 6-Dimethylheptanone(4), (Me2.CH.CH2)2.CO.-NaHSO3 gives no comp. 190 0-82520/0 Ethyl Hexyl Ketone, Et.CO.C6H13.-Solid at -8°. 192-3 0-947(19) t [ + ]-Fenchone, C10HlcO (from oil of fennel.)-Odor pleas- ant and camphorous!-M. p. +5°-6°.-Heated w. P2OS gives m-isocymene.-S. without decomposition in cone. H2SO4.-Gives an oxime, m. p. 164°-5° (r. h.). 194 (th. i.) 0-97020'74 j Acetonylacetone, Me.CO.(CH2)2.CO.Me.-E. s. aq., ale., or eth.-Gives pyrrol test (Test 703) w. splinter.-Combines w. x's phenylhydrazine on warming to osazone, cryst. fr dil ale., m. p. 120°. 196-8 4-Methyloctonone(2), C10H20O. 202 (th. i.) 1-032(15) f Acetophenone, Me.CO.Ph.-Alm. i. aq.-M. p. 20.5°.-Gives Test VII-2 readily in the cold.-Identify by Test 712 ! GENUS VII, DIV. B. 143 (ORDER I, SUBORDER I.) Boiling-point (C.°). Specific Gravity. KETONES.-Colorless and Liquid. 200-5 0-939(12) Camphorphoron, Me2C: C5H5O.Me. - Odor spicy. - Tribrom- comp., m. p. 52°. 203 0-913(20) t Thujone (Tanacetone), C10HlflO (fr. tansy-oil, Tanacetum vulgare).-Odor somewhat like tansy.-Opt. active [ + ]. -(NaHSO3 comp. i. eth., forms very slowly.)-Dist. fr. P2O5 gives cymene -Boiling w. FeCl3 gives carvacrol.- a-oxime, m. p. 54-5°.-5 cc. Br+5 grms. thujone and 30 cc. Igr. (cold) gives tribrom-deriv., d. s. ale., m. p. 121°-2°. 204-5 Ditetramethylene Ketone, (C4H7)2.CO.- Peppermint odor.- NaHSO3 comp. e. s.-Combines w. phenylhydrazine. 200-10 0-841(17) Isopropyl Hexyl Ketone, Me2.CH.CO.C6Hl3.-Gives no NaHSO3 comp. 206c. 0-913(0) a-Menthone, C10HlsO.-Faint peppermint odor. Does not give Test 702.-Opt. active [+].-P2OS gives a terpene, b. p. 170°-3° and a diterpene b. p. 320°-5°. 206-7 0-82420<5/0 Propyl Hexyl Ketone, Pr.CO.C6H13.-M. p. -9°.-Gives no NaHSO3 comp. 206-8 0-900(20) [ + ]-Menthone, C,0HlsO.- Similar to [ -]-menthone.- Oxime syrupy. 207 0-896(20) j-[-1-Menthone, C10HlsO.- Odor peppermint-like. - D. s. aq.; misc. ale. or eth.-Oxime by Test VII-1, m. p. 118°-19°. 208-9d 1-016(0) Acetylpropyl Ale., Me.CO.(CH2)2.CH2OH.-Slow dist. gives unstable anhydride, b. p. 72°-5°.-Misc. aq.; e. s. ale. or eth.-NaHSO3 comp. e. s. aq. or ale.-May be oxid. by CrO3 mixture to Levulinic ac. . 211 0-825(20) Methyl Octyl Ketone, Me.CO.C8H17.-M. p. +3-5°.-Odor orange-like.-Gives a NaHSO3 comp. 210-15 0 - 9482% Eucarvol, C,„H. ,0.-Boiled w. cone. sol. of KOH in CH3OH z 1 (J 14 O gives unstable blue color. 215 1-010(3) Methyl Benzyl Ketone, Ph.CH2.CO.Me.-Cf. Div. A, m. p. 27°. 217 Isopropyl Phenyl Ketone, Pr.CO.Ph.-Phenylhydrazone, m. p. 71°.-Oxime, m. p. 58°. 218 1-009(0) Propiophenone, Ph.CO.Et.-M. p. +21°.-Gives no NaHSO3 comp.-Oxime melts at 52°-53°. 220-2 Propyl Phenyl Ketone, Pr.CO.Ph.-No NaHSO3 comp.- Test 702 gives benzoic and propionic acids (Tests 312 and 311). 221-2 0-932(20) f Pulegone, C19HlcO.-Odor of pennyroyal (Mentha pule- gium).--Gives a NaHSO3 comp, (forms very slowly); i. ale. or eth.-Opt. active [ - ].-Adds Br2.-Oxime, m. p. 157°, silky ndl. d. s. ale.! 221-2 0-928(19) Dihydrocarvone, C10H,6O.-Opt. active [+ or - ].-Gives NaHSO3 comp, slowly.-Adds Br2.-Oxime, m. p. 87°-9°. 222 1-013 p-Methyl Tolyl Ketone, Me.CO.C,5H4.Me.-Oxid. by KMnO4 gives terephthalic ac.-Dibrom-derivative, m. p. 100°. 224 0-829(17-5) Methyl Nonyl Ketone, Me.CO.CeH19.-Chief constituent of oil of rue (Ruta graveolens). Freezes at +6°; m. p. + 15°.-Test 702 gives acetic and pelargonic acids. 223-6 0-998(17-5) Ethyl Benzyl Ketone, Et.CO.C7H7.-Gives no NaHSO3 comp.- Test 702 gives benzoic and propionic acids (Tests 312 and 311). 224-5 0-996(19) f 2-Methyl-i, 4-Xylyl Ketone, Me.CO.CfH3.Me2.-(Sol. in Test VII-2, becomes opaque and yellow after heating 1 min.)- No NaHSO3 comp.-E. s. ale. or eth.-Oxime, m. p. 58°. 224-5 0-989(20) m-Methyl Tolyl Ketone, Me.C6H4.CO.Me.-Gives isophthalic ac. on oxid. by alkaline KMnO4. 144 GENUS VII, DIV. B. (ORDER I, SUBORDER I.) Boiling-point (0.°)- Specific Gravity. KETONES.-Colorless and Liquid. 225-6 0-993(17-5) Isobutyl Phenyl Ketone, Bu.CO.Ph.-Test 702 gives benzoic and isobutyric acids,-Gives no NaHSO3 comp.-Oxime, m. p. 74° 226c 0-826(20) t Caprone, (C5Hn)2.CO.-M. p. 14-6°.-Gives no NaHSO3 comp. -Sol becomes opaque and the undissolved drop deep yel- low in Test VI1-2 (This is the highest symmet. fatty ketone in its series known to give Test VII-2.) 226 Diisoamyl Ketone, (C5Hn)2.CO.-Yellow oil. 230-2 Diethylacetophenone, Ph.CO.CHEt2. 232-3 p-Tolylacetone, Me.C6H4.CH2.CO.Me.-Gives no NaHSO3 comp. -Oxime, m. p. 90°-l°. 235 0-989(0) Acetylmesitylene, Me.CO.C6H2.Me3. 235-6 0-98923/17 Benzylacetone, Ph.CH2.CH2.CO.Me.-Test 702 oxid. to benzoic and acetic acids.-Gives NaHSO3 comp., rather d. s. aq. 235-6 Isopropyl Tolyl Ketone, C3H7.CO.C7H7.-Oxime, m. p. 92°. 237-8 Ethyl p-Xylyl Ketone, Et.CO.CGH3.Me2. 237-5-8-5 Butyl Phenyl Ketone, Bu.CO.Ph. 237-9 Ethyl p-Tolyl Ketone, Et.CO.C.()H4.Me.-Nitration w. fuming HNO3 gives comp, having m. p. 50°-l°.-Oxime, m. p. 86-7°. 237-40 Allylacetophenone, Ph.CO.CH2.C3H5.-Adds Br2 easily. 238-9c. a-Methylbenzylacetone, Me.CO.CH(Me)(C7H7). 238-9 Ethyl m-Xylyl Ketone, Et.CO.C6H3.Me2.-Phenylhydrazone, m. p 126°.-Oxime, m. p. 72°. 239-40 2-Isopropyl-1,4-Xylyl Ketone, C3H7.CO.C6H3.Me2.-Odor like mushrooms.-Oxime, m. p. 76°. 240-5-1 Benzoyltrimethylene, Ph.CO.C3Hs.-Br acts only at high temp. -Oxime, 1ft. fr. Igr., m. p. 90°-2°. 241-5-2-5 Isoamyl Phenyl Ketone, CgHjj.CO.Ph. 244-5 4-Isopropyl 1,3-Xylyl Ketone, C3H7.CO.CGH3.Me2.-Oxime, m. p. 97° 245-5-6-5c. /?-Methylhydrindone, C10H10O.-Peppermint odor.-KMnO4oxid. to phthalic ac.-Sol. in cone. H2SO4 fluoresces blue-violet. 246-7 (th. i.) 1-019(0) Methyl o-Xylyl Ketone, Me.CO.CGH3.Me2.-E. s. ale. or eth.- KMnO4 oxid. to p-xylic ac.-Oxime, m. p. 85°. 246-5 Methyl Pseudocumyl Ketone, Me.CO.C0H2.Me3.-M. p. 10°.- E. s. ale. and eth. 249 2-Propyl 1,4-Xylyl Ketone, Pr.CO.C6H3.Me2.-Aromatic oil.- Oxime, m. p. 47°. 251 4-Propyl 1,3-Xylyl Ketone, Pr.CO.C0H3.Me2. - E. s. ale. or eth.-Odor turpentine-like. 251-2 Xylitone, C12H18O.-Geranium odor.-I. aq.-Easily oxid.- KMnO4 gives CO2, acetic, and a-dimethylsuccinic acids.- Resinified by cone, acids. 253-5 Methyl a-Duryl Ketone, Me.CO.C6H.Me4.-E. s. ale. or eth. 254c 0-975(15) p-Acetylcumene, C3H7.CfH4.CO.Me.-Nitrates to comp, having m. p. 49°.-Oxime, m. p. 70°-l°. 255-8 4-Isopropyl 1,2-Xylyl Ketone, Pr.CO.C0H3.Me2. - Turpentine odor.-Oxime, m. p. 68°. 256-60 Methyl o-Cymyl Ketone, Me.CO.C10Ht3.-Aromatic oil. 259 (th. i.) 0-978(15) p-Acetylpropylbenzene, Me.CO.C6H4.Pr.-Oxid. by alkaline KMnO4 gives terephthalic and benzoic acids. (Tests 318-3 and 312.) 259 0-957(19) 2-Isopropyl 1, 4-Isocymyl Ketone, Pr.CO.C10H13.-Oxime is oily. 259 1-052(15) Benzoylcyclobutane, C4H7.CO.Ph.-Oxime, d. s. Igr., m. p. 92°. 259 Methyl v-Duryl Ketone, Me.CO.C6H.Me4.-Phenylhydrazone, m. p. 129°. GENUS VII, DIV. B. 145 (ORDER I, SUBORDER I.) Boiling-point (C.°). Specific Gravity. KETONES.-Colorless and Liquid. 260-5c. Cumylacetone, Pr.CcH4.CH2.CH2.CO.Me.-Oxime, m. p. 56°. 266-9 Ethyl o-Cymyl Ketone, Et.CO.C]0H13.-Aromatic oil. 270-7 Phenyl Hexyl Ketone, Ph.CO.C6H13.-Lft. m. p. 17°.-Gives an oxime, m. p. 55°. 270-72 0-944(19) 2-Isobutyl i, 4-Isocymyl Ketone, Bu.CO.C10H13.-Oxime is oily. 295-6 1•134(0) a-Methyl Naphthyl Ketone, Me.CO.C10H7.-V. s. ale. or eth.- Oxime, m. p. 145°.-Picrate, fr. ale. sol., m. p. 116°.-Br substitutes readily. 300-4 0-826(17) Diheptylacetone, Me.CO.CH.(C7H15)2.-Gives a NaHSO3 comp. 305-7 1-108(0) a-Propanoylnaphthene, Et.CO.C10H7.-~V. s. ale. or eth.- Oxime, m. p. 57°-8°.-Picrate, yellow ndl., m. p. 77°-8°. 308-10 1-076(0) a-Isopropyl Naphthyl Ketone, Pr.CO.C10H7.-Oxime, m. p. 140°. -Picrate, m. p. 66-7°. a. 300 p-Ethylbenzophenone, Ph.CO.C0H4.Et.-Gives isomeric oximes. 312-14 1-062(0) ^-Isopropyl Naphthyl Ketone, Pr.CO.C10H;.-V. s. ale.-Oxime, m. p. 121°-2°. 314-16 1-088(17-5) m-Phenyl Tolyl Ketone, Ph.CO.CcH4.Me.-V. s. ale. or eth.- Oxime, m. p. 100°-l°. 315-16 o-Phenyl Tolyl Ketone, Ph.CO.C0H4.Me.-Gives isomeric oximes. 322 (th. i.) a-Phenyl-m-Xylyl Ketone, Ph.CO.C0H3.Me2.-Gives isomeric oximes. 325-30 Dioctylacetone, Me.CO.CH.(C8H, 7)2. NUMBERED SPECIFIC AND SEMI-SPECIFIC TESTS FOR THE KETONES. [TESTS 701-800.] 7oi. Colorations with Sodium Nitroprusside. Shake five drops of the ketone with 2 cc. of cold water. If the substance does not dissolve completely, filter through a wet filter. Add to the clear solution two drops of a 1% aqueous solution of sodium nitroprusside, and then two drops of sodium-hydroxide solution (1 : 10). Without any unnecessary delay, carefully note the color, and then quickly divide the solution into two equal portions, a and b, in small glass "weighing-tubes." To portion b add three drops of glacial acetic acid, and immediately note the color. Allow both solutions to stand for twenty minutes, and again carefully compare the color of each with the color standard. Many of the aldehydes as well as ketones of Order I give colorations in this test; but its most important practical application is its use as a convenient specific reaction for acetone and acetophenone. It distinguishes these ketones readily from all related ketone species with which either is likely to be confused. In the case of acetone, portion a at first is orange (0), but changes to a clear yellow (Y-YT1) within twenty minutes. Portion b after the acidification with acetic acid is a red (R-RT1) when viewed against a white background, with a very slight tendency to purple, that is most noticeable when the solution is viewed by a strong transmitted light. This hue will be found unchanged at the end of twenty minutes, though its intensity will have fallen about one tint, i.e. to (RT1-RT2). The persistency of this hue in acetic-acid solution is the most characteristic part of the test when used to distinguish acetone from its homologues. In the case of acetophenone, the color of portion a is at first red with a very slight tendency to violet-red, just as in part b of the acetone test after acidification. This changes to yellow before the end of twenty minutes. Portion b upon acidification with acetic acid changes at once to a strong blue (B-VB), whose hue is not materially changed at the end of twenty minutes, although it will have faded nearly one tint to about (BT1-VBT1). The most characteristic part of the acetophenone test is the strong blue coloration of portion b. Homologues of acetophenone, CH3.CO.R, like methyltolyl- and methylxylyl ketone, do indeed give pale violet or bluish colorations, but they are much fainter than T3 of the color standard. Fatty-aromatic ketones, like ethyl-phenyl ketone, which contain no methyl radical in combination with-CO.R, appear not to give any blue coloration at all. [Sodium-nitroprusside solution does not keep well, and should not be more than a few days old when used.] 146 SEMI-SPECIFIC TESTS FOR THE KETONES. 147 702. Oxidations with Chromic Acid. The aliphatic ketones and alcohols may all be easily oxidized by chromic acid to mixtures of fatty acids. These mixtures may then often be resolved into their constituents, and the latter identified by forming their silver salts. The method is not especially difficult if the acids are not too near one another in the homologous series. The oxidation of an unsymmetrical ketone or secondary alcohol may occur in two ways; i.e. the splitting of the molecule may take place on either side of the carbonyl or hydroxyl group, as illustrated in the folio-wing reactions for the oxidation of ethyl-propyl ketone: CH3.CH2.CO.CH2.CH2.CH3 + 3O-2CH3.CH2.CO2H, ch3.ch2.co.ch2.ch2.ch3+30=CH3.CO2H+CH3. (CH2)2.CO2H. or Frequently, however, the tendency for one of the reactions to take place is so much greater than for the other, that only one acid will actually be formed in quantity large enough for isolation. The chromic acid mixture for these oxidations is prepared by dissolving 10 grms. (2 molecules) of crystallized commercial chromic anhydride in a mixture of 60 cc. of water and 8 cc. (3 molecules) of concentrated sulphuric acid. Calculate how much of the mix- ture will be needed for any oxidation, by assuming that each cubic centimeter contains 0.05 grm. of "available oxygen," and that the reaction will take place according to the theoretical equation without secondary oxidations-which is not strictly true, since some of the substance will always remain unattacked. Perform the oxidation in a round-bot- tomed flask having a capacity of at least five times the volume of the solution. The flask should be fitted with a return-flow condenser. It is best to use as much as one or two grams of substance for each experiment. Support the flask on a piece of wire gauze, and boil briskly until the reduction of the chromic acid is complete. This will not require more than an hour if the substance is at all soluble in the mixture. Bumping may be prevented by dropping an ebullator tube (cf. p. 223) into the flask before bringing to a boil. The oxidation being ended, connect the flask with an inclined condenser; add a fresh ebullator tube, and distil rapidly until only a few cubic centimeters of liquid remain in the flask. Add 25 cc. more water, and distil again. If only volatile fatty acids are to be sought, place the combined distillates in a flask • heat nearly to boiling, without attempting to remove any oily or solid matter that may be held in suspension; add an excess of moist silver oxide; and shake persistently to hasten the neutralization of the organic acids. Then dilute with hot water,-from 100 to 1000 cc., according to the solubility of the silver salts that it is expected will be formed,- bring to a boil, and filter hot. Repeat the extraction of the residue on the filter with a second but smaller quantity of boiling water. Filter. Unite this filtrate with the first, and separate the mixed silver salts by fractional crystallization. Since the solubility of the salts diminishes as their molecular weight increases, those of higher molecular weight will separate first, when a saturated solution is cooled or evaporated.* The determination of silver in the salts is made by drying to constant weight at 100° in a porcelain crucible, igniting to destroy organic matter, and then weighing the residue of * In the case of the mixture of silver caproate and acetate, that is formed when 1 grm. of secondary octyl alcohol or methylhexyl ketone is oxidized, a single recrystallization from boiling water of the salt that separates from the original hot saturated solution on cooling, gives a silver caproate that contains the theoretical percentage of silver. The purification of the more soluble silver acetate in the mother liquors requires two or three additional crystalliza- tions, in which the first crystals that separate are each time rejected. The separation of two salts whose acids lie nearer to each other in the homologous series is more difficult. 148 SPECIFIC AND SEMI-SPECIFIC TESTS FOR THE KETONES. metallic silver. The following table gives the percentage of silver, and the approximate solubility of a few of the silver salts of the more important of the fatty volatile acids: Per Cent, Ag. 100 Parts of Water Dissolve Silver Acetate, Ag.C2H3O2 ' ' Propionate, Ag.C3H5O2 .... " Butyrate, Ag.C4H7O2 .... ' ' Isobutyrate, " " Valerianate, Ag.C5H9O2 .. . ' ' Methyl ethylacetate, " ' ' Isovalerianate, " " Caproate, Ag.C6HuO2... . 64.67 59.67 55.38 51.67 ( c 48.43 at 20° 1.04 pts. " 0.84 " " 0.48 " " 0.96 " " 0.30 " " 1.18 " " 0.25 " " 0.11 " at 80° 2.52 pts. " . 2.03 " " 1.14 " " 1.90 " "70°0.64 " "80°2.40 " " 0.49 " " 0.34 " 703. Pyrrol-red Reaction for 7-Diketones. Place one drop of the ketone if a liquid, or about 0.01 grm. if a solid, in a small test- tube, add 1 cc. of glacial acetic acid, three drops of concentrated ammonia, and a freshly cut splinter of soft pine wood, and boil gently for half a minute. Remove the splinter from the tube and moisten it at once with a drop of concentrated hydrochloric acid. If no pro- nounced color is produced in this way, return the splinter to the test-tube, add five drops of concentrated hydrochloric acid, and boil again for about one minute. r-Diketones of Genus VII, as well as certain species like diethyl diacetylsuccinate in other genera whose symbols contain the group-CO.CH2.CH2.CO-undergo condensation with ammonia in this test to pyrrol derivatives, which, in the presence of the mineral acid, produce an intense red stain upon the wood. With the simple r-diketones like acetonyl- acetone the stain appears instantly and with the greatest brilliancy when the wood is moistened with hydrochloric acid in the first part of the test. The subsequent boiling with hydrochloric acid is, however, necessary to develop the color in the case of bodies like diethyl diacetylsuccinate. 711. Acetone. (Properties tabulated on p. 141.) 1. Apply the color reactions with sodium nitroprusside described in Test 701, bear- ing in mind that since nearly all soluble ketones and aldehydes give colorations of some kind when thus treated, the result will be significant only when the colors obtained corre- spond closely to the specified hues of the color standard. This procedure is to be especially recommended for the preliminary examination of aqueous solutions and distillates supposed to contain at least several per cent of acetone. In examining such a solution, simply substitute 2 cc. of it for the same volume of the solu- tion of definite concentration prescribed in the general directions. Very dilute solutions should first be somewhat concentrated by a rectification with the assistance of a small distilling-tower. If a solution contains only 1% of acetone, the color of "portion a" will at first be yellow-orange (YO), instead of orange; while "portion 6," with acetic acid, will give a very pale tint of red, RTS, instead of R-RT1, which, after standing for twenty minutes, will fade to a tone of the same hue, but so pale as to be barely distinguish- able. 2. Place in a dry six-inch test-tube two drops of the ketone and 0.4 cc. of cold water. Add 0.4 cc. of benzaldehyde, 2.0 cc. of strong alcohol, and 0.5 cc. of a ten per cent aqueous sodium-hydroxide solution. Mix by shaking. Boil very gently over a small flame for one minute, counting the time from the moment when the mixture first actually boils. If no precipitate appears, cool and shake vigorously. Filter off the crystals,* and wash * If the precipitate, instead of consisting of crystals, is an oil or pasty mass, the procedure given requires no modification. Such products usually become crystalline, either during the washing with alcohol, or upon the cooling of the solution prepared from the washed oil. SPECIFIC TESTS FOR THE KETONES. 149 with 2 cc. of cold strong alcohol. Recrystallize from 2 cc. of boiling alcohol. Cool, and, if necessary, shake persistently until crystals appear. Filter. Wash with 1 cc. of cold alcohol. Press on filter-paper or porous tile. Then transfer to a watch-glass and dry half an hour or longer at 100°. In taking the melting-point raise the temperature at the rate of about one degree in twenty seconds. The product formed in this test is dibenzylideneacetone (CaH5.CH: CH)2.CO. It crystallizes in pale yellow lustrous plates which melt at 111.0°-112° (uncor.). Observations on the application of Procedure 2 to aqueous solutions of acetone.-If a solution contains less than 75% of acetone, take 1 cc. instead of two drops as above directed, and add no water. The quantities of the other reagents and the method of procedure may be allowed to remain unchanged. The test has been used for solutions containing as little as 2% of acetone. But with solutions between 5% and 2%, cooling and shaking after heating frequently gives only an emulsion. The addition of 1 cc. of strong cold alcohol and shaking will, in such cases, produce a crystalline precipitate, which can then be treated in the usual manner. If the quantity of crystals obtained from an acetone solution after the first filtration is small, wash with 1 cc. of alcohol (instead of 2.0 cc.), and recrystallize from 1 cc. of boil- ing alcohol (instead of 2 cc.). If no crystals then appear on cooling and shaking,add cold water (0.5 cc.-l.O cc. is usually enough) until the solution becomes turbid. Shaking will then produce crystals. Wash these with 0.5 cc. of cold alcohol (instead of 1 cc.). Crystals thus obtained from dilute alcohol will be found to melt at 0.5°-1.5° lower than those from strong alcohol. It is, on the whole, advisable to concentrate very dilute acetone solutions by distillation rather than to test them by this method at very low concentrations. For the detection of traces of acetone by this method, see Vorlander, Hobohm B. 29, 1840. 712. Acetophenone. (Properties tabulated on p. 136.) 1. Apply color reaction 701 with sodium nitroprusside. This is a very satisfactory and simple preliminary test. A single drop of the ketone will be enough for the prepara- tion of the saturated aqueous solution required. If a negative result is not obtained in the experiment, proceed to part (2) of the test, which follows. 2. Place two drops of the ketone and four of phenylhydrazine in a dry test-tube. Heat until the mixture begins to boil. Cool. Add ten drops of glacial acetic acid, then 10 cc. of water, and shake. Collect on a filter and wash thoroughly with water. Dissolve in 12 cc. of boiling 50 per cent alcohol. Allow to cool. Filter off the abundant precipitate of thin flat crystals, and wash with 2 cc. of cold 50 per cent alcohol. Remove the mother- liquor by pressing on a porous tile, and recrystallize from 12 cc. of boiling 50 per cent alcohol.. Allow to cool slowly. Filter. Wash with 3 cc. of 50 per cent alcohol. Remove the mother-liquor on a porous tile, and then dry ten to fifteen minutes at 50°-60° in the dark. Determine the melting-point at once. Acetophenonephenylhydrazone is a rather unstable body, and is liable to undergo slight decomposition in drying. According to Reisenegger and Just, the pure compound melts at 105°. As obtained in this test it is perhaps not perfectly pure, as it shows signs of softening at 100°, and is completely melted at 103°. 713. Benzoin. (Properties tabulated on p. 139.) Place in a dry test-tube 0.05 grm. of the compound and 0.4 cc. of acetyl chloride. Add one drop of concentrated hydrochloric acid. Allow to stand two or three minutes, until the vigorous action that will occur ceases. Then heat very gently over a small flame until everything is dissolved, removing the tube from time to time to prevent overheating. Cool with running water for 5-10 seconds. Add 2.5 cc. of strong alcohol, and then 5 cc. 150 SPECIFIC TESTS FOR THE KETONES. of cold water. Cool well, and shake until the precipitate has separated sufficiently to leave the mother-liquor nearly clear. Filter. Wash with 2 cc. of cold dilute alcohol (1 : 2). Heat to boiling with 9 cc. of dilute alcohol (1 : 2). Boil briskly for 10-15 seconds, and filter hot from any undissolved residue. Cool and shake as before. Filter. Wash with 2 cc. of cold dilute alcohol (1 : 2). Remove mother-liquor by pressing on a piece of porous tile. Dry in the air on a fresh piece of porous tile for 20-30 minutes. The product in this test is acetylbenzoin, crystallizing in small white needles and melting at 79.5-80.5 (uncor.). 714. Benzophenone. (Properties tabulated on p. 137.) Convert 0.05 grm. into benzophenoneoximc, following the regular procedure of Generic Test VII-1, except that the period of heating should be extended to ten minutes. After the precipitation of the oxime with acid, collect in the point of a small filter, and wash thoroughly with 10-15 cc. of cold water applied in small successive portions. Dry for half an hour at 100° on a piece of porous tile, and determine the melting-point. Benzophenoneoxime is obtained in this test as a flocculent white precipitate soluble in acids or caustic alkalies, and melting at 141°-142° (uncor.). 715. Camphor. (Properties tabulated on p. 139.) Convert into camphor oxime by the method of Generic Test VII-1, using twice the specified quantities of substance, hydroxylamine-hydrochloride solution, and caustic-soda solution, and boiling for one hour instead of for five minutes. In all other details follow the general directions literally. After the precipitation of the oxime following the neutralization with acid, collect on a very small filter, and wash with at least 10 cc. of cold water applied in small portions, the filter being allowed to drain after each addition. Transfer the washed precipitate from the point of the filter to a piece of porous tile. Dry at about 50°, and determine the melting-point. Camphor oxime as obtained by the foregoing method is a white, indistinctly crystal- line powder melting at 118°-119° (uncor.). CHAPTER X. GENUS VIII. ALCOHOLS OF SUBORDER I, ORDER I. (Colorless Compounds of Carbon, Hydrogen, and Oxygen.) Genus VIII embraces all species of the suborder that contain the hydroxyl radical and have not been described in the foregoing genera. The few ketones that do not react readily with hydroxylamine or phenylhydrazine, but meet the requirements of Test VIII for alcohols, also receive mention in this section of the tables. GENERIC TEST VIII. IF THE COMPOUND UNDER EXAMINATION IS SOLUBLE IN LESS THAN FIFTY PARTS OF COLD WATER, SEE PROCEDURE 1 BELOW, THE APPLICATION OF PRO- CEDURES 2 AND 3 BEING UNNECESSARY. IF IT DOES NOT DISSOLVE IN FIFTY PARTS OF COLD WATER AND IS A LIQUID AT THE TEMPERATURE OF 75°, APPLY PROCEDURE 2 ONLY. IF IT IS NOT SOLUBLE IN FIFTY PARTS OF COLD WATER AND IS SOLID AT OR BELOW 75°, SEE PROCEDURE 3. (The Test by Solubility.) PROCEDURE 1. If the solubility of the compound in cold water is not already known, deter- mine it approximately by the method given on p. 38. Any compound, either solid or liquid, that has failed to give the earlier generic tests, and which is completely dissolved by fifty parts of water at 20°, can not be a hydrocarbon, and should be looked for among the species of Genus VIII. (The Test with Sodium.) PROCEDURE 2. If the compound is not soluble in fifty parts of cold water and is a liquid at temperatures below 75°, place about five drops in a narrow glass " weighing-tube " (internal diameter 5-6 mm., length 75 mm.) that has been carefully dried out just before use. Support the tube in a vertical position by thrusting it through a perforated cork held in a clamp. Place a piece of clean sodium, from which the crust has been removed, in a small porcelain dish containing a clear dry hydrocarbon oil. Grasping the sodium under the oil with crucible tongs or forceps, cut out a bright bit of the metal, about half as large as a grain of wheat (.01-.02 grm.), by the aid of a penknife. Seize the fragment with the forceps. Touch it quickly to a piece of dry filter-paper to remove most of the adhering oil; and then, without delay, drop it into the liquid in the weighing-tube. Allow to stand at the tempera- ture of the laboratory for two minutes, and observe any disengagement of gas, or change in appearance of the metal. 151 152 ALCOHOLS. At the end of this time, if the sodium has not disappeared, lower the clamp holding thn tube so as to immerse the end of the latter in clear paraffin oil, the sulphuric acid mixture described on page 218, or any other anhydrous non-volatile liquid, previously heated to 75°, and contained in a beaker supported on a lamp- stand.* Continue the heating with the bath at 75° for about five minutes, carefully watching for the disengagement of gas, and for the disappearance of the sodium, or the formation of any incrustation or coloration on its surface. [The test at 75° will be omitted in the case of compounds that boil below this temperature.] If a brisk effervescence, which continues well sustained until the sodium is either dissolved or the contents of the tube are changed to a thick paste, takes place in either part of this test, the compound is an alcohol. If the evolution of gas is rather slow, but is nevertheless well sustained after the first minute-espe- cially if the bubbles approach the size of a small pin-head, or if the sodium shows signs of being more than superficially attacked-the compound is very likely to be found described with the alcohols. If there is no effervescence, and the sodium remains unattacked during both parts of the test, the compound is not an alcohol. The same conclusion is usually to be drawn whenever there is a very scanty gas evolution which diminishes percep- tibly after a minute or two-especially if the bubbles (which may be quite numerous) are nearly all microscopic in size. [For remarks on the interpretation of doubtful cases, read the "observations" on this test on page 154.] PROCEDURE 3. (The Test by Acetylation.) As the test by acetylation is rather long, and is often not indispensable, it is well to precede its application by an examination of the descriptions of species having the proper melting-point both in Genus IX, Div. A, and in Genus VIII, Div. A, Sec. 3. If this does not lead to an identification, the employment of the acetylation test which follows will sometimes become desirable. Weigh out accurately in a dry, thick-walled, six- inch test-tube, standing upright in the metal support usually furnished with analytical balances for such uses, 0.1000 to 0.1100 grm. of the unknown com- pound. A soft, sound, tight-fitting cork stopper * Fig. 4 represents a convenient form of bath for general use in heating small tubes to definite temperatures in Testa V-l, VII-1, and some of the numbered specific tests, as well as in the present procedure. The beaker has a height of 10 cm. and a diameter of 7.5 cm. The cover is best made from brass, or may be constructed from tinned iron or wood. Its three perforations are fitted with cork stoppers to bear the tubes and a thermometer. The diameters of the two larger perforations should be 23 to 25 mm. The cover, be- sides supporting the tubes, protects their upper portions from the radiated heat of the bath-which in some tests is a considerable advantage-and excludes dust when the bath is laid aside between experiments. Fig. 4. ALCOHOLS. 153 should be provided for the tube, and weighed with it. The substance having been weighed, drop in upon it--best from a safety pipette especially reserved for the purpose (cf. page 236)-0.40 cc. .of good acetic anhydride, taking care not to allow the anhydride to wet the upper part of the tube, and ascertain the exact weight of the anhydride by weighing again. Next remove the cork, which must be inserted during the weighings, and hold the lower part of it, which will come within the test-tube, in clean hard paraffin that has been melted and heated to above 100° in a small porcelain evaporating-dish. The immersion in the hot paraffin should be continued for about half a minute, or long enough to bring about the expulsion of all the small air-bubbles that are seen to detach themselves from the cork as the hot paraffin penetrates and fills the minute cavities in its surface. By a quick movement shake off most of the excess of paraffin, and then quickly insert the cork in the test-tube; press it firmly into place; and hold it until the wax hardens. Next thrust the tube through a circular hole cut by a brass cork-borer in a square piece of asbestos-board, and place the latter like a cover on a small beaker, so that the lower end of the test-tube shall be 1 cm. below the surface of the hot liquid bath within. The beaker is filled to within 2 cc. of its lip with paraffin- or cottonseed-oil, glycerine, concentrated sulphuric acid, melted paraffin, or some other stable liquid of high boiling-point, which has previously been brought to a nearly constant tem- perature of between 95° and 105° by heating with a very small flame. Or, if such an apparatus is at hand, heat the tube in the covered bath shown in Fig. 4 on page 152. Continue the heating at this temperature for fifteen minutes. Then remove the tube from the bath; cool; unstopper; and add 10 cc. of normal aqueous sodium- hydroxide solution from an accurately calibrated 10-cc. pipette. Reinsert the stopper firmly, and shake well, cooling with running water from time to time if the mixture tends to become warm. Again remove the stopper and wash it with distilled water, collecting the washings in a 75-cc. beaker. If the undissolved reaction product is solid or pasty, it may enclose unneutralized acetic anhydride. Hence the lumps must now be well crushed and churned up, while still in contact with an excess of alkali, by means of a glass rod with a flattened end. Then, rinse the mixture into the beaker containing the washings from the stopper, and titrate the free alkali with decinormal hydrochloric or sulphuric acid, using phenolphthalein as the indicator. Finally, calculate from the data obtained how many milligrams of the acetic anhydride heated with the substance have combined with it to form a neutral acetate. If the loss of anhydride due to this cause ("acetylation"') exceeds 6 mgrms. when 0.1000 to 0.1100 grm. of substance was weighed out for the experiment, the compozmd is probably an alcohol, and should be sought in Genus VIII. If the loss of anhydride is less than 6 mgrm., it is probably not an alcohol, but may be a species described in Genus IX. The calculation of the weight in milligrams of the anhydride con- sumed in acetylation will be facilitated by substituting the proper quantities in the following formula: Wt. in milligrams of anhydride consumed = a-[51. b(d-e')]. In this formula: a = mgrm. pure anhydride* weighed out (i.e. apparent wt. Xpercentage purity). * A 100-cc. bottle of an anhydride whose percentage purity has been determined by careful titration should be specially reserved for these tests. The reagent will always contain traces 154 ALCOHOLS. b = the exact normality of the approximately decinormal acid. c= " " " " " " normal alkali. d=cc. of above acid equivalent to 10 cc. of above alkali.* e = cc. " " " required to neutralize alkali remaining uncombined (from 10 cc. por- tion) after shaking with products of acetylation experiment. Observations on Generic Test VIII. " The Test by Solubility (1)" requires no special comment. In " The Test with Sodium (2)" the correct interpretation of the phenomena requires good judgment and some experience on the part of the observer. Very few commercial specimens of compounds of Genus IX are so free from traces of moisture as to give off no gas at all. The ability to make the right decision is most quickly gained by examining the behavior of a few representative compounds. Heat is employed in the second part of the test, partly to increase the number of species to which it is applicable, and partly to make the result more decisive when the alcohol is one that is attacked slowly in the cold. The temperature of 75° is one at which it is not known that any species of Genus IX is decomposed by sodium. At a much higher temperature, however, sodium attacks some of the hydrocarbons (e.g. melted anthracene) with considerable violence. Whenever the sodium test proves inconclusive, it may be supplemented by Procedure 3. " The Test by Acetylation (3)," although requiring careful manipulation, will give no trouble if directions are closely followed. But if the cork stopper is not protected by paraffin, or if the test-tube is heated on a rapidly boiling water-bath so that the paraffin softens, or if a rubber stopper is used, the results will be worthless. The average accidental loss of acetic anhydride in a properly conducted experiment is a little less than 1 mgrm. Heating with the anhydride at 100° for fifteen minutes as recommended in the regular procedure is insufficient to com- pletely acetylate many of the solid alcohols; but it appears that most monatomic alcohols whose acetates are insoluble in cold water will be found to combine with very nearly the theoretical quantity of anhydride if the heating is prolonged to thirty minutes. Procedure 3 is not applicable to soluble polyatomic alcohols of Div. A Sec. 1, because they usually give soluble acetates which are rapidly saponified upon shaking with cold normal alkali. No more acetic anhydride is found to dis- appear in an acetylation experiment with ethylene glycol or erythrite, for instance than in a blank test. of acetic acid, but it will be allowable, for the present purpose to base the calculation of the per- centage purity on the assumption that all alkali consumed in the titration is neutralized by anhydride only. On account of its peculiar action on phenolphthalein, in titrating acet'c anhydride, always dissolve it first in an excess of alkali, and then add the indicator and titrate back with acid. c * d= 10 y Calculations will be simplified by recording the numerical value of d on the label of the alkali bottle. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER 1} GENUS VIII, ALCOHOLS. DIVISION A, SECTION 1 - SOLID ALCOHOLS SOLUBLE IN LESS THAN 50 PARTS OF COLD WATER. [Containing all soluble solid species of the suborder not described in the preceding genera.] Melting-point (C.°). SOLID ALCOHOLS.-Colorless and soluble in less than 50 parts of cold water. 35-8 t Pinacone, Me2.C(OH).C(OH).Me2.-B. p. 172°-3°.-Clear cryst. w. faint pecu- liar odor.-S. c. aq.; e. s. h. aq. or c. ale.-Boiled w. dil. H2SO4 gives a very strong peppermint-like odor of pinacoline!-The hot aq. sol. on cooling de- posits a hydrate, m. p. 56°. 46-7 m-Tolylene Ale., C6H4.(CH2.OH)2.-V. s. aq.; s. eth.-Oxidation gives iso- phthalic ac (Tests 905 and 318-2). 49-5 (a)-Dimethylpinacone, Et.C(OH)(Me).C(OH)(Me).Et.-Fairly s. aq.; e. s. ale. or eth. 51-5 Diisopropyl Glycol, Pr.CH(OH).CH(OH)Pr.-B. p. 222°-3°.-E. s. ale., or eth.- Combines w. CaCL. 52-3 tert.-Butylcarbinol, Me3.C.CH2.OH.-B. p. 112°-3°!-Odor camphorous.- "Somewhat" s. aq.-Test 702 gives trimethylacetic ac.-Very volatile. 52-3 Methylphenylethylene Glycol, Me.CH(OH).CH(OH).Ph.-E. s. aq., ale., or eth.- Tends to separate oily fr. solutions. 56 Pinacone Hydrate, C„H14O2.6H2O.-4-sided tbl.-Sbl. at ord. temperature.- Loses aq. over H2SO4, or on dist., giving pinacone.-E. s. h. aq. 64 Phthalic Ale., o-CnH4.(CH2.OH)2.-Tbl. fr. eth.-V. s. aq., ale., or eth.-Cone. H2SO4 resinifi.es.-Test 905 gives phthalic ac. 67-8 Styrolene Ale., Ph.CH(OH).CH2.OH.-B. p. 273° (th. i.).-V. s. aq., ale., or eth. •-Oxid. by Test 702 to benzoic ac. (Test 312).-65% H2SO4 gives hydro- carbon, C1GH12. 87 Isomannide, C(,H]0O4.-B. p. 274° d.-Hygroscopic cryst., v. s. aq ; s. ale.; i. eth.-Warmed w. 2 pt. PC15 gives chloride, m. p. 49°. 102 [-] Arabite, C5H7.(OH)5.-Warty masses, v. s. aq. or h. 90% ale.-Does not reduce Fehling's sol.-Aq. sol. + borax weakly opt. act. [ -]. 112-13 p-Tolylene Ale., CoH4.(CH2.OH)2.-Ndl., v. s. aq., ale., or eth.-Oxid. by Test 702 gives terephthalic ac. (Test 318-3). 121 Rhamnite, Me.(CH.OH)4.CH2.OH.-Triclinic pr. fr. ale.-Opt. active.-V. s. aq. or ale.; alm. i. eth. 126 f Erythrite, C4Hc.(OH)4.-B. p. 330°.-Clear cryst.-Taste sweet.-V. s. aq.; d. s. ale.; i. eth.-Does not reduce Fehling's sol -The aq. sol. dissolves CaO in the cold. The sol. coagulates on boiling.-Schotten-Baumann reaction gives tetrabenzoate, mic. cryst. fr. Ac, m. p. 186-5°-7°. 150 Pinolhydrate, C10H18O2.-B. p. 270°-l°.-S. in 30 pt. aq. at 15°; e. s. ale. or eth.! Br2 dropped into cooled 5% CHC13 sol. gives cryst. dibromide, d. s. CHC13, m. p. 131°-2°.-Warmed w. dil. H2SO4 gives oily pinol, b. p. 183°-4°. 163-4 [-] Mannite, C6HS.(OH)S.-Ndl., v. s. aq.; d. s. absolute ale.-Aq. sol. + borax is strongly [ - ]. 166 t[+]Mannite, CcHs.(0H)c-Taste sweet.-Ndl., s. in 6-4 pt. aq. at 18°; v. d. s. abs. ale.; i. eth.-Aq. sol. + borax is strongly [ + ]; alone is opt. i.-Pre- vents ppt. of Fc2O3 fr. FeCl3 by NaOH.-Oxid. by HNO3 (cf. lest 205) gives no mucic ac. (dif. fr. dulcite).-Sbl. slowly when kept for some time at tem- perature somewhat above m. p.-1.8 pt. mannite dissolved in 3.6 pt. conc' HC1 and shaken with 3.2 pt. benzaldehyde gives cryst. ppt. of mannitetri- benzacetol, m. p. 207°; v. d. s. aq.; s. eth.! 155 156 GENUS VIII, DIV. A, SECT. 1. (ORDER I, SUBORDER I.) Melting-point (C.°). SOLID ALCOHOLS.-Colorless and soluble in less than 50 parts of cold water. 168 i.-Mannite, C6H3.(0H)a.-Plates v. s. h. aq.; v. d. s. abs. ale.-Aq. sol. + borax is optically i. 173 Rhamnohexite, Me.(CH.OH)5.CH2.OH.-Pr., e. s. aq.; s. h. ale.-Opt. act. [ + ]. 184-5 i, 3, 5-Cyclohexantriol (Phloroglucite), C8H8.(OH)3.-Cryst. fr. aq. Faint but pure sweet taste. (Cryst. w. aq. which is easily expelled at 100°.)-E. s. aq. or ale.; i. eth. 188c, [+ or - ] Perseite, C7H16O7.-Ndl., s. 18 pt. aq. at 18°; d. s. c. ale.-Aq. sol. opt. i.-Does not reduce Fehling's solution. 188-5 Dulcite CaHs.(0H)8.-Nearly tasteless.-Cryst. s. in about 25 pt. c. aq.; e. s. h. aq.; alm. i. ale. or eth.-Oxid. by HN03 (cf. Test 205) yields some mucic 'ac.!-Opt. i. even after addition of borax to sol.-Reactions similar to those of mannite. 203c. rac.-Persei'te, C7H9.(OH)7.-Cf. [ + or -] compound, m. p. 188° c. 225c. Inosite, C6H6.(OH)6.-Taste sweet.-Efflorescent cryst. w. 2H2O fr. cold aq.; cryst. fr. aq. above 50° anhydrous.-S. in 5 • 7 pt. aq. at 24°; i. abs. ale. or eth. -Opt. i.-' ' A bit of inosite evaporated to dryness w. a little dil. HN03 on a crucible cover gives a reddish-colored mass when treated w. a little ammonia and CaCl2 and again evaporated." 234 or 225 (?) [ + ] Quercite, CaH7.(OH)5.-Crvst. s. in 8-10 pt. c. aq.; d. s. ale.; i. eth. Boiled w. dil. H,SO4 and MnO2 gives pungent quinone odor.-Oxid. by HNO3 gives oxalic ac., but no mucic ac. (cf. Test 205). 253 Pentaerythrite, C.(CH.,.OH)4.-Tetragonal cryst. s. 18 pt. aq. at 15°.-Opt. i.- Oxid. by dil. HN03 to glycollic and oxalic acids. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I]. GENUS VIII, ALCOFIOLS. DIVISION A, SECTION 2,-SOLID ALCOHOLS NOT SOLUBLE IN 50 PARTS OF COLD WATER. Melting-point (C.°). Boiling-point (C.°). SOLID ALCOHOLS.-Not soluble in 50 parts of cold water. 24 143-5(15 mm.) Dodecyl Ale., C12H25.OH.-Silvery 1ft. fr. dil. ale. 27-8 s-Tetramethylpinacone, Et2.C(OH).C(OH).Et2.- Alm. i. aq.; v. s. ale. or eth. 33 254 f Cinnamyl Ale., Ph.CH: CH.CH,.0H. - Aromatic hyacinth- like odor.-D. s. aq.; v. s. ale or eth. Dropping Br in cold CHC13 solution gives bromide, m. p. 74°; i. aq.; e. s. ale. or eth. 34 223 (th. i.) o-Tolylcarbinol, Me.C6H4.CH2.OH.-S. 100 pt. c. aq.; e. s. ale. or eth. 35 218 Terpineol, ClaH17.OH.-Cf. Div. B, 2, b. p. 218°.-Lilac odor! 38 167(15 mm.) Tetradecyl Ale., C!4H29.OH. 41-2 Dihexylcarbinol, (CAH,3)2.CH.OH.-V. s. CHC13 or bz. 42 210 f [ - ]-Menthol, CI0H19.OH.- Cryst. w. strong peppermint odor!-D. s. aq.; e. s. ale., eth., or cone. HC1.-May be identified by conversion into its benzoate of m. p. 54-5°. (Cf. Beckmann, A, 262, 31.) 42 dist. Phenylbenzylcarbinol, Ph.CH2.CH(OH).Ph.-Boiling w. 20% H2SO4 gives stilbene. 45 258-8 Anisic Ale., p-MeO.CcH4.CH2.OH.-Cone. H2SO4 gives a reddish resin.-Oxid. by dil. HNO3 gives anisic ac. 50 344 f Cetyl Ale., C16H34O.-Cryst. in small 1ft. fr ale.-(When fused gives off H easily in Test VIII-2.) 51 Piperonyl Ale., CH2O2.C6H3.CH2.OH.-Dec. on dist. w. forma- tion of piperonal (heliotrope odor) !-Long cryst. not vol. w. st.-D. s. c. aq.; v. s ale. or eth. 52-3 p-Phenyltolylcarbinol, Me.C6H4.CH(OH).Ph.-Silky ndl. 52-3 tert.-Butylcarbinol.-Cf. Sec. A. ("Somewhat s. aq.") 54-4-5 220d. a-Oxyhydrindene, C9H9.OH.-Naphthalene-like odor. 59 210-5(15 mm.) Octadecyl Ale., C]3H37.OH.-Silvery 1ft. fr. ale. 59 217 p-Tolylcarbinol, Me.C0H4.CH2.OH.-D. s. c. aq.; e. s. ale. or eth. 60 303c. a-Naphthylmethyl Ale., C10H7.CH2.OH.-Ndl., somewhat s. aq.; v. s. ale or eth. 67-5-8 297-8 Benzhydrol, Ph,.CH.OH.-Silky ndl., s. in 2000 pt. c. aq.; v. s. ale or eth.-Easily oxid. in Test 702, giving ben- zophenone (Test 714). 68-9 Carnaubyl Ale., C24H49.OH.-CrO3 gives carnaubic ac.-Fr. dil. ale. cryst w 73-3% aq. 69 Ditolylcarbinol, (C7H7),.CH.OH.-I. aq.; v. s. ale.. 75 220(15 mm.) Cetene Glycol, C16H32.(OH),.-I aq.-Cryst fr h. ale 75-6 Dilauryl Ale., (C.jH^j.CH.OH.-Tbl. fr. eth. 79 Ceryl Ale., C27H55.OH.-S. ale-Heated w. soda-lime gives cerotic ac 157 158 GENUS VIII, DIV. A, SECT. 2. (order I, SUBORDER I.) Melting-point (C.°). B oiling-point (C.°). SOLID ALCOHOLS.-Not soluble in 50 parts of cold water. 80-0-5 /?-Naphthylmethyl Ale., C10H7.CH2.OH.-Lft. e. vol. w. st.- V. d. s. c. aq; e. s. ale. or eth. 82 Cerosine, C24H4SO.-Lft. i. c. ale.; d. s. h. eth.; alm. i. c. eth. 84-5 Dipalmitylcarbinol, (C1SH31)2.CH.OH.-Silky cryst. fr. ale. 85 Myricyl Ale., C3oH(il.OH (fr. carnauba wax).-Small ndl- fr. eth.-W. soda-lime at 200° gives melissic ac. 90 Methyl-p-tolylpinacone, ClsH2o.(OH)2.-Sbl.-Hexagonal tbl. fr. ale.; i. aq., v. s. ale. or eth. 101-4 Coccerylic Ale., C3oH,;202.-Cryst. powder fr. ale.-Oxid. by CrO3 in Ac sol. gives pentadecylic ac.-(Fr. cochineal.) 119-5 Isohydrobenzoin, C14HI2.(OH)2.-Cryst. fr. aq.; efflorescent.- S. in 526 pt. aq. at 15°, or 820 pt. at 100°; e. s. ale. or eth.-Oxid. by Test 702 gives benzoic ac.-Diacetate (fr. acetyl chloride), lft. fr. h. ale.; m. p. 117°-18°. 120 Acetophenonepinacone, (Ph.C(OH).Me)2.-Ndl., i. aq.; e. s. ale. or eth.-In tube at 280° gives acetophenone and methylphenylcarbinol.-Acetic anhyd. gives a hydro- carbon, C10H14. 125 Quebrachol, C2oH33.OH. - Lft. fr. ale.-Cryst. also w. x H2O (easily lost).-I. c. aq. or alkalies; v. s. eth., bz., or ace- tone.-A sol. in CHC13 shaken w. equal vol. of H2SO4 (sp. gr. 1-76) becomes purple-red after 5 minutes. 132-3 Phytosterine, C2^H43.OH. - (In peas, beans, etc.) - From CHC13 or eth. in ndl.; cryst. fr. dil. ale. w. 1H2O.-S. in 6-65 pt. eth. at 20°.-Color reactions w. H2SO4 same as for cholesterine. (Cf. m. p. 148-5°.)-Acetate, lft. fr. ale., m. p. 120°. 133-4 Retenefluorene Ale., C17H]7.OH.- Silky ndl., fr. ale. - Alm. i. aq.; e. s. ale.-Oxid. gives retene ketone.-Acetate, m. p. 70°-l. 134-4-5 Paracholesterine, C26M43.OH.-(In Aethalium septicum.)-■ Cryst. w. aq. fr. dil. ale.; silky ndl. fr. eth. or CHC13; i. aq. -Gives same color reactions as cholesterine w. H2SO4 in CHC13 sol. 137-8 Isocholesterine, C20H43.OH.-(In suint.)-Gelatinous flocks fr. ale., d. s. c. ale.; e. s. h. ale. or eth.-Does not give the cholesterine reaction w. H2SO4 and CHC13, but gives a brown color.-When evaporated w. a few drops of cone. HN03 leaves yellow spot which becomes yellow-red w. ammonia. 138 Hydrobenzoin, Ph.CH(OH).CH(OH)Ph.-B. p. a. 300°.-Ad- amantine lft. fr. dil. ale.; s. in 400 pt. c., or 80 pt. h. aq.; e. s. h. ale.-Oxid. by CrO3 gives benzaldehyde.-E. acted upon by PC15 in cold.-Heated w. acetyl chloride or anhydride gives diacetate, pr. fr. eth., d. s. c. ale., m. p. 134°. 139 Cholestol, C22H38O. - Ndl. - Dist. - With CHC13 or acetic anhyd. and H2SO4 gives the same colors as cholesterine. 140 Cupreol, C2oH33.OH.-(In cinchona barks.)-Cryst. w. aq. which is lost in desiccator.-I. aq.; e. s. eth.-CHC13 sol. shaken w. H,SO4 (sp. gr. 1-76) gives blood-red color.- Opt. active [-]. 148-5c. f Cholesterine, C26H43.OH.[ + H,O, lost over H2SOJ.-Dist. in vacuo above 360°-S. in 5 pt. h. ale.; c s. eth. or CS2.- Dissolve a few cgrms. in 2 cc. chloroform and shake w. 2 cc. H2SO4 (sp. gr. 1 • 76). The CHC13 becomes blood-red, cherry- red, and finally a beautiful purple color w. strong green fluo- rescence in the acid layer. The CHC13 poured into a dish soon changes through blue and green to a dirty yellow!-This color reaction is also given by several other alcohols stand- ing near cholesterine in this section.-Identify by Test 821! GENUS VIII, DIV. A, SECT. 2. 159 (ORDER I, SUBORDER I.) Melting-point (0.°)- Boiling-point (C.°). SOLID ALCOHOLS.-Not soluble in 50 parts of cold water. 149-50 Paraphytosterine, C24H39.OH.-D. s. c. ale.; e. s. eth. or CHC1S. 150 Diphenyltolylcarbinol, Me.C0H4.C(OH).Ph2.-Hexagonal tbl. fr. Igr.-E. s. ale. or eth.; less s. Igr.-Dist. undec. 153 Fluorene Ale., C13H9.OH.-S. ale., eth., orbz.-W. cone. H2SO< turns blue !-Oxid. by Test 702 gives diphenylene ketone. 154 Ergosterine, C2(iH39.OH. + H,0 (from Ergot).-B. p. 185° (20 mm.).-Pearly 1ft. fr. ale.-S. in 500 pt. c. or 32 pt. h. 94% ale.; s. h. eth. or c. CHC13.-Sol. in cone. H2SO4 is orange- red, becoming red and then violet on addition of aq. The orange sol. when shaken w. CHC13 does not color the latter. (Dif. fr. cholesterine.) 162 t Triphenylcarbinol, Ph3.C.OH.-B. p. a. 360° undec.-E. s. ale., eth., or bz.-Stable. 164-5 Phenyltolylpinacone, C2SH24.(OH)2.-E. s. bz.; d. s. ale.; s. eth. -E. oxid. by CrO3 giving phenyltolyl ketone.-Decomposed by heating with acids. 166-7 Chrysofluorene Ale., CirHln.CH.OH.-E. s. ale. or eth.-S. cone. H2SO4 w. red-violet color.-Ale. sol. on addition of cone. H2SO4 becomes blue. 168d. Benzopinacone, Ph,.C(OH).C(OH)Ph2.-S. in 39 pt. h. ale.-In melting splits into benzophenone (Test 714) and diphenyl- carbinol. 170 Hydranisoin, ClfiHloO2.(OH)2.-V. d. s. c. aq., c. ale., or eth.; e. s. h. ale.-Oxid. by CrO3 mixture to anisic aid. and anisic ac. 175 Illicyl Ale., C22H37OH. (fr. bird lime).-B. p. a. 350°.-I. aq.; d. s. c. ale. or eth.-M. p. acetate 204°-6°. 182d. Anthrapinacone, C2sH2o.(OH)2.-Ndl. fr. bz. 183 Homocholesterine, C28H48O. (fr. Dalmatian insect powder).- V. s. eth. or CHC13; d. s. ale.-Gives the cholesterine color reactions. 