UC-NRLF 7fl LIBRARY OF THK LMVKRSITV OF CALIFORNIA. 1M1VSICS DEPARTMENT. r.in 01 Miss ROSE WHITING. September, 1896. Accession No. oLL j? ^ // WOHLER'S OUTLINES v ORGANIC CHEMISTRY BY RUDOLPH FITTIG, PH.D., NAT. So. D., PROFESSOR OF CHEMISTRY IN THE UNIVERSITY OF TUBINGEN. TRANSLATED FROM THE EIGHTH GERMAN EDITION, WITH ADDITIONS, BY IRA REMSEN, M.D., Pn.D., PROFESSOR OF CHEMISTRY AND PHYSICS IN WILLIAMS COLLEGE, MASSACHUSETTS. *• Of TOT 7BRSIT7 PHILADELPHIA: HENRY G. LEA 1873 PHVWCS-BSPI. Entered according to Act of Congress, in the year 1872, by HENRY C. LEA, in the Office of the Librarian of Congress. All rights reserved. PHILADELPHIA: COLLINS, PRINTER, 705 JAYNE STREET. PREFACE AMEEICAN EDITION IN presenting this book to the American scientific public, I need only, as an excuse, refer to the success which it has met in Germany, as indicated by the appearance of eight editions in rapid sequence. The grounds of its success may, in part, be looked for in the fact that it is adapted as well to the use of beginners as to that of those advanced in the science. o The beginner will find a simple principle of classifica tion, carefully carried out, eminently fitted to his first object of obtaining a general view of the subject; the advanced will find it exceedingly rich in statements of facts with which he has constantly to deal. The year that has elapsed since the appearance of the last German edition, with its quota of investiga tions in this branch of science, has caused the neces sity of a revision in order that the work might be equal to its avowed object. The additions and correc tions have been made as nearly as possible in the spirit of the original, with the view merely of rendering the book a representative of the science at the date of publication. An introductory chapter on the "Constitution ot Chemical Compounds" has been prefixed in order to iv PREFACE TO THE AMERICAN EDITION. aid the beginner in his attempt to comprehend certain terms, upon which he would otherwise, perhaps, stum ble at the very outset of his study, and to render his entrance into the apparently labyrinthic structure somewhat less dark and indefinite. The time, during which the strict division of Chem istry into Inorganic and Organic was held upright, has long passed away, and we now recognize that this division is merely conventional, intended to aid the work of classification. There is but one chemistry, but one set of laws govering the formation, existence, and decomposition of chemical compounds. The com pounds of carbon, owing, in general terms, to their comparative instability and other properties, are, how ever, particularly susceptible to the action of reagents, and are, hence, particularly adapted to the uses of the investigator, who is endeavoring to discover the secrets of the science. Hence, further, most of the great advances of chemistry of late years have been due to the results of the study of chemical phenomena in connection with so-called organic compounds, and the subsequent application of the results obtained to the whole field. It is, therefore, natural that of late the attention of Americans should have been attracted towards this field; and there begin to be slight indications of a desire on their part to aid in clearing up its many mysteries, a work in which for some years the Ger mans have been engaged almost to the exclusion of the chemists of other countries. Should the publica tion of this work tend in the slightest degree to increase this desire, I shall feel that my labor has not been in vain. IRA REMSEIST. WILLIAMSTOWN, Mass., October, 1872. AUTHOR'S PREFACE TO THE SEVENTH EDITION AT the desire of Professor Wohler, I have with