192 si. d. Camphene Glycol, C10H16.(OH)2.-Sbl. above 100°.-D. s. h. aq.; v. s. ale. or eth.; d. s. Igr. 203-4 t [ + ]-Borneol( Borneo Camphor), C10H17.OH.-B. p. 211°-12°.- Sbl. in 1ft.-Odor scarcely distinguishable fr. that of com- mon camphor!-E. s. Igr.; v. d. s. aq.; e. s. ale. or eth.- Does not give an oxime. (Dif. fr. ordinary camphor.) 208-8 [ -]-Borneol, C10H17.OH.-Closely resembles the [ + ] comp.-• (Occurs in several natural oils.) 210-5 i-Borneol, C]0Hi7.OH.-Closely resembles the [ + ] comp. 216 Isoborneol, CI(IH17.OH.-Closely resembles the [ + ] comp.-Opt. active [ + ]. 258c. Betulin, C0HGO3 (fr. birch bark).-Ndl. fr. ale.-Sbl. w. dec. -S. in 148 pt. cold, or 23 pt. h. ale.; s. h. eth.; d. s. c. eth.- Heated w. acetic anhyd. gives diacetate, pr. s. eth., m. p. 217°.-Emits odor like morocco leather when strongly heated. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER 1 OF ORDER I]. GENUS VIII, ALCOHOLS. DIVISION B, SECTION 1-LIQUID ALCOHOLS (AND SOLUBLE ETHERS) WITH SPECIFIC GRAVITY LESS THAN 0 -90 AT 20°/4°. Boiling-point (C.°). Specific Gravity. ALCOHOLS.-Colorless and liquid, with Specific Gravity less than 0-90 at 20°/4°. - 24 Methyl Eth., Me2.O.-Is absorbed in large quantity by c. cone. H2SO4; the sol. on dil. w. aq. evolves the gaseous ether un- changed. + 10-8 0-725(0) Methyl Ethyl Eth., Me.O.Et.-Odor ethereal. 14 0-897(0) Ethylene Oxide, C2H4O.-Mise. w. aq.-Aq. sol. reduces Tollen's reagent.-f Gives ppt. of MgO after long standing w. cone. MgCl2 sol.-W. HC1 gives chlorhydrine.-W. aq. and Na amalgam gives C2H6.OH. 35 0-71915/, f Ethyl Eth., Et,.O.-Mobile liq. of ethereal odor; s. in 12 pt. aq. at 17-5°. 35 0-859(0) Propylene Oxide, Me.(CH.CH2).O.-S. in 3 vol. aq.; misc. w. ale. or eth.-Heated w. aq. gives propylene glycol.-Heated w. cone. MgCl2 sol. ppts. MgO.-Reduced by aq. and Na amalgam to isopropyl ale. 35-5 0-763u'8/17.6 Vinyl Ethyl Eth., C2H3O.Et.-Gives Test 901.-Distil w. dil. H2SO4. The distillate gives reactions for acetaldehyde and ethyl ale. (Cf. Tests ill and 814.) 38-9 0-747(0) Methyl Propyl Eth., Me.O.Pr. 39 Vinyl Eth., (CH2:CH)2.O.-Gives Test 901.-Probably gives some acetaldehyde when dist. w. dil. H2SO4. 45-5 0-87216/4 t Methylal, CH2.(OMe)2.-Described in Genus I. 46 0-77(11) Methyl Allyl Eth., Me.O.C3H5.-Gives Test 901.-B. p. dibro- mide, 185°. 50 1,3-Propylene Oxide, (CH2.CH2.CH,).O.-B. p. a. 320°.-Misc. w. aq.-Boiled w. cone. aq. KOH gives polymeric oxides. 51-2 0-831(0) Isobutylene Oxide, Me2.(C.CH2).O.-Combines w. aq. w. evol. of heat, giving isobutylene glycol. 54 0-745(0) Ethyl Isopropyl Eth., Et.O.C,H7.-Dec. by 1% H2SO4 at 150° into its constituent alcohols. 56-7 0-834(0) s-Dimethylethylene Oxide, (Me.CH.CHMe): O.-Unites quickly w. h. aq. to form corresponding glycol. 61-2 0-83(12) Methyl Propargyl Eth., Me.O.C3H3.-Gives lemon-yellow gelati- nous ppt. w. ammon. AgNO3! 62-3 0-769(20) Ethyl Isopropenyl Eth., Et.O.CMe: CH2.-Dec. by 1% H2SO4 quickly and completely in the cold into acetone and ethyl ale. (Cf. Test 711-1.) 62-3 Allylene Oxide, Me.(C:CH).O.-S. aq. but separated fr. sol. by K2CO3.-Very stable. 63-6 0-755(0) Ethyl Propyl Eth., Et.O.Pr. 66 Ethyl Allyl Eth., Et.O.C3H5.-Gives Test 901.-Dec. by heating w. 2% H2SO4 to ethyl and allyl alcohols (cf. Tests 814 and 811). 66 0-79815/15 t Methyl Ale., Me.OH. - Misc. w. aq. - Odor alcoholic.- Identify by Test 819 ! 69c. 0-725(21) Isopropyl Eth., (C3H7)2O. 160 GENUS VIII, DIV. B, SECT. 1. 161 Boiling-point (C.°). Specific Gravity. ALCOHOLS.-Colorless and liquid, with Specific Gravity less than 0-90 at 20°/4°. 78 0-875(0) i, 4-Oxypentane, Me.(CH.(CH2)3): O.-S. in 10 pt. c. aq.; more s. c. than h.; v. s. ale. or etlm-Not attacked by aq. at 200°.-When heated w. a 60% HBr sol. gives C5H10Br2. 78-4 0.794>5-715.5 f Ethyl Ale., Et.OH.-Odor alcoholic.-Mise. w. aq.-Identify by Test 814! 80 0-8332% Ethyl Propargyl Eth., Et.O.C3H3.-Penetrating odor.-D. s. aq.; misc. ale.-Unsat.-Gives yellow ppt. w. ammon. CuCl.-Heated w. 1% H2SO4 gives propargyl and ethyl alcohols. 81-2 0-880(0) Pentamethylene Oxide, (CH2)5.O.-Less s. in h. than c. aq.; misc. ale. or eth.-Does not unite w. aq. at 200°. 82-8c. 0-7892% f Isopropyl Ale., Me.CH(0H).Me.-Misc. w. aq.-Test 819-1 gives amber ring.-Test 801 applied in the cold to a 1% aq. sol. gives an immediate ppt. of iodoform.-Identify by Test 818! 82-9c. 0-780264 f Trimethylcarbinol, Me3.C.0H. - M. p. 25°. - V. s. aq. - Deliq. - Odor mild alcoholic. - The color produced in Test 819 resembles that given by methyl ale.!-Does not give iodoform in Test 801. 83-4 0-891(0) Glycol Dimethyl Eth., C2H4.(OMe)2.-HI gas gives glycol and methyl iodide. 90-7 (th. i.) 0-744(21) f Propyl Eth., Pr2O.-Gives Test 907. 94-3 0-805(18) Allyl Eth., (C3H5)2.O.-Gives Test 901. 96-6c. 0-871(0) t Allyl Ale., CH2: CH.CH20H.-Odor very penetrating and mustard-like !-Misc. aq.-Gives Test 901.-Test 819-1 gives a brown ring.-Identify by Test 8111 97-4c. 0-80420/, f Propyl Ale., Pr.OH.-Odor mild alcoholic.-Misc. aq.- Test 819-1 gives amber-colored ring.-Identify by Test 820! 99-8 0-827(0) f sec.-Butyl Ale., Me.CH(OH).CH2.Me.-Odor mild alcoholic. -E. s. aq.-1% aq. sol. gives some iodoform in the cold after a few seconds by Test 801.-Test 819-1 gives a pale lemon-yellow ring below a pale rose-red ring. 101-8 0-814(15) f Dimethylethylcarbinol, Me2.C(OH).Et.-Odor mild alcoholic. -Not v. s. aq.-Color given in Test 819-1 is similar to that from methyl ale.-Does not give iodoform in Test 801. 104-5-6 0-874(0) i, 5-Oxyhexane, Me.(CH.(CH2)4): O.-Odor ethereal.-Rather d. s. aq.-Does not unite w. aq. at 230°.-Combines w. HC1 to form its chlorhydrine. 106-5 0-817(0) f Isobutyl Ale., Me,.CH.CH,.0H.-Odor alcoholic.-S. in 10-5 pt. aq.-Test 819-1 gives amber-colored ring.-Identify by Test 817! 112-5 0-833(0) Methylisopropylcarbinol, Me,.CH.CH.(OH)Me.-Oxid. by Test 702 w. cold, very dil. CrO3 gives acetone, methylisopropyl ketone, and acetic acid. 114 0-84020/0 Vinylethylcarbinol, CH2: CH.CH(OH) .Et. - Unsat. (Cf. Test 901.) 115-16 0-83420/0 Methylallylcarbinol, CH2:CH.CH2.CH(OH).Me.-S. in 8 pt. aq. -Oxid. by KMnO4 gives /--pentenylglycerine. 116-5 0-832(0) Diethylcarbinol, Et2.CH.OH. 117 0-873(0) Crotyl Ale., Me.CH: CH.CH2.0H.-See Test 901. 117c. o-sio20/. f Butyl Ale., C4H9.OH.-Odor alcoholic.-S. in 12 pt. aq.-■ Identify by Test 813 ! 117-6 0-839(0) Dimethylisopropylcarbinol, Me2.(C3H7)C.OH. - Camphorous odor. 118-5 0-824(0) Methylpropylcarbinol, Me.CH(OH).Pr.-S. in 6 vol. aq.-Is said to give iodoform in Test 801. (ORDER I, SUBORDER I.) 162 GENUS VIII, DIV. B, SECT. 1. (ORDER I, SUBORDER I.) Boiling-point (C.°). Specific Gravity. ALCOHOLS.-Colorless and liquid, with Specific Gravity less than 0 • 90 at 20°/4°. 119-5 0-844(0) Dimethylallylcarbinol, Me2.C(OH).C3H5.--Oxid. by Test 702 gives acetone (Test 711), formic ac., etc. 120-1 0-835(0) Pinacoline Ale., Me3.C.CH(OH).Me.-M. p. 4°.-Silky ndl. w. camphorous odor. 123c. • 0-824(20) Methyldiethylcarbinol, Me.C(OH).Et,.-Test 702 gives acetic ac. (Test 311). 123 Dimethylpropylcarbinol, Me2.(Pr).C.OH.-Test 702 gives acetic and propionic acids. 123-5 0-863(0) Glycol Diethyl Eth., C2H4.(OEt)2. 128 0-838(0) Ethylisopropylcarbinol, Et.CH(OH) .Pr. 128-7 0-833% act. Amyl Ale., Me(Et)CH.CH2.OH.-Test 702 gives valerianic and acetic acids. 130 Dimethylisobutylcarbinol, Me2.C(OH).C4H8. - V. d. s. aq. - Test 702 gives acetic and isobutyric acids (Test 311). 130 0-8102% t Isoamyl Ale., Me2.CH.(CH2),.OH.-Odor disagreeable, pro- voking coughing.-S. in 30-4 pt. aq. at 22°.-Burns w. smoky flame.-A few drops warmed w. x's of CrO3 mix- ture gives at first the sweetish and fruity odor of valerianic aldehyde, soon followed by the unpleasant odor of iso- valerianic ac.!-Warmed w. 1J pt. cone. H2SO4 gives a red sol. 130-1 0-827(0) Methylisobutylcarbinol, Me.CH(OH).Bu. 131 2, 3, 3-Trimethylbutanol(2), Me3.C.CMe2.OH.-Odor camphor- ous.-M. p. 17°.-Hygroscopic, giving a hydrate, m. p. 83°. 134 0-868(18) «-Ethylallyl Ale., Et.C3H4.OH.-Unsat. (Cf. Test 901.) 135c. 0-834(0) Ethylpropylcarbinol, Et.CH(OH) .Pr. 136 0-833(0) Methylbutylcarbinol, Me.CH(OH). Bu.-Oxid. by Test 702 gives acetic and butyric ac. 137 Hexenyl Ale., C0H12O.-Odor pungent and peppermint-like. --E. s. c. aq. 137-8 (th. i.) 0-828(0) Amyl Ale., CSHU.OH.-I. aq.-Test 702 gives valerianic ac. (very unpleasant odor). 138-9 0-8421%7 Methylcrotylcarbinol, Me.CH(OH).C4H7.-D. s. aq.-Unsat. (Cf. Test 901 ) 140 0-8292% Diisopropylcarbinol, (C3H7)2.CH.OH.-Oxid. by Test 702 gives diisopropylketone, isobutyric ac., and acetone. 140-3c. 0-8232% Methylethylpropylcarbinol, (Me)(Et)(Pr).C.OH.-Test 702 gives acetic and propionic acids. 140-2 0-840(20) Triethylcarbinol, Et;.C.OH.-Test 702 gives acetic and pro- pionic acids and diethyl ketone. 147 0-838(0) Methylpropylcarbincarbinol, (Me)(Pr).CH.CH2.OH.-Test 702 gives methylpropylacetic ac. and methyl propyl ketone. 147-8 Ethylisobutylcarbinol Et (Bu).CH.OH.-Test 702 gives acetic and isovalerianic acids, etc. 148-50 0-819(17-5) Methylisoamylcarbinol, (Me)(C5H11).CH.OH.-Odor like fusel oil.-Oxid. by Test 702 gives methyl isoamyl ketone, iso- valerianic ac., etc. 150 Isohexyl Ale., Me2.CH.(CH2)3.OH. 151c. 0-876(0) Diallylcarbinol, (C3HS)2.CH.OH.-Alm. i. aq.-Test 702 gives CO2 and some formic ac. 154 (th. i.) 0-830(15) act. Hexyl Ale., Me.CH(Et)2.(CH2)2.OH (?).-Test 702 gives act. caproic ac. 154 0-820(20) Dipropylcarbinol, Pr2.CH.GH.-Test 702 gives propionic and butyric acids. GENUS VIII, DIV. B, SECT. 1. 163 (ORDER I, SUBORDER I.) Boiling-point (C.°). Specific Gravity. ALCOHOLS.-Colorless and liquid, with Specific Gravity less than 0-90 at 20°/4°. 157c. 0-833(0) Hexyl Ale., C6H*13.OH. 157 O-87127o Diethylallylcarbinol, Et2(C3H6).C.OH.-Odor like camphor.- Test 702 gives diethyl ketone, etc. 158-4c. 0-864(0) Methyldiallylcarbinol, Me(C3H5)2.C.OH.-Test 702 gives acetic ac. (Test 311) and CO2. 160 0-830(20) Diethylisopropylcarbinol, Et2(C3H 7). C. OH. 160-lc. Cyclohexanol, (CH3)5: CH.OH.-M. p. 16°-17°.-Odor like cap- ryl ale.-S. in 28 vol. aq.-HNO3 oxid. to adipic ac.-CrO3 oxid. to cyclohexanone. 160-5c. 0-83820/0 Diethylpropylcarbinol, Et2(Pr).C.OH.-Test 702 gives propionic and butyric acids. 161-5c. 0-825(20) Methyldipropylcarbinol, Me(Pr2).C.OH.-Test 702 gives pro- pionic and butyric acids. 164-5 Methylamylcarbinol, (Me) (CsHn).CH.OH.-Test 702 gives acetic and valerianic acids. 175 0-855(20) 2-Methylheptene(2)-ol(6), CSH15.OH.-Adds Br directly.-Heat several hours w. dil. H2SO4 to form the oxide, b. p. 127°-9°. 175-6 0-878(0) Ethyldiallylcarbinol, (Et)(C3Hs)2.C.OH.-Oxid. by CrO3 gives oxalic ac. 175-8 (th. i.) 0-834(0) t Heptyl Ale., C7H15.OH. 179 0-8192% f Methylhexylcarbinol, (Me)(C,H13).CH.OH.-Test 702 gives acetic and caproic acids. (Cf. foot-note on p. 147.) ! 179-5 0-835(20) Ethyldipropylcarbinol, (Et)(Pr,).C.OH.-Test 702 gives acetic, propionic, and butyric acids. 190-5 0-870(20) [ -] Linalol, C10HlsO.-(In origanum and other essential oils.)- Agreeable perfume odor!-Adds Br4.-KMnO4 oxid. to citral, Isevulinic ac., and acetone. 195-5 (th. i.) 0-838(0) Octyl Ale., CsH17.0H. 194-8 si. d. 0-868(20) Coriandrol, C10H17.0H.-Fragrant odor!-Shaking w. 5% H2SO4 gives terpine hydrate.-E. oxid. by KMnO4 210-11 0-839(0) Propylhexylcarbinol, (Pr) (C6H13).CH.OH. 211c. 0-849(0) Diamyl Ale., C10H21.OH.-Odor faint. 213-5 (th. i.) 0-842% Nonyl Ale., C9H19.OH. 214 si. d. Anthemol, C10H10O.-(Occurs in Roman camomile oil.)-Thick liq. w. camphorous odor.-Oxid. by CrO3 gives CO2 and aq.; by dil. HNO3 p-toluic and terebhthalic acids. (Cf. Tests 905-3 and 318-3.) 215 (th. i.) Methylbenzylcarbinol, (Me)(C7H7).CH.OH. 229-30 0'880(15) Geraniol, Me2.C: CH. (CH,),.C(Me): CH.CH2.OH.-B p. (15 mm.) 118-20°; still liq. at -15°.-Odor like the geranium and rose.-I. aq.; misc. ale. or eth.-Opt. inactive.-Oxid by KMnO4 gives acetone and laevulinic ac.; by CrO3 mixture, citral.-For identification as its diphenylurethane, cf. Journ. f. prakt. Chern. II, 56, 28. 231c. 0-830(20) Decyl Ale., C10H2l.0H.-Viscous, highly refractive oil-M p. + 7°. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I] GENUS VIII, ALCOHOLS. DIVISION B, SECTION 2,-LIQUID ALCOHOLS WITH SPECIFIC GRAVITY GREATER THAN 0-90 AT 20°/4°. Boiling-point (C.°). Specific Gravity. ALCOHOLS.-Colorless and liquid, with Specific Gravity greater than 0-90 at 20°/4°. 67 102 114-5 135 138 160-1 161-2d. 168-70 171-2 176-8 183-4 184-5c. 187-5 188-9 191 192 197-7-5c. 202-4 203-5 0-950(15) 1-048(0) 0-972?0/4 0-926(13) 1-113(18) 0-91525/25 1-165(0) 1-136(20) 1-145(0) 1-003(20) 0-960(15) 0 995(0) 1-040(19 4) 0-920(21) 1-019(0) 1-125(0) 1-013 1-011 Hydrofurane (cf. Genus IX, B, 3). Dioxyethylene, C4H8O2.-M. p. +9°. Propargyl Ale., CH • C.CH2.OH.-Odor agreeable.-S. aq.-Un- sat. (cf. Test 901), and gives an explosive greenish-yellow ppt w. ammon. CuCl in Test 906.-Heated w. solid KOH gives acetylene, CO2, and H. Ethyleneglycol Monoethyl Eth., HO.CH2.CH2.OEt. Erythrite Anhyd., C4H6O2.-Mise. w. aq.-Reduces h. ammon. AgNO3 sol.-Ppt's MgO fr. MgCL, sol. Trimethyleneglycol Ethyl Eth., Et.O.(CH2)3.OH.-Odor pleasant. -V. s. aq. Glycid, C2H3O.CH2.OH.-B. p. (15 mm.) 74°-5°.-Mise. w. aq., ale., or eth.-Dist. under ordinary pressure gives acrolein (Test 112).-Reduces Tollen's reagent in the cold (Test 101)! -Unites quickly w. aq., forming glycerine (Test 816). Furfuralcohol, C4H3O.CH2.OH.-D. s. aq.!; e. s. ale. or eth.- Very unstable towards mineral acids; becomes green when treated w. cone. HC1!-Heated w. solid KOH gives succinic ac. (Test 320), CO2, etc. Gly^§nneEfej|Jir(C3H5)2.O3.-Mise. w. aq., ale., or eth.!-At 100° ";SWumtes^waq. to form glycerine (Test 816)!-After being warmed w. dil. HC1 gives " iodoform reaction " and reduces Fehling's sol.-Br acts violently, giving dibromhydrine. I, 2-Dihydroxy-2-methylpropane, C4H10O2.-Heated w. aq. at 180°-200° gives isobutyric aid. 2, 3-Dihydroxybutane, C4H8.(OH)2. Suberyl Ale., (CH2)6: CH.OH.-Taste, burning, bitteri-PC15 gives suberyl chloride. 2, 3-Dihydroxypentane, C5H12O2.-Oxid. by Br aq. gives acetyl- propionyl. Propylene Glycol, MeCH(OH).CH2,OH. - Taste sweetish.- Mise. w. aq.; s. in 12-13 pt. eth.-Test 702 gives acetic ac. only.-Made into a paste w. ZnCl2 and ignited as in Test 816 for glycerine gives propionic aid. s-Diethylglycerine Eth., C7HieO3. I, 2-Dihydroxybutane, C4HS.(OH)2.-E. s. aq. f Ethylene Glycol, CH2(OH).CH,(OH).-Somewhat viscous liq. -Mise. w. aq.; v. s. ale.; d. s. eth.-Solidifies abt. -20° and then melts at -17.4°.-Ignited w. KHSO4 as in acrolein test for glycerine gives acetaldehyde. (Cf. Tests 816, 112, and 111.) Methylphenylcarbinol, (Me) (Ph).CH.OH. Butanediol (i, 4), C4H8.(OH)2.-Viscous. 164 GENUS VIII, DIV. B, SECT. 2. 165 (ORDER I, SUBORDER I.) Boiling-point (C.°). Specific Gravity. ALCOHOLS.-Colorless and liquid, with Specific Gravity greater than 0-90 at 20°/4°. 204 1-126 Butanediol(i, 3), C4H8.(OH)2.-V. s. aq.; i. eth.-Oxid. gives oxalic and acetic acids and crotonic aid. 204-7c. l-0432% f Benzyl Ale., Ph.CH2.OH.-Odor faintly aromatic.-S. in 25 pt. aq. at 17°.-Oxid. by Test 702 gives benzoic ac. (Test 312).-(Unless freshly prepared is likely to contain traces of benzaldehyde.)-Identify by Test 812! 206-7 2,3-Dihydroxyhexane, C0H12.(OH)2. 212 1-034(21) Benzylcarbinol, C7H7.CH2.OH. 214 (th. i.) 1-053(18) t Trimethylene Glycol, CH2(OH).CH2.CH2(OH).-Viscous; misc. w. aq.-f Distilled w. KHSO4 as in acrolein test for glycer- ine (Tests 816 and 112) gives no color w. the fuchsine- aldehyde reagent. (Dif. fr. glycol and glycerine.) 217 1-036(0) m-Tolylcarbinol, Me.C0H4.CH2.OH.-Remains liq. at -20°.- S. in 20 pt. c. aq. 218 0-936(20) f Terpineol, C10HlsO.-Separates fr. eth. sol. in transparent cryst. w. m. p. 35°. (The commercial product is always liq.)-I. aq.; v. s. ale. or eth.-Adds Br2, giving oily bromide. Gives a dihydrochloride, m. p. 50°.-The odor when suffi- ciently diluted resembles that of lilac flower 1 221 1-000(0) 1,4-Dihydroxypentane, C6H10.(OH)2.-Viscous.-Misc. w. aq. or ale.!; i. Igr. 220-5 s.-Dimethyl Dipropyl Glycol, [(Me)(Pr)C.OH],. 235 1-008(18) Phenylpropyl Ale., Ph.(CH2)3.OH.-Viscous, d. s. aq.; misc. w. ale. or eth.-May be oxid. by CrO3 to hydrocinnamic ac. 225-30 Ethyl Glyceryl Eth., CH2(OH).CH(OH).CH2.O.Et. 240d. 1-101(25) Allyl Glyceryl Eth., C3H5.O,.C3H7.-S. in 2 or 3 vol. aq.!- Unsat. (Of. Test 901.) 246-6c. 0-978(15) p-Cuminic Ale., Me2.CH.C0H4.CH2.OH.-Misc. w. ale. or eth.- Oxid. by KMnO4 to terephthalic and oxypropylbenzoic acids.-Persistent boiling w. Zn dust gives cymene. 247-5 1-120(23) Saligenin Methyl Eth., o-MeO.C6H4.CH2.OH. 250 1-132(0) Diethylene Glycol, CH2(OH).CH2.O.CH2.CH2.OH.-S. aq. ale. or eth. 254 l-0442% Cinnamyl Ale., Ph.CH:CH.CH2.OH.-Aromatic odor like hy- acinths.-D. s. aq.; v. s. ale. or eth.-Gives Test 304 easily. 290 1-138 Triethylene Glycol, C0H14O4.-Misc. w. aq.; d. s. eth. 290c. l-2602% f Glycerine, CH2(OH).CH(OH).CH2.OH.-Viscous sweet-tast- ing syrup.-Misc. w. aq. or ale.; i. abs. eth.-Identify by Test 816!-(Commercial glycerine usually contains so much water that it may begin to boil 100° lower than the b. p. given. The temperature will rise nearly to the true b. p., however, if the distillation is continued.)- [N.B.-Several of the higher homologues of glycerine have been prepared. They are syrups, v. s. in water and almost insoluble in ether; but as they possess little interest, and can not be distilled without decomposition under the usual atmospheric pressure, their description is omitted.] 327 1-062(16-5) Dibenzylcarbinol, (Ph.CH2)2.CH.OH.-E. s. ale. or eth. NUMBERED SPECIFIC AND SEMI-SPECIFIC TESTS FOR THE ALCOHOLS. [TESTS 801-900.] 8oi. The Iodoform Test. The more or less ready formation of iodoform when certain aliphatic compounds are treated with iodine in dilute alkaline solution, furnishes a qualitative test that has found many applications in organic analysis. When the use of this reaction is directed in the tables for the purpose of distinguishing between some of the lower boiling liquid alcohols and ketones, proceed as follows: Prepare a cold aqueous solution containing one drop of the pure compound in each cubic centimeter of water. If the test is to be made with a single centimeter of the solu- tion, carry it out in a three-inch test-tube ("weighing-tube"). For each centimeter of solution used, add two drops of sodium-hydroxide solution (1 : 10); then, drop by drop, from a medicine-dropper, a concentrated iodine solution,* until a barely perceptible tint of yellow, that persists after standing for several seconds, remains. If too much iodine should be inadvertently used, cautiously add just enough more soda to destroy the excess of color. Let the mixture stand at the temperature of the laboratory for two minutes. Then shake and notice whether any iodoform has separated. If no iodoform separates in the cold, immerse the bulb of a small thermometer in the solution; heat to 60°, and maintain this temperature for one minute. If the solution becomes entirely colorless during the heating, add just enough more iodine to restore the trace of yellow that was previously present. If no precipitate appears at once, set the tube aside for two minutes before making the final observation. In the first part of the test, in the cold, isopropyl alcohol and acetone give good precipi- tates of iodoform immediately; secondary butyl alcohol rather slowly. Methyl, ethyl, propyl, isobutyl, tertiary butyl, isoamyl, and allyl alcohols give no precipitates under the same conditions. A fter heating at 60°, ethyl alcohol gives a good precipitate, and allyl alcohol a very scanty one. The other compounds mentioned in the preceding paragraph which do not give iodoform in the cold, do not give any at 60° within the specified time limit. The interpretation here given to the results of the test will not hold for solutions that vary greatly from the prescribed concentration. It is applicable, however, in testing the saponification distillates obtained by the procedure of Generic Test V-2, B. Under other conditions, which were first carefully studied by Lieben,f the delicacy of the reac- tion when used for the detection of smaller quantities of ethyl alcohol, etc., may be greatly increased. According to Lieben, most compounds containing the CH3.CO.C and CH3.CHOH.C groups may be made to yield iodoform by appropriate treatment with iodine and alkali; some, like levulinic acid, giving it very readily in the cold. Hence * This iodine solution should be kept in stock, and is prepared by rubbing 1 part iodine in a mortar with 5 parts of potassium iodide and 15 parts of cold water. t Cf. Lieben, Liebig's Annalen, Spl. 7, 221.-The lower alcohols and acetone, if in very weak solutions, are easily concentrated by distilling through a tower. The first runnings will contain nearly all of the organic compound so that the second half of the distillate may be safely rejected. The process of "salting out" with potassium carbonate may be combined with distillation, as is illustrated in paragraph (i) of Generic Test V-2, B. 166 SPECIFIC TESTS FOR THE ALCOHOLS. 167 while the test is more used than any other as a preliminary reaction for the detection of ethyl alcohol and acetone in aqueous solutions, the result requires confirmation by additional evidence. Iodoform is ordinarily recognized by its peculiar pervasive odor and pale-yellow color, though it is said that neither of these properties are characteristic of the chemically pure substance. Indeed, under the conditions of the test, the precipitate is at first often prac- tically white, and the odor is not always well developed at the moment of formation. An iodoform odor, unaccompanied by a precipitate, should never be accepted as satisfactory evidence of the presence of any of the compounds giving the reaction. An iodoform pre- cipitate, if washed with cold water, dissolved in a little warm and quite dilute alcohol, and then allowed to crystallize out very slowly, separates from the solvent in regular hexagonal plates of decidedly characteristic appearance, in which the opposite corners of the hexagon are connected by straight lines crossing its geometrical centre; or, sometimes, in regular six-rayed stars whose primary rays branch into a system of symmetrical subordinate rays after the manner seen in frost crystals. 8n. Allyl Alcohol. (Properties tabulated on p. 161.) Support a 25 cc. distilling-flask with a long side-tube in a vertical position by a clamp. Cool the bulb by surrounding it with cold water. Introduce two drops of the alcohol, and then three drops of a solution made by dissolving 1 grm. of chromic anhydride in a mixture of 6 cc. of water and 0.8 cc. of concentrated sulphuric acid. The liquids should be dropped from a medicine-dropper in such a manner that they will not come in contact with the side walls of the flask in falling. Cork quickly. Loosen the clamp, and incline the flask so that the lower end of the side tube shall dip into 2 cc. of water contained in a test-tube standing in a beaker partly filled with cold water. Boil the solution in the flask over a very small flame until it has evaporated nearly to dryness. Loosen the stopper before taking away the lamp. Mix the aqueous solution in the test-tube with 5 cc. of the fuchsine-aldehyde reagent used in Test 112 (1). Allow to stand overnight and observe the color the next morning. Mix 2 cc. of the solution with 2 cc. of hydrochloric acid (sp. gr. 1.20), and again observe the color. Finally note the color of this acid mixture after it has been diluted with water to 100 cc. In this test allyl alcohol is oxidized to acrolein. The violet-red coloration which makes its appearance within a few seconds after adding the aldehyde reagent, and which within ten minutes renders the solution practically opaque, is not characteristic, very similar colors being obtained from many other alcohols when treated in the same manner. If, however, the color after standing overnight is a red-violet (RV), of such intensity as to appear opaque except in thin layers, and if this color upon addition of the hydrochloric acid changes to an impure dark yellow or dark yellow-green (about YS2 to YGS2, when viewed in very thin layers against a white background), and this color in turn, upon the dilution with water to 100 cc. gives a pure blue (BTI, occasionally approximating VBTI, the comparison being made in a six-inch test-tube against a white background), the compound, if it has the proper physical properties, must be allyl alcohol. 812. Benzyl Alcohol. (Properties tabulated on p. 165.) Place in a 25-50 cc. distilling-flask two drops of the chromic-acid mixture used in Test 811 for allyl alcohol, 10 cc. of water, and four drops of the alcohol. Heat over a small flame, while shaking, for two or three minutes, until the solution appears distinctly greenish; the temperature meanwhile being kept a little below boiling, so that no vapor shall escape through the side tube. Next distil, collecting about 2 cc. of distillate in a test-tube containing 1 cc. of cold water. Do not use a condenser, but let the extremity 168 SPECIFIC TESTS FOR THE ALCOHOLS. of the side-tube of the flask almost touch the surface of the water in the test-tube. The test-tube should stand in a beaker half filled with cold water. When the distillation is finished, wash down the sides of the test-tube with 3 cc. of water and 6 cc. of strong alcohol. Add one drop of pure phenylhydrazine and boil for half a minute. From this point on, follow literally the directions given in part 1 of Test 113 for benzaldehyde. The oxidation with chromic acid gives benzaldehyde; and the treatment with phenylhy- drazine gives its phenylhydrazone, melting-point 156°. The hydrazone, being rather unstable in the light, will sometimes be found to melt one or two degrees below its true melting-point. (Benzyl alcohol oxidizes so readily, that specimens which have been ex- posed for some weeks to the air will be found to give aldehyde reactions.) 813. Butyl Alcohol (Normal).* (Properties tabulated on p. 161. Convert six drops of the alcohol into n-butyl 3,5-dinitrobenzoate by the procedure given in the first paragraph of Test 814-1. To purify the ester, crush the reaction product when cold with a stirring-rod. Dissolve it in 10 cc. of ethyl alcohol (2:1). Filter hot if not clear. Cool well, shake persistently, and filter. Wash with 3 cc. of cold ethyl alcohol (2 :1). Recrystallize from 8 cc. of the same alcohol and wash with 2 cc. Spread on a porous tile and allow to become air dry in a warm place. Determine the melting-point. The ester obtained in this test is distinctly crystalline, has a pearly lustre, and melts at 64° (uncor.). 814. Ethyl Alcohol. (Properties tabulated on p. 161.) The ready formation of iodoform at 50°-60°-but not in the cold-in Test 801 is the most convenient preliminary test for ethyl alcohol. The following very satisfactory confirmatory test is, of course, applicable only to a nearly pure alcohol containing not more than about 10 per cent of water. The same general procedure with slight modifica- tions may be used in the identification of many of the homologues of ethyl alcohol. 1. Heat together gently in a three-inch test-tube held over a small flame, 0.15 grm. of 3, 5-dinitrobenzoic acid f and 0.20 grm. of phosphorus pentachloride. When signs of chemical action are seen, remove the heat for a few seconds. Then heat again, boiling the liquefied mixture very gently for one minute. Pour out on a very small watch-glass, and allow to solidify. As soon as solidification occurs, remove the liquid phosphorus oxychloride with which the crystalline mass is impregnated by rubbing the latter between two small pieces of porous tile. Place the powder in a dry five- or six-inch test-tube. Allow four drops of the alcohol to fall upon it, and then stopper the tube tightly without delay.- [When employing this procedure for the propyl and butyl alcohols, use six drops of the alcohol instead of four; for the alcohol must always be present in moderate excess.]- Immerse the lower part of the test-tube in water having a temperature of 75°-85°. Shake gently, and continue the heating for 10 minutes. To purify the ester produced in the reaction, crush any hard lumps that may form when the mixture cools with a stirring-rod, and boil gently with 15 cc. of methyl alcohol (2 :1) until all is dissolved, or for a minute or two.-[In testing for other alcohols than ethyl, all directions for the use of the solvent in this paragraph must be modified as else- where specified. Cf. tests for methyl, propyl, butyl, and isobutyl alcohols.]-Filter boiling hot if the solution is not clear. Cool. Shake, and filter. Wash with 3 cc. cold methyl alcohol (2 : 1). Recrystallize from 9 cc. of boiling methyl alcohol (2 : 1). Wash with * A preparation from Kahlbaum of Berlin. j- This new reagent is listed by C. A. F. Kahlbaum of Berlin at 8 marks per 100 grams, and may be obtained in New York from Eimer & Amend. It may also be readily prepared in the laboratory from benzoic acid. SPECIFIC TESTS FOR THE ALCOHOLS. 169 2 cc. of the same solvent. Spread out the product on a piece of tile. Allow to become air dry, and determine the melting-point. Ethyl 3,b-Dinitrobenzoate, the product in this test, crystallizes in white needles melting at 92°-93° (uncor.). 815. Ethylene Glycol. (Properties tabulated on p. 164.) Shake vigorously in a stoppered six-inch test-tube for five minutes, occasionally cooling with water, one drop of the alcohol, 0.4 cc. benzoyl chloride, and 5.0 cc. of a 10 pen cent aqueous solution of sodium hydroxide. Add 10 cc. of cold water. Shake again for a few seconds, and then filter. Wash the precipitate with 20 cc. of cold water. Dis- solve in 20 cc. of hot dilute alcohol (1:1), filtering hot if the solution is not clear. Cool and filter. Wash with 4 cc. of cold alcohol (1 : 1). Dry on a porous tile at the room temperature for an hour. The ethylene dibenzoate, as obtained in this test, melts at 70.5°-71° (uncor.). The melting-point may be slightly raised by repeated crystallization. 816. Glycerine. (Properties tabulated on p. 165.) Of the three tests for glycerine here described, color reaction 1 with pyrogallol has the advantage, as a preliminary test, of being rapid and directly applicable to rather dilute aqueous solutions, but results by procedures 2 and 3 are more conclusive. In testing for glycerine in the presence of other organic compounds, such for example as in the aqueous solution resulting from the saponification of an ester by the method of Generic Test V-2, the glycerine should first be isolated in a nearly pure state by evap- orating to dryness on a water-bath, and extracting the powdered saline residue- with a mixture of equal volumes of nearly absolute alcohol and ether. Evaporation of the solvent will then give a syrup that will often be pure enough for identification by either one of the following methods. In the presence of sugars this purification will prove insufficient to permit the use of procedures 1 and 3; but method 2 may be safely used. 1. Dissolve one drop of the glycerine in 2 cc. of cold water. Add five drops of a one per cent aqueous solution of pyrogallol, and 2 cc. of concentrated sulphuric acid. Shake. Heat quickly to boiling and boil for 20-25 seconds. Cool immediately with running water. Dilute to 20 cc. with strong alcohol in a six-inch test-tube. Without delay compare the coloration produced with the color standard, holding the tube in front of a white back- ground. Glycerine in this test gives a characteristic purplish-red coloration to the alcohol that matches VRT1-T2 of the standard. The color fades away after standing for some minutes. This procedure is directly applicable to quite dilute aqueous solutions if " 2 cc. of the solution" is substituted for the "drop of glycerine, and 2 cc. of cold water" called for in the directions. The color from a one per cent solution will then be found to be as pure, and nearly as intense, as when a drop of pure glycerine is taken. The color given by solutions containing 0.1 per cent of glycerine is very pale indeed and fades rapidly, but it is still quite noticeable, and of the correct hue. Very weak solutions may require heating for thirty seconds or more. The presence of sugars, or of certain other polyatomic alcohols like erythrite, may obscure the reaction by giving rise to reddish- or yellowish-brown color- ations. 2. Stir up into a stiff uniform paste on a watch-glass, by means of a thin wire, one drop of the syrupy compound and 0.5 grm. of powdered acid potassium sulphate. Drop the mass into a dry six-inch test-tube supported by a clamp in a slightly inclined position on a lamp-stand. Fit the tube with a clean perforated cork stopper carrying a glass gas- delivery tube, 20-25 cm. long, and bent downward so that one end is barely immersed beneath the surface of 2 cc. of distilled water contained in a second test-tube that stands 170 SPECIFIC TESTS FOR THE ALCOHOLS. in a beaker partly filled with cold water. Ignite the sulphate mixture strongly with a gas-flame until frothing ceases and the mass is completely liquefied. Test the aqueous solution in the second test-tube for acrolein by observing its odor, and by color reaction 112-1. The vapors of acrolein, the dehydration product of glycerine in this test, are remark- able for their painfully irritating action on the mucous membranes of the nose and eyes. Their effect must not be confounded with that due to sulphur dioxide, which is usually formed during the ignition, even in the absence of glycerine. Little difficulty will be found in making the distinction by any one who has ever performed the experiment with pure glycerine. The phenomena of the color reaction between acrolein and the fuchsine-aldehyde reagent are fully discussed under the specific test for acrolein, and are very characteristic. Ethylene glycol gives acetic aldehyde, but like trimethylene glycol, erythrite, or man- nite, does not give an acrolein odor or interfering color reaction in the fuchsine test* This latter reaction is also not seriously interfered with by the small quantities of grape- or cane-sugar that remain with glycerine after the purification of a crude glycerine by the ether-alcohol extraction referred to in the introduction to this test. Sugars, if present in larger quantity, are likely to give confusing colorations, but never any acrolein odor. 3. Place in a six-inch test-tube one drop of glycerine, 0.4 cc. benzoyl chloride, and 5.0 cc. of a 10 per cent aqueous solution of sodium hydroxide. Stopper, and shake vigorously, occa- sionally cooling under cold water, until a solid separates. This requires from five to eight minutes. Add 10 cc. of cold water, and shake again for ten to twenty seconds. Filter. Wash with 20 cc. cold water; then with 10 cc. of a cold mixture of 2 cc. glacial acetic acid and 8 cc. water. Crystallize from 15 cc. of boiling dilute alcohol (2 vols. alcohol: 1 volume aq.). Filter hot if all does not dissolve on boiling. Cool and shake till a precipitate gathers. Filter. Wash with 3 cc. of dilute alcohol (2 : 1). Dry on a porous tile in the air. The product in this test is a white crystalline substance melting at 71°-72° (uncor.). It is presumably glycerine tribenzoate, for which several melting-points with the extreme values of 70° and 76° are to be found in the literature. This procedure is applicable with only slight modification, to not too dilute solutions of glycerine in water. Thus, a fair yield of benzoate is obtained when one drop of glycerine dissolved in 1 cc. of water is substituted for one drop of pure glycerine as prescribed in the directions. It is of course inapplicable in the presence of polyatomic alcohols or other substances giving the Schotten-Baumann reaction. 817. Isobutyl Alcohol. (Properties tabulated on p. 161.) Convert six drops of the alcohol into isobutyl 3, 5-dinitrobenzoate by the procedure given in Test 819-2 for preparing the methyl ester of the same acid. The isobutyl ester is obtained in this test in white flocks melting at 83°-83.5° (uncor.). 818. Isopropyl Alcohol. (Properties tabulated on p. 161.) Oxidize four drops of the alcohol with six drops of the chromic-acid mixture used in Test 811 for allyl alcohol. The procedure for the oxidation is identical with that given for allyl alcohol, except that the vapors are to be conducted into a six-inch test-tube con- taining 0.4 cc. of cold water, 0.4 cc. of benzaldehyde, and 2 cc. of strong alcohol. Shake and add 0.5 cc. of a ten per cent caustic-soda solution, and boil very gently over a small flame for one minute, counting from the time when actual boiling begins. Cool and shake. Filter off the crystalline precipitate and wash with 1 cc. of strong alcohol. Boil up with 1 oc. of strong alcohol. Cool, and shake vigorously, adding from one to four drops of water, if necessary, to start the separation of crystals. Filter, and wash with 0.5 cc. of cold alcohol. Press on a porous tile, and then dry fifteen minutes at a temperature not above 100°. Isopropyl alcohol is oxidized in this test to acetone, which is then condensed with SPECIFIC TESTS FOR THE ALCOHOLS. 171 the benzaldehyde to dibenzylidene-acetone (cf. Test 711-2), crystallizing in pale-yellow lustrous plates that melt at 111°-112° (uncor.). 819. Methyl Alcohol. (Properties tabulated on p. 160.) 1. (Color reaction.)-Dissolve one drop of the alcohol in 3 cc. of water in a six-inch test-tube. Wind a piece of rather light copper wire around a lead-pencil so that the closely coiled spiral shall form a cylinder 2 cm. in length, while 20 cm. of the wire is left unbent to serve as a handle. Oxidize the spiral superficially by holding it in the upper part of the flame of a Bunsen burner; and then, while still at a red heat, plunge it into the alcoholic solution. (This treatment oxidizes a portion of the methyl alcohol to formic aldehyde.) Withdraw the spiral immediately and cool the test-tube with running water. Repeat the oxidation of the solution twice more by the method given. Add one or two drops of 0.5 per cent aqueous solution of resorcin. Pour the mixture slowly into a second inclined test-tube containing 3-5 cc. of pure concentrated sulphuric acid. The procedure and the phenomena in the test from this point on, are the same as described in the latter part of Test 114-1 for formic aldehyde. Many methyl ethers, and methyl esters that are sufficiently soluble in water to be tested by this method, and tertiary butyl alcohol,'show the same behavior as methyl alcohol. Remember that the actual separation of bright-red solid flocks from the aqueous layer above the sulphuric acid, after standing, is essential to the proof that methyl alcohol is present. Many compounds besides those mentioned give traces of formic aldehyde when oxidized by a hot copper wire, but not enough to give a separation of the characteristic flocks. Test 114-2 for formic aldehyde will often show the presence of these traces, and there- fore must not be substituted for Test 114-1. Ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, and allyl alcohols, ethyl ether, and acetone, give strong yellow, amber, ocher- ous, or dirty greenish colorations; and, if present in relatively large quantities in mixtures containing methyl alcohol, will interfere with its detection by destroying the purity of color required in the flocks. Weak aqueous solutions suspected to contain methyl alcohol may be oxidized directly with the copper wire and then tested with resorcin in the usual manner, solutions much weaker than the one recommended in the procedure giving entirely satisfactory results. In examining organic mixtures for methyl alcohol the precautions mentioned in the following paragraphs should be observed. (a) Use for the test only that part of any mixture that can be completely distilled between 50° and 100°, and which, after distillation, gives a clear, colorless solution when diluted with several volumes of water. (b) Make a blank experiment, before oxidation with the copper spiral, by pouring 2 cc. of a clear aqueous distillate of the proper boiling-point, to which one drop of 0.5 per cent resorcin solution has been added, so as to form a layer upon concentrated sulphuric acid in a test-tube. If a precipitate or strongly colored ring makes its appearance, the solution is not suitable for testing without preliminary treatment. (c) Do not test by this method any solution that is suspected to contain phenols or organic bases. 2. Convert four drops of the alcohol into its 3,5-dinitrobenzoate by the procedure detailed in the first paragraph of Test 814-1 for ethyl alcohol. Boil the reaction product with 12 cc. of dilute ethyl alcohol (3 : 1). Cool, shake, allow to stand for a minute or two, and filter. Wash with 2 cc. strong cold alcohol. Recrystallize from 12 cc. of boiling dilute alcohol (3 : 1). Cool, shake, and allow to stand for a minute or two, and filter. Wash the crystals with 2 cc. of cold strong alcohol. Dry at a temperature not above 100°, and determine the melting-point. The crystalline methyl dinitrobenzoate obtained in this test melts at 107.5° (uncor.). 172 SPECIFIC TESTS FOR THE ALCOHOLS. 820. Propyl Alcohol. (Properties tabulated on p. 161.) 1. Oxidize four drops of the alcohol with six drops of the chromic-acid mixture used in Test 811 for allyl alcohol. The procedure for the oxidation is identical with that given for allyl alcohol, except that the aldehydic vapors are to be conducted into a three-inch test-tube containing a solution of 0.2 grm. /?-naphthol in a mixture of 2.0 cc. glacial acetic acid and two drops of concentrated hydrochloric acid. Warm the mixture for at least half a minute over a small flame, and then boil gently for one minute. Cool and shake. If no precipitate appears, add one drop of water and shake again. Continue the addition of water in this way until a scanty permanent solid precipitate is produced, and the mixture begins to show signs of becoming milky. Allow the precipitate to settle. Filter and wash with 2 cc. of dilute alcohol (1 : 1). Boil the precipitate 30 seconds with 3 cc. of strong alcohol and 1 cc. of water. Cool, shake, and filter. Wash with 2 cc. of alcohol (1 : 1). Press on a tile and dry 15 minutes at 100°. The condensation product formed in this test crystallizes in colorless plates, and melts at 153° (uncor.). 2. Convert into propyl 3,5-dinitrobenozate, following exactly the directions given in Test 819-2 for methyl alcohol, except that the product must be dried at a tempera- ture below 70°. The melting-point of propyl 3,5-dinitrobenozate is 73°-73.5° (uncor.). 821. Cholesterine. (Properties tabulated on p. 158.) So many compounds closely resembling cholesterine have been described that tests (1) and (2) should both be applied. 1. Place 0.1 grm. of the compound and 0.5 cc. benzoyl chloride in a dry test-tube. Immerse the end of the test-tube in a paraffin bath and heat at about 160° for 5 minutes. Cool. Add 10 c.c. of strong alcohol and boil. Cool. Filter off the precipitate and wash it with 5 cc. of cold strong alcohol. Redissolve in 10 cc. of hot alcohol; cool; filter and wash as before. Then repeat these operations for a third time. Dry the product for 15 minutes at 100° and determine its melting-point in a wide capillary. After the com- pound has fused to a perfectly clear liquid, withdraw the tube quickly from the bath, hold it before a piece of black paper, and watch closely for color changes during solidification. Cholesterine benzoate, formed in this test, crystallizes in pearly white leaflets which fuse to a turbid liquid at 145.5° (uncor.). At 178.5° (uncor.) the turbidity suddenly dis- appears. In cooling, a brilliant display of opalescent colors is exhibited, among which a brilliant blue, appearing at about the temperature of the higher melting-point, followed by a violet-blue just before complete solidification, are most prominent. The colors dis- appear very quickly. 2. Place 0.1 grm. of the substance, 0.1 grm. of anhydrous sodium acetate, and 1 cc. of acetic anhydride in a dry test-tube. Immerse the end of the test-tube in a paraffin- bath at 130°-135° and heat for fifteen minutes. Dissolve the reaction product in 5 cc. of hot dilute alcohol (4 : 1). Cool. Filter. Wash the precipitate with 2 cc. of the same dilute alcohol. Recrystallize from 10 cc. of the same alcohol. Recrystallize again from 3 cc. of boiling strong alcohol, and wash the precipitate with 1 cc. of cold strong alcohol. Dry on a porous tile, and then in an oven at 100° for fifteen minutes. Determine the melting-point of the substance, and observe any change in color during solidification, in the manner described for the benzoate in the preceding paragraph. Cholesterine acetate, formed in this test, melts at 114° (uncor.). A play of opalescent color is observed during the few seconds that elapse between incipient and complete solidi- fication. CHAPTER XL GENUS IX. HYDROCARBONS AND OTHER COLORLESS COMPOUNDS OF CARBON, HYDROGEN, AND OXYGEN NOT INCLUDED IN" EARLIER GENERA OF SUBORDER I, ORDER I. GENUS IX COMPRISES ALL COLORLESS COMPOUNDS OF THE SUBORDER THAT FAIL TO GIVE GENERIC TESTS I-VIII INCLUSIVE. WITH THE EXCEPTION OF SOME ETHERS AND A FEW UNREACTIVE KETONES AND ESTERS, THESE SPECIES ARE ALL HYDROCARBONS. ALL ARE INSOLUBLE OR NEARLY IN- SOLUBLE IN WATER. THE GENUS HAS NO SPECIAL GENERIC TEST OF ITS OWN. The solid species of the genus constituting Division A are not subdivided into sections. The liquid species, Division B, are, however, arranged in three sections: Sec- tion 1 contains the paraffins, CrtH2n+2, and some saturated cyclic hydrocarbons; Section 2, unsaturated hydrocarbons from both the aliphatic and cyclic series, together with some alky] oxides (ethers'); and Section 3, the liquid aromatic hydrocarbons, terpenes, and a few fatty-aromatic ethers. Sectional Tests. To find the section of the tables to which any liquid species of the genus belongs, its specific gravity must first be known. Detailed directions for the deter- mination of this constant with the necessary degree of accuracy, by a simple metho I requiring not more than 0.2 cc. of substance, will be found on page 228. If the specific gravity at 20°/4° is found to be less than 0.850, the compound is to be sought in Section 1 or 2, Section 3 containing all liquid species having a higher gravity. In this case, in order to decide whether the body belongs to Section 1 or 2, apply Tests 901 902. and 903. If a compound with specific gravity below 0.850 does not decolorize bromine solution in the cold in Test 901 and is not attacked or dissolved by the fuming- sulphuric acid in Test 902. nor by the fuming nitric acid in Test 903, it is to be sought in Section 1* If it shows the opposite behavior in any one of these tests, its place is among the unsaturated hydrocarbons and alkyl ethers of Section 2. * A few liquid paraffins like diisopropyl of tertiary structure (i.e., containing a CH group joined to three carbon atoms) are said to be more reactive in these tests than their isomers, and may be misplaced in Section 1. (Cf. Engler-Hofer's 'Das Erdbl, I, 231-5, for discussion.) 173 COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER 1} GENUS IX, HYDROCARBONS, ETC. DIVISION A-SOLID HYDROCARBONS. Melting-point (C.°). Boiling-point (C.°). HYDROCARBONS, ETC.-Colorless and Solid. 4 274 Cetene, C16H32.-G. 0-78915/4.-Gives Test 901. Dibromide an oil. 6-5 134 (15 mm.) Tetradecine(4), ChH20.-G. 0-80015/4.-Gives Test 901. 10 270-5 • Pentadecane, C15H32.-G. 0-7692°/4--Does not give Tests 901 to 903. 11 233 Safrol, C10H10O2.-Odor like sassafras. Cf. Div. B, Sec. 3, of this genus. 11-12 236 (15 mm.) m-Methylhexadecylbenzene, Me.C6H4.C1GH33.-G. 0-86211/4. 13 250 (th. i.) 1,2,4, 5-Tetraethylbenzene, CGH2.Et4.-Oxid. gives pyromellitic ac. 14 190-2 (13 mm.) Diphenylheptane, Ph2.CH.C6H13.-Nitrates easily. 15 155 (15 mm.) Hexadecine(i), C16H30.-G. 0-797(20°).-Unsat. (Test 901). Gives floc. ppt. when shaken with AgNO3 sol. IS 287-5 Hexadecane, C1(iH34.-G. 0-77518/4.-Does not give Tests 901 to 903. 18 179 (15 mm.) Octadecylene, C18H30.-G. 0-79118/4. 20 160 (15 mm.) Hexadecine(2), CloH30.-G. 0 - 80 420/4. No ppt. w. ale. sol. of AgNO3. 21-6 233c. f Anethol, Me.C2H2.CGH4.O.Me.-Has odor and taste of anise oil, in which it occurs!-G. 0-985522/4; ND (18°) =1-5615.- V. d. s. aq.; misc. ale. or eth.-Shaken w. a little cone. H2SO4 gives anisoin, m. p. 140°-5°.-Heated w. solid KOH at 200°-30° gives p-oxybenzoic ac. and anol. 22-3 289 Ditolylmethane, (Me.CGH4)2.CH2.-Oxid. by CrO3 to dimethyl- benzophenone, etc. 22-5 303 Heptadecane, C17H36.-G. 0-77722/4.-Does not give Tests 901 to 903. 26 180 (15 mm.) Octadecine(i), C18H34.-Gives cryst. ppt. w. ale. AgNO3 sol. (ClsH33Ag.AgNO3). 26-7 261-2 f Diphenylmethane, Ph2.CH2.-G. 1 -0012G/4.-Agreeable orange- like odor.-Oxid. by CrO3 gives benzophenone (cf. Tests 702 and 714).-See color reaction 904. 27 286 Benzyl-p-tolyl-methane, Ph.CH2.CH2.CGH4.Me.-E. s. ale. 27 230 (15 mm.) Cetylbenzene, C1GH33.Ph.-G. 0-85727/4.-D. s. c. ale.; e. s. eth. or bz. 27-5 240 (15 mm.) p-Methylhexadecylbenzene, Me.CGH4.C16H33.-Test 905-3 gives p-toluic acid. 28 317 Octadecane, C1SH38.-G. 0-77728/4.-Does not give Tests 901-3. 28 252-S Phenyl Eth., Ph,.O.-Odor like geranium!-Alm. i. aq.; e. s. ale.-Unchanged by CrO3 in Ac, by ignition w. Zn dust, or by HI at 200°.-Dissolves in fuming HNO3, giving dinitro- comp., m. p. 135°. 30 294 f Apiol, CH2.O2.C,H(C3H5).(OMe)2.-I. aq.; e. s. ale. or eth.- S. H2SO4 w. blood-red color.-Vol. w. st. 30 184 (15 mm.) 0ctadecine(2), C]SH34.-G. 0-8023°/4.-Gives no ppt. w. ale. AgNO3 sol.-Gives Test 901. 174 GENUS IX, DIV. A. 175 (ORDER I, SUBORDER I.) Melting-point (C.°). Boiling-point (C.°). HYDROCARBONS, ETC.-Colorless and Solid. 32 330c. Nonadecane, C19H4 .-G. 0-77732/4.-Does not give Tests 901- 903. 32-5 241-2 (th. i.) /?-Methylnaphthalene, Me.C10H7.-Picrate dark-yellow ndl., m. p. 115°. 32-9 170d. Dicyclopentadiene(i, 3), C10H12.-G. 0 • 97733/4.-Lustrous stel- late aggregates, e. s. ale. or eth.-On dist. partially decom- poses to cyclopentadiene (IX, B, 2), b. p. 42-5°. 33-5 250 (15 mm.) 1,3- Dimethyl - 4 - hexadecyl - benzene, Me2.CBH3.C,RH„. - G. 0-84933/4. 35-5 350 /?-Benzylnaphthalene, C7H,.C1GH17.-G. 1-176(0°).-CrO3 oxid. to benzoic ac.(Test 312).-Picrate yellow ndl. fr. ale. w. m. p. 93°. 36 249 (15 mm.) Octadecylbenzene, ClsH37.Ph.-Silvery 1ft. 36 ^-Naphthylacetylene, C10H7.C:CH.-Ag salt, AgC12H7 (w. am- mon. AgNO3), colorless ppt. 36-7 300-3 Benzoylmesitylene, C6H2.(Me3)(C7H7)(i, 3, 5, 6).-Lustrous ndl. -Tribrom-deriv. yellowish pr. fr. ale., m. p. 185°. 36-7 205 (15 mm.) Eicosane, C20H42.-G. 0 - 77 836-7/4.-Does not give Tests 901-903. 37 274-5 Ethyl /3-Naphthyl Eth., Et.O.CioH?.-Odor anise-like!-Cryst. mass. 38-9 286-7 Phenyl Benzyl Eth., Ph.O.C7H7.-Heated at 100° w. cone. HC1 gives phenol and benzyl chloride. 39 1,4-Diphenylbutene(i), Ph2.C4He.-S. ale. or eth. 40 258 1, 3, 5-Trimethyl-6-hexadecyl-benzene, Me3.CfiH2.C10H33. 40-4 215 (15 mm.) Heneicosane, C21H44.-G.0-77840/4.-Does not give Tests 901-903. 41-2 241 Methylphenylfurfurane, Me.C4H2O.Ph.-Ndl. fr. c. ale.; e. s. ale. or eth.; i. aq.-Vol. w. st.-On long standing changes to yellow oil.-E. oxid. by alkaline KMnO4 to benzoic ac.- Br gives brown-colored i. 1ft., m. p. 208°-10°. 43 Phloroglucin Triethyl Eth., C0H3.(OEt)3.-I. aq.; v. s. ale. or eth.-Vol. w. st. 44-4 224-5 (15 mm.) Docosane, C22H46.-G. 0 - 77 8 44/4.-Does not give Tests 901-903. 47 235 Pyrogallol Trimethyl Eth., CGH3.(OMe)3.-E. s. ale. or eth. 47 157c. i-Camphene, C10Hlc.-Feathery ndl., v. s. ale. or eth.-Proper- ties like those of [+ or - ] comp, of m. p. 51°-2°. 47-7 234 (15 mm.) Tricosane, C23H48.-G. 0 • 77847'7/4.-Does not give Tests 901-903. 48-50 9,9-Diethylanthracene-9,10-dihydride, C]8H20.-Easily oxid. by cold sol. of CrO3 in glacial Ac to diethylanthrone, m. p. 136°. 50 dist. p-Cresyl Eth., (Me.CGH4)2.O.-V. s. eth.; s. ale. 51-1 243 (15 mm.) Tetracosane,C24H50.-G.O • 77951/4.-Does not give Tests 901-903. 51-2 159 (th. i.) [+ or - ] Camphene, C10H16.-(In many essential oils like citro- nella oil.)-Feathery cryst.fr. ale.; v. slowly attacked by cone. H2SO4.-Gives Test 901; is attacked in Test 905. -The hydrochloride (C1OH1O.HC1) is solid but unstable. 52 284 Dibenzyl, Ph.CH2.CH2.Ph.-G. 0-995.-Mod. s. c. ale.; e. s. eth. 52 255-5c. Phloroglucin Trimethyl Eth., CrH3.(OMe)3(i, 3, 5).-S in cone. HNO3 w. deep-blue color! E. s. ale. or eth. 52 s-Diphenylbutane, Ph.(CH2)4.Ph.-E. s. ale. or eth. 53 230 Pentamethylbenzene, Me6.CGH.-W. cone. H2SO4 gives hexa- methylbenzene, m. p. 164°. 55 300 Cetyl Eth., (C16H33)2.O.-Lft. 55-6 Phenyl-ditolyl-methane, Ph.CH.(C7H7)2.-Ndl s ale ; v s. bz. 55-6 Dimethyl Hydroquinonyl Eth., p-CGH4.(OMe)2. 57 Isobutylanthracene, C1SH1S.-Fluorescent ndl.-Reddish-brown picrate. 176 GENUS IX, DIV. A. (ORDER I, SUBORDER I.) Melting-point (C.°). Boiling-point (C.°). HYDROCARBONS, ETC.-Colorless and Solid. 57-8 Cerotene, C27H64.-Gives Test 901. - Paraffin-like mass fr. Chinese wax. 58 f Dinonyl Ketone, (C9H19)2.CO.-Description w. Ketones. Cf. VII, A, p. 137. 59 g-Isoamylanthracene, C19H20.-Ale. sol. shows bluish fluores- cence.-Picrate forms brown-red ndl. fr. ale., w. m. p. 115°. -Sol. in cone. H2SO4 is green, becoming red on warming. 59 350 a-Benzylnaphthalene, PhCH2.C10H7.-S. in 30 pt. h. ale.; s. in 2 pt. eth.-Picrate forms yellow ndl., w. m. p. 100°-l°. 59-5 354 Diphenyl-o-tolyl-methane, Ph2.CH.CGH4.Me.-D. s. c. ale.-May be characterized by conversion into rosaniline. 59-5 270 (15 mm.) Heptacosane, C27H56.-G. 0-78058-5/4--Does not give Tests 901-903. 60 275-300 Tolane, PhC-CPh.-Lft. s. ale.-CHC13 sol. saturated w. Cl gives tetrachloride, m. p. 163°; s. in h. bz.-Gives Test 901. 60-5 310 Benzylduryl, PhCH2.CGH.Me4(Me4 = 1,2,4, 5)--D. s. ale. or eth. 60-1 Ethylanthracene, C14H9Et.-Lft. s. ale.-Picrate melts at 120°. 62 a. 360 m-Methyl-triphenylmethane, Ph,.CH.CGH4.Me.-Ndl. v. s. ale.- No picrate.-Shows blue phosphorescence on friction. 62 370-80 Melene, C30HG0.-Cryst. s. h. ale. 63 290 Anthracenehexahydride, C14H16.-Lft. v s. ale. 63 2, 5-Dimethyl-3,4-Diacetylfurane, C10H12O3.-Cf. VII, A. 63-4 440 Anthemene, C18H36.-G. 0-942(15°).-V. d. s. c. ale.; s. eth. 64 129-30 Hexadiene(i,4), CGH10.-G. 0-739(0°).-Gives Test 901. 67 Asarone, (MeO)3.C0H2.C2H2.Me.-(In root of Asarum Europium.) -S. h. aq.; e. s. ale. or eth. 68-1 302 (15 mm.) Hentriacontane, C31HG4.-G. 0 • 7868/4.-Does not give Tests 901- 903. 69 Laurone, (CnH,3)2.CO.-Description w. Ketones. Cf. VII, A, p. 137. 70 231-6 tert.-Dibutylbenzene, C0H4.[C.Me3]2. 70-5 254-6c. f Diphenyl, Ph.Ph.-G. 1 • 165.-S. in 10 pt. c. ale.-p-Brom- derivative prepared by action of Br in cold CS2 sol.; m. p. 310°.-Test 904 gives an intense and quite permanent blue (B) color! 70-5 310(th.i.l5mm.) Dotriacontane, C32H66.-Alm. i. c. ale.; s. h. eth.; v. s. h. gla- cial Ac.-Does not give Tests 901-903. 71 a. 360 p-Diphenyl-tolyl-methane, Ph2.CH.CGH4.Me.-Pr. v. s. h. ale. 71 2,4-(/?)-Dimethylanthracene, C]4Hs.Me,.-Ndl. fr ale.-CrO3 in Ac. sol oxid. to dimethylanthraquinone having m. p. 157°-8°. 72 274 Methyl a-Naphthyl Eth. (Nerolin), Me.O.C10H7.-Odor like oil of neroli (Orange blossoms.)-Lft fr. eth.; d. s ale. 74-7 331 (15 mm.) Pentatriacontane, C35H72.-G. 0 - 78 274'7/4.-Does not give Tests 901-903. 76-3 f Myristone, (C13H27)2.CO.-Description w. Ketones, VII, A, p. 138. 78 /9-Dibenzylbenzene, (C7H7)2.CGH4.-Flat ndl., s. ale.-Does not give a picrate. abt. 79 a/J-Dinaphthyl, (Cli)H7)2.-S. ale.-Picrate forms golden ndl., m. p. 155°-6°. 79 abt. 190 Durene, CGH2.Me4, (Me4 = i,2,4,5).-V. s ale.-Odor like cam- phor.- Sbl 80 218-2 f Naphthalene, C1OHS.-G. 1-152(15°).-Lft., s c. ale.-Char- acteristic odor.-Test 904 w. A1C13 gives a green-blue color!-• Br substitutes very easily.-Oxid. w. KMnO4 (Test 905-1) gives o-phthalic acid (yield small).-Identify by Test 915! GENUS IX, DIV. A. 177 (ORDER I, SUBORDER I.) Melting-point (C.°). Boiling-point (C.°). HYDROCARBONS, ETC.-Colorless and Solid. 82-8 Palmitone, (C15H31)2.CO.-Description w. Ketones, VII, A, on p. 138. 83-4 Isopropylstilbene, C3H7.CGH4.C2H2.Ph.-Scales, v. s. h. ale.- Adds Br2 (Test 901). 85 285(100 mm.) p-Benzyl-diphenyl, C7H7.CGH4.Ph.-Lft. s. ale.-Heated w. H2SO4 evolves SO2 and finally gives intense blue-red color.- Does not give a picrate.-Oxidation gives benzophenone (Test 714).. 86 a-Dibenzylbenzene, (C7H7)2.CBH4.-Flat ndl., V. s. h. ale.-No picrate. 86-7 287-8 (th. i.) Biphenylene Oxide, C12H8O.-Small 1ft. fr. ale.; v. s. eth.; i. aq.-Picrate fr. ale. m. p. 94°.-Sol. in CS2 gives with Br4 a cryst. dibrom-deriv., m. p. 185°, d. s. ale. 87-8 f Stearone, (C17H36)2.CO.-Description w. Ketones, VII, A, p. 138. 88 270 Perhydroanthracene, C14H24.-Completely oxid. by CrO3 (cf. Test 905-2).-Scarcely attacked by Br. 88 Diphenyl-diacetylene, PhC •;C.C:.CPh.-Long ndl., e. s ale.- Picrate light yellow rhombic cryst. fr. ale., m. p. 108°.- Adds Br (cf. Test 901).-Carbonized by h. cone. H2SO4.- Gives no ppt. w amnion. AgNO3 or CuCl. 88-9 a. 360 Benzyl-pentaethyl-benzene, C7H7.Ca.Et6.-100 pt. ale. at 18° dissolve 0 • 9 pt. 89-90 Ethylstilbene, p-Ph.C2H2.CGH4.Et.-Lft. v. s. h. ale.-Unsat. (cf. Test 901) 91 343-5 Diphenylfurfurane, C10HI2O.-E. s. ale. or eth.-S. cone. H2SO4 w. green color 1 92 358-9 f Triphenylmethane, Ph3.CH.-Lft. d. s. c., e. s. h. ale.; e. s. eth. or CHCl3.-t Nitrate 0-1 grm. by dissolving in 2 cc. fuming HNO3 without application of heat. Ppt. the yel- lowish trinitro-compound by diluting w. aq. Dissolve the ppt. in 10 cc. hot glacial acetic ac. and reduce by successive additions of small portions of Zn dust to the hot sol., until the strong red color that at first appears is nearly discharged. Decant, and add a few cgrm. PbO2to the solution. A very intense fuchsine-red color (pararosaniline) forms at once.- For color reaction w. A1C13 see Test 904. 92 fl-Dinaphthylmethane, (Cl0H7)2.CH2. - M. p. of dibrom-deriv- ative 164°. 92-5 a. 360 Phenyl-di-p-xylyl-methane, Ph.CH.(C0H3Me2)2.-E s. ale.-Sols, show bluish fluorescence. 92-3 265-75d. Acenaphthylene, C12H8.-Golden yellow tbl. v. s. ale. Picrate forms yellow ndl., v. d. s. c. ale ; m. p. 201°-2°. 94 323 Dicamphenehydride, C20H34.-Very stable.-Little attacked by CrO3 mixture. 95 277-5 t Acenaphthene, C12HI0.-Long ndl fr ale.-D. s. c. ale.; e. s. h. ale.-Identify by Test 911! 96-5-7 Retenefluorene, C17H18.-S. in alc. w. violet fluorescence.-Com- pletely destroyed by CrO3 in Ac sol.-HNO3, G 1-43, gives a dinitro-compound, d s ale., m. p. 245°. 98-5 390 Retene, C18H18.-G 1 • 1316/1O.-Micaceous lft.-V. s h. ale.- Picrate forms orange ndl., m. p. 123°-4°. - Dibrom-com- pound. fr. Br + aq., tbl. fr. CS2, m. p. 180°; alm. i. aq. 98-5 Ethylene Diphenyl Eth., C2H4.(OPh)2.-D. s. c. aq.; e. s. h. aq. or eth. 100 340 (th. i.) + Phenanthrene, C,4H10.-Sbl easily. Lft., s. in 10 pt. h. ale. Identify by Test 916! 100-5 | 315c. Xanthene, C13S10O.-Lft fr. ale.; alm. i. aq.; s. eth., s. cone. H,SO4 w. yellow color and green fluorescence. 178 GENUS IX, DIV. A. (ORDER I, SUBORDER I.) Melting-point (C.°). Boiling-point (C.°). HYDROCARBONS, ETC.-Colorless and Solid. 102 Benzylfluorene, C7H7.C13H9. 102-2-5 345c. /3-Phenylnaphthalene, Ph.C10H7.-Lft., e. s. h. ale.-Cryst. show blue fluorescence.-Vol. w. st. 105 a. 360 /?-Naphthyl Eth., (C10H7)2.O.-E. s. h. ale.; v. s. eth.-Picrate, orange 1ft. fr. warm eth., m. p. 122°. 105 290-300 Sequoiene, C13H10.-(In needles of Californian Sequoia gigantea.) -Odorless 1ft. w. faint bluish fluorescence.-Red picrate. 105-6 dist. Tetramethyl-m-stilbene, Me2.CGH3.C2H2.CcH3.Me2.-S. h. ale.-■ Adds Br2 (cf. Test 901). 108-5 313 Anthracenedihydride, C]4H12.-Sbl. in ndl.-Warmed w. cone. H2SO4 gives SO2 and anthracene (Test 912). 109 a. 360 a-Dinaphthylmethane, (C10H7)2.CH2.-S. in 15 pt. h., or 120 pt. c. ale.-Picrate (fr. h. CHC13 sol.) red-yellow ndl., m. p. 142°-3°. 109-10' 217 (30 mm ) Fluoranthene, C15H10.-Cryst. d. s. c. ale.-Equal parts of picric ac. and hydrocarbon in h. ale. give a stable picrate; long orange ndl , m. p. 182°-3°! 110 dist. a-Naphthyl Eth., (C10H7)2.O.-E. s. h. ale.; s. eth.-Picrate, m. p. 115°.-Sols, show pale bluish fluorescence. 111 315 Benzhydrol Eth., Ph4C2O.-Monoclinic cryst. fr. bz.; d. s. h. ale.-Boiled w. glacial Ac, Zn, and a little HC1 gives tetra- phenyl ethane. 112-13 295 (th. i.) Fluorene, C13H10.-Lft. d. s. c. ale.-Unstable red-brown picrate fr. eth. sol., m. p. 79°-S0°.-Diphenylene ketone is formed by oxid. w. CrO3 mixture. The ketone may be dist. w. steam, slowly cryst. fr. ale., and mechanically separated from the unoxid. hydrocarbon (A, 166, 368). 113 Dibenzyl-biphenyl, C12HS. (C7H7)2.-Lft., s. ale. 116 295 ^-Methylenebiphenyl, C13H10.-S. h. ale. w. pale-blue fluores- cence.-Picrate forms blood-red ndl., m. p. 79°-81°.-CrO3 mixture gives a quinone. 116-17 Di-o-Oxyhydrobenzoin-Diesoanhydride, C]4H10O2.-Ndl. fr. ale.; e. s. ale. or eth.-Not attacked by h. dil. HC1 or NaOH. 117-20 dist. Phenyl-p-tolylethylene, Ph.CH: CH.(C0H4.Me)(i: 4).-Pearly lft., d. s. ale.-M. p. dibromide 186°-7°. 119 Methyl-phenyl-anthracene, Me.C14Hs.Ph.-Yellowish cryst.- Dil. ale. sol. shows strong green-blue fluorescence--CrO3 oxid. to methyl-phenyl-oxanthranol. 120-0-5 dist. Phenylanthracenedihydride, C20H10.-Hot ale. sol. shows blue fluorescence.-Brown-red picrate.-Oxid. by CrO3 to phenyl- oxanthranol. 121 dist. p-Ditolyl, C7H7.C7H7.-Glassy pr. fr. eth. 123-5 Dimethyl-diphenyl-ethane, Me.CHPh.MeCH.Ph. 124 Distyrene, (C8Hg)2.-Tbl. 124 306-7 (th. i.) f Stilbene, Ph.CH: CH.Ph.-Tbl., d. s. ale.-Adds Br2 hot.- Warmed w. CrO3 mixture gives benzaldehyde (Test 113) and benzoic ac. (Test 312). 125 Di-p-xylyl, (C6H3.Me2)2. 126-7 Hydrobenzoin Anhyd., C28H24O2.-Cryst. fr. eth., i. aq.; e. s. h. ale.-Heated at 250°-70° gives benzaldehyde and stilbene.- Not vol. w. st. 128 Diphenylene-tolyl-methane, C12H8.CH.C7H7.-Silky ndl.-Gives no picrate. 128 292 tert-Tributylbenzene, C0H3.(CMe3)3.-Scales fr. ale. 128 Methyl-ethyl-diphenyl-methane, (Me) (Et) .C.Ph2. 129 298c. Hexaethylbenzene, C6Et6.-May be cryst. fr. warm fuming H2SO4. GENUS IX, DIV. A. 179 Melting-point (Cd). Boiling-point (C.°). HYDROCARBONS, ETC.-Colorless and Solid. 131 355 (12 mm.) Dibenzylmesitylene, (C7H7)2.C0H.Me3.-Cryst., v. d. s. ale. 132 Metanethol, (C10H12O)a,.-Sbl. at 115°-20°.-Not vol. w. st.- Ndl. fr. eth.,. d. s. c. ale.-Oxid. by CrO3 gives acetic acid. 133-5-4-5 Isoanthracene, C14H10.-Pearly 1ft., d. s. c. ale.-CrO3 in Ac sol. oxid. to a quinone w. m p. 211°-12°. 134-5 p-Diethylstilbene, (Et.C8H4)2.C2H2.-Pearly 1ft,, d. s. c. ale.- Oxid. gives terephthalic ac. (Tests 905 and 318-3.) 136 i, i-a-Dinaphthylethane, (C10H7)2.CH.CH3.-Lft.-Solutions flu- oresce violet.-S. c. ale. 141 Naphthanthracene, C18H12.-Sbl. in 1ft.-Shows intense yellow- ish-green fluorescence.-Forms a red picrate, ndl. fr. bz.' m. p. 133°. 140-5 Anisoin, (C10H]2O)x.-(Not identical with compound bearing same name in Genus VII.)-Small ndl. fr. eth.-Dec. on dist. to liq. metanethol.-Not attacked by dil. ac. or alk. 145 326 Benzylduryl, C7H7.C6H.Me4.-D. s. ale. 145-5 a. 360 Biphenylene-phenyl-methane, C13H9.Ph.-Ndl. d s. ale.-No picrate.-With Br in h. Ac sol. gives dibromide, m. p. 181°-2°. 148 250 i, 4-Diphenylbutadiene( 1,3), C18H14.-Pearly tbl.-Tetrabromide melts at 230° d. 148-9 much a. 360 Pyrene (Phenylenenaphthalene), C18H10.-Tbl. s. h. ale.-Pic- rate, stable red ndl. fr. ale. sol. v. d. s. c. ale., m p. 222°. 148-5 Phenylene-diphenyl-methane, C8H4.C.Ph2.-Oxid by CrO3 mix- ture to benzophenone (Test 714) and benzoic ac (Test 312). 149 1, i-Dinaphthylethylene, (C10H7)2.C2H3.-Silky ndl. s h ale. 152-3 417 Phenylanthracene, Ph.C^Hg.-Lft. s. h. ale.-Solutions show blue fluorescence.-Gives red cryst. picrate. 154 a. 360 aa-Binaphthyl, (C10H7)2.-Tbl. s. ale.-Unstable red-brown picrate fr. bz., m. p. 145°, decomposes in air. 155-6 Benzylphenanthrene, C21H16.-V. d. s. ale.-Oxid. by CrO3 in Ac sol. to phenanthrene quinone (Test 1013) and benzoic ac. (Test 312). 157 dist. Tetramethyl-p-stilbene, (Me2.C6H3)2.C2H2.-Lft. d. s. h. ale 160 1, 2-a-Dinaphthylethane, (Cj0H7)2.(CH2)2.-Greenish-yellow fl- sided tbl.; d. s. ale. w. green-blue fluorescence. 161 Hexamethylstilbene, (Me3.C8H2)2.C2H2.-S. ale.-Picrate garnet cryst. fr. bz., m. p. 123°.-Adds Br2. 161 cu-Dinaphthostilbene, (C10H7)2.C2H2.-D. s. ale. or eth.; e. s. bz. -CrO3 gives a-naphtnoic ac. 161 dist. 2,6(,5)-Dinaphthylene Oxide, C20H12O.-Silvery lft., d. s. h. ale.; e. s. eth.; s. cone. H2SO4 w. red color (dif. fr. a), which changes to violet and dark blue on heating, and on dilution w. aq. gives an orange-red fluorescent sol.!-Picrate ver- milion ndl., m, p. 135°. 162 360 Bi-phenylphenylene-methane, (Ph.C0H4)2.CH2.-V. d. s. ale.- S. w. blue color in cone. H2SO4.-Gives no picrate.-CrO3 oxid. to a ketone. 164 264 Hexamethylbenzene, C(iMe6.-V. d. s. tbl. fr. ale.-Sbl. in lft.- Picrate, yellow rectangular tbl., m. p. 170° (dec. by ale.). 169-70 dist. s-Triphenylbenzene, Ph3.CGH3.-G. 1-206.-D. s. ale.-Oxid by CrO3 in Ac sol. to benzoic ac. (Test 312).-Br comp. fr. sol. in CS2, m. p. 104°. 171 Tri-p-tolylbenzene, (C7H7)3.C6H3.-Alm. i. c. ale.; cryst. fr. CHC13. 171-1-5 s-Tetramethylanthracenehydride, C18H20.-Alm. i. ale.; tbl. fr. bz.-Oxid. by CrO3 in Ac sol. to dimethylanthraquinone, m. p. 236°.-Picrate red-brown ndl., m. p. 165°. (ORDER I, SUBORDER I.) 180 GENUS IX, DIV. A. (ORDER I, SUBORDER I.) Melting-point (C.°)- Boiling-point HYDROCARBONS, ETC.-Colorless and Solid. 173-4 dist. 350-1 f o-Benzophenone Oxide (Xanthone), Cl3H8O2.-Long ndl. fr. 173 175 176-4 179 304-5 ale., i. c. aq.; s. h. ale.; d. s. eth.; s. cone. H2SO4 w. yellow color and intense light-blue fluorescence!-(Does not react w. phenylhydrazine or hydroxylamine.)-Fusion w KOH gives salicylic acid and phenol!-CrO3 mixture oxid. to CO2. Phthalacene, C21H16.-D. s. h. ale.-W. an equal weight of Br in Ac sol. gives brom-derivative w. m. p. 184°. Tetraphenylfurane (Lepidene), Ph4.C4O.-Scales, i. aq.; s. 170 pt. h. ale., 52 pt. c. eth., or 85 pt. c. bz.--Dibrom-derivative (by heating Ac sol. w. Br), 1ft., m. p. 190°. t Camphor, C10H!GO.-B. p. 205-3°.-Description w. Ketones, VII, A, p. 139, and Test 715. p2-Dimethylstilbene, (Me.CcH4)2.C2H2.-Lft. d. s. h. ale.-Oxid. 181-1-5 184 187 187-8 a. 360 by CrO3 (Test 905-2) gives terephthalic ac. (Test 318-3). 9,10-Dimethylanthracenehydride, C14H10.Me2.-Yellow ndl., s. ale.-Oxid. by CrO3 in Ac to anthraquinone (Test 1011). a-Dinaphthylene Oxide, C2oH120.-I. aq. or alkalies; d. s. ale.; e. s. eth.-Picrate, dark-red ndl., e. s. ale. or bz., m. p. 173°. Binaphthyl, (C10H7)2.-D. s. ale.-Picrate orange ndl., m. p. 184°-5° (B. 20, 662). Dibiphenylene-ethylene, (C12Hg)2.C2. - Yellowish-red ndl. - 188 Tri-p-xylylmet Heated w. Zn dust gives fluorene.-The picrate forms un- stable red-brown ndl. fr. ale. bane, CH.(C6H3Me2)3 -Grains, s. ale. 189 Benzal-/?-dinaphthyl Oxide, C7HG.C20H12O.-D. s. ale. or eth.; i. alkalies. 196 Isochrysene, C, 8H12.-Long ndl.-Gives no picrate. 199-200 a-Methylanthracene, C14H9.Me.-Gives unstable red picrate.-Oxid. by CrO3 t<J 199-200 1 -methylanthraquinone. /?-Methylanthracene, C14H8.Me.-Gives unstable red picrate.-Oxid. by CrO3 in 203 h. Ac to anthraquinonecarbonic ac. Isomethylanthracene, C14H8.Me.-Oxid. by CrO3 in Ac gives ^-anthraquinone- 204-5 carbonic ac. a-Benzpinacoline, C2GH2nO.-Stable at 350°.-Alm. i. c. ale.; e. s. bz. or CS2.- 205 Does not react w. KOH or phenylhydrazine.-CrO3 oxid. gives benzophenone (cf. Tests 905-2 and 714). p-Diphenylbenzene, Ph2.C6H4.-B. p. 383°.-Lft., v. d. s. h. ale. - Gives no picrate.-Oxid. by CrO3 to terephthalic ac. (Tests 905-2 and 318-3). Photoanethol, C10H12O.-(Fr. anethol in sunlight.)-Odorless, tasteless, pearly 207 209 1ft.-Sbl.-D. s. ale.; v. d. s. eth. s-Tetraphenylethane, Ph2.CH.CH.Ph2.-B. p. 379°-83° c.-Ndl. fr. CHOU-G. 216-5c. 1 • 182.-D. 714). t Anthracene, s. h. ale.-Gives no picrate.-CrO3 oxid. to benzophenone (Test 214H,n.-B. p. 351°.-Lft. or tbl., usually yellowish, but when per- 215 fectly pure, colorless w. beautiful violet fluorescence.-D. s. h. ale.-Gives a deep-red unstable picrate (fr. bz. sol.), e. s. bz., and melting at 138°.- Identify by Test 912 ! Tetratolylethylene, (C7H7)4.C2. 221 f Tetraphenylethylene, Ph4.C2.-B p. 415°-25°.-V. d. s. ale.; e. s. bz.-CrO3 222 in Ac sol. gives benzophenone (Test 714).-f Fails to give Test 901 for unsat- uration, and is not acted upon by alkaline permanganate in Test 304. i, 3, 6-Trimethylanthracene, C14H7.Me3.-D. s. ale. 227 i, 4, 6-Trimethylanthracene, C14H7.Me3.-D. s. ale. - CrO3 in Ac sol. gives tri- methylanthraquinone. Dimethylanthracene, C14Hg.Me2.-CrO3 in Ac oxid. to a quinone w. m. p. 161°-2°. 231-2 243 i, 2, 4-Trimethylanthracene, Me3.CI4H7. 244-5 Tetraxylylethylene, (Me2.C6H3)4.C2.-Yellowish 1ft. GENUS IX, DIV. A. 181 (ORDER I, SUBORDER I.) Melting-point (C.°). HYDROCARBONS, ETC.-Colorless and Solid. 246 2, 3-Dimethylanthracene, Me2.C14Hs.-Lft. w. blue-green fluorescence. 250 Chrysene, ClgH12.-Scales w. red-violet fluorescence.-V. d. s. h. ale.; V. d. s. eth. or CS2.-The picrate fr. bz. sol. of components cryst. in long red ndl., m. p. 273°; it is not stable in ale. sol.-CrO3 oxid. to chrysoquinone, which dis- solves in cone. H2SO4 w. deep-blue color. 253 i, 2-(/?)-Dinaphthylethane, (C10H7)2.C2H4.-Pearly tbl., d. s. h. ale.-Solutions fluoresce blue-violet. 254-5 Hydroxylepidene, C28H22O2.-S. 100 pt. h. glacial Ac; s. after long boiling in ale., then melting at 260°-l°; i. eth. or alkalies.-Said not to give a phenylhydra- zone or oxime. (Position in classification open to question.)-W. cone. HC1 at 130°-40° gives lepidene. 268 Carbopetrocene, C24Hg.-Lft. or ndl. i. c. ale. or eth.; s. CS2 or h. bz.--Gives orange-colored picrates. abt. 280d. Tetramethylanthracene, ClgHls. 300 Bianthranyl, C28Hlg.-Lft. fr. toluene.-Convert into dinitro-compound, m. p. 337° d. (B. 20, 2433). 307-8 Benzerythrene, C24H18(?).-Lft. fr. bz.-Alm. i. ale.; v. d. s. c. bz.-Dissolves w. green color in cone. H2SO4. 315 Tetraphenylethylene Dioxide, C26H16O2.-Sbl.-Ndl. fr. bz., i. ale.; s. cone. H2SO4 w. yellow color.-Adds Br2.-Boiled w. dil. HNO3 gives xanthone.- Sols, show bluish-green fluorescence. 364c. Picene, C22O]4.-B. p. 518°-20°.-Colorless lft. w. blue fluorescence.-D. s. h. bz. or CHC13; s. cone. H2SO4 w. green color.-Oxid. by CrO3 in Ac sol. to a quinone. Sol. in CHC13 gives with Br a comp., m p. 294°. a. 360 Truxene, C18H,2.-Tbl. fr. h. xylene.-Alm. i. most solvents.-CrO3 mixture gives a deep yellow i. quinone. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER 1} GENUS IX, HYDROCARBONS. DIVISION B, SECTION 1,-LIQUID HYDROCARBONS WITH SPECIFIC GRAVITY LESS THAN 0*85 AT 20°/4° THAT DO NOT GIVE TESTS 901 TO 903 IN THE COLD. Boiling-point (C.°). Specific Gravity. HYDROCARBONS.-Colorless Liquids with Specific Gravity less than 0-85 at 20°/4° that do not give Tests 901 to 903. -153 Methane, CH4. -86 0-446(0) Ethane, C2H6. -38-9 0-535(0) Propane, Me.CH2.Me. abt. 0 0-603(0) Trimethylmethane, Me3.CH. + 1 0-60(0) Butane, C4H10.-S. in IS vol. c. ale. 9-5 Tetramethylmethane, Me4.C.-M. p. -20°. 31 0-62813'7/4 2-Methylbutane, Me2.CH.CH2.Me. 37 0-634(15) Pentane, CSH12. 39-42 Methylcyclobutane, Me.C4H7.-Does not add HI cold. 49-7 0-6492% Trimethyl-ethyl-methane, Me3.C.Et. 50-1 O-7512o-5/4 Cyclopentane, CSH1O.-Br substitutes, but only at a high tem- perature.-Oxid. by HNO3 gives glutaric ac., etc. 58 0-668(17-5) Diisopropyl, Me2.CH.CH.Me2. 62 0-677(0) 2-Methylpentane, Me.(CH2)2.CH.Me2. 64 0-67720'5/4 Methyldiethylmethane, Me.(Et2).CH. 69 0-658(20-9) f Hexane, CBH14. f No evidence whatever of chem. action in Tests 901-903. 71-2 0-75021/4 Methylcyclopentane, Me.C6H9.-Not easily attacked by warm HNO3 + H2SO4.-Fuming HNO3 oxid. to formic, acetic, and glutaric acids. 80-8 0-7902% Cyclohexane (Hexanaphthene), C0H12.-M. p. 4-7°.-"Not at- tacked by cold mixture of equal vol. cone. H2SO4 and fuming HN03." ''Attacked by Br at 100°-110°" 86-7 0-711(0) Dimethyldiethylmethane, Me2. C. Et2. 90-3c. 0-682(17-5) 2-Methylhexane, Me2.CH.(CH2)3.Me. 91 0-690(20) 3-Methylhexane, Me.CH(Et).(CH2),.Me. 94 0 7542% i, 3-Dimethylcyclopentane, Me2.C5Hs. 95-8 0-689(27) Triethylmethane, Et3.CH. 98-4 0-689(14-9) Heptane, C7H16. 101-2 0-769(20/4) Hexahydrotoluene (Heptanaphthene), Me.C6Hn.-"Not at- tacked by c. nitro-sulphuric " ac. W. Br and AlBr3 gives pentabromtoluene, m. p. 282°, 108 0-711% 2, 5-Dimethylhexane, Me2.CH.CH,.CH2.CH.Me2. 118-9 0-759(2%) Hexahydro-m-xylene (Octonaphthene), Me2.CGH10.-Cf. p. 186, Section 2. 118 (th. i.) 0-809(20) Cycloheptane, C7H14.-Heated w. Br in sealed tube gives penta- bromtoluene. 120-5-21 0-769(2%) Hexahydro-p-xylene, Me2.CfiH10.-Cf. p. 186, Section 2. 182 GENUS IX, DIV. B, SECT. 1. 183 (ORDER I, SUBORDER I.) Boiling-point (C.°). Specific Gravity. HYDROCARBONS.-Colorless Liquids with Specific Gravity less than 0-85-at 20°/4° that do not give Tests 901 to 903. 124 Methylethylcyclopentane, Me.C5H8.Et. 125-5c. 0-719% t Octane, CSH]S. j- No evidence whatever of chem. action in Tests 901-903! 129-5-31-5 0-725(24-7) /9-Nonane, C9H20. 135-6 0-767(2%) Hexahydropseudocumene (Nonaphthene), Me3.C6H9(i, 3, 4). 135-8 Mesitylenehexahydride, Me3.C0H9(i, 3, 5). 135-7 0-742(12-4) a-Nonane, C9H,0. 147-50 0-787(20) Hexahydrocumene, Pr.C6Hn. 149-7c. 0-7182% Nonasne, C9H20.-M. p. -51°. 159-5 0 - 7368'74 f 2, 7-Dimethyloctane, Me2.CH(CH2)4.CH.Me2.-S. in 12 pt. c. glacial Ac. 159-62 0-746(22) 3, 6-Dimethyloctane, Et.CHMe.(CH2)2.CH(Me)Et.-Opt. active. 160-62 0-783(18) Dekanaphthene, C^H^. (Fr. petroleum.) 160-62 0-7882% n-Terpenetetrahydride, CloH2o.-"Not attacked by cone. H2SO4. With fuming H2SO4 heat is evolved, but the hydrocarbon is apparently not changed." 164 O-79319/o ^-Terpenetetrahydride, C^H^.-"Br substitutes when hot.-- Nitro-sulphuric ac. gives no cryst. nitro product." abt. 170 0-80(15) Hexahydro-p-cymene (" Terpane," " Terpilenehydride "), C10H20. -' ' Is not attacked by cold fuming HN03, fuming H2SO4, or Br." 173c. 0-730(20) Decane, C10H23.-M. p. - 30°-32°. 173-80 O-837(19/o) Naphthalenedecahydride, C10H18. abt. 190 abt. 0-805(20) Undekanaphthene, CUH22. (Fr. petroleum.) 194-5c. 0-7412% Undecane, CnH24.-M. p. -26-5°. 197 0-801(20) Dodekanaphthene, C]2H24. (Fr. petroleum.) 208-10 0-813(20) Tridekanaphthene, C13H2G. (Fr. petroleum.) 214-5c. 0-7512% Dodecane, CJ2H26.-M. p. -12°. 234 0-7572% Tridecane, C13H28.-M. p. -6-2°. 240-46 0-819(17) Tetradekanaphthene, CHH2b. (Fr. petroleum.) 246-8 0-829(17) Pentadekanaphthene, C15H3O. (Fr. petroleum.) 252-5c. 0-7652% Tetradecane, ChH3 .-M. p. +5-5°. 268c. 0-792(14) 7, 8-Dimethyltetradecane, C10H34.-Still liq. at -30°. 270-5c. 0-7692% Pentadecane, C16H32.-M. p. 10° 287-5c. 0-775'% Hexadecane, C16H34.-M. p. 18°. 303 0-7772% Heptadecane, C17H36.-Does not give Test 901-3. 317c. 0-77728/, Octadecane, C18Hs8.-M. p. 28°.-Does not give Test 901-3. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I]. GENUS IX, HYDROCARBONS. DIVISION B, SECTION 2-LIQUID HYDROCARBONS AND LIQUID ALIPHATIC ETHERS WITH SPECIFIC GRAVITY LESS THAN 0-85 AT 20%° THAT ARE ATTACKED OR DISSOLVED EITHER IN TEST 901, 902, OR 903. Boiling-point (0.°)- Specific Gravity. HYDROCARBONS, ETC. - Colorless Liquids with Specific Gravity less than 0-85 at 20°/4° that are attacked or dis- solved either in Test 901, 902, or 903. -102-7 0-610 Ethylene, CH2:CH2.-f Easily absorbed by liq. Br, giving C2H4Br2, b. p. 130°, m. p. +9-5°. -85 0-451(0) Acetylene, CH - CH.-V. d. s. aq.-f Apply Test 906 w. ammon. CuCl sol.! (Dull-red ppt.)-Absorbed in Br gives liq. tetra- bromide, b. p. 124°-6° (15 min.). -50-2 Propylene, Me.CH: CH2.-f The gas is freely absorbed by c. cone. H2SO4 or liq. Br.-Dist. of tne H2SO4 sol. largely diluted w. aq. gives isopropyl ale. (cf. Test 818).-B. p. of dibromide 141-5° c.! abt. -35 Cyclopropane,(CH2)3.-Absorbed slowly by cone. H2SO. or Br. -B. p. of dibromide 165°; G. 1-92317'%. + 1 Butadiene(i, 3), CH2:CH.CH:CH2. 1-5 0-635(13-5) cis-Butene(2), MeCH:MeCH.-B. p. of dibromide 158°.-Not absorbed by cone. H2SO4 +J vol. aq. 2-5 trans-Butene(2), Me.CH :HC.Me.-M. p. of dibromide 161°. 4-5 0-691(20) Methylcyclopropane, Me.C3H5. 14-5 0-65(-20) Caoutchene, C4H0.-M. p. -10°. 18 Ethylacetylene, Et.C • CH.-Gives Test 906 w. ammon. CuCl.- Bromide, C4H6Br4, cryst. solid. 18-19 Butadiene(i, 2), CH2:C:CH.Me.-Odor like garlic. 21-2 Isopropylethylene, Me2CH.CH: CH2.-I. at 0° in 2 vols. cone. H2SO4 and 1 vol. aq. 21 0-6602% 1, r-Dimethylcyclopropane, Me2C.(CH3)2.-Easily attacked by Br, but "rather stable toward 1% KMnO4."-Soluble at 0° in 2 vols. cone. H2SO4 and 1 vol. aq. 28 Butine(2), MeC -CMe.-Strong odor.-B p. of dibromide 147°-8°. -Shaking w. cone. HC1 polymerizes to hexamethylbenzene. 28-9 0-685(0) Isopropylacetylene, Me2.CH.C: CH.-Gives Test 906 w. ammon. CuCl. 31-2 0-670(0) uns.-Methylethylethylene, MeCEt: CH2. 35-8 0-691% Isoprene, CH,: CH.CMe: CH2.-Very unstable.-Treated w cone. HC1 and distilled w steam leaves rubber-like mass ! 36-5 s-Methylethylethylene, MeCH:CHEt.-HI gives methylpropyl- carbinol, b. p. 145° 37-1 0-685% Trimethylethylene, Me,C:CHMe.-Polymerized by cone. H,SO, ■ - S. in 2 vol H2SO4 + 1 vol. aq. * 38-9 3, 3-Dimethylbutine(i), Me3C.C: CH. 39-40 Propylethylene, PrCH: CH2. 40-5-41-5 0-6942% 2-Methylbutadiene(2, 3), Me2.C:C:CH2. 184 GENUS IX, DIV. B, SECT. 2. 185 (ORDER I, SUBORDER I.) Boiling-point Specific Gravity. HYDROCARBONS, ETC. - Colorless Liquids with Specific Gravity less .than 0-85 at 20°/4° that are attacked or dis- solved either in Test 901, 902, or 903. 42 Piperylene, CH2:CH.CH2.CH:CH2.-The tetrabromide cryst. fr. ale in pearly ndl., m. p. 114-5°. 42-5 0-80519/4 Cyclopentadiene(i, 3), C5H6.-Cone. H2SO4 or HN03 attacks violently.-Reduces ammon. AgNO3 sol.-Polymerizes easily to dicyclopentadiene, m. p. 32-9°. 45 Cyclopentene, C5Hg. 48-9 Propylacetylene, PrC -CH.-Gives Test 906 w. ammon. CuCl and AgNO3. 50 Valylene, C5H6.-Odor of garlic.-Test 906 gives yellow ppt.- Br gives cryst. hexabromide. 55-5-6 Valerylene, CSHS.-Test 906 gives no ppt.-Heated w. dil. H2SO4 gives methyl propyl ketone. 59-5c. 0-690(20-7) Diallyl, (CH2: CH.CH2)2.-Odor pungent.-H2SO4 attacks w. violence.-Br gives cryst. tetrabromide, m. p. 63°. 60 Pirylene, C5H6.-Peculiar odor.-Test 906 gives no ppt. 65-7 0-687(19) Dimethylethylethylene, Me2C:CHEt.-Gives iodide w. HI, b. p. 142°. 68 • 0-670(0) s-Methylpropylethylene, Pr.CH: CH.Me.-S. in 3 vol. c. H2SO4 + 1 vol. aq.; the sol. is ppt'd by aq. 68-70 Butylethylene, Bu.CH:CH2. 69-71 0-785(20) i-Methylcyclopentene(2), Me.CsH7.-Oxid. by KMnO4 gives a~ methylglutaric ac. abt. 70 Butylacetylene, BuC : CH.-Gives Test 906. 70 0-858(18-2) Diallylene, C3H5.CH2.C: CH (?).-Test 906 gives yellow-green ppt.-Ale. AgNO3 gives ppt. of Ag compound. 69-5-71 0-698(19) Methylethylpropylene, Me(Et)C: CH.Me. 70-1 0-731(0) 3-Methylpentadiene(i, 2), Et.C.Me:C:CH2. 70-3 0-763(0) Methyl Butyl Eth., Me.O.Bu.-See Test 907! 71-2 0-7502'/4 Methylcyclopentane, C6H12.-Cf. IX, B, 1. 71-2-5 0-732(0) 2-Methylpentine(3), Me2.CH.C-C.Me.-Adds HBr. 70-74 Methyl Isocrotyl Eth., Me2.C: CH.O.Me.-Dec by 2-3 hrs. heat- ing at 140° w. 1% H2SO4 giving methyl alcohol and isobutyl aldehyde. 72 0-7762% i-Methylcyclopentene(i), Me.C5H7. 72-4 0-714(12) Hexadiene(i, 3), Et.CH:CH.CH:CH2. 72-4 /LEthyldivinyl, CH2: CEt.CH.CH2. 73 0-712(0) Tetramethylethylene, Me2.C:C.Me2.-S in 2 vols. cone. H2SO4 + 1 vol. aq.-Acetone is among products of oxidation by c. dil. CrO3 sol. (cf. Tests 702 and 711). 75-80 0-719(21) 2, 3- Dimethyipentene(2), Me2.C: C(Me)Et. 77-8 0-730(0) 2-Methylpentadiene(2, 3), Me2.C: C: CH.Me.-W. Br in CS2 gives C6H6Br3 78-80 0-751 Ethyl Isobutyl Eth., Et.O.C4H9.-See Test 907! 78-80 2, 2, 3-Trimethylbutene(3), Me3.C.CMe:CH2.-Odor of camphor and turpentine 78-83 0-825(0) Hexadiine(i, 4), Me.C: C.CH,.C • CH. - Polymerizes readily - Gives Test 906. 82-5 1, 2-Dihydrobenzene, CcHs. 83-4 0-714(0) 2, 5-Dimethylpentene(2), Me,.C : CH.CH.Me2.-Adds HI easily. 83-4 0-738(13) Methylpropylacetylene, MeC: CPr.-CrO3 mixture oxid to acetic and butyric ac. (cf Test 702) - Br reacts violently.-Pro- longed shaking w- 5 pt cone H2SO4 + 1 pt. aq. gives methyl butyl ketone. 85-6 1, 4-Dihvd"nbenzene, C,HS. 186 GENUS IX, DIV. B, SECT. 2. (ORDER I, SUBORDER I.) Boiling-point (C.°). Specific Gravity. HYDROCARBONS, ETC. - Colorless Liquids with Specific Gravity less than 0-85 at 20°/4° that are attacked or dis- solved either in Test 901, 902, or 903. 86-7 0-819(0) Hexadiine(i, 5), CH:C.CH2.CH2.C:'CH.-Ammon. CuCl in Test 906 gives greenish-yellow ppt.-Ale. AgNO3 gives white ppt. -Adds Br4 violently. 92 0•752(20) Ethyl Butyl Eth., Et.O.Bu.-See Test 907! 92-4 Ethyl Isocrotyl Eth., Me2.C: CH.O.Et.-Unsat.-Dec. by heating w. 1% H2SO4 giving isobutyric aid. and C2H5OH. 96-8 0-748% 3-Ethylpentadiene(i, 2), Et2.C:C:CH2. 97-8 0-72515/4 3-Ethylpentene(2), Et,C: CHMe. 98 Heptene(2), Me.(CH2)3.CH:CHMe.-CrO3 mixture oxid. to va- lerianic and acetic acids. (Cf. Test 702.)-In the cold adds fuming HC1. 98-9 0-703(19-5) Heptene(i), Me.(CH2)4.CH: CH2.-Does not unite w. cold fum- ing HC1. 102 0-751(0) CEnanthylidene, Me.(CH2)4.C-CH.-Ammon. CuCl (Test 906) gives yellow ppt.; ammon. AgNO3 also gives ppt.-Gives a liq. dibromide. 102-5c. 0-715(25) Diisobutylene, Me2.C: CH.CMe3.-CrO3 mixture, cold, oxid. to acetone, etc. (cf. Test 702).-Adds HC1 or HI at 100°. 103-4 0-803(20) Heptine, C7H,2.-Odor peculiar.-Absorbs O.-HN03 attacks violently.-H2SO4 polymerizes to diheptine, b. p. 247°.- Adds Br.-Does not give Test 906.-(Fr. dist. of rosin.) 105 0-814% Toluenetetrahydride, Me.C0Hs.-Nitrated by nitrosulphuric ac. 105-6 0-760(0) Ethylpropylacetylene, PrCiCEt.-H2SO4 gives butyrone. 105-8 Dihydrotoluene, Me.C(iH7. 108-5 0-796(15) 1, 1, 2-Trimethylcyclopentene, CSH14.-Faint odor like camphor and turpentine. 111-3 0-763(0) Methylbutylacetylene, Me.C:C.C4H9.-Ale. AgNO3 gives no ppt. 111-4 Ethyl Valeryl Eth., Me.C(Et) : CH.O.Et.-Heated w. 1% H2SO4 at 130°-40° gives methylethylacetaldehyde and C2H5OH. 112 0-764(18) Ethyl Isoamyl Eth., Et.O.C5Hn.-See Test 907 ! 113-4 2, 5-Dimethylhexadiene(i, 5), CH2: C(Me).CH2.CH2.C(Me) :CH2. 114-5 0-841(0) Cycloheptene, C7H12. 115 Heptone, C7H10.-Gives oily hexabromide, C7H10Br6. 115-5 s-Dimethyldiethylethylene, Me2C: CEt2. 116-8 Hexenyl Eth., (C8Hn)2.O.-Oil w. very pungent odor; i. aq. 116-8 0-741(22) 2-Methylheptadiene (4, 6), CSH14. 117-1 0-777(0) Propyl Butyl Eth., Pr.O.Bu.-See Test 907! 116-20 s-Diisopropylethylene, Pr.CH: CH.Pr. 117-9 0ctadiene(2, 6), CSH14. 118-9 0-759(2%) Hexahydro-m-xylene, Me2.CGH10.-Hot nitrosulphuric ac. gives trinitro-m-xylene, m. p 172°-4° 120.5-21 0-7692% Hexahydro-p-xylene, CcH10(CH3)2.-E. s. on warming in mix. of HNO, and H2SO4 120 Allyl Isoamyl Eth., C3H5.d.C5Hu. 120-1 0-756(21) sec.-Butyl Eth., (Me(Et).CH)5O. 122-2-5 0-762(15) Isobutyl Eth., Bu2.0.-See Test 907! 122-3 0-760(14) 4-Ethylhexadiene(i, 4), CH2:CH.CH2.CEt:CHMe.-Absorbs O fr. air slowly-CrO3 mixture oxid. to Ac and propionic ac. (Tests 905-2 and 311) 123-5 0-799(0) Glycol Diethyl Eth., C2H4.(OEt)2.-See Test 907! 124-6 0-722(17) Octene(x), C6H13.CH:CH2. 131-2 0-770(0) Octine(i), C6H13.C:CH. GENUS IX, DIV. B, SECT. 2. 187 (ORDER I, SUBORDER I.) Boiling-point (C.°). Specific Gravity. HYDROCARBONS, ETC. - Colorless Liquids with Specific Gravity less. than 0-85 at 20°/4° that are attacked or dis- solved either in Test 901, 902, or 903. 132-4 0-773(18) 2, 5-Dimethylhexadiene(2, 4), Me2C: CH.CH: CMe2.-M. p. + 6°. -Very unstable, absorbing O rapidly fr. the air.-Polymer- izes on keeping.-Gives liquid tetrabromide. 132-4 0-828(20) m-Dihydroxylene, Me2.C6H6.-Cone. HNO3gives nitro-m-xylene- 133-4 0ctine(2), Me.(CH2)4.C:C.Me.-The tetrabromide is oily. 133-5 Octone, CsH]2.-Absorbs O fr. air.-Br or HC1 gives a resin. 134-5 o-Dihydroxylene, Me2.CcHn.-Odor like camphor.-Quickly oxid. in air to a resin.-Adds HC1 in eth. sol. 134-5-5-5 p-Dihydroxylene, Me2.CflH6.-Odor like turpentine.-HBr gives cryst. addition product. 134-7 Ethyl Hexyl Eth., Et.O.C0H13.-See Test 907 ! abt. 135 0-803(20) Campholene, C9H16.-Odor like turpentine.-Absorbs Br2 in dil CHC13 sol. 138 0-798(22) Trimethylcyclohexene, C0H16. 139-5c. 0-7432% Nonylene, C0Hlg.-(Several isomers boiling between 140° and 150°.) 141 0-769(20) Butyl Eth., Bu,0.-See Test 907 ! 140-1 0-83525/2s Trimethyleneglycol Diethyl Eth., (CH2)3.(OEt)2.-Fruity odor. -I. aq. 141-5 2-Methyloctene(i), Me.C(C6H]3): CH2.-Odor aromatic. 142-3 0-757(20) 2, 6-Dimethylheptadiene(2, 6), C9H16. 145 0-831(15) Octylene Oxide, C]SH1GO. 145-50 Decone, CIOH,0.-Odor like turpentine.-Absorbs O rapidly. 147-5-9-5 Propylhexamethylene, Pr.C(iHn. 149-8 0-795(0) Methyl Heptyl Eth., Me.O.C7H15.-See Test 907! 150 Decenylene and Rutylene, C1OH1S. 150-2 1, 2-Methylethylcyclohexane, Me.C(H,0.Et. 153 1, 2-Dimethylcycloheptane, Me2.C7H12. 154-6 0-772(20) Diamylene, C,0H20. 155-7 Nonone (Carpene), C9H14.-Oxid. to a resin in the air. 156 0-86(20) Pinene (Terebenthene), C10H10.-Cf. (IX, B, 3). 158 0-7662I/n 4-Propyl-3, 6-heptadiene, C,0Hls.-Unstable oily tetrabromide. 166 0-795(0) Ethyl Heptyl Eth., Et.O.C7H15.-Cf. Test 907! 167-4c. 0-8062% Menthene, C1OH.S.-Opt. act-Easily oxid. by shaking with c 1% permanganate sol.-(Descriptions conflicting.) 167-70 3, 6-Dimethyloctadiene(3, 5), C10H18. 171-2 0-856(10) Phellandrene, C,OH1C.-Cf (IX. B. 3). 173 0-801(0} Methyl Octyl Eth., Me.0.CsH17.-Cf Test 907! 173c. 0 781(15) t Isoamyl Eth., (CBHU)2.O.-Cf Test 907! 175 (th. i) 0 853(25) Cymene, C,0H14. 176-7 0-851(16) Sylvestrene, C10H16.-(In Swedish turpentine oil.) 176 5 0-853'% [+ or - ] Limonene, (Hesperidene, Citrene, Carvene), C10H16.- ([ + ] variety in lemon oil, etc )-Cf IX, B, 3. 173-80 0-8371!% Naphthalenedecahydride, C10H18.-Hot fuming HNO3 attacks violently - 177-8 0-774(0) Triisobutylene, Me2.C:C.(CMe3)2.-Oxid. slowly in air; Br acts w. violence. 180 Diallyl Eth., (C6Hn)2.O. 179-82 Terpinene, C10H16.-Cf. IX, B, 3 181-2 0-844(20) i-Limonene, C10H16.-Odor like oil of lemons-Cf. IX, B, 3. 183-5c. Terpinolene, C10HI6.-Cf IX, B, 3. 188 GENUS IX, DIV. B, SECT. 2. (ORDER I, SUBORDER I.) Boiling-point (C.°). Specific Gravity. HYDROCARBONS, ETC. - Colorless Liquids with Gravity less than 0-85 at 20°/4° that are attacked solved either in Test 901, 902, or 903. Specific or dis- 189-2 0-801(0) Ethyl Octyl Eth., Et.O.CsH17.-Cf. Test 907 ! abt. 195 abt. 0 • 8 Undecylene, CnH22. 196-8c. 0-8392% Dodecon, C12H20.-Easily oxid.-Action of Br violent. abt. 210-15 213-215 0-785(20) Undecine, CuH20.-Ammon. AgNO3 gives white ppt. Duodecylene, C12H24.-(Er. Canadian petroleum.) 233c. 0-845(0) Tridecylene, C13H26.-(Fr. Burmese petroleum.) 245-8 0-814 Triamylene, C15H30.-Turpentine odor.-Adds Br2 cold. 261 0-815(0) Heptyl Eth., (C7H15)2.O.-Cf. Test 907! 274 0-78415/, Cetene, C16H32.-Br gives dibromide.-M. p. 4°. 280-5 0-8042% Cetylene, C16H30.-M. p. 20°. 291-7 0-820(0) Octyl Eth., (C8H17)2.O.-Cf. Test 907! 314-5 0-818(24) Eicosylene, C20H38. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I]. GENUS IX, HYDROCARBONS, ETC. DIVISION B, SECTION 3-LIQUID HYDROCARBONS AND ETHERS WITH SPECIFIC GRAVITY GREATER THAN 0-85 AT 20°/4°. Boiling-point (C.°). Specific Gravity. HYDROCARBONS, ETC. - Colorless Liquids with Specific Gravity greater than 0-85 at 20°/4°. 31-5 0-944(15) Furfurane, C4H4O.-Peculiar odor.-I. aq.; e. s. ale. or eth.- Colors a pine splinter moistened w. cone. HC1 emerald green! -Cone. HC1 attacks vigorously giving a brown resinous body. 67 0-950(15) Hydrofurfurane, C4Hfi0 (?).-Adds Br2 cold.-Not attacked by Na, KOH, or acetic anhyd.-PC15 gives furfurane. 80-36 0-8792% t Benzene, C6H6.-M. p. 5-42°.-Identify by Test 913! 93 0-90317'7/, 2, 5(a)-Dimethylfurfurane, Me2.C4H2O.-I. aq.; misc. w. ale.- Cone. HC1 changes to a resinous body.-Dil. HC1 at 170° gives acetonylacetone. 111 0-8662% f Toluene, Me.C6H5.-Identify by Test 918! 114 0-913% Tropilidene, C7Hg.-CrO3 mixture (cf. Test 905-2) gives benzoic ac. (cf. Test 312) and benzaldehyde.-Br gives an oily di- bromide. 120-1 0-893% Cycloheptadiene, C7H10.-Odor garlicky. 136-5 (th. i.) 0-883(0) f Ethylbenzene, Et.C6H5.-f Oxidize 1 grm. to benzoic ac. by Test 905-1! 138 0-880(0) t p-Xylene, Me2.C6H4.-M. p. 15°.-Identify by Test 920 ! 139-2 0-8662% f m-Xylene, Me2.C0H4.-M. p. -54°.-Identify by Test 919 ! 141-6 (th. i.) 0-9302% Phenylacetylene, PhCiCH.-Test 906 w. ammon. CuCl gives a yellow flocculent ppt. fr. ale. sol., which when dry detonates on heating.-HNO3 or cone. H2SO4 resinifies.-f Heated w. dil. H2SO4 gives acetophenone (Test 712). 142c. 0-893(0) f o-Xylene, Me2.C0H4.-M. p. -28°.-Identify by Test 921! 143-5 0-890(0) Crotonyl Eth., (Me.CH: CH.CH2)2.O. 146 0-925(0) Styrene, PhCH:CH2.-I. aq.; misc. with ale. or eth.-Slowly polymerizes to glassy mass;-cone. H2SO4 polymerizes im- mediately.-Gives Test 903!-Odor aromatic and rather characteristic. 152-5-3 0-859(25) Cumene, Ph.CH.Me,.-Test 905-1 gives benzoic ac. (Test 312). 155 Benzylethylene, Ph.CH2.CH: CH2.-Unsat. (cf. Test 901).-Test 905-1 gives benzoic ac. (Test 312). 155 0-9882% Anisol, Me.O.Ph.-Aromatic odor!-I. aq.-W. cone.HI at 130°- 40° gives phenol and methyl iodide. 156 0-86(20) Pinene (Terebenthene), C10Hie.-(The chief constituent of f oil of turpentine). The American or English, fr. Finns Aus- tralis, is [ + ]; the French, fr. Pinus maritima, is [-].-Odor penetrating and characteristic.-Gives Test 901.-Fum- ing HNO3 attacks w. almost explosive violence.-Well cooled and saturated w. dry HC1 gas, gives hydrochloride (C1?H16.HC1), stable volatile cryst. (m. p. 125°), fr. dil. ale., and of camphor-like odor ("artificial camphor"). 158 0-8709'% Propylbenzene, Pr.C0H5.-Test 905 gives benzoic ac. 158-9 0-873(16) o-Methylethylbenzene, Me.CGH4.Et.-Oxid. by Test 905-3 gives phthalic ac. 189 190 GENUS IX, DIV. B, SECT. 3. (ORDER I, SUBORDER I.) Boiling-point Specific Gravity. HYDROCARBONS, ETC.-Colorless Liquids with Specific Grav- ity greater than 0-85 at 20°/4°. 158-9 0-869(20) m-Methylethylbenzene, Me.CGH4.Et.-Test 905-1 gives iso- phthalic ac. 160-2 0-788 2% a-Terpenetetrahydride, C10H20.-(Cf. IX, B, 1.) 162 0-865(21) p-Methylethylbenzene, Me.C0H4.Et.-Test 905-1 gives tere- phthalic ac. (Test 318-3). 164 O-793I9/o /LTerpenetetrahydride, CloH2o.-(Cf. IX, B, 1.) 164-5 0-8699'8/4 f Mesitylene, C6H3.Me3(i: 3:5).-Identify by Test 914! 167-8 0-938(18) Methyl Benzyl Eth., C7H7.O.Me. 168-8-5 tert.-Butylbenzene, Ph.C.Me3.-Oxidation (cf. Test 905) gives benzoic ac. 169-8c. 0-8792% f Pseudocumene, C6H3.Me3(i, 2, 4).-For coloration w. A1C13 cf. Test 904.-Identify by Test 917 ! 170-72 0-873(16) sec.-Butylbenzene, Me.CHEt.CGH5.-Test 905 gives benzoic ac. 171-1-5 0-858(15) Isobutylbenzene, Ph.CH2.CHMe2.-Test 905 gives benzoic ac. 171-3 0-996(0) o-Cresyl Methyl Eth., Me.O.C7H7. 171-2 0-856(10) [+] Phellandrene, C10H16.-(In fennel and other essential oils.)- I. ale.; s. eth.-Identify as nitrosite. (Cf. A, 246, 282; and 287, 374.) 170-5 p-Methylstyrene, Me.CGH4.CH: CH2.--Unsat. (cf. Test 901).- Test 905-1 gives terephthalic ac. (Test 318). 172 0-982(0) Phenetol, Et.O.Ph.-Odor aromatic.-I. aq.-At 400° gives phenol (Test 414) and ethylene. 173 0-846(23) Amenylbenzene, Ph.CH(Et).CH: CH,.-Gives Test 901.-Con- tinued boiling gives diamenylbenzene, b. p. 208°-12°.-Test 905 gives benzoic ac. (Test 312). 174-5 0-91815/15 Allylbenzene, PhCH: CHMe.-Unsat. (cf. 901).-Dibromide, ndl. d. s. c. ale., m. p. 66-5°. 170-80 Diamylene Oxide, C10H20O.-Reduces ammon. AgNO3 sol. 175 (th. i.) 0-853(25) Cymene, p-Me.CGH4.CHMe2.-Test 905-2 gives terephthalic ac. (Test 318). 175 0•987(0) p-Cresyl Methyl Eth., Me.O.C7H7. 175-5-5 1, 2, 3-Trimethylbenzene, CGH3.Me3. 175-6 0-862(20) m-Methylisopropylbenzene, Me.CGH4.Pr.-Br substitutes readily cold.-Test 905-2 gives isophthalic ac. (Test 318). 176c. 0-957(15) 1, 2-Hydrindene, C6H4: C2H4: CH,.-Br substitutes. - Sulpho- nated by cold cone. H2SO4. M. p. sulphonamide 91°-2°. 176 0-927(20) f Eucalyptol (Cineol), C]0HlsO. - Agreeable odor like car- damon and camphor! - M. p. - l°-3°. - Unsat.; dibro- mide very unstable.-Dry HC1 conducted into mixture of equal vols. eucalyptol and Igr. gives cryst. ppt. of unstable (C10H!SO)2.HCl.-Shaken w. saturated sol. of I in saturated KI sol. gives ppt. of minute cryst. w. greenish lustre. 176-5 O-8531o/4 [+ or -] Limonene (Hesperidene, Citrene, Carvene), C]0H16. -([ + ] in oil of lemons.) - General behavior _ in Test 901-3 as with pinene.-Dilute w. 4 vol. glac. Ac , cool well, and drop in Br as long as color disappears. Allow to stand until crystals separate. Drain, and then recryst fr. acetic ether. The tetrabromide formed melts at 104 • 5°. (A, 239, 3)! GENUS IX, DIV. B, SECT. 3. 191 (ORDER I, SUBORDER I.) Boiling-point (C°)- Specific Gravity. HYDROCARBONS, ETC. - Colorless Liquids with Specific Gravity greater than 0-85 at 20°/4°. 176-7 0-851(16) [+] Sylvestrene, C1QH10.-(In Russian and Swedish turpentine oils.)-The sol. in acetic anhyd. is colored intensely blue by a drop of cone. H2SO4 (a reac. that may be interfered with by the presence of some other terpenes).-Br in Ac sol. (pro- cedure as w. limonene above) gives tetrabromide, m. p. 135°-6°; but it is said to be preferable to identify as dihy- drochloride, m. p. 72° (cf. A, 230, 241; 239, 25), obtained by action of dry HC1 gas. 176-8 p-Butyltoluene, Bu.C6H4.Me.-Oxid.bydil HN03 (Test 905-3), giving p-toluic ac. 176-8 0-901(15-5) Phenylbutylene, Ph.C4H7.-Unsat. (cf. Test 901).-Test 905-1 gives benzoic ac. 178 0-873(21) Diethylphenylmethane, Ph.CH.Et2.-Test 905-1 gives benzoic ac. 180 0-864(15) Butylbenzene, C4H^.C6H5.-Test 905-1 gives benzoic ac. 180c. 1-040(15) i, 2-Indene, C9HS.-(In light coal-tar oils.)-Cone. H2SO4 gives brown resin.-Adds Br.-Forms picrate.-Dil. HNO3 gives phthalic ac. 179-82 Terpinene, C10H10.-(In cardamon and other essential oils.)- Opt. inactive.-Resinifies on keeping, or by action of cone. H2SO4.-Unlike pinene is completely destroyed in the cold (except a few brown flocks) by a mixture of 6 pt. Na2Cr2O7, 5 pt. H2SO4 + 30 pt. aq.-For identification as nitrosite, see A, 239, 36! 180-1 0-958 o-Cresyl Ethyl Eth., Et.O.C7H7. 181 (th. i.) Isobutenylbenzene, Ph.CH: CMe2.-Test 905-2 gives benzoic and acetic acids.-Br gives liq. bromide. 181-2 0-844(20) i-Limonene, C10H16.--(Syn.-Dipentene, diisoprene, cinene, caout- chin, etc.)-Odor lemon-like.-Absorbs O fr. the air.-Pre- pare the tetrabromide, m. p. 124°-5°, by the procedure given under + or - limonene on p. 190! 181-2 0-8602% m-Diethylbenzene, C8H4.Et2.-Oxid. by Test 905-1 gives iso- phthalic ac. (Test 318). 182-3 0-86218/4 p-Diethylbenzene, C8H4.Et2.-Test 905-1 gives terephthalic ac. 183-4 ' 0-878(20) i, 3, 4-Dimethylethylbenzene, Me2.C0H3.Et.-May be oxidized to xylic ac. 183-4 0-942(0) Pinol, C10H1GO.-Odor like that of eucalyptol!-Unsat.-Dis- solved in 2 vols. glacial Ac and treated w. Br2 gives stable dibromide which cryst. well fr. eth.-alc. w. m. p. 94°. 183-5c. Terpinolene, C10H1(i. 185 0-86618/4 o-Diethylbenzene, Et2.CGH4.-Test 905-1 gives some phthalic ac. 185 Ethyl Benzyl Eth., Et.O.C7H7.-Treatment w. P2O5 gives ethyl- ene and anthracene (Test 912). 185 0-861(20) i, 3, 5-Dimethylethylbenzene, Me2.C0H3.Et.-Test 905-2 gives mesitylenic ac. 185 ■ Phenylallylene, Ph.C'-C.Me.-Tetrabromide, lft.fr. ale., m. p.75°. 186-7 x'-Butenylbenzene, Ph.CH: CHEt.-Unsat. (cf. Test 901).-Test 905-1 gives benzoic ac. (Test 312). 186-8 m-Pseudobutyltoluene, Me3C.CGH4.Me.-Test 905-2 gives iso- phthalic ac. (Test 318). 185-90 Phenylcrotonylene, Ph.C4Hs.-Unsat. (cf. Test 901).-Test 905-1 gives benzoic ac. (Test 312). 185-90 0-89222/a Naphthaleneoctahydride, C10H16.-Odor like turpentine.-Ab- sorbs O fr. air. 189 0-966(0) p-Cresyl Ethyl Eth., C7H7.O.Et. 189-5-91 0-874(15) Dimethylethylphenylmethane, Me,(Et)(Ph).C.-Br substitution product is oily. 192 GENUS IX, DIV. B, SECT. 3. (ORDER I, SUBORDER I.) Boiling-point (C.°). Specific Gravity. HYDROCARBONS, ETC. - Colorless Liquids with Specific Gravity greater than 0-85 at 20°/4°. 190-2 i, 3-Ethylisopropylbenzene, Et.C0H4.Pr.-Test 905-1 gives iso- phthalic ac. (Test 318-2). 193 0-885(18) Isoamylbenzene, Ph.CsHn.-Slowly oxid. by Test 905-2 to ben- zoic ac. (Test 312).-Br in sunlight gives Br derivative, m. p. 128°-9°. 194-5 Isopropyl-m-xylene, Pr.C6H3.Me2. 195 m-Tolylbutylene, C7H7.C4H7.-Unsat. (cf. Test 901); the di- bromide is oily. 195-7 0-896% i, 2, 3, 5-Tetramethylbenzene, Me4.C6H2.-Test 905-1 gives only mellophanic ac., m. p. 238° d. 198-200 p-Tolylpropylene, C7H7.C3H5.-Unsat. (cf. Test 901). 199-200 0-879(20) (s), U 3, 5-Diethyltoluene, Et2.C0H3.Me.-Test 905-3 gives uvitic ac., m. p. 287°-8°. 201 0-860(22) Amylbenzene, C5Hn.CcH5.-Test 905-2 gives benzoic ac. (Test 312). 201-3 0-923(21) Ethylphenylacetylene, PhC • CEt.-Unsat. (cf. Test 901). Test 905-1 gives benzoic ac. (Test 312). 200-5 Ethylbutylbenzene, C12H18. 204 (th. i.) i, 2, 3, 4-Tetramethylbenzene, Me4.C0H2.-Large cryst., m. p. - 4°.-Test 905-3 gives prehnitic ac. (Ill, A, 1, m. p. 237°). 205 (th. i.) 0-981(12-5) Naphthalenetetrahydride, C10H12.-Feeble odor.-Test 905 gives phthalic ac.-Cone. HNO3 gives picric ac.-Oxid. on stand- ing in air.-Br gives unstable substitution product. abt. 205 (th. i.) O-93423/o Naphthalenehexahydride, C10H14.-Absorbs O fr. air.-HN03 or cold Br attacks w. violence.-Fuming H2SO4 sulphonates. 205-6 0-96827/, %Methylindene, C10H10.-Naphthalene odor.-Absorbs O fr. air. -Cone. H2SO4 or HC1 resinifies.-Forms very unstable pic- rate, m. p. 75°-6°. 205-6 1-086(15) Veratrol, o-C6H4.(OMe)2.-Solid at 15°.-Heated w. HI gives pyrocatechin and methyl iodide. 206-7 Propyl-p-xylene, Pr.CcH3.Me2. 206-10 s-Dimethylpropylbenzene, Me2.C6H3.Pr(3:5: i). - Test 905-3 gives mesitylenic ac. (Ill, A, 2, m. p. 166°). 208-8-5 Propyl-m-xylene, Pr.CeH3.Me2(4, 3, 1). 209 Propyl-o-xylene, Pr.C6H3.Me2(4, 2, 1). 211-13c. 0-871(0) p-Propylisopropylbenzene, Pr.C0H4.Pr.-Test 905-3 gives tere- phthalic ac. and propylbenzoic ac. 212 Naphthalenedihydride, C10H10.-Frozen at +15-5°.-Adds Br2 in the cold; m. p. of unstable dibromide 74°.-Fuming H2SO4 sulphonates. 213 0-864(9) p-Isoamyltoluene, Me.C6H4.C6Hn.-Test 905-2 gives terephthalic ac. (Test 318-3). 214-15 0-857(16) Isohexylbenzene, Ph.(CH2)3.CHMe2. 214-15 1-080% Dimethyl Resorcinyl Eth., m-(MeO)2.C0H4.-Vol. w. st. 216-2 0-953(0) Methyl Thymyl Eth., Me.O.C10H13. 214-18 s-Triethylbenzene, C6H3.Et3.-Test 905-2 gives trimesic ac. (Ill, A, 1, m. p. 345°-50°). 215-20 0-9202% Isoamyl Phenyl Eth., CfiHn.O.Ph. 220-5-1-5 p-Dipropylbenzene, Pr,.CKH4.-Test 905-3 gives p-propylbenzoic ac. (Ill, A, 2, m. p. 140°). 223-8 0-911(0) Benylene, C16H28.-Unsat. (cf. Test 901). 