pleasure again undertaken the preparation of the present edition of the " Outlines," required by the publishers. Since the appearance of the last edition, however, such great advances have been made in the field of Organic Chemistry, that the book demanded a material transformation to place it- in concordance with the later theoretical views; and the entire rewriting of several sections was necessitated. The principle upon which it is based remains, however, the same as before. It is not intended to be a text-book of Organic Chemistry in the usual acceptation of the term, but a guide in connection with instruction. Hence, facts have been placed in the foreground, and particular attention has been given to the occurrence, the formation, and the characteristic properties of individual compounds. The development of theoretical relations, the demonstration of the connections between the various groups of bodies, and of the general laws which govern them, must be left to the teacher in his oral exercises. In the treatment of the individual groups, the guiding principle throughout has been this : Of every homologous series, that com pound, which is most thoroughly investigated, and which may be considered as a type of the whole series (as, for instance, ethyl alcohol in the series of saturated, monatomic alcohols, acetic acid in the fatty-acid series), is, with its derivatives, considered very exhaust ively; while, for the other members of the same series, only the physical properties of the more important ones are briefly stated, and their characteristic derivatives mentioned. Although the book is intended as a guide in first instruction in Organic Chemistry, it stilj contains much more than is required for vi AUTHOR'S PREFACE. this purpose. A practical object was here kept in view. The teacher is, of course, always obliged to confine himself in first in struction to the drawing of a sketch of the science in rough outlines, as it were ; for the student, however, a course of lectures of this character undoubtedly becomes much more comprehensible, if the material is at hand, by the aid of which he can, in private study, follow the general rules and laws more in detail. Further, the book is designed for reference in connection with laboratory work, and, in order to make it comply with this object, it was necessary to embody in it a great deal that could otherwise have been omitted. R FITTIG. GOTTINGEN, 1868. PREFACE TO THE EIGHTH EDITION. THE rapid advances in the field of Organic Chemistry have again necessitated the entire rewriting of some parts of the " Outlines." The same principle has been followed as in previous editions, but the system of selecting the hydrocarbons as the starting-points in the consideration of all the other groups of bodies, has been more rigidly carried out than formerly ; and more attention has been paid to those isomeric relations which are theoretically possible, and those which have been really observed in the individual groups. KUD. FITTIG. TUBINGEN, 1871. TABLE OF CONTENTS. PAOB INTRODUCTION. Physical properties of organic bodies .... 13 Valence of carbon and of groups containing carbon . 14 Saturated and non-saturated compounds .... Isonierism ......... 16 Homologous series ........ 17 Decomposition and transformations of organic bodies, Conduct in higher temperatures, Putrefaction, Fer mentation, Decay, Action of certain reagents . . 18 Ultimate analysis ........ 22 I. MARSH-GAS DERIVATIVES (FATTY BODIES). FIRST GROUP. ' A. HYDROCARBONS, CnH2n+2 (Marsh-gas series) . . 27 Marsh-gas and its Jiomologues ..... 28 B. MONATOMIC ALCOHOLS, CnH2»+2O .... 32 Primary, secondary, and tertiary alcohols ... 