226-9 0-933(0) Ethyl Thymyl Eth., Et.O.C10H13.-At 360°-400° splits to thymol and ethylene. 229-30 0-890(15) Allylisopropylbenzene, Me.CH: CH.CcH4.C3H7.-Adds Br2 to form dibromide, v. s. h. ale., m. p. 59°. GENUS IX, DIV. B, SECT. 3. 193 (ORDER I, SUBORDER I.) Boiling-point (C.°). Specific Gravity. HYDROCARBONS, ETC.-Colorless Liquids with Specific Gravity greater than 0-85 at 20°/4°. 233 1-108(15°) Safrol, C8H3.(C3H5)(O2CH?)[i:(3, 4)].-Strong sassafras odor! M. p. after solidification by cold+ 11°; ND = 1-53836.- Quickly reduces a 1% neutral KMnO4 sol. upon shaking. Is violently attacked and completely carbonized in Test 907 with cone. H2SO4. 233c. 233 230-40 0-989(28) Anethol, Me.O.C9Hg.-Cf. IX, A, m. p. 21-6°. Heptylbenzene, C7H1S.CGH5.-(Several compounds isomeric w. this substance w. b. p.'s between 225°-48° have been de- scribed.) Diisobutylbenzene, (C4H9)2.C6H4. 240-2 (th. i.) 1-001(19) a-Methylnaphthalene, CnHI0.-Freezes at -22°.-Long boiling w. cone. HNO3 gives isonaphthoic acid, CUH8O2.-Picrate fr. ale. forms yellow ndl., m. p. 116°. 242 (th. i.) 244 250 (th. i.) /LMethylnaphthalene, CnH10.-M. p. 32-5°.-The picrate forms yellow ndl. w. m. p. 115°. Dimethyl Orcinyl Eth., (MeO)2.CGH3.Me.-Alm. i. aq. i, 2, 4, 5-Tetraethylbenzene, Et4.C6H2.-M. p. 13°.-Oxid. gives pyromellitic ac. (Ill, A, 1, m. p. 264°). 251 1-008(0) /?-Ethylnaphthalene, Et.C10H7.-The picrate cryst. fr. h. ale. in fine yellow ndl. w. m. p. 69°-71°. 258 si. d. 258-60 l-01810/w a-Ethylnaphthalene, Et.Cj0H7.-Forms a picrate, lemon-yellow ndl., m. p. 98°. Phenyltolyl, Ph.C7H7. 261-2 i-ooi274 Diphenylmethane, Ph2.CH2.-Ndl. m. p. 26°-7°.-Cf. Div. A of this genus. 261-3 0-849(15) Octylbenzene, CSH)7.C6H5.-M. p. -7°.-Test 905-2 gives ben- zoic ac. w. difficulty.-{Isomeric hydrocarbons exist w. b. p.'s between 230°-260°.) 262-4 1-020(12) i, 4-(a)Dimethylnaphthalene, Me2.C10H6. - Remains liq. at - 18°.-Picrate forms orange ndl., m. p. 139°; s. h. ale.; v. s. eth. 263-7 1-015(27) p-Phenyltolyl, Ph.CGH4.Me.-Freezes at -2°-3°. 265 0-990(0) /?-Propylnaphthalene, C10H7.Pr.-Picrate lemon-yellow ndl., m. p 89° 250-80 0-904-0-927 Sesquiterpenes, C^H^.-(Important constituents of many essen- tial oils, like oils of cedar, calamus, cubebs, patchouli, etc.) -D. s. ale.; somewhat viscous.-Give solid hydrochlorides when HC1 gas is passed into the cooled ethereal sol. 265 0-887(0) Diisoamylbenzene, (C5H1J)2.CGH4.-Liq. at -20°. 269c. l-096u/4 Methyl a-Naphthyl Eth., Me.O.C,0H7.-Gives red cryst. comp, w picric ac.-Split by cone. HC1 at 150°. 270-5 0-933(20) Phenanthreneperhydride, C14H24.-M. p. -3°.-Not attacked cold by fuming HN03, by H2SO4, or Br, and by CrO3 only w. difficulty. 272-7 1-031(0) m-Phenyltolyl, Ph.C7H7.-"Not attacked by KMnO4." 275 (th. i.) abt. 275 0-929(0) Cadinene, C15H24.-(A sesquiterpene present in cubeb, patchouli, and some other essential oils.)-D. s. ale.-Resinifies easily. -Gives a solid dihydrochloride, m. p. 117°-1_8°.-When slightly resinified and dissolved in much glacial Ac becomes green and then indigo-blue on addition of small successive portions of cone. H2SO4. o-o and o-p-Ditolyl, (Me.CGH4)2. 275-5 (th.i.) 0-997(17-5) m-Benzyltoluene, Ph.CH,.C7H7.-Much cone. HN03 at 90° gives nitro-compound, cryst. fr. h. glacial Ac, m. p. 141°. 277 (th. i.) 0-899(19) Pentaethylbenzene, CGH.Et5.-Dec. by fuming H2SO4 to tetra- ethyl- and hexaethyl-benzene. 194 GENUS IX, DIV. B, SECT. 3. (ORDER I, SUBORDER I.) Boiling-point (C.°). Specific Gravity. HYDROCARBONS, ETC.-Colorless Liquids with Specific Gravity greater than 0-85 at 20°/4°. 277 a-Diphenylethylene, C14H12.-CrO3 mixture oxid. to benzophe- none. (Unsat.-Br addition product unstable.) 277-90c. 0-996(0) «/?-Diphenylpropane, Me. CHPh. CH2. Ph. 280 /3-Isobutylnaphthalene, C4H9.C10H7.-The picrate forms yellow ndh, e. s. ale., m. p. 96°. 280-1 3-Bitolyl, C7H7.C7H .-CrO, oxid. to isophthalic ac. (cf. Tests 905-2 and 318). ' 281c. 1-075% Ethyl a-Naphthyl Eth., Et.O.C10H7. 281-2 Dimethyldiphenylmethane, Me2.C.Ph2. 283-4 1-043 m-Ethylbiphenyl, Et.CGH4.Ph.-CrO3 oxid. to m-phenylbenzoic ac. (Ill, A, 2, m. p. 160°). 286 0-98 p-Phenyltolylethane, Ph.C2H4.C7H7.-M. p. 27°. 286 Ditolylmethane, CH2.(C6H4Me)2.-M. p. 22°-3°.-Slowly sul- phonated by fuming H2SO4.-CrO3 oxid. to dimethylben- zophenone. 288 0-99916/4 o-m-Bitolyl, C7H7.C7H-.-CrO3 oxid. to isophthalic ac. (Test 318). 293-4 0-987(15) s-Benzyltolylethane, C7H7.C2H4.C6H4.Me. 293-5 p-Ethyldibenzyl, Ph.CH2.CH2.C0H4.Et.-Shows bluish fluores- cence. 294 Benzyl-p-xylene, Ph.CH,.CGH3.Me2. 294-5 (th. 0-985(18-9) Ethylbenzylbenzene, Et.CGH4.CH2.Ph.-E. s. ale., eth., or CHC13. 295-8 0-9742% p2-Ditolylethane, Me.CH.(C7H7)2.-Test 905-2 gives dimethyl phenyl ketone and tolylbenzoic ac. 295-8 (th. i.) 1-036(16) Benzyl Eth., (Ph.CH2)2.O.-Heated above 315° yields benzal- dehyde, toluene, and resinous matter. 304-5 Ditolylethylene, (Me.CRH,)2.C : CH2.-Test 905-2 gives ditolyl ketone, m. p. 94°.-Dibromide v. unstable, losing HBr. 308 0-969(15) Benzylcymene, C7H7.CGH3.(Me)Pr. 310 (th. i.) 1-067(10-2) Phenanthrenetetrahydride, C14H14.-Oxid. by CrO3 in Ac sol. to anthraquinone (Test 1011). a. 300 0-939 Diterpenes, C20H32.-(In copaiva balsam, etc.)-Very viscous; i. ale. 323-5 0-9662% m-Dixylyl-ethane, (CGH3.Me2)2.CH.Me.-Exhibits a blue fluo- rescence. 324c. a, ,5-Phenylxylylpropane, Ph,(C8H3.Me2).C3H6. 324-5 a-Phenylnaphthalene, Ph.C1(lH7.-Shows a feeble blue fluores- cence.-Oxid. to o-benzoylbenzoic ac. in alkaline sol. 343-6 0-969(18) Diterebenthyl, C20H30.-Absorbs O fr. air.-Is easily oxid. by oxid. agents.-Not attacked by cold H2SO4.-Fuming HNO3 nitrates.-Br substitutes. 350 Cuminyl Eth., (C10H13)2.O.-Dist. w. partial dec. to cymene and cuminic aldehyde. 392-6 1-049 Dibenzyltoluene, Me.CGH3.(CH,Ph)2. 392-6 Dixylylbenzene, C6H4.(CH2.C6H4.Me)2.-E. s. ale., eth., or Ac. 390-400 0-871(0) Tetramylene, C20H40. 396-400 s-Triphenylethane, Ph.CH,.CH.Ph2.-Shows a violet fluorescence. NUMBERED SPECIFIC AND SEMI-SPECIFIC TESTS FOR SPECIES OF GENUS IX. [TESTS 901-1000.] poi. Bromine Test for Unsaturation. This test for unsaturation finds many applications, but is most frequently employed in connection with the species of Genera IX and III. Dissolve or suspend 0.1 grm. of the pure compound-finely powdered, if it is an in- soluble solid-in 2 cc. of dry carbon tetrachloride in a three-inch test-tube. Add three drops of a bromine solution * prepared by dissolving 2.0 cc. of bromine in 50 cc. of carbon tetrachloride. If decolorization does not take place at once, stopper the tube loosely, and allow to stand for three minutes in the cold, shaking occasionally if the body is insoluble. If the solution becomes colorless before the end of two minutes, drop in more bromine solution until a color that is permanent for a minute or two is produced. Then blow sharply across the mouth of the tube, and notice whether a white cloud (hydrated hydro- bromic acid) makes its appearance. If no signs of action in the cold are observed, hold the tube high above a small flame and boil very gently for two minutes. If decolorization results, drop in more bromine until the coloration remains permanent for nearly a minute when the solution is again boiled. Test for hydrobromic acid as before by blowing across the mouth of the tube. Complete decolorization in either part of this test {either in the cold or after heating), if unaccompanied by evolution of hydrobromic-acid gas, shows that the compound under exami- nation is unsaturated; that is, that it can add bromine. The presence of double or triple bondings in hydrocarbons may in the great majority of cases be detected by use of the test in the cold only; but there are a few unsaturated hydrocarbons like stilbene which require short heating, and in tetraphenylethylene we have one which remains unchanged even when heated. Among the unsaturated acids, maleic and fumaric acids f also show an exceptional behavior in not decolorizing the tetrachloride solution after two minutes' boiling. Some other unsaturated acids, like aconitic, do not decolorize the solution until it has been heated, but the number of such species is not large. Decolorization in either part of the test when accompanied by a copious evolution of hydro- bromic acid always indicates substitution; but since addition may, or may not, have taken place at the same time, satisfactory inferences as to the existence of unsaturation in such cases can * Carbon tetrachloride is given the preference as the solvent, because bromine solutions pre- pared by its use may be kept for weeks without spoiling; because such solutions do not entirely lose their orange-yellow color on heating unless boiled for more than twice the time prescribed in the test procedure; and because the tetrachloride is such a poor solvent for hydrobromic acid that the gas escapes as soon as formed, and thus is easily detected by the fumes f Fumaric or maleic acids will, however, decolorize hot bromine water. (Bromine water is as a rule a very unsatisfactory substitute for the carbon tetrachloride reagent, since it is fre- quently decolorized by acting as an oxidizing agent, holds back hydrobromic acid, and loses its color rather quickly on boiling.) 195 196 SEMI-SPECIFIC TESTS FOR SPECIES OF GENUS IX. not be drawn. The appearance of scanty traces of hydrobromic acid towards the end of an experiment in which a considerable quantity of bromine has been consumed, may, however, be due to minor secondary reactions and may be disregarded. In the heat, the number of compounds in Order 1 that are attacked by the treatment with bromine is greatly increased. The saturated hydrocarbons of the marsh-gas series, (CnH2n+2), with unbranched carbon skeletons, and the members of the acetic-acid series, (CnH2nO2), are conspicuous examples of compounds unaffected under these circumstances. Some paraffin hydrocarbons like diisoamyl with branched carbon skeletons are, on the contrary, quite readily attacked in the heat, although not in the cold. Many of the aromatic hydrocarbons like mesitylene and anthracene are so easily substituted that decolorization occurs within a fraction of a minute in the cold; but pure benzene is so. comparatively ( unreactive that it does not cause decolorization within the two minutes' limit on boiling. Most phenols, and many aldehydes and ketones, cause decolorization cold within a few seconds. Whenever decolorization takes place readily in consequence of addition or substitution in a homogeneous compound, if the experiment is continued after the first disappearance of color, it will be found that the quantity of bromine eventually consumed will be at least several times greater than what was added at the beginning of the experiment. 902. Action of Fuming Sulphuric Acid. Support a three-inch test-tube containing 1 cc. of fuming sulphuric acid (sp. gr. 1.89) by means of a small clamp in a nearly vertical position, but so that it shall be slightly inclined away from the operator. Drop in slowly from a medicine-dropper about five drops of the compound. If there are no immediate signs of solution or chemical action, shake the mixture cautiously for about one minute. Then allow to stand for a short time, and notice whether the compound added separates apparently unchanged as an upper layer. If the substance does not dissolve, if heat is not evolved, and if the mixture does not be- come strongly discolored, the compound, if a liquid species of Genus IX, with a specific grav- ity less than 0.85 at 20°//4o, may belong to Section 1 (the paraffin section) of Division B. 903. Action of Fuming Nitric Acid. [This test is dangerous unless performed cautiously as directed!] In a three-inch test-tube, supported as in Test 902, place 1 cc. of fuming nitric acid of specific gravity 1.48. Then add from a medicine-dropper, held at arm's length, a single drop of the compound to be tested. A violent reaction often ensues, and there may be a slight explosion, or the substance may even ignite. If there are no signs of action, cautiously add a few more drops of the substance, and shake gently. If the substance is a liquid species of Genus IX with a specific gravity at 20o/4o less than 0.85, and does not dissolve in the acid, and is not attacked by it (as will be in- dicated by absence of sputtering and evolution of heat, and by the non-appearance of a copious disengagement of red nitrous fumes), it is to be sought for in Section 1 (the paraffin section) of Division B.* It is improbable that any of the Species of Section 2 remains entirely unchanged after such treatment. The liquid paraffins, although they are unattacked, and do not dissolve, always dissolve oxides of nitrogen so as to acquire a color much like that of the nitric acid. The presence of two layers after shaking may, therefore, be easily overlooked in a hasty observation. 904. Colorations with Aluminium Chloride. Drop a hard lump of sublimed aluminium chloride weighing about 0.2-0.3 grm. into a clean 6-8-inch test-tube that has just been taken from a hot drying oven. Stopper the tube loosely. Hold it in a nearly horizontal position, and by means of a small flame placed * The tertiary paraffin diisopropyl is said to be violently attacked by cold nitric acid of specific gravity 1.52. SEMI-SPECIFIC TESTS FOR SPECIES OF GENUS IX. 197 under one end slowly sublime the chloride until it forms a thin light-yellow coating cov- ering a considerable portion of the glass surface. Allow to cool. Drop in 0.5]cc. of a solution containing 0.05 grm. of the hydrocarbon dissolved in 2.5 cc. of chloroform. Stopper the tube tightly. Lay it on its side upon a sheet of white paper that rests upon and partly covers the color standard. Then roll it back and forth so that the solution shall flow over and wet all parts of the sublimate. Observe the color after a few seconds, and again after 15-20 minutes. Most aromatic hydrocarbons give colorations when thus treated. The colors are often very intense, and sometimes admit of employment as minor preliminary or confirmatory tests; but since the hue may be much modified by the presence of small quantities of impuri- ties, too great importance ought not to be attached to the indications obtained by their use. The initial colorations given by the liquid homologues of benzene approximate orange; e.g. pseudocumene, RO; m-xylene, O; benzene, OY (after five minutes). After standing fifteen minutes these colors will either remain unchanged, or will change by about one hue of the standard in the direction of the red end of the spectrum. The initial coloration with diphenylmethane and triphenylmethane is YO, darkening within a few minutes to YOT1; with anthracene it is OYS2-YS2. Initial colorations of great intensity which persist unchanged for more than twenty minutes and approximate blue, are given by several important solid hydrocarbons; e.g. blue (B), by diphenyl; blue to green-blue (GB-B), by phenanthrene; and blue-green (BG), by naphthalene. 905. Oxidation of Side Chains. The oxidation of the side chains in aromatic hydrocarbons to carboxyl groups by hot aqueous solutions of potassium permanganate, chromic acid, or nitric acid, has been em- ployed in determining the constitution of many species of Genus IX. The most serious difficulty encountered in adapting these methods for use as practical specific tests arises from the extreme insolubility of all hydrocarbons in aqueous solutions. This renders the oxidations very slow. During the oxidation period-which is seldom less than several hours-the oxidation product, which is itself never entirely stable, is exposed to the de- structive action of the oxidant. Hence the yield, which even under favorable circum- stances falls much under the theoretical, is often very poor indeed. Hydrocarbons which are themselves stable, but give unstable oxidation products, are therefore the most difficult to treat successfully. Whenever it is suggested in the tables that some particular oxidant may be used in the identification of a hydrocarbon, it does not always follow that the oxidant mentioned is the best that could have been selected for the purpose, or that the yield will be good, but merely that the product named has been obtained by its use. It should also be understood that the following general directions are given as suggestions rather than mandatory procedures; and that what is said refers more especially to aro- matic hydrocarbons having one or two side chains. 1. (Oxidations with Potassium Permanganate.')-The oxidation with permanganate, when applicable, will usually be preferred to either of the other methods. The reagent is a neutral aqueous solution containing 61.6 grms. of potassium permanganate to the liter. In organic oxidations it is said to be reduced according to the equation 2KMnO4 + zH2O = 2MnO2.zAq. + 2K0H +30. 1 cc. of the solution accordingly contains 0.01 grm. of "available oxygen," and the alkali liberated is sufficient to combine with the full quantity of organic acid and carbon dioxide that will be produced in any ordinary oxidation. The latter fact makes it possible to perform these oxidations in closed vessels, and thus avoid the violent bumping that is one of the greatest objections to the use of permanganate when the oxidation is performed by boiling in flasks. 198 SEMI-SPECIFIC TESTS FOR SPECIES OF GENUS IX. Calculate by aid of the equation given above how much permanganate solution will be theoretically needed to produce the desired effect, and place it in a strong wide flask or bottle of about one-liter capacity. If, as will sometimes happen, the hydrocarbon is lighter than water, and a liquid, the extended contact surface presented by the permanganate solution, which will be spread out in rather a thin layer, will do much to accelerate the reaction. When the oxidation product expected is benzoic, isophthalic, or terephthalic acid, about 1 grm. of the hydrocarbon should be enough for an experiment. Suspend the bottle by a wire, so that the lower part will be immersed in a boiling water-bath; and, as soon as the air within has been expanded by the heat, and the hydro- carbon introduced, stopper tightly to prevent loss of substance by volatilization. Then heat until the red color of the permanganate is seen to have completely disappeared. This may require from two to eight hours, and some of the hydrocarbon will always remain unattacked. Separate the colorless alkaline solution from the bulky brown precipitate of hydrated manganese oxide by filtration. Evaporate to a small volume. Filter if neces- sary, and cool. Acidify the solution with a moderate excess of hydrochloric acid, and shake vigorously. Benzoic, isophthalic, and terephthalic acid will precipitate at this point. The two former may then be identified by their melting-points and specific tests, after a single crystallization from boiling water; the latter after being well washed with water. Phthalic acid being comparatively easily oxidized by hot permanganate, will not be detected, unless the hydrocarbon is one that oxidizes quite rapidly. The loss of benzoic acid in long-continued oxidations is also large, though less serious. In an oxidation of 1 grm. of ethylbenzene requiring six hours, the yield of pure benzoic acid was 0.20 grm. Benzoic acid is easily separated from any of the phthalic acids by treatment with chloroform, in which it is very soluble. 2. {Oxidations with Chromic-acid Mixture.)-Boil the hydrocarbon in a round-bot- tomed flask containing ebullator tubes (cf. p. 223) with the quantity of chromic-acid mixture theoretically required to produce the desired effect, until the chromic acid is completely reduced. The apparatus, chromic-acid mixture, and general procedure for the oxidation are the same as have been more fully described in Test 702 for the oxidation of ketones and alcohols, except that longer heating will be necessary. As the action of hot chromic acid on most of the aromatic acids is even more destructive than that of permanga- nate, it is advisable to use at least 2 grms. of the hydrocarbon for each experiment, and even larger quantities may sometimes be found necessary. Collect the insoluble residue of oxidation products, and unchanged hydrocarbon that separates from the well-cooled solu- tion, on a small filter. Wash with a little cold water. Dissolve out the aromatic acids by boiling with a slight excess of sodium-carbonate solution. Reprecipitate with an excess of hydrochloric acid, and identify them by appropriate tests. 3. {Oxidations with Dilute Nitric Acid.)-Although nitric acid, being a milder oxidant than either permanganate or chromic acid, may be successfully employed in some cases in which the latter are inapplicable, and is occasionally mentioned in the tables, it has the disadvantage of being exceedingly slow in its action, and of giving products which sometimes consist largely of nitrosubstitution derivatives whose removal is troublesome. The proper procedure depends so much on the properties of the particular hydrocarbon to be oxidized, that in the few instances in which this method is referred to in the tables, it will always be best to consult the original literature relating to the subject before pro- ceeding to the experiment. The following general statement and suggestions may, how- ever, be of some assistance. It is best to oxidize at least 2 grms. of the hydrocarbon with a large excess of acid. The nitric acid is usually a mixture of one part of concentrated commercial nitric acid with three parts of water, though in some cases a stronger acid can be used, shortening the SEMI-SPECIFIC TESTS FOR SPECIES OF GENUS IX. 199 time without causing much substitution.* The time of boiling varies from six to forty- eight hours. In general it is best to boil at least eight hours. If it is expected, that a solid aromatic acid, not volatile with steam, will be formed, the excess of nitric acid should be removed by evaporation on a water-bath. The residue is next extracted -with boiling sodium-carbonate solution, the solution filtered, and the organic acids precipitated from the filtrate by a moderate excess of hydrochloric acid. Nitro-acids may then be reduced by warming with tin and hydrochloric acid, so as to form soluble hydrochlorides of the corresponding amino-acids, which, upon filtration, will pass into the filtrate. Or, if the acid sought should also be soluble in dilute hydrochloric acid, it may be separated from the amino-acid by crystallization, after precipitating the tin with sulphuretted hydrogen. 906. Test for Triple-bonding in Compounds Containing the (-CECH) Group. Dilute 1 cc. of ammoniacal cuprous chloride solution,f in a test-tube, with 5 cc. of coid water. Add a few drops of the hydrocarbon, if a liquid, and shake. If the hydro- carbon is a gas, conduct it directly into the copper solution. Collect the precipitate on a filter. Wash with cold water and observe the color. The hydrogen atoms in compounds containing the EE CH group are usually replace- able by copper when thus treated. These copper compounds appear as insoluble floccu- lent precipitates, varying in color, according to the body from which they are obtained, from a dark brick-red to a greenish yellow. When washed with alcohol and ether and dried with proper precautions, they often explode violently when struck a sharp blow or when strongly heated. 907. Saturated Ethers of Division B. Drop 1 cc. of the compound slowly into 2 cc. of ice-cold sulphuric acid (sp. gr. 1.84) contained in a five-inch test-tube standing in a beaker of ice-water. Without removing the test-tube from the ice-water, shake briskly for half a minute or more. Then, after allowing to stand for a minute or two, observe whether the compound has dissolved completely to a colorless or nearly colorless solution. In case such a solution has been formed, pour it slowly into a second test-tube containing 3 cc. of cold water, shaking and cooling mean- while, just as was done during the preparation of the acid solution. If the mixture on standing separates into two layers, remove and reject the lower layer, which will consist of dilute sulphuric acid, with the aid of along capillary-pointed medicine-dropper. Wash the upper layer by shaking with 2 cc. of sodium-carbonate solution. If an emulsion forms, hasten the separation into layers by warming. Remove the carbonate solution as before by the aid of the dropper, and transfer the organic liquid to a dry three-inch test-tube. Add a small fragment of solid potassium carbonate, and heat nearly to boiling to hasten the drying action. Then after a few minutes, in order to ascertain whether the product obtained is identical with the original substance, determine the boiling-point of the clear dried * Thus Fileti (G. 21, I, 5 and 22) used one part of acid to one of water in oxidizing p-propyl- isopropylbenzene, obtaining terephthalic acid with only a trace of a nitro-acid. | Ammoniacal Cuprous Chloride Reagent.-This is the reagent used in gas analysis for the absorption of carbon monoxide.-It is prepared from an acid cuprous chloride solution as re- quired for use. To prepare the acid solution, cover the bottom of a bottle with a layer of pow- dered copper oxide 1 cm. deep. Place in the bottle a number of pieces of rather stout copper wire, reaching from top to bottom, sufficient to make a bundle an inch in diameter, and fill the bottle with common hydrochloric acid of 1.10 sp. gr. Stopper, and allow to stand with occa- sional shaking for some days, or until the solution becomes nearly or quite colorless. When about to make a test, decant a little of the clear acid solution, and add ammonia to it until present in slight excess, i.e., until the mixture has a distinctly ammoniacal odor. The space left in the stock bottle after every withdrawal of solution should be immediately filled with more hydrochloric acid (1.10 sp. gr.), and the bottle always be kept tightly stoppered to pre- vent absorption of oxygen from the air. 200 SPECIFIC TESTS FOR SPECIES OF GENUS IX. liquid by Siwoloboff's method. For a more detailed description of the manipulations involved in the washing and drying, and in the boiling-point determination, read the latter half of paragraph i. on the identification of soluble alcohols obtained in saponification tests (cf. p. 115). Any species of Genus IX, Division B, that dissolves in sulphuric acid in this test to a clear, nearly colorless solution, which, upon dilution, gives a liquid identical in boiling- point with the original substance, is probably the oxide of a saturated hydrocarbon radi- cal or, possibly, an " unsaponifiable ester." Unsaturated ethers and unsaturated hydro- carbons may also dissolve completely in the cold acid, or may be entirely decomposed by the reagent; but when a clear solution does result, dilution with water can not be expected to yield the original substance. Saturated hydrocarbons, even the aromatic ones, do not dissolve in the cold acid to any considerable extent. 911. Acenaphthene. (Properties tabulated on p. 177.) Dissolve 0.05 grm. of the hydrocarbon and 0.10 grm. of picric acid in 2.5 cc. of boiling 95 per cent alcohol in a dry test-tube. Allow the solution to cool down to the temperature of the laboratory gradually. Acenaphthene under these conditions yields a beautifully crystallized orange-colored picric-acid compound, C12H10.C(lH3(NO2)3O,> whose slender flat needles shoot from the bottom of the tube to the surface of the solution. Collect on a small filter, and wash with 3 cc. of cold alcohol. Dry for fifteen minutes on a piece of porous tile at 100°, and determine the melting-point. The color of the dry crystals is nearly the orange of the color standard (O-YO). They melt at 161°-162° (uncor.). 912. Anthracene. (Properties tabulated on p. 180.) Place in a six-inch test-tube 0.05 grm. of the hydrocarbon, 1.5 grms. of chromic acid (CrO3), 4 cc. of glacial acetic acid, and 1 cc. of water. Support the tube by a clamp so that its lower end shall rest in a circular perforation in a piece of asbestos board arranged as in Test 312-2, and boil for ten minutes over a small flame, so gently that the vapors shall all condense on the sides of the tube. Pour into 20 cc. of cold water. Collect the floc- culent precipitate on a filter. Wash thoroughly with much water, and finally with 5 cc. of cold alcohol. Transfer the precipitate to a dry test-tube and boil with 10 cc. of strong alcohol. Cool. Collect the nearly white precipitate on a small filter. Wash with 5 cc. of cold alcohol. Boil up a second time with 10 cc. of strong alcohol, and again cool. Filter, and wash with 5 cc. of cold alcohol. Dry the residue fifteen minutes at 100° on a piece of porous tile, and determine the melting-point. Anthraquinone, the product obtained in this test, is a pale yellowish compound, crys- tallizing from alcohol in minute needles which melt at 279°-280° (uncor.). For other characteristic properties of anthraquinone see Test 1011. 913. Benzene. (Properties tabulated on p. 189.) Mix in a dry test-tube three drops of the hydrocarbon, 1 cc. of nitric acid (sp. gr. 1.42), and 1 cc. of sulphuric acid (sp. gr. 1.84). Heat the mixture until it begins to boil, and maintain it at this temperature for half a minute. Then pour slowly into 10 cc. of cold water. Cool quickly. Shake. Collect the bulky flocculent precipitate on a small filter, and wash until the washings are no longer colored. Dissolve in 8 cc. of boiling dilute alcohol (1:1). Allow to stand until the solution has assumed the room temperature. The liquid will become filled with long, fine, nearly white needles of m-dinitrobenzene. Collect on a small filter. Wash with 5 cc. of cold dilute alcohol (1:1). Drain on a piece of porous tile and dry fifteen minutes at 50°. The dinitrobenzene formed in this test melts at 89°-S9.5° (uncor.). SPECIFIC TESTS FOR SPECIES OF GENUS IX. 201 914. Mesitylene. (Properties tabulated on p. 190.) Allow one drop of the hydrocarbon to fall into a mixture of 2 cc. of sulphuric acid (sp. gr. 1.84) and 1 cc. of fuming nitric acid (sp. gr. 1.48) contained in a dry test-tube. Shake, and then boil verygently for one minute over a small flame. Break up any hard lumps that may form with a stirring-rod, and pour into 10-12 cc. of cold water. Collect the solid nitro-compound on a very small filter and wash well with cold water. Then wash once with 5 cc. of cold strong alcohol. Transfer to a test-tube and boil gently with 15 cc. of 95 per cent alcohol (*) until all dissolves. (The compound dissolves quite slowly.) Allow to cool. Shake vigorously. Collect the crystalline precipitate in the point of a very small filter. Wash with 5 cc. of cold 95 per cent alcohol (**). Drain on a piece of porous tile; dry for fifteen minutes at 100°, and determine the melting-point. The product in this test, trinitromesitylene, is obtained in the form of minute colorless needles melting at 235° (uncor.). 915. Naphthalene. (Properties tabulated on p. 176.) Dissolve 0.05 grm. of the hydrocarbon and 0.10 grm. of picric acid in 2 cc. of boiling 95 per cent alcohol. Allow the solution to cool gradually. Collect the long, hair-like yellow (Y-YT1) needles of the picric-acid compound, C10H8.C6H3(NO2)3O, on a small filter, and wash with 1 cc. of strong alcohol. After draining, transfer to a piece of porous tile, and press out adhering mother-liquor. Form the crystals into a little mound on a dry part of the tile; rinse them off with 5-10 drops of strong alcohol. Repeat the washing with alcohol twice more in the same manner, pressing out the adhering alcohol on a dry part of the tile each time with a small spatula. Spread out the crystals on a bit of dry tile and dry for 15-20 minutes at 50°. Then determine the melting-point. The picric-acid compound of naphthalene, thus purified, melts at 150-5° (uncor.7. (Long-continued drying at a high temperature is inadmissible since it causes a gradual loss of naphthalene.) 916. Phenanthrene. (Properties tabulated on p. 177.) Dissolve 0.10 grm. of the hydrocarbon and 0.20 grm. of picric acid in 5.0 cc. of boil- ing 95 per cent alcohol. Allow to stand until quite cold. The picric-acid derivative of phenanthrene that forms separates in crystals. Collect on a filter, and allow to drain well without washing. Transfer to a piece of porous tile to absorb the last of the mother- liquor. Redissolve in 1 cc. of boiling alcohol. Allow to cool slowly as before. Collect the crystals on a piece of tile to absorb the mother-liquor, and wash with five drops of strong alcohol. When the alcohol has nearly all disappeared, place on a fresh piece of tile; dry fifteen minutes at 100°, and determine the melting-point. The picric-acid compound of phenanthrene, C14H10.C8H3(NO2)3.O, obtained in this test, forms long, hair-like needles which are orange-yellow (OY) when dry, and melt at 143° (uncor.). 917. Pseudocumene. (Properties tabulated on p. 190.) Nitrate two drops of the hydrocarbon by the procedure of Test 914 for mesitylene. Do not increase the quantities of acids and solvents prescribed, but follow the directions given literally, except that more than usual care must be taken not to overheat during nitration. During the operation the test-tube should be held at some distance above the flame, and the heating should be interrupted before the expiration of the minute if the mixture show signs of darkening, or if a sublimate should begin to appear on the sides of the tube. The trinitro-pseudocumene formed in this test is a nearly white crystalline compound melting at 184° (uncor. . 202 SPECIFIC TESTS FOR SPECIES OF GENUS IX. qi8. Toluene. (Properties tabulated on p. 189.) Dissolve three drops of the hydrocarbon in 1.5 cc. of the strongest fuming nitric acid. Then add at once, without cooling, 1.5 cc. of fuming sulphuric acid (concentrated sulphuric acid containing in solution about 10 per cent of sulphuric anhydride-the same reagent that is used for Test 902). After half a minute pour the mixture into 10 cc. of cold water in a test-tube. Cool well with running water. Close the tube with the thumb and shake vigorously and persistently until the nitro-compound separates in yellowish-white flocks, leaving the solution clear. Collect the precipitate on a very small filter and wash with cold water. Dissolve in 8 cc. of boiling 50 per cent alcohol. Cool in running water. Shake vigorously. Filter. Wash the precipitate with 5 cc. of cold 50 per cent alcohol. Redissolve the washed pre- cipitate a second time in 8 cc. of boiling 50 per cent alcohol. Cool. Shake. Wash with 5 cc. of 50 per cent alcohol. Dry, and determine the melting-point. 2, 4-Dinitro toluene, the product in this test, is a nearly white precipitate of crystal- line structure melting at 70°-71° (uncor.). (If the solution, in making the last crystalliza- tion, is allowed to cool slowly, the compound will separate out in the form of delicate white needles.) 919. m-Xylene. (Properties tabulated on p. 189.) Nitrate two drops of the hydrocarbon by the procedure of Test 914 for mesitylene Do not increase the quantities of acids or solvents prescribed, but follow the directions given literally in every detail, except that the precipitate referred to at the point marked by the double asterisk (**) should receive one additional crystallization from 10 cc. of boiling 95 per cent alcohol before being dried. The trinitro-m-xylene formed in this test is a nearly white crystalline compound melt- ing at 181°-181.5° (uncor.). 920. p-Xylene. (Properties tabulated on p. 189.) Nitrate two drops of the hydrocarbon by the procedure of Test 914 for mesitylene. Do not increase the quantities of acids or solvents prescribed, but follow the directions given literally in every detail, except that the quantity of 95 per cent alcohol used in crystal- lizing at the point marked by the single asterisk (*) should be reduced from 15 cc. to 5 cc. The trinitro-p-xylene formed in this test is a nearly white crystalline compound melt- ing at 138.5°-139° (uncor.). 921. o-Xylene. (Properties tabulated on p. 189.) This hydrocarbon is easily distinguished from the meta and para compounds by the fact that when nitrated by the procedure prescribed in Tests 919 and 920, it gives an oily instead of a solid high-melting nitro-derivative. The following test may also be applied. Sulphonate 0.25 cc. of the hydrocarbon by persistently shaking in a test-tube with 1 cc. of sulphuric acid (sp. gr. 1.84). During the shaking the tube should be gently warmed from time to time by dipping it for a second or two into boiling water. When the hydro- carbon has all dissolved (this will require 3-5 minutes), cool, and pour slowly into 10 cc. of a saturated solution of common salt. Cool well, and shake vigorously. The mixture will soon become pasty from the separation of a heavy precipitate of sodium o-xylenesulphonate. Filter, and wash with 10 cc. of a cold saturated salt solution. Press on a tile, and dry 10 minutes at 125°. Crush. Mix 4 parts by weight of phosphorus pentachloride with 3 parts of the dry sulpho- nate in a test-tube, and heat for 10 minutes at about 100°. Cool, and pour in 5 cc. of ice-cold water. Shake. Allow to settle. Decant the water through a wet filter. Wash again SPECIFIC TESTS FOR SPECIES OF GENUS IX. 203 by shaking with 5 cc. of cold water, followed by decantation. Return any precipitate that may have collected on the filter to the test-tube. Add 2 cc. of the most concentrated ammonia. Boil gently until the ammonia odor has almost disappeared. Dilute with 10 cc. of water. Heat to boiling. Filter hot. Cool the filtrate well with ice water. Shake vigorously, and collect the precipitate of the sulphonamide on a small filter. Wash with 5 cc. of cold water. Redissolve in 5 cc. of boiling water, and cool. Shake, filter, and wash as before. Repeat these operations twice more. Then dry for 15 minutes at 110° and determine the melting-point. o-Xylenesulphonamide, the product of this test, crystallizes in pearly-white scales which melt at 143.5°-144°. CHAPTER XII. SUBORDER. II. THE COLORED COMPOUNDS OF ORDER I. (Containing Carbon, Hydrogen, and Oxygen.) THE CONTENTS OF SUBORDER II ARE INDICATED BY THE TITLE " COLORED COM- POUNDS." ANY CAREFULLY PURIFIED SOLID SPECIES OF ORDER I WHOSE COLOR EXCEEDS TINT 3 OF THE COLOR STANDARD (CF. PAGE 231) IN SATU- RATION, OR ANY YELLOW LIQUID SPECIES WHOSE COLOR WHEN VIEWED IN A LAYER 1 CM. THICK AGAINST A WHITE BACKGROUND IS MORE SATURATED THAN YT1 OF THE STANDARD, WILL BE CONSIDERED COLORED. A very faint tinge of straw-yellow, caused by traces of impurities or decom- position products so small as to have no appreciable effect on the general chemical behavior of the substance, is often observed in specimens of compounds belonging to Suborder I. In doubtful cases the attempt should be made to decolorize such substances by boiling their solutions with purified bone-black. Compounds with colors less saturated than the tints of Series 3 of the color standard are described in Suborder I with the colorless compounds, but also sometimes receive mention in Suborder II. Subdivisions of Suborder II.-The species described in Suborder II are arranged in two divisions, A for solids, and B for liquids; but are not numerous enough to require further subdivision into genera. They are all either ketones, quinones, or phenols. The solid species are grouped in two sections. The arrangement in Section 1 is based upon melting-point, as is customary for solids in other parts of the work. Section 2 is virtually an appendix to Section 1, added to provide for the partial identification of certain important bodies, dyes, and acidimetric indicators, which have the common property of giving intensely colored solutions in alkali, but which fuse with so much decomposition, or at such high temperatures, or which are so difficult to isolate in a state of perfect purity, that their melting-points are unknown or have little practical significance. Some of these bodies are not met with except in the form of moist pastes and amorphous powders of rather variable compo- sition, and are only admitted to the tables as compounds by courtesy because of the interest attaching to them as colors. The arrangement of species in Section 2 is dependent on the color of the solution of the substance in dilute aqueous alkali, as is more fully explained on page 212. To make the color comparison, dissolve a few milligrams of the finely powdered sub- stance by shaking in a test-tube with 5 cc. of 1 per cent cold sodium-hydroxide solution; and then dilute, if necessary, with water, until the mixture when held before a white background shows a depth of color that approaches either the normal tone, or the first tint of that hue of the standard which the color of the solution most closely resembles. The comparison should be made quickly, as many of the solutions absorb oxygen from the air, or change rapidly in both hue and tone on standing. 204 COMPOUNDS CONTAINING C, H, AND O [ORDER I]. SUBORDER II, COLORED COMPOUNDS. DIVISION A, SECTION 1 - SOLID SPECIES OF DETERMINED MELTING-POINT. Melting-point (C.°). COLORED COMPOUNDS.-Solid Species of Determined Melting-point. 28 f Phoron, C9H14O.-B. p. 198-5°.-Pale-yellow cryst.-Cf. VII, A, p. 136. 41 Benzfuril, Ph.CO.CO.C4H3O.-Fine yellow ndl.fr. h. dil. ale.-Volatile undec.- S. alkalies giving benzfurilic ac. (dec. 108°).-25 pt. c. Br give tetrabromide, yellow ndl. fr. ale., m. p. 127°-8°. 45-5 f Thymoquinone, (Me).(Me2CH).O2.CflH2(x, 4,2,5).-B. p. 232°.-Orange-yel- low (OY) tbl. v. d. s. aq.; e. s. ale. or eth.-Odor sharp like quinone, but also like thymol!-S. without decomposition in c. cone. H2SO4 or HNO3.- For characteristic color reactions cf. B. 18, 3196.-Heat 0-1 grm w. 5 cc. aq. and 0-2 grm. Br for | hr. on boiling water-bath. Wash the red oil with c. aq. until it is yellow and crystalline. Recryst. twice fr. 2 cc. h. ale. (add- ing a little eth. if oil should not crystallize readily). Gives dibromide, yel- low Ifts., m. p. 73°. 55 1, 2-Dimethylquinone(3,6), Me2.C6H2.O2. - Sbl. in yellow ndl., d. s. aq.; e. s ale. or eth. 57-8 t Benzylideneacetophenone.-Pale yellowish pr.-Cf. VII, A, p. 137. 59-60 Dioxybenzophenone, (C6H4.OH)2.CO.-B. p. 330°-40° d.-Light-yellow ndl. fr. Igr.-Alm. i. aq.; v. s. ale. or eth.; s. K2CO3 but ppt'd by CO2.-Sol. in dil. ale. colored brown-red by FeCl3.-Warming w. cone. H2SO4 or boiling w KOH sol. gives o-benzophenone oxide, ndl. fr. ale., m. p. 173°-4°, v. d. s. c. aq. 68 Methyl Cinnamenylvinyl Ketone, C12HI2O.-Cf. VII, A, p. 137. 68-9 Toluquinone(2, 5), Me.C0H3.O2.-Sbl. in rhombic-yellow 1ft., d. s. c. aq.; v. s. ale. or eth.-Odor pungent, quinone-like!-Aq. sol. is colored brown-red by alkalies.-Reduced by SO2 to hydrotoluquinone, v. s. aq.; pearly 1ft. fr. bz.; m. p. 124°. 69-70 Diphenylpropanetrione, (PhCO)2.CO.-B. p. 247° (60 mm.).-Golden-yellow ndl. fr. Igr.; e. s. ale.-Very hygroscopic.-Sapon. by NaOH gives benzoic and mandelic acids, benzoin, and CO2.-2 pt. boiled w. 5 pt. aniline and 10 pt. ale. give a dianil, yellow pyramids fr. bz., m. p. 148°. 71 Phenoquinone, CflH4O2.2CGH6O.-Fine red ndl. w. green reflections!-S. c. aq.; e. s. ale. or eth.; s. Igr. (dif. fr. quinone and quinhydrone).-The red crystals become blue-black upon addition of alkali.-Reduced to hydroquinone (Test 411) by SO2. 72-3 1, 3-Dimethylquinone(2, 5), Me2.C0H2.O2.-Yellow ndl. 83-5-4 Diphenylene Ketone, (CGH4)2.CO.-B. p. 341-5°.-Large yellow tbl. fr. ale., i. aq.; v. s. ale. or eth.-Slowly oxid. by alkaline KMnO4 to phthalic ac.- Oxime, m. p. 195°.-Well-cooled, fuming HN03 gives yellow nitro-comp. which sbl. easily, is d. s. c. ale., and melts at 220°.-Fusion w. KOH gives phenylbenzoic ac. 85 Pseudodiphenylene Ketone, C,3H8O.-Dark-red cryst. fr. eth.-C. fuming HNO3 gives dinitro-comp., ndl. fr. h. glacial Ac; i. ale.; m. p. 310°.-Boiled w. dil. ale. quickly gives diphenylene ketone (cf. above). 90 Acetonephenanthrenequinone, C]7H14O3.-Thin pale-yellow tbl. fr. eth.; i. aq.- Phenanthrenequinone separates upon boiling w. KOH sol. 90 Retene Ketone, CI7HIGO.-Vitreous sulphur-yellow cryst.; vol. w. st.; e. s. ale. or eth.; i. NaHSO3.-Combines w. phenylhydrazine, but not w. hydroxyl- amine.-Ignition w. Zn dust gives retenefluorene. 205 206 SUBORDER II, DIV. A, SECT. 1. (order I.) Melting-point (C.°). COLORED COMPOUNDS.-Solid Species of Determined Melting-point 92-3 Acenaphthylene, CI2H8.-Golden-yellow cryst.-Of. IX, A. 95 j- Benzil, Ph.CO.CO.Ph.-B. p. 346°-8° c.-Fine pale-yellow (YT2) ndl., i. aq.; e. s. ale. or eth.-Dissolve 4 pt. in x's abs. ale.; add 1 pt. solid KOH and boil down in porcelain dish. An intense violet color (VR) appears, but disappears on continued boiling!-Sapon. w. NaOH gives benzilic ac. (quan- titative).-Gives oximes. 98 Benzocotoin, (OH)(COPh)(OMe)2.C0H2.-Pale-yellow pr. fr. ale.; e. s. eth.; s. dil., but i. cone. NaOH.-PbAc2 gives yellow ppt. w. NH40H sol.-Sol. gives dark-brown color w. FeCl3. 102-3 Cinnamyleneacetophenone, C17H]4O.-Golden ndl. fr. ale.-Colored cherry-red by cone. H2SO4.-Oxime, m. p. 131°. 103 Oxy-m-xyloquinone, Me2.CfiH.(OH)2.O2.-Orange-red ndl., v. vol. w. st.-Sbl. in yellow ndl.-Odor like benzoquinone !-S. h. aq.; sol. colored red-violet by alkalies, even by CaCO3! 103 Methyl Oxynaphthyl Ketone, Me.CO.C10H6.OH.-B. p. 325° si. d.-Pale-green 6-sided pr. fr. bz.!-I. aq.; d. s. ale.; s. alkalies, but ppt'd by CO2.-Oxime, m. p. 168°-9°. 103-4 Pipitzahoic Ac., (Perezon), C15H,0O3.-Golden 1ft. fr. ale.-Sbl. undec.-S. in KOH w. intense purple color.-Ba salt purple and v. d. s. aq.-CO2 sepa- rates ac. fr. salts. 104 Santalin, C]5H14O5(?).-Mie. red cryst. or red mass; miso. w. abs. ale. w. blood- red color; s. eth.-A weak acid, s. alkalies w. violet colon-Ammon, sol. gives dark-violet cryst. ppt. w. BaCl2.-KOH fusion gives Ac and resorcin (cf. Test 418). 106 Cinnamylenebenzylideneacetone, C19Hlf!O.-Yellow pr. fr ale.-Oxime, yellow Ifts., m. p. 127°-8°. 109-10 Phenylnaphthoquinone, Ph.C)0H5O2.-Golden-yellow ndl. fr. ale.; s. eth.; d. s. Igr.-Polymerized quickly by sunlight.-An ale. sol. sat. w. NH3 separates a comp, (red ndl. s. eth.) on standing, m. p. 174°.-Gives aniline derivative fr. h. ale. sol. w. aniline, dark-red ndl., m. p. 158°. 111 i, 2, 4, 5-Tetramethylquinone, Me4.Cc.O2.-Sbl. at 100° in golden ndl., d. s. c. Igr.; v. s. ale. or eth.-Very volatile with steam. 112-2-5 t Dibenzylideneacetone, (Ph.CH:CH)2.CO. - Gives Test VII-1. - Yellow 1ft., d. s. ale.; s. eth.-S. in cone. H2SO4 w. deep orange-red color.-Colored dark vermilion by cone. HC1 without being dissolved.-Adds Br4 in CHC13 sol. to form comp, of m. p. 208°-ll° cl., ndl., v. d. s. ale. or eth. 115-7 f Benzoquinone, p-C6H4.O,.-Peculiar, sharp irritating odor slightly suggesting that of chlorine !-Golden-yellow monoclinic pr. fr. h. aq.; d. s. c. aq.; e. s. ale. or eth.; s. h. Igr.-Sbl. easily in golden ndl.-Sol. in alkalies absorbs oxygen rapidly, becoming dark-colored.-Identify by Test 1012 ! d. 115-20 i, 2-(/?)-Naphthoquinone, C10H(1O2.-Small odorless red ndl. fr. eth., or orange 1ft. fr. bz.-Not vol. w. st.!-Unstable.-Sol. in dil. NaOH is yellow and absorbs O rapidly.-Add 1J pt. aniline to a cone. sol. of 1 pt. of the quinone in h. ale.; anilinonaphthoquinone separates as red ndl. w. golden to greenish reflections, i. aq.; d. s. ale., m. p 240° (differs from aniline a-naphthoqui- none in being s. in cold alkalies).-KMnO4 oxidizes to phthalic ac.-Reduced by SO2 to corresponding hydroquinone. 120-5 f Absinthin, C20H2sO4 + |H2O.-(Fr. Artemesia absinthium.)-Yellowish (OYT2) mic. cryst. fr. ale. w. bitter taste and wormwood odor (sample fr. Merck) I-• Alm. i. c. aq.; e. s. ale or eth.-Sol. in NaOH is brown-red.-Sol. in H2SO4 is brownish and then green-blue liq.-Reduces ammon. AgNO3, but not Fehling's sol.-Ale. sol. gives ppt. w. tannic ac. 125 Benzohydroquinone, Ph.CO.CcH3.(OH)2.-Long yellow ndl. fr. dil. ale.; e. s. ale. or eth. 125 i, 4-Dimethylquinone(2, 5), (Phloron), Me2.C0H,.O,.-Long golden-yellow ndl. fr. ale.; d. s. h. aq. or c. ale.-Sbl. undec.-Reduced by SO2 to hydrophloron. -Br aq. gives dibrom-derivative, golden 1ft. fr. h. ale., m. p. 184°.-Aniline derivative yellow-green ndl., m. p. 264° (A, 255, 171). SUBORDER II, DIV. A, SECT. 1. 207 (order i.) Melting-point (C.°). COLORED COMPOUNDS.-Solid Species of Determined Melting-point. 125 t i, 4-(a)-Naphthoquinone, C10HGO2.-Yellow (Y) ndl. w. pungent quinone-like odor, which is, however, much less intense than that of benzoquinone.-E. vol. w. st. (dif. fr. /?-comp.).-S. ale.; e. s. eth.; d. s. aq.-Sol. in alkali is red-brown.-Identify by Test 1013 ! 127 Oxylapachol(a), C, 5H14O4.-Yellow ndl. e. s. ale., eth., or alkalies.-AgA + H2O, chestnut-brown cryst. ppt. 129 f a/?-Dibenzoylstyrene, Ph.CO.CPh: CH.CO.Ph.-Pale-yellow ndl. (YT2) fr. ale., v. d. s. c. ale. or eth.; e. s. h. ale-Odor faint aromatic.-M. p. of nitro deriv. 155°. abt. 130 Oxypipitzahoic Ac., C15H20O4.-Reddish-yellow 1ft.-Sol. in KOH is violet-red. 130-1 + Cotoin, MeO.CGH2(OH)2.CO.Ph.-(In coto bark.)-Pale-yellow pr. fr. h. aq.- Sulphur-yellow (sample fr. Schuchardt YT2) tbl. fr. ale.-Taste sharp and biting; dust provokes sneezing.-V. d. s. c. aq.; e. s. ale., eth., NaOH, or Na2CO3, but ppt'd by CO2.-Reduces ammon. AgNO3 sol. cold and Fehling's sol. on heating.--In cone. aq. sol. FeCl3 gives brown-black ppt. and in ale. sol. brown-red color.-Warming w. cone. H2SO4 gives benzoic ac. and phloro- glucin.-Sol. in ammonia gives yellow amorphous ppt. w. PbAc2.-Yields a cryst. oxime. 132-5 Chrysoketone, C17H10O.-Silky yellow ndl. or orange-red pr. 133-4 Salicyloresorcin, HO.CGH4.CO.CGH3.(OH)2.-Yellow 1ft. fr. h. ale.-S. h. Na2CO3 sol., but ppt'd by CO2.-Fusion w. KOH gives resorcin and salicylic ac. 135 f Furoin.-When pure, slightly yellowish; usually buff colored. Sol. in NaOH violet-red.-Of. Genus IV, A. 140 f Haematoxylin, C]6H14OG + 3H2O.-Melts w. loss of aq.-Taste sweet!-Colorless tetragonal pr. when pure and freshly prepared, but soon changed by sunlight to dark red-brown.-D. s. c. aq.; e. s. ale., eth., or h. aq.; s. alkalies and alkali carbonates w. intense beautiful purple-red color, changed by acids to a clear orange-yellow (OY).-Thin layers of the very intensely colored alkaline sol. are V; largely diluted VR and R.-Gives dark color w. FeCl3 and finally a ppt.-W. alum sol. gives rich RV color, which largely diluted gives VR.- Reduces ammon. AgNO3 sol. in the cold. 140 Lapachol, C]5H14O3.-Small yellow pr. fr. eth. or bz.-Sbl. w. much difficulty.- S. NaOH or Na2CO3 w. red color.-Dissolved by shaking w. 5 pt. cone. H2SO4 and ppt'd by aq. gives /?-lapachon, which cryst. fr. ale. in flat orange-red ndl., m. p. 155°-6°.-Readily oxid. to phthalic ac. by HNO3 (sp. gr. 1-38). 140-1 f Alizarin Yellow A (Trioxybenzophenone), (HO)3.CGH2.CO.Ph.-(Cryst. w. 1 aq.).-'Yellow ndl., d. s. h. aq.; e. s. ale. or eth.; ppt'd fr. Na2CO3 sol. by CO2.-Sol. in cone. H2SO4 yellow.-Warming w. cone. H2SO4 gives benzoic ac. 112 Pyrene Ketone, C]3HgO.-Golden-yellow tbl. fr. ale.-Gives NaHSO3 comp.- Fuming HNO3 dissolves w. deep purple-red color.-KMnO4 oxid. to naph- thalic ac. 142 f Dicinnamenyl Vinyl Ketone, C21H18O.-Golden-yellow ndl. fr. abs. ale.; d. s. c. ale. or eth. 143-4 Perezinon, C18HlgO3.-Pale-yellow ndl. s. ale. or eth.-Garnet-red on warming with Millon's reagent. 143-4 2, q'-Dioxybenzophenone, (CGH4.OH)2.CO.-Pale-yellow 1ft. fr. h. aq.; e. s. ale. or eth.; s. alkalies, but ppt'd by CO2.-Fusion w. KOH gives phenol and p- oxybenzoic ac. 146-7 i-Oxyxanthone, C13H8O3.-Clear-yellow ndl. fr. ale.; d. s. h. aq.-Fusion w. KOH gives resorcin and salicylic ac.-W. Br in Ac sol. gives dibrom-derivative, yellow ndl., m. p. 222°. 146-8 f Barbaloin, CIGH1SO7 (dried at 100°).-(Before drying, yellow ndl., w. zH20, m. p. 70°-80°).-Taste sweetish and then very bitter.-S. 60 pt. aq.; 20 pt. ale., or 470 pt. eth.; v. s. NaOH to deep orange-red sol.; e. s. acids.-A trace of FeCl3 gives fine red-violet color w. aq. sol.; more FeCl3 gives a green- ish black!-Br water added drop by drop w. a pause of J min. between each addition gives a fine VRT2 color. An x's of Br immediately changes the color to yellow, and then gives a yellow ppt. of tribromaloin.-A little of the powder stirred into a drop of HNO, (sp. gr. 1-2) gives a deep carmine-red, soon changing to orange. (The carmine color w. nataloin is permanent, but is not given at all by socralo'in.) 208 SUBORDER II, DIV. A, SECT. 1. (order i.) Melting-point (C.°). COLORED COMPOUNDS.-Solid Species of Determined Melting-point. 148 Vulpic Ac., C19H14O5.-(In Cetraria vulpina.)-Yellow monoclinic 1ft. fr. ale., v. d. s. ale.; e. s. eth.-Heated above 200° gives MeOH and pulvic anhyd.-• Sapon. by boiling Ba(OH)2 gives MeOH, oxalic, and a-toluic ac. 149 2, 3, 4, 2'-Tetraoxybenzophenone, (OH)3.CGH2.CO.C6H4.OH.-Cryst. w. 1H2O in greenish-yellow 1ft.; e. s. ale. or eth.-W. warm cone. H2SO4 splits to sali- cylic ac., etc. 152 Paracotoin, C19H8O4.-Pale-yellow 1ft., d. s. h. aq.; e. s. eth. or h. ale.-S. in alkalies, sapon. giving a yellow i. ac., m. p. 108°.-Fusion w. KOH gives piperonylic ac.-Br substitutes in c. CHC13 sol. giving comp, cryst. fr. ale., m. p. 200°-l°. 151-4 5-«-Oxynaphthoquinone (Jugion), HO.C1()H5.O2.-Yellowish to brick-red ndl. fr. CHC13.-Begins to darken on heating to abt. 125°.-Somewhat vol. w. st.-I. aq.; e. s. ale.; s. cone. H2SO4 w. intense blood-red color, s. in very dil. NaOH w. purple color, changing to brown.-Boiling w. aq. gives i. green- ish-brown powder, s. in alkalies w. deep-violet color.-CuAc2 added to ale. sol. gives dark-violet mic. pr. w. metallic lustre. 156-8d. Euxanthic Ac., CigH,sOn.-Straw-yellow ndl., anhydrous when fr. ale.-D. s. c. ale.; e. s. eth.-PbAc2, yellow gelatinous ppt.-Dist. w. HC1 gives furfurol (Test 115). 162 Furil, C4H:)O.CO.CO.C4H3O.-Golden-yellow ndl. alm. i. aq.; d. s. eth. or c. ale.; e. s. CHC13.-Sapon. gives furilic ac. (v. unstable).-E. dec. by cone. HC1.- Reduced to furoin by Na amalgam. 160-70d. J Anthranol.-Cf. Genus IV, A.-Color YT2-YT3. D. s. in alkali w. bright- yellow color. 170 Diphenylbutanoltrion, Ph.CO.CH(OH).CO.CO.Ph.-Yellow pr.; e. s. ale. or eth. 170-1 Dioxydimethyltriphenylmethane, (Me.CGH3.OH)2.CH.Ph.-Pale-yellow ndl. fr. dil. ale.; d. s. aq.; c. s. ale. or eth.; e. s. dil. NaOH.-Gradually turns red on exposure to air, especially if warmed. Diacetate by boiling w. x's acetic anhyd., yellow ndl. fr. ale., m. p. 94°. 171 J Quinhydrone, CGH4.O,.CGH4.(OH)2.-Dark-green pr. w. metallic lustre, red- brown by transmitted light!-Sbl. w. slight dec.-S. h. aq.; e. s. ale. or eth. w. yellow color; i. Igr.-Boiled w. aq. splits to quinone and hydroquinone.-■ Reduces ammon. AgNO3 sol.-Reduced by SO2 to hydroquinone (Test 411). 171-2 6-Phenyl-3-benzoylpyronon, ClgH19O4.-Yellow ndl. fr. ale.; d. s. c. ale., e. s. eth.-Boiled w. ale. KOH gives acetophenone, benzoic, and acetic ac.- FeCl3 gives orange-red color w. ale. sol.-Sol. of NH4 salt gives a scarlet-red ppt. w. FeCl3.-Sol. in cone. H2SO4 is olive-green, becoming violet when warmed. 170-78 J Chrysarobin, C30H,0O7.-Yellow ndl. or 1ft. fr. acetic ac. (sample fr. Merck YS1 powd.).-Sbl. w. dec. in yellow 1ft.-I. aq. or NH4OH; s. in not too dil. KOH w. yellow color and green fluorescence.-Air passed through sol. oxid. to chrysophanic ac., m. p. 162°.-Ignition w. Zn dust gives methylanthra- cene.-Sol. in cone. H2SO4 is yellow. 177 2-Methylanthraquinone, Me.C]4H7.O2.-Pale-yellow lustrous ndl., s. eth.; v. d. s. ale.; s. cone. H2SO4 w. blood-red color, changing to violet on heating!- Ignition w. Zn dust gives 2-methylanthracene. 177 2-Naphthyl-i, 4-Naphthoquinone, C10H7.CluH5.O2.-E. s. ale. or bz.; s. cone. H2SO4 w. indigo-blue color ! 178 Curcumin, C14HI4O4.-Yellow or orange-yellow pr.; i. aq.; d. s. ale.-Sol. in eth. fluoresces green.-S. alkalies w. intense red-brown color.-Sol._in cone. H2SO4 is fine reddish purple.-Ale. sol. gives bright-red ppt. w. PbAc2 sol.-• Place piece of filter-paper in ale. sol. and evaporate to dryness at 100°. Saturate paper w. boracic ac. sol. A red color appears at once or on evap- orating. A drop of NaOH sol. will give series of fine colors, green and pur- ple most prominent; HC1 will give a red color changed to green and blue by x's of alkali. 178(?) or 190 Dioxymethylanthraquinone (Chrysophanic Ac.), C15H10O4.-6-sided tbl. fr. bz.; golden yellow ndl. fr. ale.; s. eth. or h. ale.; v. d. s. NH40H or alkaline car- bonates; v. s. NaOH; in each case w. deep-red color.-Salts dec. by CO3.- Ignition w. Zn dust gives methyl anthracene. SUBORDER II, DIV. A, SECT. 1. 209 (order i.) Melting-point (C.°). COLORED COMPOUNDS.-Solid Species of Determined Melting-point. 181-2 Fluorenequinone, C13HgO2.-Yellowish granules fr. bz.-Hot KOH sol. gives brown product w. odor like diphenyl. 185-5 Picylene Ketone, C21H]2O.-Golden-yellow cryst. powder, e. s. h. bz.-Fusion w KOH gives picenic ac. 188 Fluoranthenequinone, C16HgO2.-Small red ndl.; s. ale. or NaHSO3 sol.-Quickly oxidized to CO2 by CrO3 mixture (dif. fr. fluorenequinone).-Ignition w. soda- lime gives diphenyl. 187-92c. Sinapic Ac., C11H12OS.-Pale-yellow ndl., e. s. h. ale.; i. eth.-Na salt gives red ppt. w. FeCl3 a. 190 Rutin, C27H32O16 + 2H2O.-(In leaves of rue: Kuta graveolens.)-Clear yellow silky ndl. fr aq.-Loses 2H2O at 150°-60°.-E. s. h. aq.; i. eth.; s. alkalies. -Sol. colored dark green by FeCl3!-Hydrolyzed by boiling w. dil. ac. to quercetin and rhamnose. 191-2 o-Diphenyleneketonecarbonic Ac., C14H8O3.-Orange-red ndl. fr. dil. ale., alm. i. aq.; e. s. eth.-Ignition w. Zn dust gives fluorene. Warmed w. fuming HNO3 gives nitro ac., m. p. 245°-6°. 195 Caffeic Ac., C6H3.(OH)2.CH: CH.CO2H.-(Cryst. w. |H2O.)-Straw-yellow pr. fr. aq.; e. s. ale.-Aq. sol. becomes grass-green w. FeCl3, changing to blue or violet upon addition of Na2CO3.-Alkaline sols, brown in the air.-Aq. sol. reduces h. AgNO3 and gives a yellow ppt. w. PbAc2.-Dist. gives pyrocatechin, Test 416. 195-6 a-Usnic Ac., C18H16O7.-(Fr. various lichens.)-Sulphur-yellow pr. fr. h. ale.; d. s. c. ale. or eth.-Very weak acid.-Salts are yellow.-FeCl3 gives a dark brownish-red color w. ale. sol. 197-7-5 Retenequinone, C18H16O2.-Flat orange ndl.; s. h. ale.; d. s. h. eth. or Igr.; i. c. NaOH; s. cone. H2SO4 w. green color!-A drop of ale. KOH added to an ale. sol. gives dark Bordeaux-red color which disappears on shaking w. air! Upon warming w. exclusion of air, color reappears.-Ignition w. Zn dust gives retenfi, m. p. 94°. 199-201 Carbousnic Ac., ClsH10O7.-(In lichens.)-Yellow pr. similar in properties to a-usnic ac. (cf. m. p. 195°-6°). 200d. Eupittonic Ac., (MeO)Q.C,9H O3.-Hair-like orange ndl. fr. ethyl ale.-Dibasic.-■ The blue solution in NaOH gives blue ppt. of Na salt with x's alkali which changes to green cryst. after 24 hrs. 200-1 Bithymoquinone, C^H^O^-Long clear yellow silky ndl., not vol. w. st.-V. d. s. solvents; i. abs. eth.; s. undec, in h. fuming HNO3.-Dist. gives much thymoquinone (cf. p. 205) !-Not reduced by SO2, but gives hydrothymo- quinone when dist. fr. Zn dust. 200-2 Euxanthonic Ac., [CeH3.(OH)2]2.CO.-Yellow warts or cryst. fr. h. aq.; s in KOH w. yellow color which darkens rapidly in the air.-Red-yellow ppt w. PbAc2 sol.-Fusion splits to euxanthone and H2O.-FeCl3 gives red color. 202 Quinacetophenone, Me.CO.C6H3(OH)2.-Pale yellow-green cryst.; v. d. s. c. aq. -Reduces Fehling's sol.-FeCl3 gives transient deep-blue color w. aq. sol. 202 j Phenanthrenequinone, C6H4.CO.CO.CGH4.-B. p. a. 360°.-Yellow-orange (YO) ndl.; sbl. in cryst.; d. s. h. aq.; d. s. ale. or eth.: e. s. h. Ac; e. s. warm NaHSO3 sol.!-Ignition w. Zn dust gives phenanthrene; w. soda-lime, di- phenyl.-Identify by Test 1014 ! 206d. a-Anthracenecarbonic Ac., Cj5H10O2.-Cf. Ill, A, 2. 202-19d. Scoparin, MeO.CGH3.(OH).C13HgO3.(OH)5+5H2O.-(In Spartium scoparium.)- Small clear yellow cryst. fr. 70% ale.; v. d. s. c. aq.; e. s. h. aq.; i. eth.; e. s. NaOH or Na2CO3 giving greenish-yellow sol.-Bleaching powder colors dark red.-HNO3 gives picric ac.-Fusion w. KOH gives phloroglucin, va- nillic, protocatechuic, and acetic acids. 211-12 Isoanthraquinone, C,4HSO2.-Pale-yellow ndl.-Fusion w. KOH gives blue mass. -More s. in H2SO4 than anthraquinone. 214-15 Pulvic Ac., C1sH12O5.-Orange pr. fr. ale. which effloresce to orange powder• s. aq., eth., CHC13, or bz.-Adds Br, and is oxid. by alkaline KMnO4. 210 SUBORDER II, DIV. A, SECT. 1. (order 1.) Melting-point (C.°). COLORED COMPOUNDS.-Solid Species of Determined Melting-point. 216-17 t Piperic Ac., CH2.O2.C0H3.CH:C2H2:CH.CO2H(3, 4, 1).-Pale-yellow (YT2) ndl., alm. i. aq.; s. h. ale. or eth.-f The sol. in dil. Na2CO3 when gently oxid. by warming on a watch-glass w. a few drops of KMnO4 sol. emits the delicate heliotrope aroma of piperonal!-BaA2, i. c. aq. 219 Purpurin-1-carbonic Ac., C]4H4(OH)3O2.CO2H.-Red 1ft., i. c. aq. or ale.; d. s. h. CHC13.-Sol. in Na2CO3 is orange-colored.-Boiling w. aq. or ale. gives CO2 and purpurin. d. 220 a-Dioxyanthracene, C14H1(1O2.-Yellow 1ft. or ndl., v. s. ale; the yellow sol, fluoresces strongly blue.-FeCl3 or Br gives blue-green color w. ale. sol. 220 Oxylepidene (" Needle-shaped"), C28H,0O2.-Yellow ndl., i. aq.; d. s. h. ale.; alm. i. eth. 227c. Diphenyleneketonecarbonic Ac., CO.C12H7.CO2H.-Yellow ndl. fr. alc.; i. aq.; s. cone. H2SO4 w. yellow color.-Gives oxime, m. p. 263°.-AgA yellow ppt. 231 Purpurinxanthinecarbonic Ac., C14H5(OH),O2.CO2H.-Golden 1ft. fr. glacial Ac, s. eth. or h. aq.; s. in NaOH w. red color, or in cone. H2SO4 w. intense yellow color.-Dec. above m. p. 231 2-Oxyxanthone, C13H8O3.-Yellowish ndl. fr. dil. ale.-Acetyl deriv., m. p. 161°. 232 Oxylepidene ("Octahedral"), C28H20O2.-Yellowish octahedra fr. h. Ac, alm. i. ale.; i. h. alcoholic KOH.-Heated nearly to boiling gives isomer, s. ale., w. m. p. 136°. 235 Chrysoquinone, C(H4.CO.CO.C10Hf).-Orange-red ndl.; s. h. ale.; v. d. s. eth.; s. in cold H2SO4 w. corn-flower-blue color, ppt'd by aq. (delicate). Sbl. in red ndl. Oxid. by KMnO4 to phthalic ac.-Ignition w. Zn dust gives chrysene. 240c. f Euxanthone, C13H8O4.-Pale-yellow (YT1) 1ft. or ndl.; sbl. w. dec.-I. aq.; e. s. h. ale.; d. s. eth.; s. NaOH or cone. NH4OH w. yellow color.--Green color w. FeCl3.-PbAc2 gives ppt. w. ale. sol.-Gives no oxime or phenyl- hydrazone. abt. 250 f Brazilin. - Cf. Gen. IV, A! - Cryst. red-brown after exposure to air and light. Sol. in NaOH intense red! Taste sweet! 253-6d. f Daphnetin, C9H4O2.(OH),.-When strongly heated on a watch-glass has a faint coumarin-like odor.-Pale yellowish ndl. fr. dil. ale. (preparation fr. Schuchardt YT3); s. h. aq.; v. d. s. eth.-FeCl3 added to a 1:4000 aq. sol. gives a permanent green (G) color, changing to red (RS2) when Na2CO3 is added (cf. Test 401).-Reduces ammon. AgNO3 or Fehling's sol. instantly.- Gives a yellow gelatinous ppt. w. PbAc2. 256 f Purpurin, 1, 2, 4-Trioxyanthraquinone, CGH4.(CO),.C0H.(OH)3.-Deep-red ndl. fr. abs. ale.-Long orange ndl. ( + H2O) fr. dil. ale.-S. aq. w. deep-yellow color (no absorption bands).-Sol. in eth. shows absorption bands at E and F.-Sol. in NaOH or Na2CO3 is bright red w. two absorption bands in the green.-Sol. in cone. H2SO4 is cherry-red.-Oxid. byHNO3 (cf. Test 905-3) gives phthalic ac.-W. alumina mordant dyes scarlet. 261 Acenaphthenequinone, C12H0O2.-Sbl. in yellow ndl.-V. d. s. ale. or c. Ac.- Dissolved to an acid by boiling w. KOH.-Reduction w. Zn dust in boiling Ac sol. gives acenaphthenon. 262-3 Xanthopurpurin, C0H4.(CO)2.CGH2.(OH)2.-Yellow ndl. fr. Ac.-Sbl. in orange ndl.-s. in Ba(0H)2 sol. (dif. fr. alizarin and anthrachryson).-S. in NaOH is red.-Boiled w. KOH in air gives purpurin (cf. spectrum above).-Igni- tion w. Zn dust gives anthracene.-Does not color fibre mordanted w. alumina. 266-8 Resorcinphenylacetein, C20H1GO4.-Mic. brown plates, green by reflected light, fr. ale. + Ac.; i. eth. or bz.-Dil. sol. in NaOH shows intense-green fluores- cence.-Diacetate, silky ndl. fr. Ac., m. p. 150° d. 267 Gentianine, C13H7O5.Me.-Pale-yellow silky ndl., d. s. h. aq., ale., or eth.; e. s. alkalies w. golden-yellow color, reprecipitated by CO2. Diacetate (boiling w. acetyl chloride), hair-like ndl. fr. ale., m. p. 196°.-Reduces Tollen's reagent. SUBORDER II, DIV. A, SECT. 1. 211 (order I.) Melting-point (C.°). COLORED COMPOUNDS.-Solid Species of Determined Melting-point. 275 f Anthraquinone, C6H4.CO.CGH4.CO.-B. p. 380° c.-Sbl. in pale-yellow ndl.- (284-5c.) S. 44 pt. h. ale.; v. d. s. c. ale. or eth.-V. stable, not attacked by boiling NaOH or oxid. agents.-Ignition w. Zn dust gives anthracene.-Identify bv Test 1011! 275 i, 3-Dioxyflavone, C15H!0O4.-Thin pale-yellow tbl.-Sbl. in ndl.-Alm. i. aq.; s. h. Ac.; e. s. alkalies w. intense-yellow color.--Ale. sol. is dirty violet w. FeCl3.-Split by boiling KOH to acetophenone, phloroglucin, etc. 276 2, 3-a-Dioxynaphthoquinone, (HO)2.C10H4.O2.-Orange-red 1ft., green by re- flected light!-Sbl. in ndl. w. metallic lustre.-D. s. h. aq.; v. d s. ale. or eth.-Sol. in NaOH is corn-flower blue; in Na2CO3 violet-blue.-E. oxid. to phthalic ac. by Test 905-3. 280 i, 5-Dioxyanthraquinone (Anthrarufin), C14HGO2.(OH)2.-Sbl. in light-yellow toothed 1ft., alm. i. aq.; d. s. ale.; s. eth.; alm. i. NH4OH, Na2CO3, or Ba(OH)2; e. s. KOH w. violet-red color.-S. cone. H2SO4 w. very intense- red color and fluorescence, distinct even at dilution of 1:10,000,000 !-Con- tinued fusion w. KOH gives salicylic ac., etc.-Ba salt is carmine-red. 282d. Pyrenequinone, C1GH8O2.-Sbl. w. slight dec. in light purple-red ndl., v. d. s. ale., eth., or CS2; s. NaHSO3; s. cone. H2SO4 w. brown color.-Ale. sol. +1 drop NaOH is dark wine-red, unchanged upon shaking w. air.-Ignition w. Zn dust in H gives pyrene. 283 /?-Anthraquinonecarbonic Ac., CGH4: (CO)2: C6H3.CO2H.-Yellowish pr. fr. ale., v. d. s. ale. or eth.-Sbl.-Boiled w. Zn dust and KOH gives intense-red color. 289-90 t Alizarin, C6H4.(CO)2.(CoH2.(OH)j.--B. p. 430°.-T.t. partly immersed in oil- bath at 200° sbl. slowly in OR and O. ndl.-I. aq., v. d. s., ale. or eth. -S. in v. dil. NaOH; sol. has red-violet (RV) color. More cone., sols, intensify the color, but the hue remains the same.-NaOH sol. is ppt'd by CO2 (dif. fr. isopurpurin). Alkaline sol. is ppt'd by BaCl2; not soluble in Ba(OH)2.-Sol. in cone. H2SO4 is purple-red.-Ignition w. Zn dust gives anthracene. 291-3 i, 7 (m-) 3enzdioxyanthraquinone, CI4HSO4.-Sbl. w. dec. in yellow ndl., s. eth. or ale.; s. NaOH w. deep-yellow color. 295c. Diacenaphthylidendione, C24H12O2.-Sbl. brownish-red ndl., v. d. s. bz.-Adds Br2 (comp. i. ale., 1ft. fr. CHC13 and Igr.) m. p. 237°.- Phenylhydrazone, brown-red cryst. powder, m. p. 105°-10°. 302 2-(m)-Oxyanthraquinone, CGH4.(CO)2.CGH3.OH.-Yellow 1ft. or ndl. fr. ale.-Sbl. --Alm. i. aq.; e. s. ale. or eth.; e. s. ammonia giving red-yellow sol.; s. Ba(OH)2 sol., and K salt s. ale. (dif. fr. alizarin).-Ignition w. Zn dust gives anthracene (Test 912). 305 Alizarin-/?-carbonic Ac., (HO)2.CGH2: C2O2: CGH3.CO2H.-Sbl. in red ndl., s. ale.- The sol. in alkalies is blue. 308 Naphthalflucrescein, C24H]4O5.- Large yellow rhombic pr. fr. eth.-Sol. in dil. NaOH is reddish yellow w. green fluorescence.-Acetyl derivative (fr. acetic anhyd.), m. p. 191°. 310 Anthragallol, C14HSO2.(OH)3.-Sbl. at 290° in orange-red ndl.-Brown sol. in ale. or eth. - S. alkalies w. green color. - Spectrum, cf. B. 19,2331.--Igni- tion w. Zn dust gives anthracene.-Pb salt, violet-brown ppt. fr. ale. w. PbAc2. 340 2, 3-Anthraquinonedicarbonic Ac., C]6H8O6.-Yellow ndl., e. s. ale.-Salts red- dish, alm. i. aq.-Warmed w. Zn dust and NH4OH is easily reduced to an- thracenedicarbonic ac. COMPOUNDS CONTAINING C, H, AND O [ORDER I]. SUBORDER II, COLORED COMPOUNDS. DIVISION A, (SUPPLEMENTARY) SECTION 2-SOLID SPECIES, MOSTLY OF HIGH OR ILL-DEFINED MELTING-POINT, GIVING INTENSELY COLORED SOLUTIONS IN DILUTE ALKALI. [The arrangement of species in this section of the tables is such, that compounds follow one another in the order that the hues obtained by dissolving them in dilute caustic soda occupy in the spectrum or color standard, beginning with red, and proceeding through orange, yellow, green, blue, and violet.--Since the hue as well as the intensity of these colors depends very much on the concentration, the colors should be produced and observed under the conditions pre- scribed on page 204. The exact order of succession is reasonably well established only for those compounds whose color reactions have actually been examined by the author with the aid of the color standard. The colors thus determined are distinguished from those based on the verbal description of other authorities by being followed by a color symbol (e.g., red = R). The preparations used in most of the writer's experiments on the species of this supplementary sec- tion were commercial products-sometimes pastes-from reliable manufacturers. The best preparations of this class are, of course, liable to slight differences in composition, and are never absolutely homogeneous.] Color of Solution in very dilute NaOH. COLORED COMPOUNDS.-Solid Species, giving intensely colored solutions in dilute Alkali. R-RV. Haematoxylin, C10H14O(i + 3H2O.-Brown cryst. (colorless when Intense VB in cone. NaOH. pure).-Taste sweet.-Sol. in cone. NaOH, deep violet (V or BV), becoming (R) on acidification w. HC1.-Sol in cone. H2SO4 orange (0).-Cf. Sec. 1, m. p. 140°. Red (R). Brazilin.-Red-brown cryst (colorless when pure).-Taste sweet.-Cf. Gen. IV, A, m. p. abt. 250°. Red (R) Flavopvrpurin, CI4H5O2.(OH)3.-Yellow ndl. or YOS1 paste.- (slightly RV). D. s. h. aq.; e. s. h. ale.-Sol. in cone. H2SO4 is red. ' ' Deep red." 2, 7-Dioxyanthraquinone, C]4H0O2.(OH)2 + H2O, [Isoanthraflavic Ac.].-Yellow cryst.; m. p. a. 330° after losing cryst. aq. at 150°.-Sbl.-Sol. in cone. H2SO4, deep red.-S. c. Ba(OH)2 sol ; s. ale.; alm. i. eth. "Fine red." Trioxyaurine, C19H9O.(OH)5.-Dark-red 1ft. fr. eth.-alc. Red (R). Purpurin, CeH4.(CO)2.C6H.(OH)3.-{Cf. Sec. 1, m. p. 256°}- Orange-red (ORS1) paste or ndl.-Sol. in cone. H2SO4, R-OR, changing to YO on dilution w. aq. Fuchsine red. Cresolaurine, C22H1SO.(OH)2.-Amorph. red powder; i. aq.; d. s. eth.-Sol. in Ac, yellow. Intense red to brown Resorcinoxalein, C,0H9O2.(OH)5.-Red powder.-S. in cone. (yellow-green fluorescence). H2SO4 w. emerald-green color.-The alkaline sol. diluted to a pale-yellow shows moss-green fluorescence. Red (w. green-yellow Orcinaurine, CrH15O2(OH)3. - Red-brown grains, v. d. s. fluorescence). ale. Red. Carminic Ac., C17HlsO10.-Red pr. fr. ale., or red-brown powder. E. s. aq.; sol. yellowish red.-Aq. sol. gives purple ppt. w. baryta sol.-Ale. sol. heated w. aniline gives ruby-red cryst. anilide, m. p. 190° d. Carmine-red. v Brazilein, C16H12O5.-Cryst. w. 1H2O. Powder reddish-brown. D. s. aq.; sol", rose-red w. orange fluorescence.-Alkaline sol. browns in air.-Triacetyl deriv., yellow 1ft. fr. ale., m. p. 203°-7°. 212 SUBORDER II, DIV. A, (SUPPLEMENTARY) SECT. 2. 213 (ORDER I.) Color of Solution in very- dilute NaOH. COLORED COMPOUNDS.-Solid Species, giving intensely colored solutions in dilute Alkali. Brownish red (fluorescent). Orange-red (OR) (not fluorescent). Yellow-red (not fluorescent). Orange. Red to yellow (according to dilution). Intense yellow-green (YG) fluorescence. Yellow-orange (YO). Yellowish brown. Yellowish brown. Orange-yellow. Orange-yellow (OY). Orange-yellow. Yellow. Deep yellow. Green. Fisetin, CiSH10Oc + 4H2O.-Cryst. in lemon-yellow ndl. w. 4 aq. (lost at 110°). M. p. a. 360° d.-S ale ; alm. i aq.-PbAc2 gives orange-yellow ppt. in ale. sol.-Reduces Fehling's sol. hot.-Tetraacetate, ndl. fr. ale., m. p. 200°-l°. Aurine, C19H12O.(OH)2 and Rosolic Ac., Me.C19HnO.(OH)2.- Commercial article a mixture w. very variable m. p (some- times as low as 90° or 100°), and w. strong odor of phenol.- Color of powder RO. Lumps show conchoidal fracture and greenish metallic reflections.-Sol. in cone. H2SO4 yellow (OY-Y).-A (1:5000) sol. in very dil. NaOH shows absorp- tion band at DjE to b. More cone. sol. shows one-sided absorption fr. violet to D line.-Sol. in ale. orange (O). Resaurine, C19HhO.(OH)3.-Amorph. light brick-red powder; e. s. ale.; alm. i. eth. 2, 6-Dioxyanthraquinone (Anthraflavic Ac.), C14HnO2(OH)2.- Sbl. in yellow 1ft., m. p. a. 330°.-Sol. in cone. H2SO4 yellow, showing broad absorption band between blue and green.- D. s. c. ale.; i. eth. Fluorescein, C20H10O3.(OH)2.-Yellow-orange (YOS1) powder. -Sol. in cone. H2SO4 (Y) w. slight greenish fluorescence.- I. c. aq.; d. s. ale. or eth.-Paper stained a pale yellow by dil. sol. in Ac becomes pink when held in steam from boiling Br water.-The very dil. sol. in dil. NaOH shows a distinct absorption band from a little to right of E to just beyond F. Phenacetolin (Phenacetei'n), C10H12O2.-Chocolate or red-brown powder. M. p. a. 330°. Sol. in cone H2SO4 (YOS1-2) - I. aq.; sol. in ale. orange; in dil. HC1 yellow; in dil. am- monia violet-red (VR). (Colors as given by a sample pur- chased from Merck.) Resorcinbenzeine, C3SH22O.(OH)8.-Pr. or 1ft., violet- or brown- ish-red; yellow by transmitted light. E s h. ale. when freshly precipitated, otherwise v. d. s.-Loses aq. at 130°.- Dil. ammon. sol. red-violet and fluorescent. Galloflavin, C13H6O9(?).-Greenish-yellow 1ft. Sol, in cone. H2SO4 orange.-D. s. h. ale.; sol. clear yellow w. faint-green fluorescence. Alizarin Yellow " C," CH3.CO.C6H2(OH)2.-Yellowish paste, e. s. h. aq.-Sol. in cone. H2SO4 yellowish.-Cf. Gallacetophenone (IV, A, m. p. 168°). Alizarin Yellow "A," Ph.CO.C,,H2.(OH)3.-Paste, gray yellow (light YA). E. s. h. aq.-Sol. in cone. H2SO4 clear yellow (Y). Quercetin, C15H10O7 + .tH2O.-Lemon-yellow cryst. powder. Loses H2O at 130°.-S. 280 pt. h. aq. or 229 pt. c. ale.-M. p. a. 250° (r. h.).-Ale. sol. dark green w. FeCl3, turning dark red on warming; gives brick-red ppt. w. PbAc2. Croconic Ac., CO:C:C:(CO2H)2 + 3H2O.-Pale sulphur-yellow ndl. or grains, e. s. aq.; s. ale.-Sbl. after losing aq. at 100°. -BaCl2 gives lemon-yellow ppt. of BaA+l|H20.-Ag salt, orange-red ppt. Luteolin, Cj5H10O0 + 2H2O(?).-Yellow ndl., m. p. a. 320° d.- Sbl.-S. 14,000 pt. c. aq., 37 pt. ale., or 625 pt eth.-Taste, bitter-astringent.-Sol. green w. little FeCl3, brown-red w. larger quantity.-Sol. in cone. H2SO4 yellowish green giving violet ppt. on dilution.-CaCl2 gives orange ppt., which becomes red and cryst. on boiling. a-Naphtholbenzeine, C54H34(OH)4.O.-Brown powder, i aq.; s. ale., eth., or bz. w. yellow-red color.-The green sol. in alka- lies is turned reddish yellow by acids. 214 SUBORDER II, DIV. A, (SUPPLEMENTARY) SECT. 2. (ORDER I.) Color of Solution in very dilute NaOH. COLORED COMPOUNDS.-Solid Species, giving intensely colored solutions in dilute Alkali. Intense G-YG. Coeruleine, C20HsO0.-Black powd. or paste, i. aq. or ale.-Sol. in cone. H2SO4 "dirty yellow-brown" (broken OY much darker than dark OY A). Blue. Alizarincyanin "R," C14H3O2.(OH)5.-Brown 1ft. or paste.- Dist. undec.-Sol. in cone. H2SO4 blue w. red fluorescence. Cornflower-blue. 2, 3-Dioxyanthraquinone, C14H0(OH)2.O2.-Orange-yel. ndl. fr. Ac, v. d. s. h. ale. or eth.-Sol. in cone. H2SO4 blood-red.- Ba salt dark-blue ppt. Cornflower-blue. 5, 6-/?-Dioxynaphthoquinone(i,4),(Naphthazarin),C10H4O2.(OH)2. -Sbl. in red-brown ndl.-Sol. in cone. H2SC)4 fuchsine red. -D. s. h. ale.; cryst. fr. ale. sol. in "green-brown" ndl.- Diacetate, yellow ndl., m. p. 192°. Intense blue. Pyrogalloquinone, C18H14O9.-Sbl. in garnet-red ndl. M. p. a. 220°.-D. s. ale.; s. eth.-Sol. in cone. H2SO4 carmine-red or on addition of trace of nitrous acid, intense violet. Br in Ac sol. gives clear red tetrabrom-derivative, m. p. 202°-4°. Intense blue (B). Alkannin, C15H14O4.-Dark red-brown resinous mass (softens below 100°).-I. aq.-Sol. in ale. orange-red (OR), and when dilute shows conspicuous absorption bands, one at Eb, the other at D(E; also two easily overlooked bands, one at F, and the other at DJC. The sol. in ammonia is blue with conspicuous absorption bands D and D^C. Intense Blue to VRT2 Galleine, C.)(|H10O7.-Dark red-brown powder, or small cryst. w. (according to concentration). green metallic reflections (also described as violet paste or powder). S. w. red-brown color in warm ale.-Heated w. fuming H2SO4 gives olive-yellow sol. (containing cceruleine) from which olive flocks separate on dilution w. aq.; the ppt. dissolves w. intense green color (G-YG) in dil. NaOH. Impure Violet. Rufigallic Ac., C14H2O2.(OH)6.-Orange-red (ORS2) cryst. or Blue (B) w. cone. NaOH. brown-red powder, i. aq.-Sol. in cone H2SO4 intense red, becoming yellow on dilution. Blue-violet. Alizarin Bordeaux, C14H4O2.(OH)4.-Sbl. in deep-red ndl. (green w. metallic lustre by reflected light).-Not melted at 275°. -Sol. in c. cone. H2SO4 has intense blue-violet color.-Baryta water gives blue ppt. w. ale. sol.-Tetra acetyl deriv . m. p. 201°. Red-violet (RV). Alizarin, C14H6O2.(OH)2.-(Cf. Sec. 1, m. p. 289°-90°.)-Sbl. in orange (0) ndl.-("Paste" OYS1-YOS1).-Sol. in cone. H2SO4 is red (R); dilution w. aq. gives OY ppt. Violet-red. Benzaurine, C]9H13(OH)3.-Brick-red powder, e s. ale. or eth.; i. aq.-Color of alkaline solution changed to yellow by acids. Violet-red. Resorcincinnamyleine, C2]H13O.(OH)3 + H,O.-Brown amorph. powder; at 100° becomes green w. metallic lustre-Ale. sol. red. Violet-red (VR). Iso or Anthrapurpurin, C]4H-O2.(OH)3.-Orange ndl. fr. ale., m. p. a. 330°.-(Paste YOS1). E. s. ale.; d. s. h. aq. or eth. -Sol. in cone. H2SO4 red, giving OY ppt. on dilution w. aq. RV Hgemateine, C1(H12OG.-Thin, mic., gray-green, water-free cryst. w. yellowish-green metallic lustre; commercial product a (Intense VB-V w. cone. NaOH). dark-brown powder. D. s. aq. or ale.; v. d. s. eth.-Sol. in cone. NaOH deep violet or blue-violet (V or BV), becoming red (R) on acidification w. HC1. Sol. in cone- H2SO4 orange (O).-Cryst. darken and decompose abt. 250° (dif. fr. hEematoxylin). COMPOUNDS CONTAINING C, H, AND O [ORDER I]. SUBORDER II, COLORED COMPOUNDS. DIVISION B-LIQUID SPECIES. Boiling-point (C.°). Specific Gravity. COLORED COMPOUNDS.-Liquid Species. 87-5-8 0-973(22°) f Diacetyl, Me.CO.CO.Me.-Yellow (Y) liquid of peculiar sweet- ish-pungent odor! Vapor w. color of Cl.-S. 4 pt. aq. at 15°. -Treatment w. alkali by Test IV, 2 gives an opaque brown sol.!-f To identify: Mix in a 3-inch test-tube 1 drop of the ketone, 1 cc. of aq., and 0-5 grm. of hydroxylamine hydro- chloride. Bod. A heavy cryst. ppt. of the pure white di oxime separates at once. Cool. Collect on a small filter. Wash w. c. aq. Dry at 100° for 15 min. The diacetyl- dioxime formed melts at 234 • 5° (uncor.) ! 108 0-948(19) Acetylpropionyl, Me.CO.CO.Et.-Color, odor, and behavior towards alkali as w. diacetyl above.-S. in 15 pt. c. aq.- M p. of dioxime 170°-2°! 115-16 Acetylisobutyryl, Me.CO.CO.CH.Me,.-Color, odor, and be- havior towards alkali as w. diacetyl above; but d. s. aq. 128 0-934(194) Acetylbutyryl, Me.CO.CO.Pr.-Color, odor, and behavior to- wards alkali as w. diacetyl above.-M. p, of dioxime 168° ! 138 0-908(2%) Acetylisovaleryl, Me.CO.CO. Bu.-Properties as for preceding comp.-M. p. of dioxime 171°-2°! 163 0-881(in/4) Acetylisocaproyl, Me.CO.CO.(CH )2.CH.Me2.-Properties as for preceding comp-M. p. of dioxime 172°-3°! 175-6 l-072(1%) Phenyldiacetyl, Me.CO.CO.CH,.Ph.-Viscous yellow oil. Odor honey-like, but pungent 216-18- l-104(i%) t Acetylbenzoyl, Me.CO.CO.Ph.-Yellow oil of peculiar sweet- ish-pungent odor. Vapors yellow. Browns w. NaOH in Test IV, 2.--M. p. of dioxime 239°-40° (cf. B. 22, 2129). 215 NUMBERED SPECIFIC TESTS FOR SPECIES OF SUBORDER II. ion. Anthraquinone. (Properties tabulated on p. 211.) Boil together in a test-tube for half a minute, a mixture of 5 cc. of an aqueous sodium- hydroxide solution (1 :20), 0.01 grm. of the finely powdered quinone, and 0.2 grm. of zinc dust. Filter quickly while hot through a plaited filter. Anthraquinone gives a deep- red (about OR) colored filtrate, which quickly becomes decolorized on shaking in contact with the air, in consequence of absorption of oxygen; while a flocculent precipitate of light- colored anthraquinone separates. Upon adding more zinc dust, heating, filtering, and shaking, the phenomena described may be repeatedly reproduced. This color reaction, which in the modified form as described by Claus (B. 10,926), is still more delicate and striking, although less convenient, is, in connection with its physical properties, the only test that will usually be needed for the identification of anthraquinone. ioi2. Benzoquinone. (Properties tabulated on p. 206.) Dissolve 0.05 grm. of the substance in 5 cc. of hot alcohol. Add 10 drops of aniline. Boil one minute. Cool. Filter. Wash the precipitate with 3 cc. of hot alcohol. Transfer to a test-tube, and boil with 20 cc. of glacial acetic acid. Cool. Filter. Dry, and observe the behavior of the compound on heating in a melting-point capillary. 2, 5-Dianili,noquinone, the product in this test, is obtained in the form of very insoluble and lustrous scales of a peculiar violet-red color, which, when dry, give a brownish " streak." It sublimes without melting at 325°-330° (uncor.). 1013-a-Naphthoquinone. (Properties tabulated on p. 207.) Boil together for one minute in a test-tube 0.05 grm. of the quinone, 5 drops of aniline, and 2 cc. of alcohol. Cool. Add 10 cc. of water and 1 cc. of acetic acid, and shake. Filter off the precipitate, and wash with cold water. Recrystallize from 10 cc. of boiling dilute alcohol (1 :1). (Very vigorous shaking is sometimes necessary to start the separation of crystals from the well-cooled solution.) Wash with 3 cc. of the dilute alcohol. Press on a porous tile. Dry 15 minutes at 100°, and determine the melting-point. 2-Anilinonaphthoquinone, the product in this test, is obtained as a fluffy dark-red (R-RS1) powder consisting of micro-crystalline needles, and melts at 190° (uncor.). 1014. Phenanthrenequinone. (Properties tabulated on p. 209.) 1. (Color reaction.)-Apply the reaction with caustic and zinc dust described in Test 1011. The color produced by phenanthrene is a quite pure and intense green. It is seen to the best advantage on the edges of the plaited filter. The green filtrate when vigorously shaken absorbs oxygen from the air (less rapidly than in the test for anthraquinone), and becomes yellowish. 2. Dissolve 0.05 grm. of the quinone in a mixture of 2 cc. of fuming nitric acid (sp. gr. 1.48) and 2 cc. of sulphuric acid (sp. gr. 1.84). Boil gently for one minute. Cool, and pour into 10 cc. of cold water. Collect on a filter, and wash thoroughly with hot water. Dissolve the washed precipitate in 15 cc. of boiling glacial acetic acid. Cool, and filter. Wash the precipitate with 3 cc. of glacial acetic acid. Dry 15 minutes at 125°, and deter- mine the melting-point. The product in this test a-2, 7-Dinitrophenanthrenequinone is a yellowish crystal- line precipitate which begins to turn brown about 270° (uncor.), decomposes to a sticky mass at 285° (uncor.), and completely liquefies to a black drop at 294° (uncor.). [TESTS 1011-1100.] 216 CHAPTER XIII. SPECIAL METHODS, APPARATUS, AND REAGENTS. Every department of experimental science gradually acquires a more or less considerable body of special laboratory methods which experience has proved are best adapted to meet its peculiar requirements. These constitute its special 'technique. The purpose of the present chapter is to bring together for explana- tion or comment a few methods of this kind which will be helpful to persons using the procedures of this volume. It is assumed that the reader is already familiar with the simpler manipulations of analytical and organic chemistry, and of experi- mental physics. MELTING- AND BOILING-POINTS. The numerical values of the melting- and boiling-points of organic compounds have such a wide range, and can be approximately determined with so little diffi- culty, that they are more regularly met with in the original descriptions of new species than any other physical constants. Unfortunately, however, only a very small fraction of these values are the result of fully corrected thermometric meas- urements, or of observations made under conditions that can be exactly duplicated. In using published data of this kind we have no choice but to assume that all necessary corrections for irregularities in the bore of the thermometer capillary, the value of its scale unit, and the position of its zero-point at different times have been made, though it is to be feared that chemists are often very negligent in this particular. But a very serious uncertainty always exists as to the proper interpretation to put upon values obtained at higher temperatures that are not followed by the word "corrected" or "uncorrected." In the neighborhood of 300°, a melting-point that has been corrected for stem-exposure is very likely to be about 10° higher than if uncorrected-a difference which is several times greater than the probable combined error from all other causes. What proportion of the great body of these unclassified melting- and boiling-points in chemical litera- ture has been corrected for stem-exposure can only be surmised; but the author's experience inclines him to accept the conclusion of Meyer and Jacobson's "Lehr- buch der organischen Chemie" (Vol. I, pp. 115, 116), that among organic chemists the unqualified "melting-point" has come generally to mean one uncorrected for stem-exposure; while the unqualified "boiling-point" (boiling-points often being taken in long-necked distilling flasks or with short-stemmed thermometers) is in most cases substantially "corrected." The confusion arising from this unfor- tunate and unscientific practice can only be entirely remedied by the careful redetermination of all the unqualified data. The melting-points given in the " numbered specific tests " of this volume are all uncorrected for stem-exposure; but they may be readily converted into "corrected" melting-points by simply adding the proper correction from the following empir- ical table. This table is applicable only to observations made in an apparatus of 217 218 SPECIAL METHODS, APPARATUS, AND REAGENTS. approximately the form and dimensions shown in Fig. 5, and the larger corrections may even then leave a residual error of about half a degree. [Table of stem-exposure corrections to be added to the direct readings of an otherwise corrected 360° rod thermometer, with a diameter of 5 mm., and a degree length of 0.85 mm., when immersed in a liquid bath from the -10° point, and with 100° of the stem within the air- space of the inner tube of an apparatus of the form and dimensions described below.] Observation (C.°). Correction (C.°). Observation (C.°). Correction (C.°). Observation (C?). Correction (C.°). 50 0.1 140 2.0 230 6.7 60 0.2 150 2.3 240 7.2 70 0.3 160 2.7 250 7.8 80 0.5 170 3.1 260 8.4 90 0.7 180 3.6 270 9.0 100 0.9 190 4.1 280 9.6 110 1.1 200 4.6 290 10.2 120 1.4 210 5.3 300 10.9 130 1.7 220 6.0 The Usual Method for Determining Melting-points.-These determinations are most conveniently made in the apparatus figured, because the closed flask prevents the free escape of fumes into the laboratory when high temperatures are being used, and also excludes dust and moisture from the bath to such an extent that frequent renewal of the liquid is unnecessary. In a laboratory where melting-points are frequently taken, it is well to have two such flasks, one for high and the other for low temperature determinations, always in readiness for immediate use. The flasks should be round-bottomed, with bulbs 65 mm. in diameter, and with necks 75 mm. in length and 20 mm. in diameter. Their capacity is about 200 cc. The inner tube, A, is a test-tube with a diameter of 15 mm., which hangs freely suspended by its flanged lip. Both the inner tube and the flask are filled with a clear liquid to the level B, it being a very bad practice to use the test-tube as an air-bath. The best bath for temperatures between 0° and 220° is probably colorless sulphuric acid of 1.84 specific gravity. The acid in the inner tube is, it is true, easily browned by contact with organic matter of any kind, and so must be renewed occasionally; but it has the advantage over dissolved or molten solids that when splashed upon the cool upper parts of the tube it drains back quickly without leaving any cloudy film to interfere with a clear view of the lower part of the thermometer scale. A bath highly to be recommended for tem- peratures between 220° and 320°, in connection with the foregoing,-and which may be used, though less advantageously, for the Fig. 5. SPECIAL METHODS, APPARATUS, AND REAGENTS. 219 entire range of temperature between 15° and 320°,-is prepared by cautiously heating in a porcelain casserole under a hood until boiling ceases at the higher temperature, a mixture of 70 parts by weight of concentrated sulphuric acid and 30 parts of neutral potassium sulphate, and stirring constantly until the sulphate is completely dissolved; or by similar treatment of a mixture of 55 parts by weight of the acid with 45 parts of acid potassium sulphate. The mixture has the con- sistency of glycerine,* and does not fume so badly as to prevent the use of rubber bands for attaching melting-point capillaries to the thermometer. It is less cor- rosive and less easily discolored by traces of organic matter than sulphuric acid. The phenomenon of fusion is observed in a thin-walled glass capillary, sealed at the lower end f, which is occupied by a few milligrams of the substance. These melting-point tubes should have a length of 6 to 7 cm. and an internal diameter of 1 mm. They are most readily made from rather soft glass tubes having an internal diameter not less than 1 cm.-not, as is often done, from small-bore tubing. A piece of such tubing, of convenient length, is supported at both ends and rotated in a blast-lamp flame until a ring 2 cm. long has been heated to dull redness. Then, upon separating the hands rather slowly, until both arms are outstretched at full length horizontally from the shoulders, a capillary of the desired diamete', and nearly two meters in length, may be drawn out in a single operation. To charge the melting-point capillary, force its open end downward into a small mound of the finely powdered substance. Then, holding upward the open end, which will now be closed by a short plug of the compacted powder, draw the flat side of a file horizontally across the tube a little below the substance. The powder, loosened by the vibrations set up in the glass, will quickly slide down into the desired position. The charged capillary is now attached to the thermometer by a narrow rubber band sliced off from a piece of rubber tubing. The band should be placed 2 cm. above the surface of the bath, and the substance in the capillary should be situated opposite the middle of the thermometer-bulb. If a sulphuric acid bath should be used at temperatures above 170°, a piece of fine platinum wire, which will not be attacked by the hot acid fumes, should be wound spirally around tube and thermometer, as a substitute for the band. With the potassium * After long exposure to the air it may become semi-solid through absorption of water, but is easily liquefied again by heat. When a melting-point above 300° is to be taken with a bath that has not been heated much above 250° for some weeks, it is advisable first to boil it for a few minutes. Otherwise the bubbles of steam given off in the neighborhood of 300° will cause bumping and interfere with the observation. Under certain obscure conditions the mixture may solidify to a hard mass, with a considerable rise of temperature. But this is a rare occurrence, and when it happens a short boiling will bring the bath back to its normal state. By increasing the proportion of neutral sulphate from 30% to 40% this bath may be used for temperatures up to 370°. Such a bath remains pasty until the temperature has fallen to 90°-60°. Either of these sulphate baths if slightly darkened by organic matter may be cleared by a short heating above 300° As a bath for temperatures between 370° and 500° fused zinc chloride, free from dust, may be employed. Since it is very apt to crack any flask in which it may be allowed to solidify on cooling, it should be poured out upon a clean tile as soon as the temperature has fallen to about 280°. j- The melting-points of a few compounds which fuse at high temperatures with decompo- sition and loss of water, carbon dioxide, or ammonia, have been found to be sharper when observed in capillaries sealed at both ends. These melting-points are, however, of very little value unless accompanied by a statement of all the dimensions of the capillary, and of the quantity of substance fused; for they will be found often to vary many degrees with a change in these conditions, because of differences in the gas pressures of the decomposition products. 220 SPECIAL METHODS, APPARATUS, AND REAGENTS. sulphate bath, however, rubber bands are not seriously attacked, even when th® bath is at 300°. For general convenience in manipulation, and because it is probable that a majority of the organic melting-points on record have been obtained by instru- ments of approximately these dimensions, the use of a thermometer with a grad- uation extending from -25° to +360°, with degree-marks about 0.85 mm. apart, is to be preferred. A thin stem (diameter about 5 mm.) is advantageous, as it saves space and acquires the temperature of the bath quickly. The direct read- ings of such a thermometer may be sufficiently corrected for stem-exposure by means of the table on page 218. (For a discussion of the other thermometric corrections cf. Crafts, Am. V, 309.) The proper rate for heating in a melting-point determination depends some- what on the behavior of the compound. Substances that melt without any decom- position are always to be heated very slowly, as the melting-point is approached. An average rise of 2° per minute for the last 5° is fast enough; for it is only by proceeding slowly that we can feel reasonably sure that the substance and ther- mometer are both at the same temperature. On the other hand, with substances that begin to decompose slightly before fusion, slow heating increases the quantity of decomposition products, and gives mixtures which will begin to melt much too low. Substances of this class should be heated rapidly to within a few degrees of their probable melting-point, and then at a rate of about 5° per minute. As has been shown by Reissert* and others, the true melting-point of com- pounds that melt without decomposition, when the fusion is observed in capillary tubes, lies much nearer to the temperature observed at the moment when minute droplets are first formed from particles of fine powder in actual contact with the capillary wall, than that at which a more considerable portion of the mass has become liquid; for, while the temperature of the melting compound must remain constant during the period between incipient and complete fusion,-in obedience to the well-known law,-that of the bath and thermometer is meanwhile gradually rising. The temperature recorded just before the moment of complete liquefac- tion will, however, generally be nearer its true melting-point for any compound that melts with slight decomposition, or contains traces of impurities. Differences of 2° between melting-points obtained by different methods of observation are quite possible. In taking the melting-points of compounds that fuse to mobile liquids, a very common practice among organic chemists-regardless of theoretical considera- tions-seems to be to observe the thermometer at the moment when the first clear drop of sufficient size to detach itself from the solid mass and roll down the capillary under the influence of gravity makes its appearance. As this moment is usually easier to fix than that of the appearance of the first minute droplets, and with pure stable compounds gives values nearer the true melting-point than * A. Reissert, B. 23, 2239. The true melting-point of a compound is its temperature of fusion as recorded by a thermometer immersed in a considerable quantity of the melting mass, as is described on page 225. It usually differs somewhat from the melting-point that would be found by using the capillary method. The melting-points of the specific descriptions in this volume are all capillary melting-points. SPECIAL METHODS, APPARATUS, AND REAGENTS. 221 the moment of complete fusion, or than the moment of incipient fusion with com- pounds that are not free from every trace of impurity, this method of observation is to be recommended as on the whole the most satisfactory for analytical use. The Usual Method for Determining Boiling-points.-The apparatus required is shown in Fig. 6. The bulb of the distilling-flask has a capacity of 10 to 15 cc., and the volume of liquid to be distilled is preferably 5 to 10 cc. The bottom of the flask rests in a circular opening cut by a brass cork-borer in a square piece of asbestos board, A, having a thickness of 3 mm. The perforation should have a diameter of about 2 cm. and be slightly beveled by a file on the upper edge, to make it fit closely to the surface of the flask. If the contact is not good at all points when the flask is pressed down into the opening, it may be improved by the use of an annular washer of thin asbestos paper, B, which will pre- vent the upward leakage of hot gases from the flame. C is a threefold wrapping of asbestos paper reaching to a point 1 cm. above the side tube. Its object is to prevent sudden condensation of vapor and consequent thermometric fluctuations, if the apparatus should happen to be ex- posed to a draft of cold air. The thermometer should be thin-stemmed, and inserted along the central axis of the neck of the flask, with its bulb well below the side tube. If there is a stem-exposure, a light auxiliary thermometer-not shown in the cut-will be attached to the main thermometer by rubber bands with its bulb opposite to the middle of the exposed mercury column. The neck of the distilling-flask above the side tube should be as short as possible, since, if the space which it contains is large, it will not be entirely filled with vapor at the tem- perature of the boiling liquid. Unless the substance shows marked signs of decomposition when boiled, dis- til slowly, i.e., at a uniform rate of about 0.5 cc. per minute. Since some time will elapse before the thermometer can acquire the temperature of the vapor, little significance should be attached to readings taken before the end of the first minute after the fall of the first drop of distillate. Interrupt the distillation when the liquid remaining in the flask has fallen below the level of the asbestos diaphragm. Any reading taken after this point has been reached, when less than 1 cc. will remain m the flask, will be influenced by superheating,* and should be rejected. Fig. 6. * Superheating.