33 Methyl alcohol and methyl-compounds ... 33 Ethyl alcohol and ethyl-compounds ... 42 Propyl alcohol, Pseudopropyl alcohol . . .65 Butyl alcohols 67 Amyl alcohols ....... 69 Hexyl alcohols 71 Heptyl alcohols, Octyl alcohols .... 73 Nonyl, Decatyl, Cetyl, Ccryl, Myricyl alcohols, . 74 C. MONOBASIC, MONATOMIC ACIDS, CnII2n02 . 75 Formic acid ........ 76 Acetic acid 78 Derivatives of acetic acid 80 Propionic acid and its derivatives .... 89 Butyric acids (of fermentation, Isobutyric acid) . 92 Valeric acid . . . . . . . .95 Caproic acid ........ 97 (Enanthylic, Caprylic, Pelargonic, Capric, Laurie, Myristic acids 99 Palmitic, Margaric, Stearic, Arachidic, Benic, Hya- nic acids ........ 100 Cerotic, Melissic acids 101 Vlll TABLE OF CONTENTS. PAGE D. ALDEHYDES, CnH2nO 101 Formic aldehyde (Methyl aldehyde) . . . 101 Acetic aldehyde and its derivatives . . . 102 Homologous aldehydes 107 E. ACETONES (KETONES) 108 Acetone (Dimethylketone) 109 Propione (Diethylketone) 110 Homologous acetones Ill SECOND GEOUP. A. HYDROCARBONS, CMH2w (ETHYLENE SERIES) . . 112 Ethylene 113 Propylene 115 Butylene 116 Amylene 117 Hexylene 118 Homologous hydrocarbons . . . . .119 B. MONATOMIC ALCOHOLS, OH2?1O . . . .119 Allyl alcohol and allyl compounds . . .119 C. MONOBASIC, MONATOMIC ACIDS, OH2n-202 . . 122 Acrylic acid . . . . . . . .122 Crotonic acid 123 Isocrotonic, Methacrylic, Angelic acids . . 124 Methylcrotonic acid 125 Hydrosorbic, Pyroterebic, Ethylcrotonic acids . 125 Cimicic, Hypogaeic, Oleic acids .... 126 Erucic acid ........ 127 Supplement: Linoleic, Ricinoleic acids . . 128 D. ALDEHYDES, OH*l-20 128 Acrolein 128 Crotonic aldehyde 129 Supplement : Pyridin bases : Pyridin, Picolin, Lu- tidin, Collidin, etc 130 THIRD GROUP. A. HYDROCARBONS, CnII2n— 2 (ACETYLENE SERIES) . 131 Acetylene ........ 131 Allylene 132 Homologous hydrocarbons . . . . .133 B. MONOBASIC, MONATOMIC ACIDS, CnH2n— 402 . . 134 Sorbic, Palmitolic acids 134 Palmitoxylic, Stearolic, Behenolic acids . . 135 FOURTH GROUP. A. DIATOMIC ALCOHOLS, CMH2M-202 (Glycols) . . 136 Methylene compounds . . . . . .136 Ethylene alcohol 136 Propylene alcohol 142 TABLE OF CONTENTS. IX Butylene, Amylene, Hexylene, Octylene alcohols, Diallylhydrate B MONOBASIC, DIATOMIC ACIDS, CnH2n03 . . . 144 Gly colic acid ™ Oxypropionic acids l*j Oxybutyric acids 1^| Oxyvaleric acids ' • ' J ro Oxycaproic acids C. BIBASIC, DIATOMIC ACIDS, C»H»-«0* Oxalic acid . . • • • • • ' i rp Glyoxal *™ Glyoxylic acid JjJ' Malonic acid . . . > • • • • '{ ~o Amidomalonic, Mesoxalic acids . . . ' IRQ Succinic acid J'^X Pyrotartaric acid '.dipic, Suber- cellic acids yrotarac ac ..... • • Adipic, Suberic, Azelaic, Sebacic, Brassylic, Roc- D. BIBASIC, DIATOMIC ACIDS, CWH*"-403 Fumaric acid ..... • • * JJj Maleic acid . . • ...... Ita-, Citra-, Mesa-, Paraconic acids FIFTH GROUP. A. TIUATOMIC ALCOHOLS, OH^O1 .... Glycerin ......... ™ Fats ......... 171 B. MONOBASIC, TRIATOMIC ACIDS, CnII2M0* . . . 174 Gly eerie acid ...... » * lit Supplement : Pyroracemic, Carbacetoxylic acids . 175 C. BIBASIC, TRIATOMIC ACIDS, CnH2'l-205 . . ' }1? Tartronic acid ........ 1^ Malic acid ..... . • • • JJJ Oxypyrotartaric, Ita-, Citra-, Mesamalic acids . ITS Glutaric acid ........ 1'^ Adipoinalic acid ....... 17S D. TRIE ASIC, TRIATOMIC ACIDS, CnII2?l-406 . . . 179 Tricarballylic acid . . . ' • • .179 E. TRIBASIC, TRIATOMIC ACIDS, CnII2?t-606 . . • 1Z? Aconitic, Phenaconic acids ..... 1 '9 SIXTH GROUP. A. TETRATOMIC ALCOHOLS, CnH2n+204 .... Erythrite ........ lb° B. MONOBASIC, TETRATOMIC ACIDS, CnII2n05 Erythroglucic acid ...... C. BIBASIC, TETRATOMIC ACIDS, CnH2n-2O6 . . .181 Tartaric, Racemic acids ..... 181 TABLE OF CONTENTS. PAGE D. TRIBASIC, TETRATOMIC ACIDS, CnIFn— <0? . . 