-The great advantage to be derived from the use of asbestos screens in this determination is not generally appreciated; and it will surprise many to learn that a boil- ing-point taken in a 10-cc. flask with the simple precautions given, will be more worthy of con- fidence than one made with a tenfold greater quantity of substance in which they are omitted. Much time and material would be saved if such screens were generally utilized in fractional dis- tillations whenever the quantity of material to be boiled is rather small. As practical illus- trations of the danger of superheating the vapor of liquids boiling in unscreened flasks, the follow- ing instances, which are copied from the author's note-book, will be of interest. (1) 5 cc. of "frozen," thiophene-free benzene was distilled in a 10-cc. distilling-flask of the usual pattern; first, rapidly, the flask being unscreened; then, slowly, with the bottom of the 222 SPECIAL METHODS, APPARATUS, AND REAGENTS. In the case of pure compounds that boil without decomposition, the difference between the first and last significant readings (after being corrected for stem- exposure, if the temperature of the auxiliary thermometer rises considerably during the experiment) ought not to amount to one degree. The boiling-points of sub- stances that suffer slight decomposition during distillation are often expressed as falling between two limits. The stem-exposure correction may be found by substitution in the formula N(T - t)X 0.000154; in which N represents the length of the exposed thread of mercury (expressed in degrees); T, the observed boiling-point; t, the temperature of the auxiliary; and 0.000154, the apparent coefficient of expansion of mercury in glass. To reduce boiling-points taken under pressures between 720 and 7S0 mm. to their approximate values at 760 mm., apply a correction of 0.1° C. for every 2.7 mm., the correction having a plus sign below 760 mm., and a minus sign with higher pressures. Determination of Boiling-points of Small Quantities.*-If only a few drops of liquid can be spared for a boiling-point determination, the following procedure should be used: About three drops of the liquid are introduced into a na.rrow glass tube, A, by means of a medicine-dropper having a long capillary point. The tube A should have a length of 6 to 7 cm. and an internal diameter of 2.5 to 3 mm. It is sealed at the lower end; attached to the thermometer by a rubber band; and is heated in the bath used for determining melting-points (page 218, Fig. 5). To prevent the super- heating, and violent boiling that would otherwise occur on heating, the slender capillary B is dropped into the liquid. These tubes are made from narrow pieces of melting-point capillary (cf. page 219), by heating the glass at the point C in the edge of a flame, the tube being supported at both ends, until the walls melt and fuse together. This leaves a little chamber under C, closed above, but open below, which is to be cut off so as to have a length of 3 mm. To make the determination, the temperature of the bath is grad- ually raised until the single air-bubbles that begin to rise from the capil- lary chamber some degrees below the boiling-point are replaced by an apparently uninterrupted thread of small vapor-bubbles. The lamp should now be removed, until boiling ceases and the liquid is seen to be about to recede into the capillary chamber. The temperature at the moment of recession is that at which the liquid remaining in the tube would begin to boil. In the case of compounds that are not quite pure it is not necessarily Fig. 7. flask resting in an asbestos diaphragm 12 mm. in diameter. The temperatures observed at intervals of one minute in the case of the unscreened flask were-80.3°, 81.0°, 82.2°, 86.0°, and, as the last drops disappeared, 93°. With the screened flask the minute observations noted were-79.8°, 80.0°, 80.0°, 80.0°, 80.0°, 80.0°, 80.1°, 80.1°, 80.2°, of which the last two readings were taken after the liquid had reached the level of the screen, and of which the first was proba- bly registered before the thermometer had quite acquired the temperature of the heated vapor. (2) 17 cc. of pure water was rapidly distilled from an unscreened 50-cc. flask. The pre- caution was taken not to allow the visible flame of the burner to play on the glass above the surface of the liquid, and boiling was stopped when 5 cc. of water remained in the flask. The readings obtained were 100.2°. 102.0°, 106°, 108.0°, 108.0°. The intervals between all these readings, with the exception of that between the last two, which was 30 seconds, were 1 minute, as in the experiment with benzene. * Siwoloboff's method (slightly modified), B. 19, 795. SPECIAL METHODS, APPARATUS, AND REAGENTS. 223 identical with that of the chief constituent of the mixture. Hence, after noting the temperature at which recession begins, heat should always be applied again until the continuous thread of bubbles reappears, and the boiling then continued until nearly half the liquid has evaporated from the tube. If the temperature of the second recession is identical with the first, it is probably the boiling-point of a pure compound. If it differs a few degrees from the first, it may be accepted as the most probable boiling-point of the chief constituent of the mixture. If the capillary chamber should entirely fill with liquid while the observation of the first recession is being made, it will have to be emptied, or the capillary replaced by a fresh one before the experiment can be repeated; for a tube con- taining neither air nor vapor affords no protection against superheating, and gives no thread of bubbles when the boiling temperature is passed.* Two kinds of tests for chemical purity will be discussed under this head. The evidence of homogeneity that may be furnished by those of the first class is identity of the melting- or boiling-point of the original substance with the melting- or boil- ing-points of all portions into which a given mass of it may be subdivided by any method of fractionation that, without causing decomposition, would naturally tend to bring about a difference in the proximate composition of the fractions if the substance were a mixture. Tests of this class will be distinguished as "frac- tionation tests." Tests of the second class, which it will be convenient to call "sharpness tests," depend on the fact that it is rather unusual to meet with mixtures of two or more compounds that can be completely melted or distilled within a fraction of a degree of the temperature at which fusion or boiling begins, while it is characteristic of pure stable compounds to melt or boil at definite temperatures and not between limits. The temperature interval between incipient and completed fusion or boiling, when measured under fixed conditions, is a definite property of every stable mix- ture, which may be given the name of "fusion-interval" or "boiling-interval." The magnitudes of these "intervals," in the case of a substance of doubtful chemical homogeneity, are often highly significant in their indications. Examples illus- trating their interpretation as purity indices are given in the tables on pages 226 and 227. The sharpness tests have the advantage of being applicable to all stable substances without any preliminary operations. The fractionation tests involve more operations, but when completed are more conclusive. THE THERMOMETRIC INDICATIONS OF CHEMICAL PURITY. * The fact that light glass tubes containing a small chamber for air or vapor at one end prevent bumping and promote regular boiling is capable of many applications. With their aid even such troublesome liquids as concentrated sulphuric acid and concentrated potash solu- tion may be safely boiled in narrow test-tubes, if care is taken never to permit the vapor-chamber to fill by a temporary cessation of the boiling. The only precautions necessary to this end are to carefully shield the flame and the vessel from drafts of cold air after boiling first begins, and to make the vapor-chamber of such a length that it will at all times be entirely covered by the boil- ing liquid. Such ebullator-tubes are, like melting-point tubes, best made (cf. p. 219) by drawing out large-bore tubes at the blast-lamp. They must be long enough to find support against the walls'of the flask or test-tube in which they are used, but so thin and light as not to endanger its safety. The diameter of the vapor-chamber will generally be 1.5 to 3 mm., and its height always less than that of the liquid in which it is to be used. If a chamber of small diameter becomes accidentally filled, it is most quickly emptied by being passed slowly through a flame. It should then be allowed to cool before being used. 224 SPECIAL METHODS, APPARATUS, AND REAGENTS. Fractionation Tests. [For Solids.] (1).-Determine the melting-point of the substance. Recrystallize it from some volatile solvent in which it is not very soluble in the cold. (Crystallization from a hot saturated solution is the most rapid method.) If necessary, concentrate the mother-liquors by evaporation. When about three-quarters of the substance has been recovered in solid form, collect the crystals all in one portion and drain them. Press; dry; and determine the melting-point. If this melting-point differs slightly from that obtained before crystallizing, repeat the treatment. If it remains unchanged, repeat, using a different solvent. Reject the mother-liquors; or unite them and recover the dissolved matter by evaporation. If the substance is chemically homogeneous, the melting-points of the several successive crystallizations should be identical. If it is a mixture, some constitu- ents will probably pass into the mother-liquors more rapidly than others, and the melting-points of the several crystallizations will differ. This procedure is almost always used when the quantity of substance is very small, and is shorter than the method which follows. (2).-Prepare a saturated solution of the substance in some chemically inactive solvent. By cooling, or by evaporation, crystallize out the entire quantity in three fractions, of which the middle one (2) should be the largest. Wash, drain, and dry the fractions (1) and (3), and determine their melting-points carefully. If these two melting-points are identical with that of the original substance (espe- cially if they are sharp), the substance is quite probably homogeneous. The test may be made more rigorous by recrystallizing each of the end fractions, and deter- mining the melting-points of the first crystals separating from fraction (1), and of those that separate last from the mother-liquor of fraction (3); or the test may be repeated with other solvents. [For Liquids.]-Distil the substance, if practicable, through a fractionating tower, and collect three fractions, of which the middle one (2) should be the largest. Carefully determine the boiling-points of fractions (1) and (3), and compare them with that of the original liquid. A more elaborate fractionation is of course often necessary. Sharpness Tests. Three procedures for tests of this class will be given: two for solids, and one for liquids. (1).-[Fusion-interval for Solids in Capillary Tubes.] This procedure is identical with "The Usual Method for Determining Melt- ing-points" already described on page 218. The "interval" is the difference between the temperature when the first clear droplets can be distinguished on the capillary walls, and that at which the substance becomes entirely liquefied. On account of its simplicity it is in constant use in organic laboratories; but it is a crude method, and in general cannot be depended upon to do more than indicate the existence of gross impurity, apparent intervals of more than one degree often being obtained in the examination of very pure compounds, even when great pains are taken to raise the temperature regularly and slowly. The deficiencies of the method are not difficult to explain. The thermometer registers the temperature SPECIAL METHODS, APPARATUS, AND REAGENTS. 225 of the bath, and not that of the melting substance in the capillary. The substance, according to its thermal conductivity, heat capacity, state of subdivision, and the diameter of the capillary, melts more or less slowly-but, if chemically homoge- neous, without changing its temperature. The temperature of the bath and ther- mometer are, however, meanwhile slowly but constantly rising. (2).-[Fusion-interval for Solids with Thermometer Immersed in the Melting Sub- stance.] This procedure has been comparatively little used, but is more satisfactory in its results than (1). When the necessary apparatus has once been set up, it can be applied to compounds of low melting-point without any special diffi- culty. The apparatus required is shown in Fig. 8. A is a 7-inch test-tube, supported within a thin glass air- jacket B by cork or asbestos rings CC. Through the cork D pass the thermometer E for registering the melt- ing-point, an auxiliary thermometer F for use in the correction for stem-exposure-when this correction is necessary-and a light but strong stiff stirrer PI. The whole arrangement is heated by immersion in a bath of water, glycerine, or molten paraffin, contained in a tall narrow beaker provided with a stirrer. Bring 10 to 15 grams of the dry poxvdered substance into A. Heat the outer bath quickly to a temperature 10° to 15° higher than that of the melting-point, and then hold it nearly constant during the remainder of the experiment. Set the inner stirrer in motion as soon as the substance melts enough to allow it to be worked freely. This will usually be several minutes after the powder shows the first signs of shrinkage and softening. Take the first reading a minute or two later, when the bulb of the thermometer is surrounded by a pasty mass in which all interstices are evidently filled by liquid; and continue to record observa- tions at intervals of one minute, until not more than one or two centigrams of substance remain unfused. About fifteen or twenty readings in all will be made. To prevent parallax errors, that would otherwise render the readings nearly worth- less, make all observations through the horizontal tube 0. A brass cork-borer (diameter 5-10 mm.), thrust through a large cork and supported by an iron clamp, is an admirable arrangement for the purpose. It has been shown that the average of several readings of the same temperature taken in this way by practised observers, on thermometers whose degree divisions are 1 mm. in length, contains a probable error of only a few hundredths of a degree. The fusion-interval in this method is the difference between the means of the first and last three accepted observations; or, if there are not more than ten obser- vations in a series, between the means of the first and last two observations. The first and last reading in a series should, however, always be rejected, if they show a considerably more rapid change of temperature during the minute in which they Fig. 8. 226 SPECIAL METHODS, APPARATUS, AND REAGENTS. were taken than occurred during other periods of equal length; for such a behavior usually indicates that the thermometer has either not been long enough in contact with the bath at the beginning of an experiment to acquire its temperature, or else that the quantity of solid substance remaining unmelted near the end of the test was too small to prevent a measurable rise in temperature in those portions of the liquid with which it was not in immediate contact. Perfectly pure crystalline compounds that melt without decomposition should give an "interval" by this method that is not greater than the unavoidable error of observation. The true melting-point of a slightly impure compound may be assumed to lie nearest to the higher limit, since impurities cause depression. The following table* of fusion-intervals illustrates the kind of information that may be derived from the application of this test. TABLE OF MELTING-POINTS (CORRECTED) AND FUSION-INTERVALS. No. Substance. M. P. (C.°) Interval. 1 Naphthalene, specially purified 80-08 0-00 2 ' ' best commercial 79-55 0-20 3 Benzophenone, specially purified 47-93 0-06 4 " +1% of No. 1 46-83 0-54 5 Salicylic Acid, good commercial 157-81 0-04 6 Thymol " " 49-51 0-21 7 Stearic Acid, sold as ' ' C. P." 63-7 2-8 8 " (once recryst. from Alcohol) 65-65 1-70 9 " " (twice ' ' " " ) 67-80 0-80 10 ' ' (thrice " " " ) 68-80 0-00 11 Cane-sugar Crystals (melts with decomposition) .... 153-8 (?) 8-8 (?) (3).-[Sharpness Test for Liquids.] Distil 5-8 cc. of the liquid from a 10-15 co. (or larger) distilling-flask, with all the precautions mentioned in the directions given for boiling-point determinations on page 221, recording thermometer readings at intervals of one minute. The readings must be made through a narrow horizontal tube, mounted and used as in the determination of the fusion-interval (cf. Fig. 8, page 225). The "boiling- interval" will be the difference between the mean values of the first two and the last two significant readings. Results by this method are of the same order of reliability as those for the fusion-interval by procedure 2, but are so much more easily obtained that pro- cedure 3 is of far greater practical importance. The significance that may be safely attached to boiling-intervals in special cases will be best understood from an inspection of the following table, in which a considerable number of such data obtained from typical pure and commercial preparations and mixtures have been collected. * The results in this table, as well as those bn the boiling-interval on page 227, were obtained by Mr. Arthur Davis in the author's laboratory, by the use of a 360° thermometer, the length of whose degree was slightly less than one millimeter. The last significant figure in all these results was secured by the process of averaging, and has a probable error of about three units. Substances 1 and 3 had been brought to a condition of exceptional purity by distillation and repeated recrystallization from alcohol. Their behavior is that of the typical, pure stable compound. 2 and 4 illustrate the effect of slight impurity in the case of the same substances. 2, 5, and 6 are good examples of what may be expected from high-grade commercial prepara- tions of good stability. 11 shows the uselessness of sharpness tests for pure compounds that decompose noticeably in melting. Numbers 7-10 show the progressive changes in the inter- val that occur in the crystallization of an impure substance by a suitable method. SPECIAL METHODS, APPARATUS, AND REAGENTS. 227 TABLE OF BOILING-INTERVALS OF TYPICAL COMPOUNDS AND MIXTURES ILLUSTRATING PROCEDURE (3). Substance. Boiling- interval (C.°). Benzophenone, specially purified 0-00 Benzene, free from thiophene, "frozen" 0-05 Para Toluidine, Kahlbaum's 0-03 Drtho Toluidine, Kahlbaum's 0-28 Nitrobenzene, Merck's, from cryst. Benzene 0-13 " " commercial grade 0-25 Dimethylaniline, Merck's, free from mono compound " " commercial grade 0-13 0-85 Resorcin, Kahlbaum's 0-23 Acetone, from the bisulphite compound 0-35 " "56-58 chemically pure," Merck's 0-38 Ethyl Alcohol, 95% 0-25 Aniline, Kahlbaum's intermediate grade 0-52 Phenol Merck's "Synthetic" 0-83 Paraldehyde, Kahlbaum's 1-25 Methyl Acetate, Kahlbaum's ■ 1-33 Benzaldehyde, originally " C. P.," but slightly oxidized 1-80 Glacial Acetic Acid, containing about 2% water 2-50 Acetoacetic Ether, Kahlbaum's (boiled with some decomposition) 3-00 Cinnamic Acid, Merck's (boiled with decomposition) 3-45 Amvl Acetate, Kahlbaum's, a mixture of isomers 3-70 Ethyl Ether, commercial, U S. P., containing much alcohol and water 40-85 Benzene containing 5% Toluene 2-32 Nitrobenzene containing 5% o-Nitrotoluene 0-97 Acetone containing 5% Methyl Alcohol 0-92 Para Toluidine containing 5% o-Toluidine 0-60 "Constant-boiling Mixture" of Methyl Alcohol and Benzene * 0-15 SPECIFIC GRAVITIES. The specific gravity of solid organic compounds has been determined for com- paratively few species, and is consequently not at present a property of great analytical importance. Tht specific gravity of liquid compounds, on the con- trary, has been determined with almost the same regularity as the boiling-point, and sometimes affords the simplest possible means for the arrangement of such species into "Sections." The recorded values for the specific gravities of organic liquids are usually reliable in the second decimal place, often in the third, but very rarely in the fourth. As the analyst will often have too little of a pure compound to enable the deter- mination of its specific gravity by the Westphal balance or hydrometer, two other methods for the determination, which are also rapid and usually sufficiently accu- rate for his purpose, will now be described in detail. * Ryland, Am. 22, 384 [1899],-This mixture is an example of many known cases of two miscible liquids, that, when once brought together in certain proportions, boil like a pure com- pound, and can not be separated by the usual method of fractional distillation. The analyst is not very likely to meet such mixtures ready formed in commercial preparations, the chances all favoring the presence in excess of some one constituent. He may, however, somtimes pre- pare such mixtures for himself, while attempting to resolve a mixture into its constituents by fractional distillation. Such mixtures have a constant boiling-point only under the atmos- pheric pressure at which they were prepared, so that the absence of homogeneity may be detected by distilling over one half in vacuo and then determining the boiling-interval under (he ordi- nary pressure of what remains in the flask-provided both constituents do not have the same vapor-tension at all temperatures, which is a coincidence that is very unlikely to occur. 228 SPECIAL METHODS, APPARATUS, AND REAGENTS. Determination of the Specific Gravity of Small Quantities of Liquids. (1).-[Method for 0.20 cc. of Substance] Prepare a pycnometer for this purpose by bending a piece of thick-walled glass tubing 28-30 cm. in length, into the form shown in Fig. 9. The tubing should be of the kind used in gas analysis for transferring gases from one container to another, and have an internal diameter of 1 mm. and an external diameter of about 5 mm. The part between A and B should be drawn out to form a narrow-bored but thick-walled capillary, 8 cm. long. The zero- point of the instrument is a short, thin hori- zontal scratch made at C. To calibrate the pycnometer begin by attaching a few centimeters of clean rubber tubing at D. Slip the point of an ordinary medicine-dropper M into the open end of the rubber tube, and then a light brass burette-clip over the latter, so that it may be quickly clamped off at any time at D. Next incline the instrument as shown in the figure, so as to immerse the point of the capillary in cold water contained in a 3-inch test-tube. The manipulation will be facilitated by having the test-tube held in a clamp. Open the clip at D. Compress the rubber bulb of the dropper to expel air. Then allow the bulb to expand slowly again, so as to suck water into the pycnometer. When the latter has filled to the horizontal arm above the zero-mark, close the clamp. Separate the dropper from the rubber tube. Then take off the clamp and separate the rubber tube from the pycnometer. Next suspend the pycnometer for some time in the air from the hook of the analytical balance, or for five minutes in a beaker containing cold water having the desired temperature. When the instrument and its contents have acquired the temperature of their surroundings, touch the edge of a bit of dry filter-paper to the tip of the capillary A, which must be filled by the water. As the water is absorbed by the paper, its level in. the longer arm of the pycnometer will gradually fall. Bring this level exactly to the zero-mark. [If care is taken in subsequent operations not to incline the capillary AB much below a horizontal position, no water will flow out.]-The pycnometer is now ready to be weighed, unless it has been suspended in water, in which case it must first be carefully wiped dry. To determine a specific gravity by this method, fill the pycnometer with the organic liquid by the manipulations described above in connection with the cali- bration. If we then represent the weight of water required to fill the instrument to the reference-mark by w, and the weight of the same volume of the organic compound by o, the'specific gravity, uncorrected for temperature, will be The result should not differ from the true gravity by a full unit in the second decimal place. After use, the pycnometer should be washed out at once with alcohol or ether, and thoroughly dried by an aspirated current of dry air. When not in use, it Fig. 9. SPECIAL METHODS, APPARATUS, AND REAGENTS. 229 should be kept in a clean box along with a carefully adjusted counterpoise made from thick sheet lead, and a card giving the weight of water which it contains at the room temperature. As long as the counterpoise continues to balance the dry piknometer, its capacity may be assumed to have undergone no change. (2).-[Method with 1 cc. Pipette.] This very rapid method has an accuracy limit of about a unit in the third deci- mal place. Calibrate a pipette (A in Fig. 10), to contain (not deliver) one cubic centi- meter when filled to the reference-mark. If the determinations are to be made at about 20°, scratch the reference-mark on the pipette stem at the level of the lowest point of the meniscus seen when the pipette contains 0.9982 grm.* of distilled water at that temperature. Then the weight in grams of any liquid having the same volume at 20° will be the number express- ing its specific gravity at 20°/4°. The pipette is to be manipulated as follows: Suck in the liquid until it stands about half a centimeter above the reference-mark. Wipe off any traces of the liquid adher- ing to the outside of the stem. Then allow it to run out until the meniscus just touches the reference-mark. Wipe off the fraction of the last drop that hangs from the nar- row outlet of the pipette, by touching it with the finger. Stand the pipette in the recipient tube B. Support the apparatus by the aid of the attached platinum wire on the balance-pan, as shown in the cut, and weigh at once. If an accurately adjusted lead counterpoise for the entire apparatus is kept in readiness and placed upon the oppo- site pan of the balance, the weights that have to be added to produce equilibrium give the desired gravity directly without any calculation. Fig. 10. * The correct location for this mark is most easily ascertained (as suggested in Ostwald's "Physico-chemical Measurements") by gumming a strip of millimeter-paper to the stem of the pipette and determining the weight of water corresponding to two points on the scale, one on each side of the true position and 10 mm. apart. "Then, on the justifiable assumption that the stem is cylindrical throughout this short piece, we can calculate the proper position of the mark from these two weighings." If, for instance, one weighing is 1-0222, the other 0-9930, 1•0222 0•9982 and the desired weight 0 • 9982, then the reference-mark should lie --QQQnX 10 =8 • 3 mm. below the upper mark on the paper scale. If it is desired to calibrate the pipette for use in comparing the density of a liquid at some other temperature than 20° with that of water at 4°, the proper weight of water to be used may be taken from the accompanying table of the density of water at various temperatures. Tempera- ture (C.°). Densities. Tempera- ture (C.°). Densities. Tempera- ture (C.°). Densities. 15 0-9991 21 0•9980 26 0-9968 16 0 • 9990 22 0-9978 27 0-9965 17 0-9988 23 0-9976 28 0-9963 18 0-9986 24 0-9973 29 0•9960 19 0-9984 25 0-9971 30 0-9957 DENSITY OF WATER BETWEEN 15° AND 30°. 230 SPECIAL METHODS, APPARATUS AND REAGENTS. COLOR. According to Aubert there are at least one thousand hues in the solar spectrum which may be distinguished by the human eye as different. Each of these hues may again be varied many times by changes in luminosity and admixture with white light, giving in the aggregate, it is estimated, as many as two million color differences that are recognizable under favorable circumstances. Yet, although the color of a chemical compound is often its most salient physical property, and the changes which this color experiences when treated with reagents may furnish the simplest test that can be applied for its identification, careful analysts have always very properly refused to attach the same importance to verbal descriptions of subjective color phenomena as a means for specific characterization, that they willingly grant to the recorded values of melting-points, boiling-points, specific gravities, and other physical constants whose determination requires the use of comparatively slow and elaborate methods of measurement. The chief causes for the disrepute into which color tests have fallen are: the customary failure, except in spectroscopic work, to refer colors to any well-defined standard; the loose use made of the terms constituting the popular nomenclature of color; the imperfect development of the color memory; and, finally, the fre- quent omission of minor but essential experimental details from the directions given for the performance of color reactions. To minimize these defects in the original color descriptions and tests of this work, it has been considered desirable, whenever possible, to consistently adhere to a more definite color terminology than has before been used for chemical purposes. It has been necessary, how- ever, to leave all copied color descriptions recorded in terms of the crude popular standard in which they were found; i.e. a standard in which red might signify any- thing from violet-red to orange, or from pink to russet. The Terminology of Color.-To prevent possible misunderstandings, before proceeding to the subject of color comparisons, it will be necessary to define the sense in which certain common color terms will be used. It should be remarked that the restricted meanings that will be accepted for the terms have the sanction of good authority, though they are sometimes used popularly, and by artists, with very different meanings. A Pure, Full, or Saturated Color is the most intense expression of that color without admixture of white, black, or gray. No pigmentary color is absolutely pure. A surface painted with artificial ultramarine blue, for example, reflects with the blue about 25 per cent of white light, the effect of which is to soften the color and reduce its action on the eye. In the color-standard cards A and B in the back of this volume, the third hori- zontal series of color rectangles, counting from the top of the sheet, approach most nearly to the corresponding colors of the spectrum; and, as the pigmentary types of the pure colors, will sometimes be referred to as the "pure" or "full-color series fl of the standard. The Luminosity of a color is that constant of it which is dependent on the quantity of light which it transmits to the eye, and is nearly equivalent to bright- ness. Two colors may be equal in purity, each reflecting, we will say, 75 per cent SPECIAL METHODS, APPARATUS, AND REAGENTS. 231 of blue and 25 per cent of white light, but can not be made to match except by exposing the brighter surface to a feebler illumination than the other. The Hue of a color is in some respects its most fundamental quality. It is dependent entirely on the refrangibility, or wave length, of the kinds of light pro- ducing the sensation. The purity and luminosity of colors may be absolutely equal, but one may appear red and the other yellow. The difference is one of hue. Each color in the standard, in going from red to violet, is a distinct hue. A Tint of a color is the result obtained by reducing a pure or full color by the addition of white light. In the standard, the two color rectangles immediately over each full color are its "tints." Tint 1 contains less white than Tint 2. Tint 3, which is sometimes referred to in descriptions, is not a tint actually represented in the standard, but is to be imagined as a tint of about half the saturation of Tint 2. A Shade of a color is the result obtained upon viewing a full color in shadow. With pigments, shades of most colors are obtained by adding black. The two shades corresponding to each full color of the standard are placed vertically under it. Each of the upper five colors in the same vertical column of the standard- two tints, two shades, and one full color-is called a tone of that particular color scale. The full color of the scale is sometimes called the "normal tone" of the color. A Broken Color is the subdued effect obtained by mixing a full color with neutral gray (black and white), viewing the tint of a color in a shadow, or a shade of a color in strong sunlight. The lowest horizontal series of colors in each of the sheets of the standard contains "medium " tones of the broken colors. Tints and shades of these "medium tones" will sometimes be referred to in the text as "light" or "dark" broken colors, respectively. It has not been considered necessary to represent them on the color sheets. The russets, browns, citrenes, and olives, are typical broken colors. All pigmentary colors, including the so-called full-color series of the standard, are somewhat broken; and in many color reactions, partic- ularly where intense violets are under observation, it will be found that the colors to be compared are distinctly more saturated than the purest corresponding color of the standard. This will not often prevent the recognition of the fundamental hue of the color, however. The Use of Pigmentary Color Standards.-Every colored substance illumi- nated by ordinary daylight owes its color to its selective absorption of rays of certain definite wave lengths from the white light that penetrates its surface. The light that escapes absorption and is transmitted to the eye is, almost without, exception, a mixture of rays of many different wave lengths together with more or less unchanged white light. The subjective effect is, however, the perception of a simple color. Red and yellowish-green lights, for instance, give an orange which looks in all respects like the orange of the spectrum. Unaided by the spec- troscope, it is impossible for the eye to detect in it the presence of either red or yellowish green. In the same way the original ingredients of every subjective color entirely elude visual analysis, and it is therefore theoretically possible, by the use of a suitable mixture of pigments, to prepare a systematically graduated scale of apparently homogeneous colors, that may be used as a color standard, and with which all other subjective colors, however simple or complex the light 232 SPECIAL METHODS, APPARATUS, AND REAGENTS. rays producing them may be, can be compared. As the colors of all natural objects are somewhat "broken," the fact that the colors of pigmentary standards are less "saturated" than the corresponding hues of the spectrum, is often an advantage rather than otherwise, and in other cases merely limits, but does not destroy, their usefulness. The exact color descriptions of this work are all expressed in terms of the Bradley Color Standard. This standard, mounted in a special compact form, to facilitate its use in the laboratory, will be found on the two cards,* A and B, in a pocket in the back cover of this volume. It contains eighteen pure colors; and of derived tones, thirty-six tints, thirty-six shades, and twelve medium broken colors. Color Symbols are only used in the tables for describing such colors as have been actually compared with the Bradley Standard in the author's laboratory. These symbols are as follows: R=RED; OR = ORANGE-RED; RO = RED-ORANGE; 0 = ORANGE; YO=YELLOW-ORANGE; OY= ORANGE-YELLOW; Y=YELLOW; GY= GREEN-YELLOW; YG=YELLOW-GREEN; G=GREEN; BG= BLUE-GREEN; GB= GREEN- BLUE; B = BLUE; VB= VIOLET-BLUE; BV= BLUE-VIOLET; V= VIOLET; RV= RED-VIOLET; VR= VIOLET-RED. The Tints of any color are represented by the symbol of the normal tone of the color followed by the symbol Tl, T2, or T3; in which the numeral stands for the number of the tint, Tint 1 coming next to the normal tone of the color in satu- ration. The Shades of a color are in like manner represented by adding SI, or S2, to the symbol of the normal tone. The following examples will illustrate the use of these color symbols: YS2 = the second shade of yellow; YTl=the first tint of yellow; OTl-OYTl = a color between the first tint of orange and the first tint of orange-yellow. Comparisons with the Color Standard.-All comparisons with the Standard should be made near an unscreened window through which light reflected from the sky-not direct sunlight-falls upon the colored object and standard from behind the observer. * The colors used on these sheets are those of the Bradley Standard, as described in Milton Bradley's "Elementary Color", (Springfield, Mass.)- The fundamental colors, red, orange, yellow, green, blue, and violet are claimed to be careful pigmentary imitations of the hues seen at certain definite points in the solar spectrum. The wave lengths of the light emitted by the portions of the spectrum selected for imitation are, according to the measurements of Prof. A. H. Pillsbury. 6571 for red; 6085 for orange; 5793 for yellow; 5164 for green; 4695 for blue; and 4210 for violet. This series of six fundamental normal hues is increased to eighteen, by introducing twelve additional colors in such a way as to bring two new hues, separated by equal chromatic intervals, between each of the original colors. The values for these inter- mediate hues were determined, by blending the adjacent hues of the original series of six in pairs, by Maxwell's method, on a rotating color-wheel on which the areas of the two colored sectors were in the ratio of two to one. Yellow-orange, for example, is the subjective color resulting from the blending in the eye of the light from two superficial units of the funda- mental orange and one of the yellow; orange-yellow, of two parts of the yellow and one of the orange. Two "tints " and two " shades " were then derived for each of the eighteen " normal tones " by dilution with white or black. Additional copies of these color sheets, to replace the originals as they become soiled or injured, can be procured at any time from Messrs. John Wiley & Sons, the publishers of this volume. A comparison of the new color sheets with well-preserved samples of the Bradley colored papers prepared at different times during the last dozen years, indicates that the colors used are stable, and that much care has always been taken by the manufacturers to faithfully reproduce the colors of their first standard. SPECIAL METHODS, APPARATUS, AND REAGENTS. 233 If the substance is a solid, it should be placed upon a piece of white paper, and laid upon the perforated shield accompanying the Standard, close to the rect- angular window. The object of the screen is, partly to protect the Standard from accidental injury, and partly to prevent the confusion that is apt to arise from presenting many kinds of colored light to the eye at the same time. It is impor- tant to remember in color descriptions, that the color of a solid substance in masses is often different from its "streak," or color of its fine powder; and that the color of a moist precipitate is usually different from that of the same substance after drying. It is only occasionally that a color is met with which exactly matches one of the color squares of the Standard. The statement in descriptions, that a compound has a light orange-yellow color (Y0T1), is therefore to be understood to mean nothing more than that its color more closely resembles this color of the Standard than any other. If the color to be described obviously lies between two colors of the Standard, the fact is, however, often indicated by the symbol; e.g. Y0T-0YT1. To examine a solution, lay the perforated screen upon the Standard so as to expose to view one or two color patches that resemble the color to be described, and hold or support it in an upright position, so that diffused sky light, coming from behind the observer, will fall upon it. Then hold the test-tube containing the solution vertically in front of the shield at a distance of about twice or thrice its diameter, and just above or to one side of the perforation. The comparison will thus be made by transmitted white light reflected through the solution from the screen. In observing the color of a fluorescence, replace the white screen by one coated with lamp-black. The light reaching the eye is in this case reflected back from the solution and not from the screen. The color of a solution depends not only upon the nature of the substances dissolved, but also upon its concentration, the thickness of the colored layer, and sometimes upon the temperature. No description of an unfamiliar color reac- tion in a solution is entirely satisfactory unless all these conditions are given. In the greater number of cases, it is true, the result of dilution is chiefly to reduce the saturation of the original color; i.e., to produce a lighter tint of the original hue. But some change in hue is of very common occurrence, and in tests, like that for acrolein (Test 112), where the change in hue upon continued dilution with water is from orange-yellow to violet-blue, it is the most striking and essential feature of the test. The temperature is sometimes a very important condition, as in Test 401 for phenols with ferric chloride, where a pronounced yellow color is communicated to the solution in blank experiments by the reagent alone, unless the test is made cold. Unless otherwise indicated by the context, all color comparisons with solu- tions which are referred to the color standard in this work relate to solutions of approximately definite concentration, the colors being observed, as above stated, in three- to six-inch test-tubes at the temperature of the laboratory. Many color reactions, especially among those with ferric chloride for the phenols, and for the Species of Suborder II, Division A, Section 2, give colors which change rapidly on standing. In the absence of directions to the contrary, such colors should always be observed as soon as possible after their appearance. 234 SPECIAL METHODS, APPARATUS, AND REAGENTS. It is more difficult to match the colors of solutions with a pigmentary stand- ard than those of solids; for the colors in the Standard often appear distinctly "broken" and muddy by contrast, particularly if the solution happens to be a brilliant purple. But the fundamental hue, which is the most important color element, will still usually be distinguishable. Such comparisons are sometimes facilitated by using a solution of the colored substance so dilute that it will approxi- mately match the first " tint " of a hue, rather than the "full" or "normal" color of the scale. THE MANIPULATION OF SMALL QUANTITIES. As has been stated on page 2, most of the specific tests in this volume depend- ing upon the isolation of a pure derivative of a compound, are made with only a decigram or less of substance. The use of these small quantities not only saves valuable material, but also greatly shortens the time required to complete an experiment; so that, in many instances, a derivative may be prepared, filtered off, washed, recrystallized, and dried ready for a melting-point determination within half an hour. Some of the conditions and expedients that have been found conducive to success in such preparations in the small way deserve special mention. Solid Precipitates.-In making the selection of a characteristic solid deriva- tive suitable for preparation on the small scale in specific tests, it is desirable to choose one that will separate in a bulky but crystalline condition from the solvents used; and which may be recrystallized quickly by cooling its hot saturated solu- tions. Precipitates that are both crystalline and voluminous may be removed from glass surfaces and filters, and washed, recrystallized, dried, and handled with much less loss than those that are either too compact, slimy, or gelatinous. Precipitates that are very soluble in the cold, and which form only after evap- oration of a considerable portion of the solvent, are poorly adapted for these tests; evaporation being a slow operation, and the difficulty in separating crystals that are uncontaminated by by-products from the small mother-liquor being usually greater than in the method by cooling. Among the numbered specific tests are many examples of derivatives that combine all the good qualities just mentioned in a high degree. A single decigram of some of the aromatic nitro-derivatives, for example, upon separating from a hot saturated solution in dilute alcohol, is sufficient to fill entirely a five-inch test-tube with a mass of hard interlacing crystals. Some sticky resinous precipitates of equal weight would be entirely lost as inconspicuous adhesive smears on the test-tubes or filters. If no precipitate should appear upon cooling what is supposed to be a hot saturated solution of a solid derivative, always close the mouth of the test-tube firmly with the thumb, and shake vigorously and persistently. Many compounds whose preparation is directed in the numbered specific tests, tend to form super- saturated solutions; but upon being thus treated, give bulky crystalline precipi- tates. This final precautionary shaking should never be omitted. Small precipitates should be collected on correspondingly small filters and funnels. A large filter retains so much mother-liquor as to require excessive wash- ing; and the precipitate, if at all adhesive, will be very difficult to separate from the large paper surface. A supply of cut filters, 5 cm. in diameter, and a SPECIAL METHODS, APPARATUS, AND REAGENTS. 235 few very small funnels are therefore indispensable for the performance of the specific tests. When hot filtration of a saturated solution is necessary, the funnel and filter are most easily and effectively heated by first pouring through them some of the boiling liquid that is to be used as the solvent in the experiment. Clogging of the funnel-tube by separation of solid matter may be prevented by cutting off its lower end so that only about 1 cm. remains. If the solid begins to crystallize out at a temperature very little below the boiling-point of the solvent, a com- paratively large filter and funnel are to be preferred to a small one, as they will give more rapid filtration. On a very small filter there is greater danger that the free passage of the solution may become obstructed by the deposition of solid matter in the pores of the paper. In filtering from one test-tube into another, hang a short piece of thick bent copper wire over the lip of the test-tube in which the funnel is placed, so as to leave a passage for the escape of air from the tube. For mixtures that filter slowly, fit the recipient test-tube with a doubly perforated rubber stopper and use H as a filter-bottle, placing a small filter-cone in the funnel and applying gentle suction with the filter-pump. In washing small precipitates with a liquid in which they are rather soluble, the danger of using an unnecessarily large volume of solvent has been provided against in the more important procedures by the specification of some definite volume. These directions should be closely followed. The solvent should be dropped upon the precipitate in such a manner as to detach it from the sides of the filter and wash it down into the point, so as to facilitate its subsequent separa- tion from the paper. Very small precipitates which do not require much washing, and which it is thought undesirable to bring upon a filter, may be separated from most of the supernatant solution by decantation, and then shaken out upon a piece of porous tile. When the adhering solution has disappeared in the tile, it may be sprayed or moistened as many times as desired with the solvent, waiting after each treatment until the liquid disappears before adding more. If it becomes necessary to redissolve a precipitate that is very small and firmly attached to the filter, open the filter, tear off the sector to which the solid adheres, and boil it with the solvent. Do not boil up the whole filter, or the pulpy mass formed may cause explosive boiling and loss of the substance. Precipitates whose melting-points are not too low are directed to be dried in a drying-oven at some definite temperature and for a definite time. Solids of very low melting-point are air-dried at the ordinary temperature, or supported in a warm place over a drying-oven, on a piece of porous tile or filter-paper. Drying in the oven should always be preceded by rubbing the moist substance over the surface of a porous tile with a small spatula, or pressing it between filter-paper to remove all the mother-liquor. Liquids.-The- preparation of liquid derivatives is not often recommended in specific tests, because the purification of such compounds on the small scale gen- erally presents special difficulties. The procedure for the isolation and identifica- tion of liquid alcohols from the saponification of a gram or two of an ester (p. 114), the Siwoloboff boiling-point method for two or three drops of liquid (p. 222), and 236 SPECIAL METHODS, APPARATUS, AND REAGENTS. the method of page 228 for the determination of the specific gravity of liquids having a volume of only 0.2 cc., are, however, examples which show that the difficulties connected with the manipulation of small quantities of liquids may sometimes be satisfactorily overcome. Test-tube experiments with less than a centimeter of a liquid must be made in very narrow tubes. With a tube of 5 mm. internal diam- eter, five drops of a substance are all that is required to enable a satisfactory obser- vation of the action of sodium on alcohols in Test VIII-2. The separation of very small volumes of two liquids of different specific gravi- ties is best made with a pipette. The mixture is placed in a narrow test-tube, and all but a few drops of the substance that is present in the greater quantity are removed by a large pipette and rejected. The remainder of the liquid, meas- uring perhaps 1 cc., is then sucked up into a small pipette made from a piece of glass tubing that has been drawn out so as to have an average internal diameter of only about 2 mm. in the long tapering portion. The suction is most easily controlled if applied by the rubber nipple of a medicine- dropper. When both liquids have been brought into the pipette, and appear in two layers after standing, they may be separated to a fraction of a drop by slowly ejecting them, successively, into separate tubes. The most perfect control over the rate of flow in careful experi- ments is gained by the employment of the safety pipette shown in Fig. 11. This pipette is provided with a regulator A, 3 cm. in length, made by drawing out a piece of thermometer tubing at the blast-lamp until the capillary at B and C is narrowed almost to complete closure; and then cementing it with melted wax, D, into a short section of glass tube of the same diameter as the upper part of the pipette stem. The capillary, if sufficiently constricted, offers so much resistance to the passage of gas from the air-space, E to H, that the contents of the pipette can not be discharged in less than several seconds, even when the bulb is suddenly and forcibly compressed. By the use of this device the transfer of a small measured volume of a valuable or corro- sive liquid in work at the balance (as in weighing out acetic anhydride for Test VIII-3) is made a safe and simple operation. Fig. 11. SPECIAL REAGENTS. The following is a complete list of the less common chemicals and solutions required for the performance of the ordinal, generic, sectional, and numbered specific tests of this volume. All these reagents can be purchased, or easily pre- pared by following the directions given in these pages. Most of them are already used in analytical laboratories. [For Ordinal Tests] Metallic Sodium. The best commercial sodium, free from particles of salt. Sodium Nitroprusside. In small crystals or powdered. Nitrosylsulphuric Acid. Preparation described on page 13. Fluorescein Paper. Preparation described on page 14. SPECIAL METHODS, APPARATUS, AND REAGENTS. 237 [For Generic Tests.] Fuchsine Aldehyde Reagent. Preparation described on page 15. a-Naphthol Solution. A 10 per cent solution in chloroform. See page 26. Decinormal Sodium Hydroxide (aqueous) Decinormal Hydrochloric Acid (aqueous) Normal Sodium Hydroxide (aqueous) Normal Sulphuric Acid (aqueous) Carefully standardized. Approximately Normal Sodium Hydroxide (alcoholic). Unless the alcohol is very free from aldehyde it will become colored on keeping, and hence should not be prepared in large C* quantities. Phenolphthalein. A 1 : 300 solution in 50 per cent alcohol. Ferric-Chloride Solution. A 10 per cent aqueous solution made from the sublimed chloride. Hydroxylamine-hydrochloride Solution. Prepared as described on page 133. Alcoholic Sodium-hydroxide Solution for Test VII, A. Prepared as described on page 133. Phenylhydrazine. Redistilled if the color is not very light. Acetic Anhydride. Phenylhydrazine Hydrochloride. Prepared as described on page 32. Fehling's Solution. Prepared as described on page 33. Bromine Solution. 2 cc. bromine in 50 cc. dry carbon tetrachloride. See page 195. Fuming Sulphuric Acid. An acid of sp. gr. 1.89, which may be prepared by dissolving sulphur trioxide or a solid Nordhausen acid in oil of vitriol. Fuming Nitric Acid. Specific gravity 1.48. [For Sectional Tests!] [For Occasional Use in Numbered Specific Tests.] Acetyl Chloride. Aluminium Chloride. Dry, sublimed. Ammoniacal Silver-nitrate Solution. Prepared as described on page 22. Ammoniacal Cuprous-chloride Solution. Prepared as described on page 197. Aniline. Benzaldehyde. Benzoyl Chloride. Bromine. Chromic Anhydride. 3, 5-Dinitrobenzoic Acid. Prepared by Kahlbaum, and for sale by dealers. Iodine Solution. Prepared as described on page 166. Mercuric Oxide. ^-Naphthol. Phosphorus Pentachloride. Phloroglucin Solution. Prepared as described on page 33. Resorcin. Para-toluidine. SPECIAL APPARATUS. Ignition-tubes of Hard Glass or Iron. Description and cut on page 10. Asbestos-board Screens. Size Thickness Used in the sodium fusion (page 10, Fig. 1); the determination of boiling-points (page 221, Fig. 6); and in specific tests (e.g., Test 311-2). "Medicine-droppers." As shown in Fig. 1, page 10. Lipped Test-tubes. In addition to the usual assortment of test-tubes of the larger sizes, a good supply of tubes with a height of 3 inches and diameter of | inch, with cork stoppers to fit, and a few with a height of 3 inches and diameter of inch, should always be kept in readiness. (Cf. page 112, Fig. 3, and page 152, Fig. 4.) Mounted Burettes for Decinormal and Normal Alkali and Acid. Mounting shown in Fig. 2, page 78. Pipettes with Bulbs and Long Stems. Of the usual pattern and calibrated to deliver 2 cc., 25 cc., and 50 cc., respectively. i-cc. Pipette Graduated to Hundredths. Straight, without bulb; graduated by the manufacturer, i-cc. Pipette for Specific Gravities. Page 229, Fig. 10. io-cc. Graduated Cylinders. With lip and foot for general use in rough measurements. Gradu- ation to half centimeter. Capillary Piknometer. Page 228, Fig. 9. Safety Pipette. Description on page 236, Fig. 11. Covered Heating-bath. Page 152, Fig. 4. Recommended for use in several generic tests. Bath for Melting-point Determinations. Page 218, Fig. 5. Melting-point and Ebullator Capillaries. Pages 219 and 222, Fig. 7. Apparatus for Determination of True Melting-point and Fusion Intervals. Page 225, Fig. 8. Glass Funnels. Diameter 2 cm. Cut Paper Filters. Diameters 3 cm. and 5 cm. ALPHABETICAL INDEX. The alphabetical index relates primarily to classification, analytical methods, numbered tests, reagents, and apparatus, but also contains the names of such compounds-about 15 per cent of the total number described-as will be most frequently sought in the tables. To find the description of any compound of minor importance, consult the complete "Formula Index" on page 244. A Abbreviations, table of, xi Abietic acid, 63 Absinthin, 206 Acenaphthene, 200 Acetal, 19 behavior in Test I, 16 Acenaphthene, 200 Acetal, 19 Acetaldehyde, 22 Acetic acid, 80 Acetic anhydride, 73 Acetone, 148,144 Acetonylacetone, 142 Acetophenone, 149 Acetylacetone, 104 Acetylation test for alcohols, 152 Acetylene, 184 Acid anhydrides, 128, 80 Acids, general characteristics, 37 generic test for, 35 losing carbon dioxide at 200°, 78 neutralization equivalents of, 77 tests for unsaturation in, 79 titrations of, 35 Aconitic acid, 49 Acrolein, 23 Adipic acid, 63 ATsculin, 98 Affinity constants, 36 Alcohols, generic tests for, 151-154 Aldehydes, general characteristics, 16 as impurities in alcohols and ketones, 135 generic test for, 15 Alizarin, 211 Bordeaux, 214 yellow "A", 207 yellow "C", 213 cyanin "R", 214 Alkali, action on aldehydes, 16 action on anhydrides and lactones, 128 action on esters, 111, 117 action on phenols, 87-88 titrations with, 77 Allyl alcohol, 167, 114 Aluminium chloride, colorations with, 198 Ammoniacal cuprous-chloride reagent, 199 Ammoniacal siiver-nitrate solution, 22 Amyl acetate, 121 Amyl alcohols, 114, 162 Analytical procedure, the general, 1 Anethol, 174 Angelic acid, 53 Aniline acetate paper, 33 Anisic acid, 67 aldehyde, 20 Anisoin, 179 Anisol, 189 Anol, 94 Anthracene, 200 Anthraflavic acid, 213 Anthraquinone, 216 Apiol, 174 Apparatus, list of special, 237 Arabinose, 30 Arachidic acid, 55 Arbutin, 97 Asbestos-board screens, 10, 11, 81, 221 Ash constituents, test for, 9 Atropic acid, 58 Aurine, 213 Azelaic acid, 58 B Barbaloin, 207 Baths, covered, for heating tubes, 152 liquid, for melting-point determinations, 218 Behenic acid, 56 Beilstein's Handbuch, references to, 7 Benzaldehyde, 23 Benzene, 200 Benzhydrol, 157 Benzil, 206 Benzilic acid, 63 Benzoic acid, 82 anhydride, 53 Benzoin, 139 Benzophenone, 150 Benzoquinone, 216 Benzoylacetone, 92 Benzyl alcohol, 165, 114, 167 Boiling-point determination, 4, 221 of small quantities by Siwoloboff's Method, 115, 222 " Boiling-intervals," 222 table of, 227 Borneol, 159 Brassidic acid, 54 Brazilin, 102 Brazilein, 212 Bradley's color standard, 229 "Broken" colors, 231 239 240 ALPHABETICAL INDEX. Bromine, test for, 13 test for unsaturation, 195 water, in unsaturation tests, 195 water, in testing phenols, 89 Bumping, prevention of, 221 Butyl alcohol, 168, 115 Butyric acid, 81 c Caffeic acid, 209 Camphene, 175 Camphor, 150 Camphoric acid, 66 Cantharidin, 129 Capillaries, preparation of, 219 Capric acid, 52 Caproic acid, 75 Caprylic acid, 76 Carbohydrates, 26 generic test for, 26 generic characteristics, 27 Carbon, tests for, 9 dioxide, test for acids losing at 200°, 78 tetrachloride, bromine solution in, 195 Carnot's procedure for identification of halo- gens, 13 Carvacrol, 105 Cellulose, 31 Cerotic acid, 56 Ceryl alcohol, 157 Cetyl alcohol, 157 Chelidonic acid, 71 Chemical purity, thermometric indications of, 223 Chlorine, test for, 14 Cholesterine, 172 Chromic-acid mixture for oxidations, 147 Chrysarobin, 208 Chrysene, 181 Chrysophanic acid, 208 Cinnamic acid, 82 aldehyde, 21 Cinnamyl alcohol, 157 Citraconic acid, 41 Citral, 20 Citric acid, 83 Citronellal, 20 Classification of compounds in this work, 1 Coerule'in, 214 Color, 230 comparisons, 232 standards, use of, 231 symbols, table of, 232 terminology, 230 transitions, sharpness of, in titrations with indicators, 36 Colored compounds of Order I, 204 Confirmatory specific tests, 7 Coniferine, 100 Coniferyl alcohol, 93 Constant boiling mixtures, 227 Convolvulin, 98 Cotom, 207 Coriandrol, 163 Corrected boiling-points, 217, 222 melting-points, 217 Coumarin, 129 Cresols, 91, 104 Crotonic acid, 40, 74 Cymene, 190 D Daphnetin, 102 Daphnin, 100 Decinormal acid and alkali, 77 Dehydracetic acid, 58 Densities of water, table of, 229 Dextrin, 29 Dextrose, 30 Diacetyl, 215 Di benzylidene acetone, 206 Diethyl malonate, 123 oxalate, 74 succinate, 124 succinylosuccinate, 96 /-Diketones, pyrrol-red test for, 148 Dimethyl oxalate, 40 phthalates, 119, 126 Diphenyl, 176 methane, 174 Diphenylene ketone, 207 "Divisions," defined, 1 Drying precipitates, 235 Dulcite, 156 Durene, 176 E Ebullator tubes, 223 Elaidic acid, 54 Empirical formula, use in identifications, 7 Enols, 90 Erucic acid, 53 Erythrite, 155 Esters, 111 generic test for, 111 "non-saponifiable," 117 saponification procedures for, 111, 113 with characteristic odors, 79 Ethers, saturated, test for, with sulphuric acid, 199 Ethyl acetate, 120 acetoacetate, 104 alcohol, 168 benzene, 189 benzoate, 123 benzoylacetate, 106 butyrate, 121 cinnamate, 126 ether, 160 isobutyrate, 120 isovalerianate, 121 propionate, 120 salicylate, 105 Ethylene, 184 glycol, 169, 170 oxide, 160 Eucalyptol, 190 Eugenol, 106 Euxanthone, 210 Examples illustrating the analytical proced- ure, 8 Explosions in ignition tests, 10, 11 F Fehling's solution, 33 Fenchone, 142 ALPHABETICAL INDEX. 241 Ferric chloride, colorations with, 107 reagent, 87-88 test for a-hydroxy-acids, 78 Fisetin, 213 Filtration in tests on a small scale, 235 Flavopurpurin, 212 Fluoresce!'ne, 213 paper, 14 Fluorescence, observation of, 233 Fluorene, 178 Formic acid, 83 Formic aldehyde, 114 Fractionation tests for purity, 224 Fructose, 30 Fuchsine aldehyde reagent, 15 "Full" colors, 228 Fumaric acid, 68 Furfurol, 24 Furoin, 96 Fusion interval, 224, 225 Fusions with sodium, 10 G Galactose, 30 Galleine, 214 Gallic acid, 70 Galloflavin, 213 Gallotannic acid, 50 Gaseous compounds, classification of, 1 Generic subdivisions, 6 tests defined, 1 tests, conclusiveness of, 7 tests, tabular summary of, 5 Genus, definition of, 1 I, 15; II, 26; III, 35; IV, 87; V, 111; VI, 128; VII, 133; VIII, 151; IX, 173 Genus, procedure for determining, 5 Geraniol, 163 Glucose, 30 Glutaconic acid, 45 Glutaric acid, 84 Glycerine, 169 Glycogen, 31 Glycollic acid, 41 Guiacol, 91 Gum arabic, 29 H Haematei'ne, 214 Haematoxylin, 207 Halogens, tests for, when S and N are absent, 12 tests for, when S and N are present, 13 detection in presence of one another, 13 Heptane, 182 Hexane, 182 Homogeneity, chemical, 3 tests for, 3,223 Hue of colors, 231 Hydrocarbons, generic test for, 173 sectional tests for, 173 Hydrobenzoin, 158 Hydrocinnamic acid, 54 Hydrogen, test for, 9 Hydroquinone, 108, 8 a-Hydroxy-acids, tests for, 78 Hydroxylamine reagent for ketones, 133 Hypogeeic acid, 52 I Ignition test for carbon, hydrogen, and ash, 9 test with sodium for non-metallic elements, 10 tubes, 10 Indene, 191 Inosite, 156 Inuline, 31 Iodine solution, 166 test for, 13 Iodoform test for alcohols, etc., 166 Iron ignition tubes, 10 Isoamyl acetate, 121 alcohol, 162 benzoate, 126 butyrate, 122 isovalerianate, 123 Isobutyl acetate, 121 alcohol, 114, 170 benzoate, 125 Isobutyric acid, 81 aldehyde, 19 Isoprene, 184 Isopropyl alcohol, 170, 114 Isophthalic acid, 85 Isopurpurin, 214 Isovalerianic acid, 74 aldehyde, 19 Itaconic acid, 48 K Ketones, generic tests for, 133, 134 L Lactic acid, 39 Lactide, 60 Lactones, 128 Lactose, 29 Lauric acid, 53 Levulinic acid, 39, 74 Levulose, 30 Limonene, 190 Linalool, 163 Luminosity of colors, 230 Luteolin 213 M Maleic acid, 45 Malic acid, 83 Malonic acid, 45 Maltose, 29 Mandelic acid, 44 Mannite, 155 Margaric acid, 54 Meconin, 58 Melissic acid, 56 Mellitic acid, 51 Melting-point apparatus, 218, 225 corrections, 217, 218, 220 determination, 218-220 determination in sealed capillaries, 219 the true, of a compound, 220 Menthol, 157 Menthone, 143 Mesaconic acid, 50 Mesitylene, 200, 8 Mesityl oxide, 141 242 ALPHABETICAL INDEX. Mesotartaric acid, 46 Metallic salts, precipitations, 80 "Method of the empirical formula," iii, 7 Methyl acetate, 120 alcohol, 171, 114 benzoate, 120 butyrate, 120 formate, 120 ethyl ketone, 141 propyl ketone, 141 propionate, 120 salicylate, 105 Methylal, 19 Milk sugar, 29 Mixtures, examination of, 4 Molisch, test for carbohydrates, 26 Mucic acid, 69, 34 Myristic acid, 54 N Naphthalene, 201 Naphthazarin, 214 Naphthols, a and fl, 108 " Naphthoic acid, 64, 66 a-Naphthol, as reagent for Test II, 26 a-Naphthoquinone, 216 Neutralization equivalents, determination of, 77 equivalents, formula for calculating, 77 Nitric acid, oxidations with, 198 fuming, in sectional tests with the hydro- carbons, 196 Nitrogen, tests for, 12 Nitroprusside of sodium, solution, colorations with, 146 Nitrosylsulphuric acid reagent, 13 Nonane, 183 Numbered specific, semi-specific, and sectional tests 2, 7 O Octane, 183 Octyl alcohol, 163 Odors of esters in tests for acids, 79 Oleic acid, 52 Oenanthol, 20 Oenanthylic acid, 76 Opacity, 134 Opianic acid, 63 Orcin, 95 Order, definition of, 1 determination of, 4, 9 Ordinal tests, definition, 1 directions for, 9 Orsellinic acid, 66 Osazone precipitations, 32 Oxalic acid, 84 Oxidation, of carbohydrates, 34 of side-chains, 197 of alcohols, and ketones, 147 with copper spiral, 171 with chromic acid mixture, 147, 198 with dilute nitric acid, 198 with potassium permanganate, 197 Oxybenzoic acids, 64, 68, 69 P Palmitic acid, 54 Paraconic acid, 40 Paraffin, protection of corks by, 153 Paraformaldehyde, 18 Paraldehyde, 19 Pelargonic acid, 76 Pentane, 182 Perseite, 156 Peucedanin, 119 Phenacetolin, 213 Phenanthrene, 201 Phenanthrenequinone, 216 Phenetol, 190 Phenol, 108, 114 Phenols, generic tests for, 87 properties and reactions of, 89 Phenolphthalein, solution, 35 behavior as indicator, 36 Phenylacetic acid, 55 Phenylhydrazine, as reagent, 16, 32, 134 hydrochloride, preparation, 32 Phloridzin, 99 Phenylpropiolic acid, 62 Phloroglucine, as reagent, 33 test for, 109 Phoron, 136 Phosphorus, tests for, 12, 11 Phthalein fusion, 107 Phthalic acid, 84 Phthalic anhydride, description of, 61 use as reagent, 107 Phthalid, 129 Physical properties, examination of, 4 Phytosterin, 158 Picene, 181 Pycnometer, capillary, 228 Picric acid, as reagent, 89 Picrotoxine, 100 Pimelic acid, 43 Pinacone, 155 Pinacoline, 141 Pinene, 189 Piperic acid, 210 Piperonal, 17 Piperonylic acid, 72 Pipette, for specific gravities, 229 safety, 236 Polyatomic alcohols, acetylation of, 154 Polymerized aldehydes, 15 Potassium permanganate, oxidations with, 197 permanganate, in tests for unsaturation, 79 sulphate baths, 219 Precipitates, filtration and drying of, 234 Precipitation of metallic salts, 80 Propionic acid, 81 anhydride, 75 Propyl alcohol, 115, 172 acetate, 120 Protocatechuic acid, 50 Pseudocumene, 201 Pulegone, 143 Purity, chemical, evidences of, 3 of a color, 230 Purpurin, 210 Pyrene, 179 Pyrocatechin, 109 Pyrogallol, 110 Pyromucic acid, 45 Pyrrol-red, 148 ALPHABETICAL INDEX. 243 Q Quercite, 156 Quercetin, 213 Quinic acid, 48 Quinhydrone, 208 R Racemic acid, 50 Raffinose, 29 Reagents, list of special, 236 Resorcin, 110 as reagent, 85, 171 Retene, 177 Rhamnose, 30 Ricinoleic acid, 52 Rosolic acid, 213 Rufigallic acid, 214 S Saccharic acid, from oxidations, 34 Saccharose, 29 Safety pipette, 53 Safrol, 192 Salicin, 100 Salicylic acid, 85 aldehyde, 20 Saligenin, 93 "Salting-out" effect of alkali, 117 Santalin', 206 Santonin, 129 Saponifications, methods, 111, 113 equivalents, 112, 113 products, neutral, 113 products, acidic, 116 Saturated colors, 230 Schotten-Baumann reaction, 37 Scoparin, 209 Sebacic acid, 61 Section, defined, 1 Sectional tests, 2 Semi-specific tests, 2 Sesquiterpenes, 193 Shades, of a hue, 231 Sharpness, in end reactions, 36 in boiling- or melting-points, 223, 226 Side-chains, oxidation of, 197 Silver nitrate, ammoniacal, 22 salts of volatile fatty acids, 148, 149 Siwoloboff's boiling-point determination, 222 Small preparations, manipulations in, 234 Sodium,-as reagent, 16, 151, 154 bisulphite, as reagent, 16 nitroprusside, as reagent, 146 Solubility, approximate determination of, 38 degrees of, 38 Sorbic acid, 61 Sorbinose, 30 Sorbite, 155 Species, chemical, 2 chemical, identification of, 6 Specific gravity, determination of, 227 gravity, determination, for small quanti- ties of liquids, 228 gravity, pipette, 229 tests, definition of, 2 Starch, 31 Stearic acid, 55 Stearolic acid, 53 Stem-exposure corrections, 218, 222 Stilbene, 178 Styrene, 189 Suberic acid, 62 Sub-order II, 204 Substitutions by bromine, 195 Succinic acid, 86 anhydride, 60 Sulphur, tests for, 11, 12 Sulphuric acid, as reagent in testing ethers and hydrocarbons, 200 fuming, use in sectional test with hydro- carbons, 196 Superheating, prevention in boiling-point deter- minations, 221 Supersaturation of solutions, 235 T Tannic acid, 50 Tartaric acid, 83 Terephthalic acid, 85 Terpineol, 165 Thermometers, 219 Thujone, 143 Thymol, 110 Thymoquinone, 205 Tiglic acid, 40 Tiles, porous for absorption, 235 Tints, of a hue, 231 Titration, of acids, 35 of acid anhydrides, 37 Tolane, 176 Tollen's ammoniacal silver reagent, 22 Toluene, 202 Toluic acid, 66 Toluides, identification of fatty acids as, 81 Toluidine, para, as reagent, 80 Tricarballylic acid, 48 Trimethyleneglycol, 165 Tri phenylmethane, 177 Triple bonding, test for 199 Tropic acid, 61 True melting-point, 219 Truxillic acids, 70 , U Undecylenic acid, 52 Unsaturated acids, tests for, 79 Unsaturation, bromine test for, 195 permanganate test for, 79 V Valerianic acid, 74 Vanilline, 17 Vanillic acid, 69 Veratric acid, 66 Volatile fatty acids, identification of, 147 W Water, table of densities for, 229 of crystallization, removal of, 38 Wave-length of standard colors, 232 Xanthone, 180 Xanthopurpurin, 210 Xylenes, 202 Xylenols, 91, 92 Xylidene acetate paper, 33 Xylose, 30 FORMULA INDEX. The Formula Index gives the page, and usually the part of the page, on which any compound of known empirical formula described in this volume will be found. The numerals following a dash-which is commonly preceded by a melting-point or boiling-point-are the page numbers. The compounds are arranged accord- ing to the kind and number of atoms represented in their symbols. This form of index-already used in Richter's Lexicon and many of the leading chemical journals-is so simple that detailed explanations are not necessary. Polymers and compounds of unknown molecular weight are mentioned under the simplest formula expressing their percentage composition. Water of crystallization is always omitted from the formulae. To facilitate access to the original literature, the names applied to compounds are generally literal English translations of names used in the indexes of the third edition of Beilstein's Handbuch der organischen Chemie. Incidentally it is possible to use this index in identifying compounds by the "Method of the Empirical Formula." C4 GROUP. CH4 Methane, bp.-153°-182 CH2O Formalin, bp. 98°-19 Paraformaldehyde, mp. abt. 120°- 18 CH2O2 Formic ac., bp. 101°-73 CH4O Methyl ale., bp. 66°-160 C2 GROUP. C2H2 Acetylene, bp.- 85°-184 C.?H4 Ethylene, bp.- 103°-184 C2H6 Ethane, bp. -86°-182 (C2H2O2)$ Polyglycollid, mp. 220°-130 C2H2O4 Oxalic ac., mp. 189°-84 C2H4O Acetic aid., bp. 21°-19 Ethylene oxide, bp. 14°-160 Paraldehyde, bp. 124°--19 Metaldehyde, mp. 110°-18 C2H4O2 Acetic ac., bp. 118°-73 Methyl formate, bp. 32°-73 C,H4O3 GlycoIlic ac., mp. 78°-161 C:H0O Ethyl ale., bp. 78°-161 Methyl eth., bp. -24°-160 C3 GROUP. C3H6 Propylene, bp. - 50°-184 Cyclopropane, bp. -35°-184 C3Hs Propane, mp. - 38°-182 C3H,0 Propargyl aid., bp. 60°-19 C3H2O2 Propiolic ac., bp. 144°-73 C3H4O Acrolein, bp. 52°-19 Allylene oxide, bp. 62°-160 Propargyl ale., bp. 114°-164 C3H4O2 Acrylic ac., bp. 140°-73 C3H4O3 Pyruvic ac., bp. 165°-74 C3H4O4 Malonic ac., mp. 132°-45 C3H4O5 Tartronic ac., mp. 186° (?)-49 C3H4O6 Mesoxalic ac., mp. 119°-44 C3H8O Acetone., bp. 56.5°-141 Allyl ale., bp. 97°-161 Metapropionic aid., mp. 180°-18 Propionic aid., bp. 48.8° c.-19 Propylene oxides, bp. 35°, 50°-160 C,H0O2 Acetylcarbinol, bp. 147°-142 Ethyl formate, bp. 54°-120 Glycid, bp. 161°-164 Methyl acetate, bp. 57°-120 Propionic ac., bp. 141°-73 C3H6O3 Dimethyl carbonate, bp. 91°-120 Lactic ac., mp. 18°-39 Methoxyacetic ac.; bp. 203°--74 Methyl glycollate, bp. 151°-121 C3H8O Isopropyl ale., bp. 83°-161 Methyl ethyl eth., bp. 11°-160 Propyl ale., bp. 97°-161 C3HsO2 Methylal, bp. 45.5°-19 Propylene glycol, bp. 188°-164 Trimethylene glycol, bp. 214°-165 C3HsO3 Glycerine, bp. 290°-165 C4 GROUP. C4Ha Butadienes, bp. 1° and 18°-184 Caoutchene, bp. 14°-184 Ethylacetylene, bp. 18°-184 Butine(2), bp. 28°--184 C4H8 Butenes, bp. 1° and 2°-184 Methylcyclopropane, bp. 4°-184 C4H10 Butane, bp. +1°-182 Tri methylmethane, mp. 0°-182 C4H2O3 Maleic anhyd., mp. 56°-54 C4H.,O4 Acetylenedicarbonic ac., mp. 178° -49 C4H4O Furfurane, bp 31°-1S9 C4H4O2 Tetrolic ac., mp. 76°-40 C4H4O3 Succinic anhyd., mp. 119.6°-60 C4H4O4 Fumaric ac., sb. w. m. 200°-68 Glycolid, mp. 86°-129 Glutinic ac., mp. 145° d-46 Maleic ac., mp. 130°-45 C4H4O5 Oxalacetic ac., mp. 172° d-48 C4H4O0 Dioxymaleic ac., d. abt. 155°-64 C4H6O <x-Crotonic aid, bp. 104-5°-19 Hydrofurfurane, bp. 67°-189 Methyl propargyl eth., bp. 61°- 160 Vinyl eth., bp. 39°-160 C4H6O2 Allyl formate, bp. 82.5°-120 Butenoic ac., bp. 168°-74 ^-Butyrolactone, bp. 206°-131 Crotonic ac., mp. 72°-40 Diacetyl, bp 88°-215 244 FORMULA INDEX. 245 Erythrite anhyd., bp. 138°-164 Isocrotonic ac., bp. 169°-74 Methacrylic ac., bp. 162°--73 Methyl acrylate, bp. 80.3°-120 Trimethylenecarbonic ac., bp. 182° -74 C4H3O3 Acetic anhyd., bp. 137°-73 Methyl pyruvate, bp. 135°-121 C4H8O4 Acetylperoxide, mp. 30°-52 Dimethyl oxalate, mp. 54°-40 Isosuccinic ac., mp. 135°-45 Succinic ac., mp. 185°-49 C4H6O6 Diglycollic ac., mp. 14S°-47 GlycoIlic anhyd., mp. 129°-61 Isomalic ac., abt. 140°-46 Malic acids, mp. 100°, 133°-43, 45 Methyltartronic ac. mp., 178° d.-49 C4HaO8 Mesotartaric ac., mp. 142°-46 Racemic ac., mp. 205°-50 Tartaric ac., mp. 169°-48 C4HaO8 Dioxytartaric ac., mp. 115° d.-44 C4HgO Butyric aid., bp. 73-4°-19 Crotyl ale., bp. 117°-161 s-Dimethylethylene oxide, bp. 56° -160 Isobutylene oxide, bp. 51°-160 Isobutyric aid., bp. 63-4°-19 Methyl allyl eth., bp. 46°-160 Metyl ethyl ketone, bp. 81°-141 Vinyl ethyl eth., bp. 35°-160 C4H8O2 n-Butyric ac., bp. 162°-73 Dioxy ethylene, bp. 102°-164 Ethyl acetate, bp. 77°-120 Isobutyric ac., bp. 155°-73 Isopropyl formate, bp. 69°-120 Methyl propionate, bp. 79.9°-120 Propyl formate, bp. 81°-120 C4H8O3 Ethyl glycollate, bp. 160°-122 Ethoxyacetic ac., bp. 206°-74 Methyl ethyl carbonate, bp. 109°- 120 Methyl lactate, bp. 145°-73 Methyl methoxyacetate, bp. 127.3° -121 a-Oxybutyric ac., mp. 43°-39 a-Oxyisobutyric ac., mp. 79°-41 C4H8O4 «/?-Dioxybutyric ac., mp. 74°-40 Methylisoglyceric ac., mp. 74°-40 Methylpropanedioic ac., mp. 100°- 43 C4H8O5 Trioxyisobutyric ac., mp. 116°-44 C4H10O Butyl ale., bp. 117°-161 sec.-Butyl ale., bp. 100°-161 Isobutyl ale., bp. 106°-161 Ethyl eth., bp. 35°-160 Methyl propyl eth., bp. 40°-160 Trimethylcarbinol, bp. 83°-161 C4H18O2 Butanediols, bp. 204°-164, 165 Dihydroxybutane, bp. 183°-164 Dihydroxymethylpropane, bp. 177° -164 Dimethylacetal, bp. 64°-19 Ethyleneglycol monoethyl eth., bp. 135°-164 Glycol dimethyl eth., bp. 83°-161 C4H10O3 Diethylene glycol, bp. 250°-165 C4H10O4 Erythrite, mp. 126°-155 C5 GROUP. C6H8 Cyclopentadiene, bp. 42°-185 Valylene, bp. 50°-185 Pirylene, bp. 60°-185 C6H3 Isopropylacetylene, bp. 28°-184 Isoprene, bp. 36°-184 Methylbutadiene, bp. 41°-184 Piperylene, bp. 42°-185 Cyclopentene, bp. 45°-185 Propylacetylene, bp. 48°--185 Valerylene, bp. 56°-185 C5H10 Dimethylcyclopropane, bp. 21°- 184 Isopropylethylene, bp. 21°-184 Methylethylethylenes, bp. 31° and 36°-184 C5H10 Trimethylethylene, bp. 37°-184 Propylethylene, bp. 39°-184 Methylcyclobutane, bp. 40°-182 Cyclopentane, bp. 50°-182 CsH]2 2-Methylbutane, bp. 31°-182 Pentane, bp. 37°-182 CrH,Os Croconic ac.-213 C5H.O2 Coumalin, bp. 207°-131 Furfurol, bp. 161°-20 C5H4O3 Citraconic anhyd., bp. 213°-76 Glutaconic anhyd., mp. 87°-56 Pyromeconic ac., mp. 117°-59 Pyromucic ac., mp. 133°-45 C5H6O2 Ethyl propiolate, bp. 119°-121 Furfuralcohol, bp. 169°-164 Ltevulinic anhydrides, bp. 167°, 208°-131 Pentinoic ac., mp. 102°-43 Propargyl acetate, bp. 124°-121 CsHoOs Glutaric anhyd., mp. 56°-54 Tetrinic ac., mp. 189°-67 CHeO4 Citraconic ac., mp. 80°-41 Ethylenemalonic ac., mp. 140°-46 Glutaconic ac., mp. 132°-45 Itaconic ac., mp. 161° d.-48 Mesaconic ac., mp. 202°-50 Paraconic ac., mp. 57°-40 Trimethylenedi carbonic ac., mp. 175°-48 CJI6O5 Acetonedicarbonic ac., mp. 135° d.-45 C5H6O6 Ethenyltricarbonic ac., mp. 159° d.-47 C6H8O Acetyltrimethylene, bp. 114°-141 Cyclopentanone, bp. 130°-141 Ethylideneacetone, bp. 122°-141 Ethyl propargyl eth., bp. 80°-161 Laevulinic aid., 187° d.-20 Methylbutenon, bp. 100°-141 Tetramethylene aid., bp. 116°-19 Tiglic aid., bp. 116.6°-19 CflH8O2 Acetylpropionyl, bp. 108°-215 Allyl acetate, bp. 103.5°-120 Allylacetic ac., bp. 188°-75 Angelic ac , mp. 45.5°-53 Dimethylacrylic ac., mp. 70°-40 Ethyl acrylate, bp. 98.5° c.-120' a-Ethylacrylic ac., mp. 45°-39 Methylbutyrolactone, bp. 204°- 131 Methyl crotonate, bp. 120.7°-121 Methyltrimethylene carbonic ac., bp. 191°-74 Pentenoic acids, bp. 194°, 200°-74 Tetramethylenecarbonic ac., bp. 195°-75 246 FORMULA INDEX. Tiglic ac., mp. 64.5°-40 y-Valerolactone, bp. 207°-131 CjHgOa Itaconic anhyd., mp. 68°-55 Laevulinic ac., bp. 239°-74 ^-Methoxyisocrotonic ac., mp. 128° -61 C5HaO4 Acetoxylpropionic ac., mp. 166°- 48 Dimethylmalonic ac., mp. 192° d.- 50 Ethylmalonic ac., mp. 111°-43 Glutaric ac., mp. 97.5°-42 a-Hydroxyhevulinic ac., mp. 103° -43 Methyl ethyl oxalate, bp. 174°- 122 Methyl malonate, bp. 181°--122 Pyro tartaric ac., mp. 112°-43 C5H8O6 Citramalic acids, mp. 95°, 119°- 42, 44 Ethyltartronic ac., mp. 115°-44 Methylmalic ac., mp. 123°-44 /3-Oxyglutaric ac., mp. 95°-42 CTEO, Trioxyglutaric acids, mp. 128°, 152° 154° 45 47 CsH10O Diethyl ket., bp. '105°-141 Ethylallyl eth., bp. 66°-160 a-Ethylallyl ac., bp. 134°-162 Ethyl isopropenyl eth., bp. 62°- 160 Isovalerianic aid., bp. 92.5°-19 Methylallylcarbinol, bp. 115°-161 Methyl isocrotyl eth., bp. 72°-185 Methyl isopropyl ket., bp. 95°- 141 Methyl propylket., bp. 102°-141 1, 4-Oxypentane, bp. 78°-161 Pentamethylene oxide, bp. 81°-- 161 Trimethylacetic aid., bp. 74.5°-19 Valerianic aid., bp. 103°-19 Vinylethylcarbinol, bp. 114°-161 C5H10O2 Acetylcarbinolethylether, bp. 128° -141 Acetylpropyl ale., bp. 208°-143 tert.-Butylcarbinol, mp. 52°-155 Butyl formate, bp. 107°-120 Ethyl propionate, bp. 98°-120 Hydracetylacetone, bp. 176°-142 Isobutyl formate, bp. 98°-120 Isopropyl acetate, bp. 91°-120 Isovalerianic ac., bp. 176° c.-74 Methyl butyrate, bp. 102.3°-120 Methylethylacetic ac., bp. 177°-74 Methyl isobutyrate, bp. 92.3°-120 Propyl acetate, bp. 102°-120 Trimethylacetic ac., mp. 35°-39 n-Valerianic ac., bp. 187°-74 CfiHiOO, Diethyl carbonate, bp. 126°-121 Methyl ethoxyacetate, bp. 148°-• 121 a-Ethoxypropionic ac., bp. 196°- 74 Ethyl lactate, bp. 154°-73 Ethyl methoxyacetate, bp. 131°-• 121 Methyloxybutyric ac., mp. 67°-40 Oxyvalerianic acids, mp. 31°, 85°- 39, 41 Propyl glycollate, bp. 170°-122 C5H1oO4 Angliceric ac., mp. 110°-43 Tigliceric ac., mp. 88°-41 CoH10Os Arabinose, mp. 160°-30 Xylose, mp. abt. 150°-30 C5H10O6 Arabonic ac., mp. 89°-41 C5H12O5 act. Amyl ale., bp. 129°-162 n-Amyl ale., bp. 138°-162 Diethylcarbinol, bp- 116°-161 Dimethylethylcarbinol, bp. 102°- 161 Ethyl propyl eth.. bp. 64°-160 Isoamyl ale., bp. 130°-162 Methylbutylcarbinol, bp. 136°-162 Methyl butyl eth., bp. 70°-185 C5H12O Methylisopropylcarbinol, bp. 112° -161 Ethyl isopropyl eth., bp. 54°-160 Methylpropylcarbinol, bp. 118°-■ 161 C5H12O2 Trimethyleneglycol ethyl eth., bp. 160°-164 Dihydroxypentanes, bp. 187°, 221° -164, 165 Methylene diethyl ether, bp. 89°- 19 C5H12O3 Ethyl glyceryl eth., bp. 227°-165 C5H12O4 Pentaerythrite, mp. 253°-156 C5H10O5 Arabite, mp. 102°-155 C6 GROUP. C6H8 Benzene, bp. 80°-189 Hexadiene, bp. 86°-186 C6H8 Diallylene, bp. 70°-185 Hexadiene, bp. 80°-185 1, 2-Dihydrobenzene, bp. 83°-185 1, 4-Dihydrobenzene, bp. 85°-185 C6H1(, Dimethylbutine, bp. 38°-184 Diallyl, bp. 59°-185 Butylacetylene, bp. 70°-185 Methylpentadienes, bp. 70° and 77°-185 Methylcyclopentenes, bp. 70° and 72°-185 Methylpentine, bp. 72°-185 Ethyldi vinyl, bp. 73°-185 Hexadiene (1, 3), bp. 73°-185 Methylpropylacetylene, bp. 83°- 185 C0H12 Dimethylethylethylene, bp. 66°- 185 s-Methylpropylethylene, bp. 68°-• 185 Butylethylene, bp. 69°-185 Methylethylpropylene, bp. 70°- 185 Methylcyclopentane, bp. 71°-182 Tetramethylethylene, bp. 73°--185 Cyclohexane, bp. 81°-182 C6H14 Trimethylethylmethane, bp. 50°- 182 Diisopropyl, bp. 58-182 2-Methylpentane, bp. 62°-182 Methyldiethylmethane, bp. 64°- 182 Hexane, bp. 69°-182 CeH2O4 Diacetylenedicarbonic ac, mp. 177°-49 C,H4O2 Benzoquinone, mp. 116°-206 FORMULA INDEX. 247 CaH4O4 Coumalic ac., mp. 207° d.-69 Comanic ac., mp. 250°-71 C0H4O5 Comenic ac., d. 260°-71 Furfuranedicarbonic ac., sbl. w. m.-72 C6H6O Phenol, mp. 42°-91 C0H0O2 Hydroquinone, mp. 169°-99 C0H0O2 Methylfurfurol, bp. 187°-20 Pyrocatechin, mp. 104°-94 Resorcin, mp. 116°-95 C0HaO3 Betulin, mp. 258°-159 Maltol, mp. 159°-98 Methylpyromucic ac., mp. 108°-59 Oxyhydroquinone, mp. 140.5°-97 Phenoglucin, mp. 200.5°-100 Phloroglucine, mp. 217-9°-101 Pyrogallol, mp. 133°-96 C0HaO4 Dimethyl acetylenedicarbonate, bp. 196°-123 Muconic ac., d. abt. 320°-72 CeH0Ofl Aconitic ac., mp. 191° d.-49 Trimethylenetricarbonic acids, mp. 151°, 184° c., 220°-47, 49, 51 C0H0O8 s-Ethanetetracarbonic ac., mp. 170°-48 C0H8O Dimethylfurfurane, bp. 93°-189 Hexinone, bp. 149°-142 C0H8O2 Dihydroresorcin, mp. 105°-94 Propylacetylenecarbonic ac., mp. 270 39 Sorbic ac., mp. 134°-61 C0H8O3 s-Dimethylsuccinic anhyd., mp. 87°-56 Ethylsuccinylosuccinic ac., mp. 128°-96 CaH8O4 Allylmalonic ac., mp. 103°-43 Dimethyl fumarate, mp. 102°-119 Dimethyl maleate, bp. 205°-123 Ethylfumaric ac., mp. 194°-67 Monoethyl fumarate, mp. 70°-55 Ethylmaleic ac., mp. 100°-43 Hexenedioic ac., mp. 195°-67 Lactide, mp. 128°-60 Methylcyclopropanedicarbonic ac., mp. 113°-43 Methylglutaconic ac., mp. 137°-46 Methylitaconic ac., mp. 166°-48 Tetramethylenedicarbonic acids, mp. 131°, 135°, 138°, 157°, 170°- 45, 46, 47, 48 C6H8O5 Ethyl oxalylacetate, mp. 96°-94 C0H8O6 Glucuronic anhyd., mp. 176°-49 Tricarballylic ac., mp. 166°-48 C6H8O7 Citric ac., mp. 153°-47 C0H10O AllyHcetone, bp. 128°-141 Allyl eth., bp. 94°-161 Cyclohexanone, bp. 155°-142 Mesityl oxide, bp. 129.5°-141 Methylethylacrolein, bp. 137-19 Methylcyclopentanone, bp. 142°- 142 Methyl tetramethylene ket., bp. 135°-142 C6H10O2 Acetonylacetone, bp. 194°-142 Acetylisobutyryls, bp. 115°, 128°- 215 /-Caprolactone, bp. 220°-131 Dimethylbutenoic ac., mp. 70°-40 Ethyl a-crotonate, bp. 142°-121 a-Ethylcrotonic ac., mp. 41 °-53 Ethyl isocrotonate, bp. 136°-121 Ethyl methacrylate, bp. 117°-121 Hexenoic acids, mp. 33°, bp. 206° 203°-53, 75 Isocaprolactone, bp. 207°-131 Methylpentenoic acids, mp. 24°; bp. 211°, 213°-52, 76 Methylvalerolactone, bp. 206°- 131 Pentamethylenecarbonic ac., bp. 214°-76 Propionylpropionic aid., mp. 40°-■ 17 C6H10O3 7-Acetylbutyric ac., bp. 275°-74 ^-Ethoxycrotonic ac., mp. 137°-62 Ethyl isoacetoacetate, bp. 128.5°- 121 Ethyl methylformylacetate, bp. 161°-20 Glycerine eth., bp. 171°-164 Propionic anhyd., bp. 169°-75 /?-Propionylpropionic ac., mp. 32°- 39 C0HloO4 Adipic ac., mp. 153° c.-63 Diethyl oxalate, bp. 186°-74 Dimethylsuccinic acids, mp. 129°, 139°, 195°, 209°-45, 46, 67, 50 EthoxyIsuccinic ac., mp. 86°-41 Ethylsuccinic ac., mp. 98°-42 Isomannide, mp. 87°-155 Isopropylmalonic ac., mp. 87°-41 Methylethylmalonic ac., mp. 118°- 44 a-Methylglutaric ac., mp. 77°-41 Methyl isosuccinate, bp. 179°-122 3-Methylpentanedioic ac., mp. 85° Methyl succinate, bp. 195°-123 Propylmalonic ac., mp. 96°-42 (C6H10O5)x Cellulose-31 Dimethylmalic ac., mp. 130°-45 Ethoxysuccinic ac., mp. 78°-41 Glycogen, mp. abt. 240°-31 Lactic anhyd., mp. 255°-71 a-Oxyadipic ac., mp. 151°-47 Saccharin, mp. 160°-129 Starch-31 C0H1OO0 Dimethyl racemate, mp. 85°-119 Dimethyl tartrate, mp. 48°-118 Monoethyl tartrate, mp. 90°-42 C6HioO8 Isosaccharic ac., mp. 185°-49 Mucic ac., mp. 206° d.-69 Saccharic ac.-34 Talomucic ac., mp. 158° d.-47 C0H12O Caproic aid., bp. 129°--19 Cyclohexanol, bp. 160°-163 Dimethylallylcarbinol, bp. 119°- 162 Ethyl isocrotyl eth., bp. 93°-186 Ethyl isopropyl ket., bp. 114°-■ 141 Ethyl propyl ket., bp. 123°-141 Hexenyl ale , bp. 137°-162 Methyl butyl ket., bp. 127°-141 Methylcrotylcarbinol, bp. 138°- 162 Methylethylacetone, bp. 118°- 141 248 FORMULA INDEX. Methyl isobutyl ket., bp. 116°- 141 1, 5-Oxyhexane, bp. 106°-161 Pinacoline, bp. 106°-141 C6H12O2 Amyl formate, bp. 130°-121 Butyl acetate, bp. 125°-121 Caproic acids, bp. 197°, 206°-75 Diacetone ale., bp. 164°-142 Diethylacetic ac., bp. 190°-74 Dimethvlethylacetic ac., bp. 187°- 75 Ethyl butyrate, bp. 120°-121 Ethyl isobutyrate, bp. 110°-120 Isobutyl acetate, bp. 116°-121 Isobutylacetic ac., bp. 208°-75 Isoamyl formate, bp. 123°-121 Methylpropylacetic acids, bp. 190°, 193°-75, 74 Methyl iso valerianate, bp. 127°- 121 Methyl trimethylacetate, bp. 101°-120 Methyl valerianate, bp. 127°- 121 C6H12O3 Allyl glyceryl eth., bp. 240°-165 Cyclohexantriol, mp. 184°-156 Ethoxyisobutyric acids, bp. 181°, 217°-75, 74 Ethyl ethoxy acetate, bp. 152°- 121 Ethyl oxyisobutyrate, bp. 150° -121 Ethyl a-oxybutyrate, bp. 165°- 122 Methylpentanoloic ac., mp. 73°-40 a-Oxycaproic ac., mp., 61°-40 Oxy diethylacetic ac., mp. 80°-41 Paraldehyde, bp. 124°-19 C6H.2O4 Ethyl dioxybutyrate, bp. 227°- 124 C6H12O5 Quercite, mp. abt 230°-156 Rhamnose, (isodulcite)-30 C6H12Ob Fructose (Levulose), mp. 94°-30 Galactose, mp. 168°-30 Glucose, mp. 146°-30 Inosite, mp. 225° c.-156 Mannose,-29 Sorbinose mp. 164°-30 CeH]4O Dimethylisopropylcarbinol, bp 118° -161 Ethylisopropylcarbinol, bp. 128°- 162 Ethyl butyl eth.. bp. 92°-186 Ethyl isobutyl eth.. bp. 79°-185 Ethylpropylcarbinol, bp. 135°- 162 act.-Hexyl ale., bp 154°-162 Hexyl ale. bp 157°-163 Isopropyl eth. bp 69°-160 Iso hexylcarbinol, bp. 150°--162 Methyldiethylcarbinol, bp. 123°- 162 Methyhsobutylcarbinol, bp. 130°- 162 Methylpropylcarbincarbinol, bp. 147°-162 Pinacoline ale . bp .120°-162 Propyl ether, bp. 91°-161 C6H14O2 Acetal, bp 104°-19 Dihydroxy hexane, bp. 206°-165 Glycol diethyleth., bp. 123°-162 Pinacone, mp. 36°-155 C6H]4O4 Triethylene glycol, bp. 290°-165 CbH14Oc Rhamnite, mp. 121°-155 C0H14O0 Mannite, mp. 163°, 166°, 16S°-• 155 156 Dulcite, mp. 188°-156 Sorbite, mp. 110°-155 CgH26O8 Pinacone hydrate, mp. 56°-155 C7 GROUP. C7H8 Toluene, bp. 111°-189 Tropilidene, bp. 114°-189 C7H10 Dihydrotoluene, bp. 107°-186 Heptone, bp. 115°-186 Cycloheptadiene, bp. 120°-189 C7H12 Ethylpentadiene, bp. 97°-186 CEnanthylidene, bp 102°-186 Heptine, bp. 103°-186 Ethylpropylacetylene, bp. 105°- 186 Toluenetetrahydride, bp. 105°- 186 Methvlbutylacetylene, bp. 112°- 186 Cycloheptene, bp. 114°-186 C7H14 Dimethylpentene, bp. 77°-185 Trimethylbutene bp. 79°-185 Dimethyl pentene, bp. 83°-185 Dimethylcyclopentane, bp. 94°-■ 182 Ethylpentene, bp 97°-186 Heptene(l), bp. 98°-186 Hexahydrotoluene, bp. 101°-182 Cycloheptane, bp 118°-182 C7H16 Dimethvldiethylmethane, bp. 86°- 182 Methylhexanes, bp. 90° and 91°- 182 Triethylmethane, bp. 96°-182 Heptane, bp. 98°-182 C7H4O6 Chelidonic ac., mp. 262°-71 C7H O Benzaldehyde, bp. 179.5°-20 C7H6O2 Benzoic ac., mp. 121.2° c.-60 Furfuracrolein, mp. 51°-17 Oxybenzaldehydes, mp. 104°, 115°-17, 18 Salicylic aid., bp. 196.5°-20 Toluquinone, mp. 68°-205 C7H0O3 Furfuracxylic ac., mp. 141°-62 m-Oxybenzoic ac., mp. 200°-68 p-Oxybenzoic ac., mp. 210°-69 Salicylic ac., mp. 158° c.-64 C7H0O4 Dioxybenzoic acids, mp. 199°, 204°, 205°, 232°-50, 50, 69, 51 Protocatechuic ac., mp. 199° d.- 50 C7H6O5 Gallic ac., mp. abt. 230°-70 Pyrogallocarbonic ac., mp. 197° d. -68 C7H0O8 Trimethylenetetracarbonic ac., mp. abt. 97°-42 C7H8O Anisol, bp. 155°-189 Benzyl ale., bp. 205°-165 p-Cresol, mp. 36°-91 o-Cresol, mp. 30°-91 m-Cresol, bp. 203°-104 Dihydrobenzaldehyde, bp. 170° d, -20 FORMULA INDEX. 249 Guiacol, mp. 31°-91 m-Oxybenzyl ale., mp. 67°-93 C7H8O2 Dioxytoluenes, mp. 64°, 103°, 124° -92, 94, 96 Homopyrocatechin, mp. 51°-92 Hydroquinone methyl eth., mp. 53°-92 Isohomopyrocatechin, mp. 47°-92 Orcin, mp. 107°-95 p-Oxybenzyl ale., mp. 110°-95 Saligenin, mp. 86°-93 C?H8O3 Ethyl pyromucate, mp. 34°-118 Methylpyrogallol, mp. 129°-96 Uvic ac., mp. 135°-62 C7H8O4 Dicarboxyglutaric ac., mp. 167° d -48 Iretol, mp. 186°-100 C7H8OS Cinchoic ac., mp. 168°-65 C7H10O Tetrahydrobenzaldehyde, bp. 187° -20 C7H10O3 Ethyl tetrinate, mp. 30°-118 Diacetylacetone, mp. 49°-92 C7HloO4 Dimethyl citraconate, bp. 210°- 123 Dimethyl mesaconate, bp. 206°- 123 Dimethyl trimethylenedicarbonic acids, mp. 176°, 213°-49, 50 Ethylitaconic ac., mp. 164°-65 Ethylmesaconic ac., mp. 172°-65 Dimethyl itaconate bp. 211°-123 Pentamethylenedi carbonic acids, mp. 88°, 140°, 159°-41, 46, 64 Teraconic ac., mp. 162° d.-48 Terebic ac., mp. 174°-66 C7H10O5 Hydrochelidonic ac., mp. 142°-62 C7H10O6 Dicarboxylpentanoic ac., mp. 141° d. -46 C7H12O Diallylcarbinol, bp. 151°-162 Methylcyclohexanone, bp. 169°- 142 Propionylcyclobutane, bp. 155°- 142 Suberone, bp. 180°-142 C7H12O2 Acetyliso valeryl-215 Allyl butyrate, bp. 142°-121 Allyl isobutyrate, bp. 133°-121 Ethyl allylacetate, bp. 143°-121 Ethyl angelate, bp. 141°-121 Ethyl tetramethylene carbonate, bp. 161°-122 Ethyl tiglate, bp. 156°-122 Ethylvalerolactone, bp. 219°-131 Heptenoic ac., bp. 227°-76 Hexahydrobenzoic ac., mp. 30°-52 y-CEnantholactone, bp. 235°-131 Teracrylic ac., bp. 218°-76 C7H12O3 Acetylvalerianic ac., mp. 41°-39 Ethyl Isevulinate, bp. 205°-123 Ethyl 5-methoxyisocrotonate, bp. 178°-122 Mesitonic ac., mp. 74°-40 C7H12O4 Butylmalonic acids, mp. 76°, 101° -40, 43 Diethyl malonate, bp. 198°-123 Diethylmalonic ac., mp. 121°-44 Dimethyl dimethyhnalonate, bp. 178°-122 s-Dimethylglutaric acids, mp. 128°, 140°-44, 46 Dimethylpentanedioic acids, mp. 84°, 100°-41, 42 Ethvl acetoxylpropionate, bp. 178° -122 Isobutylmalonic ac., mp. 107°-43 Isopropylsuccinic ac., mp. 117°- 44 Methylcarboxylpentanoic ac., mp. 103°-43 Methyladipic ac., mp. 94°-42 Methylethvlsuccinic acids, mp. 101°, 169°, 180°-43, 65, 49 Methyl ethyl succinate, bp. 208°- 123 Methylpropylmalonic acids, mp. 106°, 121°-43, 44 Pimelic ac., mp. 105°-43 Propylsuccinic ac., mp. 91°-42 Trimethylsuccinic ac., mp. 152°- 47 C7H12O5 Diethyl tartronate, bp. 223°-124 s-Methylethylmalic ac., mp. 132°- 45 C7H12O6 Diethyl mesoxalate, mp. 57°- 118 Quinic ac., mp. 162° c.-48 C7H14O Diisopropyl ket., bp. 124°-141 Dimethylpentanones, bp. 132°, 137°, 126°-144, 142, 141 Dipropyl ket., bp. 144°-142 Ethyl isobutyl ket., bp. 136°-142 Ethylpentanone, bp. 138°-142 Ethyl valeryl eth., bp. 112°-186 Methyl amyl ketones, bp. 144°, 151°-142 CEnanthic aid., bp. 155°-20 Polycenanthylic aid., mp. 52°-17 Suberyl ale., bp. 184°-164 C7H14O2 Amyl acetates, bp. 139°, 148°-121 Amylacetic ac., bp. 221°-76 Ethyl isovalerianate, bp. 134°-121 Ethyl methylethylacetate, bp. 134° -121 Ethylpropylacetic ac., bp. 209°-75 Ethyl trimethylacetate, bp. 118°-• 121 Ethyl valerianate, bp. 144°-121 Isoamylacetic ac., bp. 209°-75 Methyldiethylacetic ac., bp. 207°-■ 75 Methyl caproate, bp. 150°-121 2-Methylhexanoic(l) ac., bp. 210°-• 75 Methyl isobutylacetate, bp. 150°- 121 Hexyl formate, bp. 154°-121 CEnanthylic ac., bp. 223°-76 C7H14O3 Dipropyl carbonate, bp. 168°-122 Ethyl a-ethoxypropionate, bp. 155° -121 Ethyl a-oxyisovalerianate, bp. 175° -122 Ethyl a-oxyvalerianate, bp. 190° -122 2-Methylhexanoloic ac., mp. 64.5° -40 Methyl oxydiethylacetate, bp. 165° -122 Oxyoenanthylic ac., mp. abt. 60°- 54 250 FORMULA INDEX. C7H14O8 Galactosecarbonic ac., mp. 145°- 47 Mannoheptonic ac., mp. 175° d.- 49 C7H18O Diisopropylcarbinol, bp. 140°-162 Dimethylisobutylcarbinol, bp. 130° -162 Dipropylcarbinol, bp. 154°-162 Ethyl isoamyl eth., bp. 112°- 186 Ethyl isobutylcarbinol, bp. 147°- 162 Heptyl ale., bp. 176°-163 Propyl butyl eth., bp. 117°-186 Methylamylcarbinol, bp. 164°-163 Methylethylpropylcarbinol, bp. 140° -162 Methylisoamylcarbinol, bp. 149°- 162 Trimethylbutanol, bp. 131°-162 Triethylcarbinol, bp. 141°-162 C7H16O2 Trimethylene glycoldiethyl eth., bp. 140°-187 C7H18O8 Rhamnohexite, mp. 173°-156 C7H16O7 Perseite, mp. 188° c., 203° c.-156 C8 GROUP. C8H8 Phenylacetylene, bp. 142°-189 CsH8 Styrene, bp. 146°-189 C8H1o Ethylbenzene, bp. 136°-189 p-Xylene, bp. 138°-189 m-Xylene, bp. 139°-189 o-Xylene, bp. 142°-189 C8H12 m-Dihydroxylene, bp. 133°-187 o-Dihydroxylene, bp. 134°-187 Octone, bp. 134°-187 p-Dihydroxylene, bp. 135°-187 C8Hu Trimethylcyclopentene, bp. 108°- 186 Dimethylhexadiene, bp. 113°, 133° -186, 187 2-Methylheptadiene, bp. 117°-186 Octadiene, bp. 118°-186 Ethylhexadiene, bp. 122°-186 Octine(l), bp. 131°-18G Octine (2), bp. 133°-187 C8H18 Diisobutylene, bp. 102°-186 s-Dimethyldiethylethylene, bp. 115° -186 s-Diisopropylethylene, bp. 117°- 186 Hexahydroxylenes, bp. 118° and 120°-182 Methylethylcyclopentane, bp. 124° 183 Octene(l), bp. 125°-186 C8H18 Dimethylhexane, bp. 108°-182 Octane, bp. 125°-183 C8H4O3 Phthalic anhyd., mp. 128°-61 C8H8O2 Phthalid, mp. 73°-129 C8H8O, Aldehydobenzoic acids, mp. 97°, . 165°, 285°-17, 18 Benzoylformic ac., mp. 65°-40 Piperonal, mp. 37°-17 C8H8O4 Aldehydosalicylic acids, mp. 179°, 234°, 243°, 248°-18 Isophthalic ac., mp. a.300°-72 o-Oxyphenylglycollic ac., mp. 43°- 39' Phthalic ac., mp. 184° d.-67 Piperonylic ac., mp. 228°-70 Terephthalic ac., sbl. w. m.-72 C8H8O5 Furalmalonic ac., mp. 205° d.-69 Oxyisophthalic acids, mp. 243°, 288° c., 305°-70, 72 Oxyphthalic ac., mp. 181° d.- 49 C8H6O9 a-Resodicarbonic ac., mp. 276°-71 C8H8O8 Tetrahydroxyterepthalic ac., mp. 139°-46 C8H8O Acetophenone, bp. 202°-142 Phenylacetic aid., bp. 193°-20 m-Toluic aldehydes, bp. 199°, 200° -20 C8H80j Anisic aid., bp. 248°-21 Dimethylquinones, mp. 55°, 72°- 205 Furfuralacetone, mp. 39°-136 Methyl benzoate, bp. 199°-423 Methylenedihydrobenzoic ac., mp. 33°-53 Methoxybenzoic aid., mp. 35°-17 Oxyacetophenone, mp. 86°-138 Oxybenzoicaldehydemethyiether, bp. 230°-20 Oxytoluic aldehydes, mp. 54°, 56°, 110°, 115°, 172°, 209°-17, 18, 65, 20 . Phenyl acetate, bp. 196°-123 Phenylacetic ac., mp. 76°-55 Phloron, mp. 125°-206 Toluic acids, mp. 102°, 110°, 176° -58, 59, 66 C8H8O3 Anisic ac., mp. 184.2° C.-67 Diphenyl p-oxybenzoate, mp. 131° -119 Mandelic ac., mp. 118°-44 m-Methoxybenzoic ac., mp. 106°- 58 Methylethersalicylic ac., mp. 98.5° -57 Methylphenolcarbonic ac., mp. 183° -66 Methylphenolmethanoic ac., mp. 168°-65 Oxyphenylacetic acids, mp. 129°, 137°, 148°-45, 46, 47 o-Oxymethylbenzoic ac., mp. 120° -60 Oxyxyloquinone, mp. 103°-206 Oxytoluic acids, mp. 151°, 163°, 172°, 177°, 183°, 206° c., 208° -63, 65, 66, 49, 69, 50 Phenoxyacetic ac., mp. 96°-42 Piperonyl ale., mp. 51°-157 Quinacetophenone, mp. 202°-209 Resacetophenone, mp. 142°-97 Vanilline, mp. 80°-17 C8H8O4 Dehydracetic ac., mp. 108.5°-58 Dihydrophthalic ac., mp. 215°-70 Gallacetophenone (alizarin yellow C), mp. 168°-99, 213 Homogentisic ac., mp. 147°-47 Isodehydracetic ac., mp. 155°-64 Methoxysalicylic ac., mp. 154°-63 Orsellinic ac., mp. 176° d.-66 Vanillic ac., mp. 207°-69 C8HsO5 Carbopyro tri taric ac., mp. 230°-70 Methyl gallate, mp. 192°-119 FORMULA INDEX. 251 Methylfurfurancarbonacetic ac., mp. 204°-68 C8H8O8' Tetramethylenetetracarbonic ac., mp. 200° d.- 50 C8H10O Benzylcarbinol, bp. 212°-165 Cresyl methyl ethers, bp. 171°, 175°-190 " p-Ethylphenol, mp. 46°-92 Methyl benzyl eth., bp. 167°--190 Methylphenylcarbinol, bp. 203°- 164 Phenetol, bp. 172°-190 Tolylcarbinols, mp. 34°, 59°, 217°- 157, 165 Xylenols, mp. 26°, 49°, 65°, 66°, 74°, 75°-91, 92, 93 C8H10O2 Anisic ale., mp. 45°-157 /?-Orcin, mp. 163°-98 Diethyl hydroquinolyl eth., mp. 55°-175 Dimethyl resorcinyl eth., bp. 214° -192 Dioxyxylol, mp. 120°, 149°-95, 97 Homosaligenin, mp. 105°-94 Hydroquinone, ethyl eth., mp. 66° 93 Phthalic ale., mp. 64°-155 Pyrocatechin, mp. 104°-94 Saligenin methyl eth., bp. 247°- 165 Styrolene ale., bp. 205°-192 Tolylene ale., mp. 112°, 46°-155 Veratrol, bp. 205°-192 m-Xylorcin, mp. 125°-96 C8H10O3 Methyluvinic ac., mp. 98°-57 Pyrogalloldimethylether, mp. 51°- 92 Pyrogallol ethyl eth., mp. 95°-94 Vanillyl ale., mp. 115°-95 C8H10O4 Biphenyldiolcarbonic ac., mp. 270° -71 Diallyl oxalate, bp. 216°-124 Dimethylapionol, mp. 105°-95 Oxalyldiacetone, mp. 120°-95 Tetrahydrophthalic acids, mp. 120°, 215°-44, 69 C8H10O6 Diacetylsuccinic ac., mp. d. 160°- .47 C8H10O8 Dicarboxyl-hexanedioic ac., mp. 189°, 236°-49, 51 C8HuO3 Diethylacetic anhyd., bp. 230°-76 CSH12O2 Diallylacetic ac., bp. 227°-76 Ethyl sorbate, bp. 195°-123 C8H12O3 Diallyloxalic ac., mp. 48°-53 s-Diethylsuccinic anhyd., bp. 245° -76 Ethyl ethyleneacetoacetate, bp. 196°-123 C8H12O4 Ethyl diacetoacetate, bp. 202°-75 Diethyl fumarate, bp. 218°-124 Diethyl maleate, bp. 225°-124 Hexahydrophthalic acids, mp. 192°, 215°-67, 69 Terpenylic ac., mp. 90°-42 C8H12O5 Trimethylpentanedioldioic ac., mp. 120°-44 C8H14O Crotonyl eth., bp. 144°-189 Diisobutylene aid., bp. 230°-20 Methyldiallylcarbinol, bp. 158°-163 Methylheptenone, bp. 173°-142 C8H14O2 Acetylisocaproyl, bp. 163°-215 Allyl isovalerianate, bp. 154°-121 Cycloheptanecarbonic ac., bp. 246° -76 Ethylcaprolactone, bp. 254°-131 Ethyl a-ethylcrotonate, bp. 165°-• 122 Methylhexamethylenecarbonic ac., bp. 235°-76 C8H14O3 n-Butyric anhyd., bp. 182°-75 Ethyl dimethylacetoacetate, bp. 184°-122 Ethyl a-propionylpropionate, bp. 199°-123 Isobutyric anhyd., bp. 182°-75 Octanonoic ac., mp. 29°-39 Dialdane, mp. 130°-IS C8H14O4 s-Diethylsuccinic acids, mp. 129°, 192°-45, 67. Diethyl isosuccinate, bp. 198°-123 Diethyl succinate, bp. 216°-124 s-Dimethyladipic ac., mp. 140°, 75° -62, 40 Dimethylethylsuccinic ac., mp. 139°-46 Dipropyl oxalate, bp. 213°-124 Isoamylmalonic ac., mp. 93°-42 Isobutylsuccinic ac., mp. 107°-43 Pentylmalonic ac., mp. 82°--41 Suberic ac., mp. 140°-62 Tetramethylsuccinic ac., mp. 195° d.