185 Citric acid ...... 185 SEVENTH GROUP. BIBASIC, PENTATOMIC ACIDS, OH271— 207 . . .187 Aposorbic acid .' 187 EIGHTH GROUP. A. HEXATOMIC ALCOHOLS, CnII2M-206 .... 187 Mannite . . . . . . . . 133 Mannitan, Quercite, Finite, Isodulcite, Hespcridine sugar 189 Dulcite 189 B. MONOBASIC, HEXATOMIC ACIDS, CwII2n07 . . . 190 Gluconic, Mannitic acids 190 Supplement : Lactonic acid 191 C. BIBASIC, HEXATOMIC ACIDS, CnH2n— 208 . . . 191 Saccharic, Mucic acids . . . . . .191 Supplement : Pyromucic acid, Furfurol . '. 192 D. CARBOHYDRATES . * 193 Grape-sugar ..... 194 Fruit-sugar, Lactose, Sorbine, Inosite . ! .' 196 Cane-sugar 198 Sugar of milk 200 Mycose, Melezitose, Melitose, Synanthrose . 201 Cellulose 201 Starch ...... 204 Inulin, Glycogen, Moss-starch . *. '. 206 Dextrin, Gum, Vegetable mucus . . . .207 NINTH GROUP. CYANOGEN COMPOUNDS 208 Cyanogen '. ! 208 Cyanhydric acid 209 Cyanogen chloride, iodide, bromide . 210 Cyanic acid 211 Sulphocyanic acid .....' 213 Mustard-oils; Ethyl, Methyl, Butyl, Allyl' mus tard-oils ....... 214 Cyanogen sulphide ...'.'. 216 Cyanuric acid ' 216 Cyanamide 217 Guanidin, Methyl-, Triethylguanidin .' .' 219 Fulminic, Fulminuric acids 220 Allophanic acid, Biuret, Trigenic acid . . . 221 TENTH GROUP. DERIVATIVES OF CARBONIC ACID . . . 222 Carbonyl chloride, Ethyl carbonate . ! 222 TABLE OF CONTENTS. XI Carbon sulphoxide, Carbon bisulphide . . . 223 Sulphocarbonic, Oxysulphocarbonic, Xanthogenic acids, Carbonyldisulphethyl .... 224 CarlDamic, Sulpliocarbamic acids .... 226 Urea (Carbamide) 227 Compound ureas ....... 230 Sulphocarbamide 231 Uric acid 232 Derivatives of Uric acid 233 Xanthine, Sarcine 246 Guanine, Glycocyamine, Glycocyamidine, Creatine, Creatinine 247 II. BENZENE DERIVATIVES (AROMATIC COMPOUNDS). FIRST GROUP. A. HYDROCARBONS, CJlH2»-6 353 Benzene 253 Addition-products and substitution-products of ben zene, anilin, etc. ....... 254 Diphenyl, Diphenylbenzene 270 Toluene 273 Toluidin, Anilin-dyes 277 Benzylbenzenc, Benzyltoluene, Ditolyl, Dibenzyl, Stilbene, Tolan 282 Hydrocarbons, C8II10 (Dimetliylbenzenes, Ethyl- benzene) 283 Hydrocarbons, C9H12 (Mesitylene, Pseudocumene, Ethylmethylbenzene, Propylbenzene) . . 286 Hydrocarbons, C10!!1* 288 Hydrocarbons with a greater number of carbon atoms 289 B. PHENOLS 290 a. Monatomic Phenols 290 Phenol 290 Cresols (Ortho-, Meta-, Paracresol) . . .298 Phenols, C8H'°O (Xylenols, Phlorol, Ethylphenol) 299 Phenols, C'°HUO (Thymol, Cyniophenol) . . 300 &. Quinones ......... 301 Quinone, Quinhydrone 301 Toluquinone, Phlorone, Thyrnoquinone . . 303 c. Diatomic Phenols 303 Dioxybenzenes (Hydroquinone, Pyrocatechin, Re- sorcin) 303 Orcin 307 Creosol 309 Hydrophloron, Betaorcin, Yeratrol . . .309 Thymohydroquinone 310 d. Triatomic Phenols 310 Pyrogallic acid, Phloroglucin . . . .310 Xll TABLE OF CONTENTS. PAGE e. Tetratomic Phenols . . . . . . .311 Derivatives of tetroxybenzene .... 311 C. ALCOHOLS ......... 312 Benzyl alcohol 312 Saligenin, Anise alcohol ..... 315 Tolyl alcohol. Stiryl alcohol, Secondary phenyl- ethyl alcohol 315 Cumine alcohol, Sycoceryl alcohol . . . 316 Supplement : Benzhydrol, Tollylene alcohol . . 316 D. ALDEHYDES 317 Benzylic aldehyde (Oil of Bitter Almonds) . .317 Hydrobenzamide, Amarin, Lophin . . .319 Hydrobenzoin, Isohydrobenzoin, Benzoin, Des- oxybenzom, Toluylenehydrate, Benzil, Benzilic acid, Benzoylbenzoic acid, Benzhydrylbenzoic acid, Benzylbenzoic acid . .... 321 Salicylic aldehyde 322 Anisic aldehyde, Dioxybenzylic aldehyde, Pipe- ronal 324 Paratolylic aldehyde ...... 325 Cuminic aldehyde . . . . . . . 325 E. ACIDS 325 a. Monobasic, monatomic acids 325 Benzoic acid ........ 325 Derivatives of benzoic acid 327 Acetones (Benzophenone, Acetophenone) . . 