- 68 C8H14O5 Diethyl diglycollate, bp. 240°-125 Diethyl i-malate, bp. 255°-126 C8Hl4O0 Diethyl tartrate, bp. 280°-126 C8H14O8 Methyl, gallate,+ 3II2O, mp. 192° d. -119 C8H16O Allyl isoamyl eth., bp. 120°-186 Diethylallylcarbinol, bp. 157°-163 Dimethylhexanone, bp. 151°-142 Ethyl amyl ket., bp. 170°-142 Methylbutyrone, bp. 180°-142 Methylheptenol, bp. 175°-163 Methylheptanone, bp. 170°-142 Methyl hexyl ket., bp. 172.5°-142 Propyl isobutyl ket., bp. 155°-142 C8H16O2 Butyl butyrate, bp. 165°-122 Caprylic ac., bp. 237°-76 Dipropylacetic ac., bp. 219°-76 Ethyl caproate, bp. 167°-122 Ethyl isobutylacetate, bp. 161°- 122 Ethyl diethylacetate, bp. 151°-121 Ethyl methylpropylacetate, bp. 153° 121 Heptyl formate, bp. 176°-122 Hexyl acetate, bp. 169°-122 Isoamyl propionate, bp. 160°-122 Isobutyl butyrate, bp. 157°-122 Methyl oenanthy late, bp. 173°- 122 CSII16O3 Ethvl ethoxybutyrate, bp. 168°- 122 Ethyl oxydiethylacetate, bp. 175° -122 a-Oxycaprylic ac., mp. 69°--55 Trimethylpentanoloic ac., mp. 92° -42 252 FORMULA INDEX. C8H18O Butyl ethers, bp. 141°, 120°-187, 186 Diethylisopropylcarbinol, bp. 160° -rl63 Diethylpropylcarbinol, bp. 160°- 163 Ethyl hexyl eth., bp. 135°-187 Isobutyl eth., bp. 122°-186 Methylhexylcarbinol, bp. 179°-163 Methyl heptyl eth., bp. 150°-187 Methyldipropylcarbinol, bp. 161°- 163 Octyl ale., bp. 195°-163 C8H18O2 Diisopropylglycol, mp. 51°-155 Dimethylpinacone, mp. 49°-155 Ethvlidene dipropyl eth., bp. 147° -20 C9 GROUP. C9H8 Indene, bp. 180°-191 Phenylallylene, bp. 185°-191 CeH10 Benzylethylene, bp. 155°-189 p-Methylstyrene, bp. 172°-190 Allylbenzene, bp. 174°-190 Hydrindene, bp. 176°-190 C9H12 Cumene, bp. 153°-189 Propylbenzene, bp. 158°-189 Methylethylbenzenes, bp. 158°, 162° -189, 190 Mesitylene, bp. 164°-190 Pseudocumene, bp. 170°-190 v-Triinethylbenzene, bp. 175°-190 C9H14 Nonone, bp. 156°-187 C9Hl8 Campholene, bp. 135°-187 Trimethylcyclohexene, bp. 138°- 187 Dimethylheptadiene, bp. 142°-187 C9H18 Nonylene, bp. 139°-187 C9H18 Methyloctene, bp. 141°-187 Propylhexamethylene, bp. 148°- 187 Methylethylcyclohexane, bp 151° -187 Dimethylcycloheptane, bp. 153°- 187 Hexahydropseudocumene, bp. 135° -183 Mesitylenehexahydride, bp. 136°- 183 Hexahydrocumene, bp. 148°-183 C9H20 /9-Nonane, bp. 130°-183 a-Nonane, bp. 136°-183 Nonane, bp. 148°--183 C9H4Os Trimellitic anhyd. mp. 157°-64 (CJ4gO) Truxone, mp. 289°-140 CaHgOg Coumarin, mp. 67°-129 Diketohydrinden, mp. 130°-96 Phenylpropiolic ac., mp. 136°-62 C9H0O3 Cumarilic ac., mp. 192°-67 C9H6O4 Daphnetin, mp. 254°-210 C9HeO6 Aldehydoxyisophthalic acids, mp. 237°, 260°-18 Hemimellitic ac., mp. 185° d.-67 Trimellitic ac., mp. 216° d.-50 Trimesic ac., mp. 345°, 347°-72, 51 C8H8O Cinnamic aid., bp. 130° (20 mm.)- 21 Hydrindones, mp. 40°, 61°-136, 137 Vinyl phenyl ket.,.mp. 42°-136 C9H8O2 Acetylbenzoyl, bp. 217°-215 Allocinnamic ac., mp. 68°-55 Atropic ac., mp. 106°-58 Cinnamic ac., mp. 133°-61 Homococaic ac., mp. 150°-63 Isocinnamic ac., mp. 57°-54 Melilotic anhyd., mp. 25°, bp. 272° -129, 132 C9HSO3 Acetophenonecarbonic ac., mp. 115° -59 p-Acetylbenzoic ac., mp. 200°-68 Acetylsalicylic aid., mp. 37°-17 Benzoylacetic ac., mp. 103°-58 Cumaric acids, mp. 191°, 206°, 208° -67, 69 Hydrocumarilic ac., mp. 116°-43 Phenylpyruvic ac., mp. 154°--63 p-Toluylcarbonic ac., mp. 96°-57 CgH8O4 Acetoxybenzoic acids, mp. 127°, 185°-60, 67 Caffeic ac., mp. 195°-209 Homophthalic ac., mp. 175°-66 Homoterephthalic ac., mp. 237°-70 Methylisophthalic ac., mp. 325°- 72 Methylphthalic ac., mp. 144°--62 Methylterephthalic ac., mp. 281°-■ 72 Methoxylphenylglyoxvlic ac., mp. 89°-41 Monomethylphthalate, mp. 82.5°- 56 Phenylmalonic ac., mp. 152°-47 Salicylic ac. acetate, mp. 118°-59 Umbellic ac., d. 260°-71 s-Uvitic ac., mp. 287°-72 C9H8O5 Aldehydovanillic acid, mp. 221°- 18 m-Oxyuvitic ac., mp. 290°-72 C9H10O p-Anol, mp. 93°-94 Cinnamyl ale., bp. 254°-165 Hydrocinnamic aid., bp. 208°-20 a-Hydroxindene, mp. 54°-157 Methyl benzyl ket., mp. 27°-136 p-Methyl tolyl ketones, bp. 222°, 224°-143 Propiophenone, bp. 218°-143 C9H10O2 Benzyl acetate, bp. 206°-123 p-Cresyl acetate, bp. 214°-124 Dimethylbenzoic acids, mp. 98°, 126°, 132° 144°, 163°, 166°-57, 60, 61, 62, 65 Ethylbenzoic acids, mp. 47°, 68°, 112°-53, 55, 59 Ethyl benzoate, bp. 212°-123 Hydrocinnamic ac., mp. 48.7°- 54 Methyl phenylacetate, bp. 220°- 124 Phenyl propionate, bp. 211°-123 Pheriylpropionic ac., bp. 264°-76 m-Oxybenzoic aldehyde ethylether, bp. 245°-21 Tolylacetic acids, mp. 61°, 88°, 91° -54, 56, 57 C9H10O, Aceto vanillon. mp. 115°-9 Alorcinic ac., mp. 97°-57 Atrolactic acid, mp. 90°-42 Dimethylphenolcarbonic ac., mp. 199°, 223°-68, 70 FORMULA INDEX. 253 Ethoxybenzoic ac., mp. 137°, 195° -62, 67 Ethylether salicylic ac., mp. 19°- 52 Ethyl oxybenzoates, mp. 116°, 72° -95, 119 Hydrocumaric acids, mp. 82°, 111°, 128°-41, 43, 61 Fluorenecarbonic ac., mp. 175°-66 Methyl anisate, mp. 45°-118 Methyl mandelate, mp. 52°-118 Methvlmandelic acids, mp. 84°, 145°-41, 62 Methyl methylethersalicylate, bp. 228°-125 Methoxyphenylacetic ac., mp. 72°- 55 Methyl oxyphenylacetate, bp. 310° -127 Orcacetophenone, mp. 146°-97 Oxymesitylenic ac., mp. 179°-66 Paonol, mp. 50°-92 Phenyllactic acids, mp. 93°, 97°-42 Phenoxvpropionic ac., mp. 112°- 59 Phloretic ac., mp. 129°-45 Tropic acids, mp. 117°, 123° and 127°-44, 60 C9H10O4 Ethyl-dioxybenzoate, mp. 75°-119 Hemipinic ac , mp. 161°-64 Hydrocaffeic ac.. mp. 139°-46 Methyl vanillate, mp. 62°-119 Phenylglyceric ac., mp. 143°-46 Veratric ac., mp. 181°-66 C9H10O8 Cyclopentane-tetracarbonic ac., mp. 187° d.-49 C9H12O o-Cresyl ethyl ethers, bp. 180°, 189° -191 Dimethyl orcinyl eth., bp. 244°- 193 Ethyl benzyl eth., bp. 185°-191 p-Isopropylphenol, mp. 61°-92 Methylbenzylcarbinol, bp. 215°- 163 Mesitol, mp. 68°-93 Phenylpropyl ale., bp. 235°-165 m-Propylphenol, mp. 26°-91 Pseudocumenol, mp. 71°-93 Trimethylphenols, mp. 81°, 95°- 93, 94 C9H12O2 Methylphenylethyleneglycol, mp. 52°-155 Trimethylbenzoic ald.,mp. 105°-17 Trimeth vlphendiole, mp. 149°, 169°, 156°-97, 99, 98 C9H12O3 Iridol, mp. 57°-92 Phloroglucin trimethyl eth., mp. 52° -175 Propyl pyrogallol, mp. 79°-93 Pyrogallol trimethyl eth., mp. 47° -175 Ethyl pyrotritarate, bp. 214°-124 Metacrolein, mp. 45°-17 Trimethylphloroglucin, mp. 184°- 99 C9H12O4 Diallylmalonic ac., mp. 133°-45 C9H,2O6 Anhydrocamphoric ac., mp. 139°- 46 CaHjaOu Hexamethylenetricarbonic ac., mp. 152°-47 Trimethvl aconitate, bp. 270°-126 C9H14O Camphenylon, mp. 36°-136 Diallylacetone, bp. 174°-142 Phoron, mp. 28°-136 C9H14O2 Campholitic ac., mp 133°, bp. 241° -61, 76 C9H14O3 Ethoxytetrahydrobenzoic ac.t mp. 73°-55 Ethyl trimethyleneacetoacetate, bp. 226°-124 Pinonic ac., mp. 128°-61 C9H14O4 Diethyl citraconate, bp. 231°-125 Diethyl ethylenemalonate, bp. 213° -124 Diethyl glutaconate, bp. 237°-125 Diethyl itaconate, bp. 228°-124 Diethyl mesaconate, bp. 229°-125 C9H14O6 Diethyl acetylmalonate, bp. 239°- 76 Diethyl ketipate, mp. 76°-93 C9H14O6 Camphoronic acids, mp. abt. 150°, 166°-47, 48 C9H]4O7 Trimethyl citrate, mp. 79°-119 C9HlfiO Ethyldiallylcarbinol, bp. 175°-163 C9HloO2 Isobutyl angelate, bp. 177°-122 Diethylacetylacetone, bp. 203°- 123 C9H16O3 Ethyl a-butvrylpropionate, bp. 208°-123 Ethyl mesitonate, bp. 210°-123 Ethyl methylethylacetoacetate, bp. 200°-123 C9H10O4 Azelaic ac., mp. 106°-58 Diethyl dimethylmalonate, bp. 196°-123 Diethyl ethylmalonate, bp. 207°- 123 Diethyl glutarate, bp. 237°-125 Dipropyl malonate, bp. 228°-125 C9H18O Dimethylheptanone, bp. 181°-142 Dipropylacetone, bp. 173°-142 Ethyl hexyl ket., bp. 190°-142 C9H18O2 Ethyl isoamylacetate, bp. 177°- 122 Heptyl acetate, bp. 190°-123 Isoamyl butyrate, bp. 179°-122 Isoamyl isobutyrate, bp. 169°-122 Methyl caprylate, bp. 193°-123 Octylformate, bp. 198°-123 Pelargonic ac., bp. 253°-76 C9H18O3 Dibutyl carbonate, bp. 208°-123 Diisobutyl carbonate, bp. 190°-■ 122 Parapropionic aid., bp. 169°-20 C9H20O Ethyldipropylcarbinol, bp. 179°- 163 Ethyl heptyl eth., bp. 166°-187 Methyl octyl eth., bp. 173°-187 Nonyl ale., bp. 213°-163 C9H20O2 Propylidenedipropyl ether, bp. 166° -20 C9H20O4 Ethyl orthocarbonate, bp. 158°- 122 C10 GROUP. C10H8 Naphthalene, mp. 80°-176 C10H10 Phenylcrotonylene, bp. 187°-191 Ethyl phenylacetylene, bp. 202°-■ 192 r-Methylindene, bp. 205°-192 254 FORMULA INDEX. Naphthalenedihydride, bp. 212°- 192 C10H12 Butenylbenzene, bp. 186°-191 Dicyclopentadiene, mp. 33°-175 Isobutenylbenzene, bp. 181°-191 p-Tolylpropylene bp. 199°-192 Naphthalenetetrahydride, bp. 205° -192 Phenylbutylene, bp. 177°-191 C1OHU Butylbenzenes, bp. 168°, 171°, and 180°-168, 190, 191 Cymene, bp. 175°-190 ni-Methylisopropylbenzene, bp. 175° -190 Diethylbenzenes, bp. 181°, 182°, and 185°-191 Dimethylethylbenzenes, bp. 183°, 185°-191 Durene, mp. 79°-176 Naphthalenehexahydride, bp. 205° -192 Tetramethylbenzenes, bp. 196°, 204° -192 Ci0H16 Camphenes, mp. 47°, 51°-175 Decone, bp. 147°-187 Pinene, bp. 156°-189 Phellandrene, bp. 171°-190 Limonenes, bp. 176°, 181°-190, 191 Sylvestrene, bp. 176°-191 Terpinene, bp. 180°-191 Terpinolene, bp. 184°-191 Naphthaleneoccahydride, bp. 187° -191 C10H18 Decenylene, bp. 150°-187 Dimethylactadiene, bp. 168°-187 Propylheptadiene, bp. 158°-187 Menthene, bp. 167°-187 Naphthalenedecahydride, bp. 176°, 177°-187, 183 C10H20 Diamylene, bp. 155°-187 Dekanaphthene, bp. 161°-183 a-Terpenetetrahydride, bp. 161°- 183 ^-Terpenetetrahydride, bp. 164°- 183 Terpane, bp. 170°-183 C10H22 Decane, bp. 173° c.-183 Dimethyloctane, bp. 160°-183 C10H0O2 a-Naphthoquinone, mp. 125°-207 ^-Naphthoquinone, d. 117°-206 C10H0O3 Jugion, mp. 152°-208 C10H6O4 a-Dioxynaphthoquinone, mp. 276° -211 Furil, mp. 162°-208 Naphthazarin-214 Ci0HbO8 Benzenetetracarbonic acids, mp. 237°, 238°, 264°-51 CinHoO a-Naphthol, mp. 94°-94 . ^-Naphthol, mp. 122°-96 CmHsOo Dioxynaphthalenes, mp. 134°, 140°, 159°, 178°, 190°-96, 97, 98, 99, 100 Flydronaphthoquinones, mp. 60°, 175°-92, 99 Indenecarbonic ac., mp. 230°-70 Methvlphenylpropiolic ac., mp. 109° -59 C10H8O3 Aldehydocinnamic ac., mp. 247°- 18 Benzoylacrylic ac., mp. 99°-57 ^-Hydrojuglon, nip. 96°-96 Methylcumarilic ac., mp. 188°-67 Tri oxynaphthalene, mp. 120°-95 C10HsO4 Anemonin, mp. 156°-98 Benzalmalonic ac., mp. 195°-68 Furoin, mp. 135°-96 C10H10O Benzalacetone, mp. 41°-136 Benzoyltrimethylene, bp. 240°-■ 144" Methvlhydrindones, mp. 59°, 63°, 95°", bp. 246°-137, 138, 144 C10H10O2 Allyl benzoate, bp. 230°-125 Benzoylacetone, mp. 60°-92 Benzalpropionic acids, mp. 74°, 82°, 86 °-55, 56 Butenylonphenol, mp. 139°-97 Hvdrindoncarbonic ac., mp. 130°- "61 Isopropenylbenzoic ac., mp. 257°- 71 Isosafrol, bp. 247°-193 Methylatropic ac., mp. 135°-61 Methylcinnamic acids, mp. 115°, 169°, 197°-59, 65, 68 Methyl cinnamate, mp. 36°-118 Phenylcrotonic ac., mp. 65°-55 Phenyldiacetyl, bp. 175°-215 Propenvlbenzoic ac., mp. 160°-64 Safrol, bp. 233°-193 CioHsOg /?-Benzoylpropionic ac., mp. 116°- 59 Cubebin, mp. 125°-96 Ethylbenzoylformate, bp. 256°- 126 Methyl m-coumarate, mp. 85°-119 Methoxycinnamic acids, mp. 88°, 115°, 171°-56, 59, 65 C10H10O4 Benzoyllactic ac., mp. 112°-59 Benzylmalonic ac., mp. 117°-44 Dimethyl isophthalate, mp. 64.5°-- 119 Dimethyl terephthalate, mp. 140°- 119 Dimethylterephthalic ac., mp. 206° -69 Dimethyl phthalate, bp. 282°-126 Dimethylphthalic ac., mp. 96°-57 Ferulic ac., mp. 16S°-65 Hydrocinnamocarbonic acids, mp. 165°, 277°-65, 71 Isoferulic ac., mp. 280°-70 Meconin, mp. 102°-58 Phenylsuccinic ac., mp. 167°-65 C10H10O5 Dimethyl oxyphthalaets, mp. 96°, 102°-119 Opianic ac., mp. 150°-63 Veratrinketonic ac., mp. 138°-46 C10H10O6 Hemipinic acids, mp. 180°, 161°- 66, 64 C10H12O Anethol, mp. 22°-174 Benzylacetone, bp. 235°-144 Anisoin, mp. 142°-179 Cuminic aid , bp. 235°-20 Ethyl benzyl ket., bp. 224°-143 Ethyl p-tolyl ket., bp. 238°-144 Isopropyl phenyl ket., bp. 217°- 143 Metanethol, mp. 132°-179 FORMULA INDEX. 255 Methyl xylyl ke tones, bp. 224°, 246° -143, 144 Photoanethol, mp. 207°-180 Propyl phenyl ket., bp. 221°-143 p-Tolylacetone, bp. 232°-144 Trimethylbenzoic aldehydes, mp. 52°, bp. 237°-17, 20 C10H12O2 Benzylpropionic ac., mp. 47°-53 Cuminic ac., mp. 116°-59 Dim ethylphenethanoic ac., mp. ] 02°-58 Etyhlphenylacetate, bp. 229°-125 Ethylphenylacetic ac., mp. 42°-53 Ethyl toluates, bp. 221°, 227°-124 Methylhydrocinnamic ac., mp. 37° -53 Methyl hvdrocinnamate, bp. 238° -125 Methyl phenylpropionate, bp. 221° -124 Prehnitylic ac., mp. 167.5°-48 p-Propionylanisol, mp. 27°-136 Propylbenzoic acids, mp. 51°, 58°, 140°-54, 62 Propyl benzoate, bp. 229°-125 Tetramethylquinone, mp. 111°- 206 Thymoquinone, mp. 45°-205 Tolvlpropionic ac., mp. 102°, 125° -58, 60 Trimethylbenzoic acids, mp. 127°, 149°, 152°, 215°-60, 63, 69 C10H12O3 Conil'eryl ale., mp. 73°-93 Dimethyldiacetylfurane, mp. 63° -176 Ethyl mandelate, mp. 34°-118 Ethyl anisate, bp. 269°-126 Ethyl methylether salicylate, bp. 235°-125 Methyl ethylether salicylate, bp. 245°-125 Methvlethermelilotic ac., mp. 92°- 57' Methoethylphenolcarbonic acids, mp. 71°, 94°, 142°-55, 57, 62 Methylphenyllactic acid, mp. 95°- 42 Oxyisopropylbenzoic ac., mp. 155° -64 Phenyloxybutyric ac., mp. 75°-55 Trim ethylphen olmethanoic acids, sbl. 14* , 181°-63, 66 C10H12O4 Cantharic ac., mp. 278° c.-71 Cantharidin, mp. 218°-129 Ethyl van iliate, mp. 44°-118 Methyl veratrate, mp. 59°-118 C10H12O5 Ethvl isocarbopyrotritarate, mp. 110°-59 Monoethyl carbopyrotritarate, mp. 83°-56 C10H12O8 Dimethvl succinylosuccinate, mp. 152°-97 C,nH,,O8 • Hexamethvlenetetracarbonic ac., mp. 219° d.- 58 C10III4O tert.-Butylphenol, mp. 99°-94 p-Cuminic ale., bp. 247°-165 Eucarvol, bp. 212°-143 Tetramethylphenol, mp. 86°, 117°, 108°-93, 95 Thymol, mp. 49.6°-92 C10H14O2 Oxythymol, mp. 139°-97 CJ0H]4O3 Camphoric anhyd., mp. 220°-70 Pyrogalloldiethylether, mp. 79°- 93 C10H14O4 Camphanic ac., mp. 201°-50, 68 Diallyl succinate, bp. 249°-126 Ci0H14O5 Pinoylformic ac., mp. 79°-56 C10H14Ofl Camphenic ac., mp. 199°-50 C10H14O8 Tetramethyl s-ethanetetracarbo nate, mp. 138°-119 C10H16O Anthemol, bp. 214°-163 Camphor, mp. 176°-139 Citral, bp. 228°-20 Dihydrocarvone, bp. 221°-143 Fenchone, bp. 192°-142 * Pinol, bp. 183°-191 Pulegone, bp. 221°-143 Thujone, bp. 203°-143 C1oH16O2 Campholenic acids, mp. 53°, bp. 265°-54, 76 Ethyl diallylacetate, bp. 195°-123 Trimethylcyclohexenecarbonic ac., mp. 106°-58 C10H16O3 Camphylenic ac., mp. 172°-65 Methoethylolheptanonolid, mp. 63° -129 Pinonic acids, mp. 98°, 103°-57, 58 C10H16O4 Diethyl allylmalonate, bp. 222°- 124' Diisopropyl fumarate, bp. 225°-■ 124 C10H16O4 Camphoric acids, mp. 181° c., 208® -66, 69 Isocamphoric ac., mp. 171°, 191°- 65, 67 Ci0Hi6Os Cineolic ac., mp, 196° d-68 C10H16O6 Triethylmethanetricarbonate, mp. 29°-52 C10H18O Borneols, mp. 203°, 210°-159 Coriandrol, bp. 196°-163 Citronellal, bp. 207°-20 Diisovalerianic aid., bp. 190°-20 Eucalyptol, bp. 176°-190 Geraniol, bp. 229°-163 Isoborneol, mp. 216°-159 Linalol, bp. 192°-163 Menthones, bp. 206°, 207°-143 Terpineol, bp. 218°-165 CwH18O2 Camphene glycol, mp. 192°-159 Campholic ac., mp. 105°-58 Citronellic ac., bp. 257°-76 Isoamyl tiglate, bp. 204°-123 Pinolhydrate, mp. 150°-155 C10H18O3 Dimethyloctanonoic ac., bp. 292° -76 Ethyl diethylacetoacetate, bp. 218° -124 Ethyl isobutylacetoacetate, bp. 217°-124 Ethyl methylpropylacetoacetate, bp. 214°-124 Valerianic anhyd., bp. 215°-76, 131 C10H1sO4 Dibutyl oxalate, bp. 243°-125 Diethyl adipate, bp. 245°-125 Diethyl s-dimethylsuccinates, bp. 221°, 232°-124, 125 Diethyl ethylsuccinate, bp. 225°- 124 256 FORMULA INDEX. Diethyl methylethylmalonate, bp. 207°--123 Diethyl propylmalonates, bp. 221°, 213° 124 Diisobutyl oxalate, bp. 229°-125 Dipropvl succinates, bp. 249°, 247° -126, 125 Sebacic ac., mp. 133°-61 C10HlgOft Diisopropyl tartrate, bp. 275°-126 C10HlgO8 Diethyl mucate, mp. 158° d.-119 C10H20O Diamylene oxide, bp. 175°-190 Isocapric aid., 169.6°-20 Isopropyl hexyl ket., bp. 205°-143 Menthol, mp. 42°-157 Methyloctonone, bp. 197°-142 Propyl hexyl ket., bp. 206°-143 C10H20O2 n-Amyl valerianate, bp. 204°-123 Capric ac., mp. 31°-52 Ethyl caprylate, bp. 207°-123 Ethyl dipropylacetate, bp. 183°- 122 Hexyl butyrate, bp. 205°-123 Isoamyl isovalerianate, bp. 194°- 123 Methyl pelargonate, bp. 213°-124 n-Octyl acetate, bp. 210°-123 C10H20O3 Ethyl oxycaprylate, bp. 231°-125 Methyl octyl ket., bp. 211°-143 C10H22O Decyl ale., bp. 231°-163 Diamyl ale., bp. 211°-163 Ethyl octyl eth., bp. 189°-188 Isoamyl eth., bp. 173°-187 Propylhexylcarbinol, bp. 210°-163 C10H22O2 s-Dimethyl dipropyl glycol, bp. 222° -165 s-Tetramethylpinacone, mp. 27°- 157 Cu GROUP. CuHi0 Methylnaphthalenes, bp. 241°, 242°, mp. 32°-193 CnH12 Amenylbenzene, bp. 173°-190 CnHu Tolylbutylene, bp. 195°-192 CnH16 Amylbenzene, bp. 201°-192 Butyltoluenes, bp. 177°, 187°-191 Diethylphenyhnethane, bp. 178°- 191 Diethyltoluene, bp. 199°-192 Dimethylethylphenylmethane, bp. 190°-191 s-Dimethvlpropylbenzene, bp. 208° -192 " Ethylisopropylbenzene, bp. 191°- 192 Isoamylbenzene, bp. 193°-192 Isopropylxylene, bp. 194°-192 Propylxylenes, bp. 206°, 208°, 209° -192 Pentamethylbenzene, bp. 53°-175 CnH20 Undecine, bp. 212°-188 CnH22 Undekanaphthene, bp. 190°-183 Undecylene, bp. 195°-188 CuH24 Undecane, bp. 194°-183 CnHsO Naphthoic aid., mp. 61°-17 CnH8O2 Iso-naphthoic ac., mp. 184° c.-66 a-Naphthoic ac., mp. 160°-64 CnH8O3 Naphtholcarbonic acids, mp. 169°, 185°-48, 67 2-Oxynaphthoic acids, mp. 156°, 216°, 210°, 235°-64, 69, 70 CnHi0O Methylnaphthol, mp. 89°-94 Methyl a-naphthyl eth., bp. 269°- 193 Methylphenylfurfurane, mp. 41°- 175 Naphthylmethyl alcohols, mp. 60°, 80°-157, 158 Nerolin, mp. 72°-176 C.,H10O, Dihydronaphthoic acids, mp. 91°, 105°, 125°, 161°-57, 58, 60, 64 Methylindenecarbonic ac., mp. 200° -68 CnH10O4 Acetcumaric ac., mp. 146°-63 CuH12O Allylacetophenone, bp. 238°-144 Benzoylcyclobutane, bp. 259°-144 CnH12O2 Cinnamenylpropionic ac., mp. 31- 52 Ethyl cinnamate, bp. 271°-126 Methylhydrinencarbonic ac., mp. 80°-56 Phenylangelic ac., mp. 104°-58 Phenylpentenoic ac., mp. 104°- 58 Tetrahydronaphthoic acids, mp. 85 94°-56. 57 CnH12O3 o-Ethoxycinnamic acids, mp. 103°, 135°-58, 61 Ethylbenzoylacetic ac., mp. 113°, 114°-59, 43 Ethyl p-toluylcarbonate, mp. 263° -119 Methyl 5-benzoylpro pi onate, bp. 290°-127 Phenylltevulinic ac., mp. 55°-40 Toluylpropionic ac., abt. 120°-60 CnH12O4 Acetylphenyllactic ac., mp. 100°- 58 a-Hydropiperic ac., mp. 75°-55 CuH12O5 Sinapic ac., mp. 189°-209 CnH,4O p-Acetylcumene, bp. 254°-144 Acetylmesitylene, bp. 235°-144 p-Acetylpropylbenzene, bp. 259°- 144 Butyl phenyl ket.-144 Ethyl xylyl ketones, bp. 237°, 238° -144 Isobutyl phenyl ket., bp. 225°- 144 Isopropyl tolyl ket., bp. 235°-144 Methvlbenzylacetone, bp. 238°- 144 CnH14O2 Butyl benzoate, bp. 247°-125 Ethylbenzylacetic ac., bp. 272°-76 Ethyl 1,3-dimethylbenzoate, bp. 241°-125 Ethyl hydrocinnamate, bp. 248°- 125 Ethyl a-phenylpropionate, bp. 230° -125 Ethyl m-tolylacetate, bp. 237°- 125 Isobutylbenzoic acids, mp. 127°, 164°-60, 65 Isobutyl benzoate, bp. 237°-125 Methcethylphenethanoic ac., mp. 52°-54 Methyl ethylphenylacetate, bp.228° -125 Methyl methylhydrocinnamate, bp. 232°-125 FORMULA INDEX. 257 Methylpropylbenzoic ac., mp. 75° -55 Methyl pseudocumyl ket., bp. 246° -144 Phenyl valerianic ac., mp. 5S°-54 Tetramethylbenzoic acids mp. 165° 179°-65, 66 T-olylisobutyric ac., mp. 91°-57 p-Propionylphenetol, mp. 30°-136 CnH 4O3 o-Ethylethermelilotic ac., mp. 80° -56 Ethyl m-ethoxybenzoate, bp. 263° -126 Ethyl ethylethersalicylate, bp. 251° -126 Ethyl o-hydrocoumarate, mp. 34° -118 Phenyloxyvalerianic ac., mp. 131° -45 o-Thymotic ac., mp. 123°-60 CnH]4O4 Ethyl veratrate, mp. 43°-118 CuH10O p-Isoamylphenol, mp. 92°-94 Isoamyl phenyl eth., bp. 217°-192 Methyl thymyl eth., bp. 216°-192 CuH16Om Camphocarbonic ac., mp. 128°-61 Pentamethylphloroglucin, mp. 114° -95 CnH]8O2 Undecolic ac., mp. 59.5°-54 CnH18O4 Diethyl pentamethylene dicarbon- ate, bp. 251°-126 Monomethyl camphorate, mp. 86° -56 CnHl8O5 Phoronic ac., mp. 184°-67 CnH18O6 Triethyl ethenyltricarbonate, bp. 278°-126 CnH2uO2 Undecylenic ac., mp. 24°-52 CuH2uO4 Dibutyl malonate, bp. 251°-126 Diethvl isobutylmalonate, bp. 225° -124 . Diethyl isopropyl succinate, bp 238°-125 Diethyl diethylmalonate, bp. 223° -124 Diethyl methylpropylmalonate, bp. 222°-124 _ Heptylsuccinic ac., mp. 90°-41 Diethyl butylmalonate, bp. 233°- 125 Diethyl methylisopropylmalonate bp. 221°-124 CuH22O Caprone, bp. 226°-144 Diisoamyl ket. bp. 226°-144 Methyl nonyl ket., bp. 224°-143 ChH22O2 Ethyl pelargonate, bp. 227°-124 Isoamyl isobutylacetate, bp. 217° -124 Methyl caprate, bp. 223°-124 Umbellulic ac. mp. 22°, bp. 277°- 52 Undecylic ac., mp. 28°-52 CnH22O3 Diisoamyl carbonate, bp. 229°-125 CnH22O4 Dioxyundecylic ac., mp. 85°-56 C12 GROUP. C12Hs /9-Naphthylacetylene, mp. 36°-175 Acenaphthylene, mp. 92°-177 C12H10 Diphenyl, mp. 70°-176 Acenaphthene, mp. 95°-177 C12H12 ^-Ethylnaphthalene, bp. 251°-193 a-Ethylnaphthalene, bp. 258°-193 Dimethylnaphthalene, bp. 263°- 193 C12H18 allvlisopropvlbenzene, bp. 229°-■ 192 C12H18 p-l)ipropylbenzene, bp. 220°-192 Ethylbuiylbenzene, bp. 202°--192 Hexamethylbenzene, nip. 164°-- 179 Isohexylbenzene, bp. 214°-192 p-Propylisopropylbenzene, bp. 2128 -192 p-Isoamyltoluene, bp. 213°-192 s-Triethylbenzene, bp. 216°-192 C12H2O Dodecon, bp. 197°-188 C12H24 Triisobutylene, bp. 178°-187 Dodekanaphthene, bp. 197°-183 Duodecylene, bp. 214°-188 C12H26 Dodecane, bp. 214°-183 C12H6O2 Acenaphenequinone, mp. 261°- 210 C12HgO12 Mellitic ac., mp. 287°-51 C12H8O Acenaphthenone, mp. 121° C.-139 Biphenylene oxide, mp. 86°-177 C12HgO3 Benzfuril, mp. 41°-205 Naphthoylformic ac., mp. 113°-43 C12H8O4 Naphthalic ac., mp. 270°-71 Naphthalenedicarbonic acids, mp. d. 300°, 175°-72, 66 C12HsO4 Paracotoi'n, mp. 152°-208 C12H10O Methyl ^-naphthyl ketones, mp. 51° 295°-137, 145 Phenyl eth., mp. 28°-174 C12Hi0O2 Acetylnapthol, mp. 173°-99 ^-Biphenol, mp. 161°-98 Methyl oxynaphthyl ket., mp. 103° -206 a-Naphthylacetic ac., mp. 131°- 61 Methyl /?-naphthoate, mp. 77°-119 C12H10O3 Methylphenylfuranecarbonic ac., mp. 180°-66 C12H]0O4 Dipyrocatechin, mp. 84°-93 Piperic ac., mp. 216°-210 Quinhydrone, mp. 171°-208 C12H12O Dimethylnaphthol, mp. 135°-96 Ethyl naphthyl ethers, mp. 37°, 281°-175, 194 Methyl cinnamenylvinyl ket., mp. 68°-137 C12H12O3 Benzallaevulinic ac., mp. 125°-60 Benzoyltetramethylenecarbonic ac., mp. 142°-62 Diacetylbenzoyl methane, mp. 35° -91 Ethyl /?-methylcoumarilate mp. 51°-118 Triacetylbenzene, mp. 162°-139 C12H12O4 Acetophenonacetacetic ac., mp. 135°-61 Ethyl benzoylpyruvate, mp. 43°- 91 C12Hj4O3 Benzyllrevulinic ac., mp. 98°-57 C12H14O4 Apiol, mp. 30°-174 Diethyl isophthalate, bp. 2S5°- 126 Diethyl phthalate, bp. 295°-127 Diethyl terephthalate, mp. 44°- 118 C12H14O5 Diethyl oxyisophthalate, mp. 52° -118 258 FORMULA INDEX. C12H14O, Diethyl hydroquinonedicarbonate, mp. 133°-96 Dimethyl hemipinate, mp. 61.5°- 119 C12H16O Diethylacetophenone, bp. 231°- 144 Isoamyl phenyl ket , bp. 242°-144 Isopropyl xylyl ket., bp. 239°, 256° -144 Methyl o-cymyl ket., bp. 258°-144 Methyl duryl ket., mp. 73°, 254°, 259°-137, 144 Propyl xylyl ket., bp. 249°, 251°, 244°-144 C12H16O2 Ethyl cuminate, bp. 240°-125 Isoamyl benzoate, bp. 261°-126 p-Isoamylbenzoic ac., mp. 15a°- 64 Pentamethylbenzoic ac., mp. 210° -69 C12H16O3 Asarone, mp. 67°-176 Isoamyl salicylate, bp. 270°-126 C12H16Os Diethyl carbopyrotritarate, bp. 234°-126 C12H18O8 Diethyl succinylosuccinate, mp. 126°-96 C12H18O Ethyl thymyl eth., bp. 227°-192 Xylitone, bp. 251°-144 C12HlgO3 Ethyl diallylacetoacetate, bp. 240° -125 Phloroghicin triethyl eth., mp. 43° -175 C,,H18Ou Diethyl diacetylsuccinate, mp. 88° -94 Triethyl aconitate, bp. 275°-126 C12H20O4 Dimethyl camphorate, bp. 265°- 126 C.2H2 O8 Triethyl tricarballylate, bp. 300°- 127 C12H„ O7 Triethyl citrate, bp. 294°-127 C12H;0O10 (?) Dextrin, -29 Inulin-31 C,2H.,2O Diallyl eth., bp. 1CO°-187 Hexenyl eth., bp. 117°-1S6 Cj2H 2O2 Methyl undecylenate, pb. 248°- 126 C12II22O3 Diethylacetic anhyd., bp. 230°-76 Ethyl dipropylacetoacetate, bp. 235°-125 Lanolic ac., mp. 76°-55 C12H22O4 Diethyl isoamylmalonate, bp. 241° Diethyl suberate, bp. 284°-126 Diisoamyl oxalate, bp. 263°-126 Diisobutyl succinate, bp. 265°-126 Dimethyl sebacate, mp. 38°-118 C12H22O6 Diisobutyl tartrate, mp. 68-119 C12H22On Lactose-29 Maltose-29 Saccharose, abt. 160° d.-29 C12H,4O Lauric aid., mp. 44°-17 C,2H24O Diisoamylacetic ac., mp. 46°-53 Ethyl caprate, bp. 244°-125 Lauric ac mp. 43.6°-53 C12H24O3 Diisoamyloxalic ac., mp. 122°-60 Paraisobutyric (fldehyde, mp. 59°- 60°-17 C12HmO Dodecyl ale., mp 24°-157 C12H2uO2 Ethylidenediisoamyl eth., bp. 211° CK GROUP. C13H!0 Sequoiene, mp. 105°-178 Fluorene, mp. 112°-178 ^-Methylenebiphenyl, mp. 116°- 178 C13H12 Phenyltolyl, bp. 259°-193 Diphenylmethane, bp. 261°-193 p-Phenyltolyl, bp. 265°-193 m-Phenyltolyl, bp. 275°-193 Diphenylmethane, mp. 26°-174 C13II14 /?-Propylnaphthalene, bp. 265°- 193 C13H20 Heptylbenzene, bp. 233°-193 C13H28 Tridekanaphthene, bp. 209°-C13H28 Tridecylene, bp. 233°-188 C13H2S Tridecane, bp 234°-183 C13H8O9 (?) Galloflavin-213 C13H8O Diphenylene ket., mp. 84°-205 Isodiphenylene ket., mp. 83°-138 Pseudodiphenylene, ket. mp. 85°- 205 Pyrene ket., mp. 142°-207 C13H8O2 Fluorenequinone, mp. 181°-209 Xanthone, mp. 173°-180 C13HbO3 Oxyxanthones, mp. 146°, 231°-- 207, 210 C13H8O4 Euxanthone, mp. 240°-210 C13H10O Benzophenone, mp. 48°-137 Benzophenone allotropic, mp. 20.6° -136 Fluorene ale., mp. 153°-159 Xanthene, mp. 100°-177 C13H10O2 p-Benzoylphenol, mp. 134°-96 Naphthylacrylic ac., mp. abt. 210° -69 Oxybenzophenones, mp. 40°, 116°- 91, 95 Phenyl benzoate, mp. 68°-119 Phenylbenzoic ac., mp. 110°, 160°, 218°-59, 64, 70 C13H10O3 Benzohydroquinone, mp 125°-206 Benzopyrocatechin, mp. 145°-97 Benzoresorcin, mp. 144°-97 Dioxybenzophenones, mp. 59°.143°, 162°-98, 205, 207 Diphenyl carbonate, mp. 78°-119 Euxanthoic ac . mp. 201°-209 Phenylethersalicylic ac., mp. 113° -59 Phenoxybenzoi'c ac., mp. 159°-64 Phenyl p-oxybenzoate, mp. 116°- 99 Salol, mp. 42°-91 C13H10O4 Alizarine yellow A, mp. 140°-207 Salicyloresorcin, mp. 133°-207 C13H 0O5 Tetraoxybenzophenone, mp. 149° -208 C13Hj2O Benzhydrol, mp. 68°-157 p-Benzylphenol, mp. 84°-93 Phenyl benzyl eth., mp. 38°-175 Propanoylnaphthene, bp. 306°- 145 C13H12O2 Benzhydroxylphenol, mp. 161°- 98 Dioxydiphenylmethane, mp 158° -93 Ethyl /?-naphthoate, bp. 309°-127 Ethyl a-naphthoate, bp. 309°-127 Ethylnaphthoic ac., mp. 132°-61 FORMULA INDEX. 259 CbH14O Camphorphoron, bp. 202°-143 Ditetramethylene ket., bp. 204°- 143 C13H14O3 Ethyl benzalacetoacetate, mp. 59° -118 Ci3H14O4 Ethyl benzoylacetoacetate, mp. 27° -118 C13H1hO2 Diacetylmesitylene, mp. 46°-137 C13H1BO7 Helicine, mp. 175°-18 C13H18O Cumvlacetone, bp. 262°-145 Methyl pentamethvlphenvl ket., mp. 85°-138 Phenyl hexyl ket., bp. 271°-145 Ethyl cymyl ket., bp. 267°-145 C13H18O2 Hexyl benzoate, lip. 272°-126 C13H18O7 Salicin, mp. 201°-100 C13H20O3 Ethyl camphocarbonate, bp. 276° -126 C13H20O4 Diethyl diallylmalonate-125 C13H24O2 Ethyl undecylenate, bp. 259°-126 C13H24O4 Brassylic ac., mp. 112°-59 Diethyl azelate, bp. 291°-127 Diisoamylmalonic ac. mp. 147°- 63 C13H26O Dihexyl ket., mp. 30°-136 Methyl undecyl ket., mp. 28°-136 C13H 8Oj Tridecylic ac., mp. 40°-53 C13H2gO Dihexylcarbinol, mp. 41°-157 C14 GROUP. C14H10 Anthracene, mp. 216° c.-180 Isoanthracene, mp. 134°-179 Phenanthrene mp. 100°-177 Tolane, mp. 60°-176 C14Hia Anthracenedihydride, mp. 108°- 178 a-Diphenylethylene, bp. 277°-194 Stilbene, mp. 124°-178 CmH14 m-Bcnzyltoluene, bp. 276°-193 Dibenzyl, mp. 52°-175 Di- or Bitolyl, bp. 275°, 280°, 288°, mp. 121°-193 194, 178 m-Ethylbiphenyl, bp. 283°-194 Phenanthrenetetrahydride, bp. 310° -194 C14H10 Anthracenehexahydride, mp. 63°- 176 Diphenylpropane, bp. 280°-194 Isobutylnaphthalene, bp. 280°- 194 CuHm tert. Dibutylbenzene mp. 70°-176 Diisobutylbenzene, bp. 235°-193 Octylbenzene, bp. 262°-193 Tetraethylbenzene, bp. 250°, mp. 13°-193, 174 C14H24 Perhydroanthracene, mp. 88°-177 Phenanthreneperhydride, bp. 272° -193 C14H2j Tetradecine(4), mp. 6°-174 C 4H28 Tetradekanaphthene, bp. 243°- R3 C14H^ Tetradecane bp. 252°-183 C.4HgO2 Anthraquinone, mp. 273^-211 Isoanthraquinone, mp. 211°-209 Phenanthrenequinone, mp. 202°- 209 C 4H8O3 Diphenvleneketonecarbonic acids, mp. 191°. 227°-209, 210 m-Oxyanthraquinone, mp. 302°- C14H8O4 Alazarin, mp. 289°-211 Anthraflavic ac.-213 Anthrarufin, mp. 280°-211 Benzdioxyanthraquinone, mp. 292° -211 Dioxyanthraquinone-214 Isoanthraflavic ac.-212 Xanthopurpurin, mp. 262°-210 C14H8O6 Anthragallol, mp. 310°-211 Flavopurpurin-212 Isopurpurin-214 Purpurin, mp. 256°-210 C14H8O6 Alizarin Bordeaux-214 C14H8O7 Alizarincyanin "R"-214 ChH8O8 Rufigallic ac.-214 C14HloO Anthranol, mp. 165°-99 C14H10O Phenanthrol, mp. 112°-95 C14H10O2 Benzil, mp. 95°-206 Dioxyanthracene, d. 220°-210 Dioxyhydrobenzo'in - diesoanhydr., mp. 116°-178 Dioxyphenanthrene, mp. 143°-97 Diphenylene acetic ac., mp. 221°-• 70 Fluorenecarbonic ac.,mp. 175°-66 Fluorenic ac., mp. 245°-71 C14H10O3 Benzoic anhyd., mp. 42°-53 Benzoylbenzoic acids, mp. 93°, 161°, 194°-57, 64, 67 Diphenyleneglycollic ac., mp. 162° -65 Disalicylic aid., mp. 128°-18 C14H10O4 Benzoylperoxide, mp. 103°-129 Diphenic ac., mp. 229°-70 Diphenyl oxalate, mp. 130°-119 C14H10Os Gentianine, mp. 267°-210 C14H10O9(?) Gallotannic ac., mp. abt. 210°-50 C14H12O Acetylbiphenyl, mp. 121°-139 Desoxybenzoin, mp. 60°-137 Dihydroanthranol, mp. 129°-96 Oxystilbene mp. 135°-97 Phenyltolyl ket., mp. 59°-bp. 315° -137. 145 C14H12O2 Benzoin, mp. 133°-139 Benzyl benzoate, bp. 323°-127 Benzvlbenzoic acids, mp. 107°, 114°, 154°-58, 59, 63 Diphenylacetic ac., mp. 148°-63 Methyl phenylbenzoate, bp. 308°-• 127 Oxyhydroanthranol, mp. 99°-94 Phenyltolyl carbonic ac., mp. 243° -70 Tolylbenzoic ac., mp. 204°-68 Ci4H12O3 Benzilic ac., mp. 150°-63 Methyl phenylethersalicylate, bp. a. 360°-127 Phenylethermandelic ac., mp. 108° -58 Phenyl methylethersalicylate, mp. 59°-118 C14H12O4 Cotoin, mp. 130°-207 C14H14O Benzyl eth., bp. 296°-194 Isopropyl naphthyl ket., bp. 309°- 145 Propyl naphthyl ket., mp. 50°-137 Phenylbenzylcarbinol, mp. 42°-• 157 Phenyltolylcarbinol, mp. 52°-157 Cresyl eth., mp. 50°-175 260 FORMULA INDEX. C14H14O2 Bicresol, mp. 161®-98 Ethylene diphenyl eth., mp. 98°- 177 Hydrobenzoin, mp. 138°-158 Isohydrobenzoin, mp. 119°-158 p-Diphenolethane. mp. 122°-96 C14H]4O4 Curcumin, mp. 178°-208 Ethyl piperate, mp. 77°-119 C14H16O4 Diethyl benzalmalonate, mp. 32°- 118 CUH16O5 Filixic ac., mp. 184°-99 C14H20O Tolyl hexyl ket., mp. 42°-136 C14H20O8 Tetraethyl ethylenetetracarbonate, mp. 57°-118 C,4H24O4 Diethyl camphorate, bp. 285°-126 ChH26O Dioenanthylic aid., bp. 279°-20 Cj4H28O3 Ethyl diisobutylacetoacetate, bp. 251°-126 (Enanthylic anhyd., bp. 269°-132 C14Hi O4 Diethyl seb ecate, bp. 307°-127 Diisoamyl succinate, bp. 295°-127 Dodecanedicarbonic ac., mp. 123°- 60 Cj4H28O Myristic aid., mp. 52°-17 Tetradecanone (2), mp. 33°-136 ChH2sO2 Amylheptylacetic ac., bp. 305°- 76 Ethyl laurate, bp. 269°-126 C14H28O2 Myristic ac., mp. 54°-54 C14H,8O3 Oxymyristic ac., mp. 51°-54 CJ4H;oO Heptyl eth., bp. 261°-188 Tetradecyl ale., mp. 38°-157 C1S GROUP. C15H10 Fluoranthene, mp. 109°-178 Ci5H12 Methylanthracenes, mp. 199°-180 Isomethylanthracene, mp. 203°- 180 C15H14 Phenyltolylethylene, mp. 118°- 178 Ci6H16 Benzyl-p-xylene, bp. 294°-194 Benzyltolylmethane, mp. 27°-174 Dimethyldiphenylmethane, bp. 281° -194 Ditolvlmethanes, bp. 286°, mp. 22° -194, 174 Ethylbenzylbenzene, bp. 294°-194 p-Phenyltolylethane, bp. 286°-194 C15H24 Sesquiterpenes, bp. 250°-280°-193 Cadinene, bp. 275°-193 C15H28 Benylene, bp. 225°-192 C15H30 Pentadekanaphthene, bp. 247°- 183 Triamylene, bp. 233°-188 C16H32 Pentadecane, bp. 270°-183 C1SH8O2 Fluoranthenequinone, mp. 188°- 209 C15H8O4 Anthraquinonecarbonic ac., mp. 283°-211 C15H8O6 Alizarincarbonic ac., mp. 305°-211 Purpurinxanthincarbonic ac., mp. 231°-210 CrHsO7 Purpurincarbonic ac., mp. 219°- 210 C16Hi0O2 Anthracenecarbonic ac., mp. 206° -209 Methylanthraquinone, mp. 177°- 208 Phenanthrenecarbonic acids, mp. 251°, 266°-71 CiSH10O3 Diphenylpropanetrione, mp. 69°- 205 C15H10O4 Chrysophanic ac., mp. 178° (?)- 208 Dioxyflavone, mp. 275°-211 C15H1oO6 Fisetin-213 Luteolin-213 C15H10O7 Quercetin-213 C16H12O Benzylideneacetophenone, mp. 57° -137 Phenylindanone, mp. 78°-138 C.5H12O2 Dibenzoylmethane, mp. 81°-93 Phenylcinnamic ac., mp. 172°-65 Phenyl cinnamate, mp. 72°-119 Stilbenecarbonic ac., mp. 159°-64 C15H12O3 Toluylbenzoic ac., mp. 146°-63 C15H12O4 Diphenylmethanedicarbonic ac., mp. 290°-72 C15H14O Benzylacetophenone, mp. 72°-137 Dibenzyl ket., mp. 34°-136 s-Dimethylbenzophenone, mp. 92° -138 p-Ethylbenzophenone, bp. a. 300° -145 • Phenyl xvlyl ket., mp. 36° 94°, bp. 322°-136. 138, 145 C1SH14O2 Methyldiphenylacetic ac., mp. 173 -65 Ethyl phenylbenzoate, bp. 314°-■ 127 Phenyltolylacetic ac., mp. 115°-59 Ci5H14O3 Benzoylveratrol, mp. 99°-138 Diphenyllactic ac., mp. 159°-64 Lapachol, mp. 140°-207 Methyl benzilate, mp. 74°-119 Cj H14O4 Benzocoto'in, mp. 98°-94 Oxylapachol, mp. 127°-207 Peucedanin, mp. 109°-119 C15H14O5 (?) Santalin, mp. 104°-206 C16H16O Dibenzylcarbinol, bp. 32T3-165 Ditolylcarbinol, mp. 69°-157 C15H16O2 Diphenyloldimethylmethane, mp. 151°-97 C15H16Og 2Esculin, mp. 160°-98 Daphnin, mp. 200°-100 C 5H1803 Perezinon, mp. 143°-207 Santonin, mp. 169°-129 C.^H^Og Pipitzahoic ac., mp. 103°-206 Santanous ac., mp. 178°-66 C,.H2nO4 Oxypipitzahoic ac., mp. 130°-207 San tonic ac., d. 120°-60 C15HotO Isobutyl isocymyl ket., bp. 271°- 145 C15H22O2 Octyl benzoate, bp. 305°-127 Octylbenzoic ac., mp. 139°-62 C15H22O3 Alantolic ac., mp. 94°-57 CisHgoOg Photosantonic ac., mp. 154°-63 C]5H2CO Ledum camphor, mp. 104°-138 C16H28O2 Cimicic ac., mp. 44°-53 C15H3 O Diheptyl ket., mp. 40°-136 Methyl tridecyl ket., mp. 39°-136 C,5H3 O2 Pentadecylic ac., mp. 51°-54 C15H30O3 Oxypentadecylic ac. mp. 51°-54 C16 GROUP. Diphenyldiacetylene, mp. 88°-177 Pyrene, mp. 148°-179 C16H12 Phenylnaphthalenes, bp. 324°, mp« 102°-194 178 FORMULA INDEX. 261 C 6H14 Dimethylanthracenes, mp. 71°. 231°, 246°-176, 180, 181 Diphenylbutadiene, mp. 148°-178 Ethylanthracene, mp. 60°-176 C16H16 Dimethylanthracenehydride, mp. 181°-180 Dimethylstilbene, mp. 179°-180 Diphenylbutene, mp. 39°-175 Distyrene, mp. 124°--178 Ethyl stilbene, mp. 89°-177 Ditolylethylene, bp. 304°-194 C16H18 - Benzylmesitylene, mp. 36°-175 s-Benzyltolylethane, bp. 293°-194 Dimethyldiphenyl ethane, mp. 123° -178 s-Diphenylbutane, mp. 52°-175 Ditolylethane, bp. 296°-194 Di-p-xylyl, mp. 125°-178 p-Ethyldibenzyl, bp. 294°-194 Methylethvldiphenylmethane, mp. 128°-178 Diisoamylbenzene, bp. 265°-193 Pentaethylbenzene, bp. 277°-193. C^Hgo Cetylene, bp. 282°-188 Hexadecine (1), mp. 15°-174 C16H32 Cetene, bp. 274°-188 CjgH^ Hexadecane, bp. 287°-183 Dimethyltetradecane, bp. 268° c.- 183 C10H8O2 Pyrenequinone, mp. 282°-211 C,'H8O4 Biphthalyl, mp. 334°-130 C10HbO. Anthraquinonedicarbonic ac., mp. 340°-211 C16H10O2 Phenylnaphthoquinone, mp. 109°- 206 C16H10O, Stilbenedicarbonic anhyd., mp. 155°-64 C18H12O Diphenylfurfurane, mp. 91°-177 C18H]2O2 Methyl anthracenecarbonate, mp. 111°-119 Phenacetolin-213 C16H12O4 Dibenzoylacetic ac., mp. 109°-59 Diphenylbutanoltrione, mp. 170°- 208 C1,H12O5 Brazilein-212 C]8H12O6 Diphenvlmethanetricarbonic ac., mp. 219°-70 Hanuateine-214 Piperonyloine, mp. 120°--139 ClcH14O Dimethyldihydroanthrenone, mp. 93°-138 C18H14O2 Diphenvlbutanedione, mp. 144°- 139 C16H14O3 Toluic anhyd., mp. 36°-53 C16H14O4 Bibenzyldicarbonic ac., mp. 252°- 71 Diphenyl succinate, mp. 118°-119 Diphenylsuccinic ac., mp. 183°- ' 66 Ethyl benzosalicylate, mp. 79°- 119 C18H14Ob Haematoxylin, mp. 140°-207 Protocotoin, mp. 141°-97 C18H18O£ Benzoinethylether, mp. 95°-138 Benzyltolylacetic ac., mp. 95°-57 Dibenzylacetic ac., mp. 87°-56 Ethyldi phenylacetic ac., mp. 173° -65 C16H16O3 Dibenzylglycollic ac., mp. 157°-64 Ethyl benzilate, mp. 34°-118 C.6H1GO4 Anisoin, mp. 109°-138 Methylhydrocotoin, mp. 115°-138 C1GH18O2 Acetophenonepinacone, mp. 120°-• 158 ClGHlsO4 Hydranisoin, mp. 170°-159 C16H18O8 Hydrocoerulignon, mp. 190°-100 Cj_H s07 Barbaloin, mp. 147°-207 C18H22O8 Coniferine, mp. 185°-100 C16H2sO2 Palmitolic ac., mp. 47°-53 C18H2<04 Palmitoxylic ac., mp. 67°-55 C16H30O2 Hypogseic ac., mp. 33°-52 C16H30O3 Caprylic anhyd., bp. 285°-132 Oxyhypogseic ac., mp. 34°-53 C16H30O5 Agaricic ac., mp. 142°-62 C16H32O Hexadecanone(2), mp. 43°-137 Palmitic aid., mp. 58°-17 C1BH32O2 Diheptylacetic ac., mp. 26°-52 Ethyl myristate, bp. 295°-127 Palmitic ac., mp. 63°-54 C16H32O3 Lanopalmitic ac., mp. 87°-56 a-Oxypalmitic ac., mp. 82°-56 C16H32O4 Dioxypalmitic ac., mp. 115°-59 C16H34O Cetvl ale., mp. 50°-157 Octyl eth., bp. 294°-188 CjgH^Oj; Cetene glycol, mp. 75°-157 Isoamyl orthoformate, bp. 266°- 126 C17 GROUP. C17Hu a-Benzylnaphthalene, mp. 59°-- 176 C17H16 Trimethylanthracenes, mp. 222°, 227°, 243°-180 C17H1O Isopropylstilbene, mp. 84°-177 Retenefluorene, mp. 97°-177 C17H2O Benzylcymene, bp. 308°-194 Benzyldurvl, mp. 60°, 145°-176, 179 Phenylxylylpropane, bp. 324°-194 C17H38 Heptadecane, mp. 22°-174 C17H10O Chrysoketone, mp. 133°-207 C17H10O2 Pyrenecarbonic ac., mp. 267°-71 C17H12O Chrysofluorene, ale., mp. 166°-159 Phenyl naphthyl ketones, mp. 75°, 82°-137, 138 C17H12O2 Chrysenic ac., mp. 186°-67 C17H14O Cinnamylene acetophenone, mp. 102°-206 Dibenzvlideneacetone, mp. 112°- 206 " C17HhO2 Atronic ac., mp. 164°-65 Isatronic ac., mp. 156°-64 Cj.H]4O3 Acetonephenanthrene ket., mp. 90° 205 Dibenzoylacetones, mp. 82°, 108°-- 93,138 C17H1BO Retene ket., mp 90°-205 C17H16O4 Diphenylglutaric ac., mp. 164°-65 C17H18O Retenefluorene ale. mp. 133°-158 CI7HlgO2 Ditolylpropionic ac., mp. 151°-63 C17H18O10 Carminic ac.-212 C17H20O2 Diethvldiphenolmethane, mp. 199° -100 C17H22O3 Podocarpic ac., mp. 187°-67 C17H3,O4 Roccellic ac., mp. 132°-61 C17H32O5 Oxyroccellic ac., mp. 128°-60 C17H34O Diheptylacetone, bp. 302°-145 Methyl quindecyl ket. mp. 48°- 137 262 FORMULA INDEX. c17h^©2 Margaric ac., mp. 60°-54 Daturic ac., mp. 54°-54 Methyl palmitate, mp. 28°-118 C18 GROUP. Cj8H12 Chrysene, mp. 250°-181 Isochrysene, mp. 196°-180 Naphthanthracene, mp. 141°-179 Truxene, mp. a. 360°-181 C]gH14 Diphenylbenzene, mp. 205°-180 C18H18 Retene, mp. 98°-177 Tetramethylanthracene, mp. 231° -180 Isobutylanthracene, mp. 57°-175 ClgH_0 Diethylstilbene, mp. 134°-179 Tetramethylanthracenehydride, mp 171°-179 Tetramethylstilbene, mp 105°, 157° -179, 178 Diethylanthracenedihydride, mp. 49°-175 Ci8H22 Dixylylethane, bp. 324°-194 C18H3O Hexaethylbenzene, mp. 129°-178 Tributylbenzene, mp. 128°-178 Ci8H34 Octadecines, mp. 26°, 30°-174 C18H30 Anthemene, mp. 63°-176 Octadecylene, mp. 18°-174 C18H38 Octadecanes, mp. 28°, bp. 317° c.- 174, 183 ClgH 0O2 Chrysoquinone, mp. 235°-210 C18H12O3 Naphthoylbenzoic ac., mp 173°- 66 C1SH12O4 Oxynaphthoylbenzoic ac., mp. 256° -71 Phenylbenzovlpyronone mp. 171° -208 C18H12O5 Diphenylfurandicarbonic ac., mp. 23§° 70 Pulvic ac., mp. 214°-209 C18H14O Benzyl naphthyl ket., mp. 57°-137 C18H14O3 Cinnamic anhyd., mp 132°-61 C.8H14O9 Pyrogalloquinone-214 C18H16O Octylene oxide, bp. 145°-187 CI8H]6O2 Retenequinone, mp. 198°-209 C18H16O4 Isoatropic acids, mp. 206°, 237°- 69, 70 Phenoquinone, mp. 71°-205 Truxillic acids, mp. 228°, 274°-70, 71 Ci8H16O7 Carbousnic ac., mp. 200°-209 Usnic ac., mp. 195°-209 C18H16O8 Irigenin, mp. 186°-100 C18H18O2 Ditoluylethane, mp. 159°-139 C18H18O3 Dibenzylacetoacetic ac., mp. 89°- 56 C18H18O, Diethyl diphenate, mp. 42°-118 C18H18O12 Hexamethyl mellitate, mp. 187°- 119 C18H22O2 Methyltolylpinacone, mp. 90°-158 C18H22O9 Camphoronic anhyd., mp. 175°-66 C18H32O2 Stearolic ac., mp. 48°-53 ClgH32O3 Ricinostearolic ac., mp. 51°-54 C18H34O3 Ricinelaidic ac., mp. 50°-54 C18H.2O4 Ricinstearoxylic ac. mp. 78°-56 Stearoxylic ac., mp. 86°-56 Ci8H320i8 Raffinose, mp. 118°-29 C^H^Oj Elaidic ac., mp. 51°-54 Isooleic ac., mp. 44°-53 Oleic ac., mp. 14°-52 C^H^Og Ricinoleic ac , mp. 16°-52 C18H34O4 Ketostearic ac., nip. 84°-56 C.gH^O^ Dioxyricinoleic ac., mp 64°-55 C18H36O Octadecanone mp. 51°-137 Stearic aid., mp. 63°-17 C^H^O. Ethyl diheptylacetate, bp. 310°- 127 Ethyl palmitate, mp. 24°-118 Stearic ac., mp. 69°-55 C18H3eO3 Oxystearic acids, mp. 84°-56 C18H36O4 Dioxystearic acids, mp. 99°, 136° 142°-57, 62 C18H36O5 Trioxystearic ac., mp. 141°-62 CI8Hj6O6 Tetra oxystearic ac., mp. 173°-65 C18H38O Octadecyl ale., mp. 59°-157 C19 GROUP. C19H14 Biphenylenediphenylmethane, mp. 145°-179 Phenylenediphenylmethane, mp. 148°-179 C19H16 Benzyldiphenyl, mp. 85°-177 Tri phenylmethane mp. 92°-177 CI8H20 Isoamylanthracene, mp. 59°-176 C19H24 Diphenylheptane, bp. 14°-174 C19H40 Nonadecane, mp. 32°-175 C19H14O3 Aurine, 213 Phenyl phenylethersalicvlate, mp. 109°-119 Phenyl phenoxybenzoate, mp. 75° -119 C19H14Oo Vulpic ac., mp 148°-208 C19H14Ou Trioxyaurine-212 Resaurine-213 C19HieO Tri phenylcarbinol, mp. 162°-159 Cinnamylenebenz yli deneacetone mp. 106°-206 C19H16O2 Dioxvtriphenylmethane, mp. 161° -98 C19H16O3 Benzaurine-214 C19H10O4 Tetraoxytriphenylmethane, mp. 171°-99 C19H18Ou Euxanthic ac., mp. 157°-208 C]9H28O2 Abietic ac., mp. 153°-63 C19H32O4 Lichen-stearic ac., mp. 124°-60 C19H3GO4 Dioctyhnalonic ac., mp. 75°-55 Cetylmalonic ac., mp. 122°-60 C19H38O Dinonyl ket., mp. 5d°-145 Dioctylacetone, bp. 327°-145 Methyl heptadecyl ket., mp. 56°- 137 C19H380j Methyl stearate, mp. 38°-118 Nondecylic ac., mp. 66°-55 C20 GROUP. C20H)4 Dinaphthyls, mp. 79°, 187°, 154°- 176, 180, 179 Phenylanthracene, mp. 152°-179 C20H16 Benzylfluorene, mp. 102°-178 Diphenyltolylmethane, mp. 128°- 178 Phenylanthracenedihydride, mp. 120°-178 C20H18 Dibenzylbenzenes, mp. 78°, 86°- 176, '177 Diphenyltolylmethanes, mp. 59° 71°-176 Methyltriphenvlmethane, mp. 62° -176 Triphenylethane, bp. 397°-194 FORMULA INDEX. 263 Hexamethylstilbene, mp. 161°- 179 C2OH3O Diterebenthyl, bp. 344°-194 C20H32 Diterpenes, bp. a. 300°-194 CjjHj, Dicamphenehydride, mp. 94°-177 C2uH38 Eicocylene, bp. 314°-188 C2nH40 Tetraamylene, bp. 395°-194 C20H42 Eicosane, mp. 37°--175 C20H8O6 Coeruleine-214 C20H10O7 Galleine-214 C20H12O Dinaphthalene oxides, mp. 184°- -180; 161°-179 C20H12O6 Hydroquinonephthalein, mp. 202° -100 Fluoresceine-213 C20H]2O2 Naphthylnaphthoquinone, m p. 177°-208 C2OH,4O Naphthyl ethers, mp. 105°, 110°, 161°-178, 179 C20H14O2 Phenyloxanthranol, mp. 208°-139 Phenylene diphenyl ket., mp. 100° -138 Terephthalophenone, mp. 159°- 139 C20H14O4 Diphenyl phthalate, mp. 70°-119 C20H14Os Fluorescine, mp. 125°-60 C20H14O7 Resorcinoxalein-212 C2OH16O2 Triphenylacetic ac., mp. 264°-71 Triphenylmethanecarbonic acids, mp. 161°, 162°-64 C20Hi6O3 Rosolic ac.-213 Triphenylcarbinolcarbonic ac., mp. 200°-68 C20H16O4 Resorcinphenylacetein, mp. 267°- 210 C20H18O Diphenyltolylcarbinol, mp. 150°- 159 C20H18O3 Phenolphthalol, mp. 190°-100 C20H18O4 Diacetyldibenzylethane, mp. 174° 139 C^HjgOjo Scoparin, mp. abt. 210°-209 C20H22O3 Ethvl dibenzylacetoacetate, mp. 57°-118 C20H2.O8 Benzoylsalicin, mp. 180°-99 C20H24O4 Bithymoquinone, mp. 200°-209 C20H26O Cuminyl eth., bp. 350°-194 C20H26O2 Bi carvacrol, mp. 154°-98 Bithymol, mp. 165°-99 C2()H28O4 Absinthin, mp. -122°-206 C2uH28O6 (?) Cholanic ac., mp. 285°-72 C20H34O Cupreol, mp. 140°-158 Quebrachol, mp. 125°-158 C20H36O2 Eikosinic ac., mp. 69°-55 C20H36O4 Lithofellic ac., mp. 204°-68 C20H38O2 Eikosenic ac., mp. 50°-54 C20H40O2 Arachidic ac., mp. 77°-55 Ethyl stearate, mp. 34°-118 C20H40O3 Eikosanoloic ac., mp. 91°-57 C21 GROUP. C21H18 Benzylphenanthrene, mp. 155°- 179 Dinaphthylmethane, mp. 92°-177 Methylphenylanthracene, mp. 119° -176 Phthalacene, mp. 173°-180 C2iHw Dibenzyltoluene, bp. 394°-194 Phenylditolylmethane, mp. 55°- 175 C21H44 Heneicosane, mp. 40°-175 C21H12O Picylene, ket. mp. 185°-209 C2IH14O Dinaphthyl ket., mp. 135°-139 C21H14O2 Picenic ac., mp. 201°-68 C21H16O2 Methylenedinaphthol, mp. 194°- 100 Phenyldibenzoylmethane, mp. 119° -139 C21H16O4 Resorcin cinnamyleine-214 Triphenvlmethanedicarbonic ac., mp. 278°-72 C21H18O Dicinnamenyl vinyl ket., mp. 142° -207 C21H18O2 Methyltriphenylmethanecarb o n i c ac., mp. 203°-68 Methyltriphen ylmethaneca rb o n i c ac., mp. 217°-70 Tolyldiphenylmethanecarbonic ac., mp. 154°-63 Triphenvlpropionic ac., mp. 177°- 66 C21H20O2 Dioxy dimethyl triphenylme thane, mp. 170°-208 C21H24Oj0 Phloridzin, mp. abt. 170°-99 C22 GROUP. C^H^ Picene, mp. 364° c.-181 C22H18 Dinaphthylethylene, mp. 149°-179 Dinaphthostilbene, mp. 161°-179 C22Hlg Dinaphthvlethanes, mp. 136°, 160°, 253°-179, 181 Dixylylbenzenes, bp. 394°-194 C22Hdg Cetylbenzene, mp. 27°-174 Docosane, mp. 44°-175 C22HI4O3 Naphthoic anhydrides, mp. 133°, 145°-61, 62 C22H16O2 Dibenzoylstyrene, mp. 129°-207 C22Hi8O2 Triphenylbutanedione, mp. 126°- 139 C22H18O5 Orcinaurine-212 C22H20O3 Cresolaurine-212 C22H24O4 Diethyl truxillate, mp. 146°-119 C22H30O2 Dithymolethane, mp. 185°-100 C22H32O3 Anacardic ac., mp. 26°-52 C22H36O Phenvl pentadecyl ket., mp. 59°-- 137 C22H38O Cholestol, mp. 139°-158 Illicyl ale., mp. 175°-159 C22H48O2 Behenolic ac., mp. 57°-54 C^H^Oj Brassidic ac., mp. 60°- 54 Erucic ac., mp. 33 °-53 Isoerucic ac., mp. 55°-54 C22H44O2 Behenic ac., mp. 84°-56 C^H^Oa Oxybehenic ac., mp. 96°-57 C22H44O4 Isodioxybehenic ac., mp. 98°-57 C23 GROUP. C^H^ Benzylnaphthalene, mp. 35°-175 Dibenzylmesitylene, mp. 131°-179 Phenyldixylylmethane, mp. 92°-• 177 C23H32 Benzylpentaethylbenzene, mp. 88° -177 , C23H40 Methylhexadecylbenzenes, mp. 11°, 27°-174 C23H4g Tricosane, mp. 48°-175 C23H20O2 Dibenzoylmesitylene, mp. 117°- 138 264 FORMULA INDEX. C23H38O Tolylpentadecyl ket., mp. 60°-137 C23H40O4 Fellic ac., mp. 120°-60 C23H42O2 Methyl behenolate, mp. 22°-118 C23H46O Laurone, mp. 69°-137 C23H48O Dilauryl ale., mp. 75°-157 C24 GROUP. C24H8 Carbopetrocene, mp. 268°-181 C24H18 Benzerythrene, mp. 307°-181 Triphenylbenzene, mp. 169°-179 C24H42 Octadecylbenzene, mp. 36°-175 Dimethylhexadecylbenzene, mp. 33°-175 C24H50 Tetracosane, mp. 51°-175 C24H12O2 Diacenaphthylidendione, mp. 295° -211 C24H74O3 Naphthalfluoresceine, mp. 308°- 211 C24H22O2 Duryldibenzoyl, mp. 269°-140 C24H3OO12 Hexaethyl mellitate, mp. 73°-119 C24H40O Paraphyto sterine, mp. 149°-159 C24H40O4 Choleic ac., mp. 187°-67 C24H40O5 Cholic ac., mp. 195°-68 C24H46O2 Ethyl brassidate, mp. 29°-118 C24H48O Cerosine, mp. 82°-158 C24H48O2 Carnaubic ac., mp. 72°-55 Lignoceric ac , mp. 80°-56 Paraffinic ac., mp. 46°-53 C24H50O Carnaubyl ale., mp. 68°-157 C2S GROUP. C25H20 Biphenylphenylenemethane, mp. 162°-179 C25H28 Trixylylmethane, mp. 188°-180 C25H44 Trimethylhexadecylbenzene, mp. 40°-175 C25H2GO0 Eupittonic ac., mp. 200°-209 C25H34O14(?) Arbutin, mp. 145°-97 C25H38O7 Cholanic ac., mp. 285°-72 Isocholanic ac., mp. 245°-71 C25H42O Tolyl heptadecyl ket., mp. 67°-137 C25H50O2 Hyaenic ac., mp. 77°-56 C2G GROUP. C2GH16 Dibiphenyleneethylene, mp. 187°- 180 C2GH20 Tetraphenylethylene, mp. 221°-• 180 C20H22 Dibenzylbiphenyl, mp. 113°-178 Tetraphenylethane, m. p. 209°- 180 C26H1GO2 Tetraphenylethylene dioxide, mp. 315°-LSI C2GH20O Benzhydrol eth., mp. 111°-178 Benzpinacoline, mp. 204°-180 C26H22O2 Benzopinacone, mp. 168°-159 C26H4GO Ergosterine, mp. 154°-159 C2GH44O Cholesterine, mp. 148°-158 Paracholesterine, mp. 134°-158 Phytosterine, mp. 132°-158 C2GH52O2 Cerotic ac., mp. 78°-56 C27 GROUP. C27H24 Tritolylbenzene, mp. 171°-179 C27H54 Cerotene, mp. 57°-176 C27H56 Heptacosane, mp. 59°-176 C27H18O Benzaldinaphthyl oxide, mp. 189° -180 C27H32O16 Rutin, mp. a. 190°-209 C27H44O Isocholesterine, mp. 137°-158 C27Hr<0 Myristone, mp. 76°-138 C27H5GO Ceryl ale., mp. 79°-157 C28 GROUP. C28H18 Bianthranyl, mp. 300°-181 C28H20O Lepidene, mp. 175°-180 C28H20O2 Oxylepidenes, mp. 220°, 232°-210, 139 C28H22O2 Anthrapinacone, mp. 182°-159 Hydroxylepidene, mp. 254°-181 C28H22O4 Tetraphenvlsuccinic ac., mp. 261° -71 C^O, Hydrobenzoin anhyd., mp. 126°- 178 C28H2GO2 Phenyltolylpinacone, mp. 164°- 159 C28H48O Homocholesterine, mp. 183°-159 CM GROUP. C2BH58O Lactarone, mp. 82°-138 C3U GROUP. C30H28 Tetratolylethylene, mp. 215°-180 C30Hc0 Melene, mp. 62°-176 C30H26O7 Chrysarobin, mp. 175°-208 C30H34O13 Picrotoxin, mp. 200°-100 C30H38Og Santononic ac., mp. 215°-70 C30HssO6 Lithobilic ac., mp. 199°-68 C30H60O2 Melissic ac., mp. 90°-56 C30H60O3 Oxymelissic ac., mp. 95°-57 C,„HfinO4 Lanoceric ac., mp. 104°-58 C30H62O Myricyl ale., mp. 85°-158 Coccerylic ale., mp. 102°-158 C31 GROUP. C31Hf4 Hentriacontane, mp. 68°-176 C31H02O Palmitone, mp. 83°-138 C3,HGQO3 Coceric ac., mp. 92°-57 Palmitic anhyd., mp. 64°-129 C31HG4O Dipalmitylcarbino 1, mp. 84°-158 C32 GROUP. C,„Hrr Dotriacontane, mp. 70°-176 C32H52O16(?) Convolvulin, mp. 158°-98 C32H64O2 Ethylmelissate, mp. 73°-119 c2h86O Cetyl eth., mp. 55°-17 5 C34 GROUP. C34H36 Tetraxylylethylene, mp. 244°-18F C35 GROUP. CoJIt, Pentriacontane, mp. 75°-176 C35H70O Stearone, mp. 88°-138 C36 GROUP. C36Hg,O31 Inulin, mp. 178°-31 C36HtoO3 Stearic anhyd., mp. 73 -129 C38 GROUP. C38H30O9 Resorcinbenzeine,-213 C,aH,,O, Dibenzaltriacetophenones, mp. 19 '• 256°-139, 140 COLOR STANDARD. SHEET A. This standard, which has been prepared for use in Mulliken's Method for the Identification of Pure Organic Compounds from colors furnished by the courtesy of the Milton Bradley Company, will be replaced, in case of injury, by the publishers, John Wiley & Sons, 432 Fourth Ave., New York, upon receipt of a postal money order for one dollar - or fifty cents for either one of the two separate sheets. It is not for sale except to persons owning the work with which it is issued. COLOR STANDARD.-SHEET B. Violet-red, VR. Red, R. Orange=red, OR. Red=orange, RO. Orange, O. Yellow=orange, YO. Orange=yellow, OY. Yellow, Y. Green=yellow, GY. Yellow=green, YG. Green, G. Blue-green, BG. Green blue, GB. Blue, B. Violet-blue, VB. Blue=violet, BV. Violet, V. Red=violet, RV.