335 Hippuric acid . . . . . . . .336 Acids, CSH802 (Ortko-, Meta-, and Paratolnic acids, Alphatoluic acid) 338 Acids, C9II'°02 (Mesitylenic, Xylylic, Paraxylylic, Ethylbenzoic, Alphaxylylic, Hydrocinnarnic, Hydratropic acids) ...... 340 Acids, C10H1202 (Dnrylic, Cuminic acids) . . 342 Acids, CUHI4O2 (Homocuininic acid) . . .343 b. Monobasic, diatomic acids 343 Oxy benzoic acids (Salicylic, Oxybenzoic, Paraoxy- benzoic acids) ....... 343 Acids, C8H803 (Cresotic acids, Oxymethylphenyl- formic, Mandelic acids) ..... 351 Acids, C9H>°03 (Oxymesitylenic, Phloretic, Alorcic, Melilotic, Hydroparacoumaric, Tropic, Phenyl- lactic acids) ...... 352 Acids, CnH1403 (Thymotic acid) . . . .'355 c. Monobasic, triatomic acids ..... 355 Dioxybenzoic acids (Oxysalicylic, Protocateclmic, Dioxybenzoic acids) ...... 355 Orsellic acid- 358 Erythrin, Lecanoric acid 358 Acids, C9H1004 (Veratric, Everninic, Umbellic, Hydrocatfeic acid) .... 359 TABLE OF CONTENTS. Xlll PAGE d. Monobasic tetratomic acids 360 Gallic acid 360 Rufigallic acid 361 Supplement : Quinic acid ..... 361 e. Sibasic acids ........ 362 Benzenedicarbonic acids (Plitalic, Isoplitalic, Tere- phtalic acids) 362 Acids, C2H804 (Uvitic, Xylidinic, Isuvitic acids) . 366 Acids, C10HI004 (Cumidinic acid) . . . .367 /. Tribasic acids 367 Benzenetricarbonic acids (Trimesic, Heinimellitic, Trimellitic acids) 367 g. Tetrabasic acids ....... 368 Benzenetetracarbonic acids (Pyromcllitic, Prehni- tic, Mellophanic acids) 368 h. Hexabasic acids ........ 370 Mellitic, Hydromellitic acids .... 370 SECOND GROUP. Cinnamene (Styrol) 372 Styryl alcohol 373 Cinnamic aldehyde ...... 373 Cinnamic acid 374 Atropic, Isatropic acids ...... 376 Phenylangelic acid ...... 376 Coumarin and homologous compounds . . . 377 Coumaric, Paracoumaric acids .... 378 Caffei'c acid 378 THIRD GROUP. Acetcnylbenzene (Phenylacetylene) . . . 379 Diacetenylphenyl • . 379 Phenylpropiolic acid 380 Supplement : Anethol . . . . . . . . . 380 Eugenol, Eugctic, Sinapic, Hemipinic, Opianic acids, Meconin, Hydropiperic acid . . . 381 FOURTH GROUP, INDIGO-GROUP. Indigo-blue 383 Indigo-white 385 Isatin 387 Trioxindol (Isatic acid), Dioxindol (Hydrindic acid) 388 Oxindol, Indol, Isatyde, Indin . . . .389 III. NAPHTHALENE-DERIVATIVES. A. HYDROCARBONS, CnH2*-12 391 Naphthalene . B XIV TABLE OF CONTENTS. PAGE Addition-products and substitution-products of Naphthalene 392 Dinaphthyl 396 Methylnaphthalene, Ethylnaphthalene . . . 396 B. PHENOLS 397 Naphthol, Naphthyl sulphydrate, Naphthyl sul phide, Isonaphthol 397 Dioxynaphthalene ....... 399 Trioxynaphthalene ...... 400 C. QUINONES 400 Dichlornaphthoquinone ...... 400 Oxy-, Chloroxy-, Dioxynaphthoquinone . . 400 D. ACIDS 402 Naphtoi'c acid, Isonaphtoic acid .... 402 Oxynaphtoic acid ....... 403 IV. ANTHRACENE-DERIVATIVES. Anthracene, Paranthracene 404 Anthraquinone 406 Oxyanthraquinone, Alizarin 408 Crysophanic acid, Chrysammic acid, Purpurin . 409 Anthracenecarbonic acid 410 Supplement: Pyrene, Chrysene, Retenc . . . 410 V. GLUCOSIDES. Amygdalin 412 Solanin 413 Solanidin, Salicin . • 414 Populin, Helicin, ^Esculin 415 • ^sculetin, Phlorizin 416 Phloretin, Quercitrin 417 Quercitin, Quercetic acid, Kutin, Frangulin, Rubi- anic acid 418 Arbutin, Fraxin 419 Phillyrin, Daphnin, Myronic acid, Convolvulin, . 420 Jalappin, Turpethin, Saponin . . . 421 Cai'ncin, Quinovin, Pinipicrin, Carminic acid . 422 Ilelleborein, Helleborin, Glycyrrhizin . . . 423 Digitalin 424 Tannic acids ......... 424 Gallo-tannic acid (Tannin) 424 Catechutannic acid . . . . . . 425 Oatechin, Kinotannic acid, Morintannic acid . 426 Morin, Quinotannic acid, Oak-bark- tannic acid . 427 Cafl'etannic acid 428 VI. VEGETABLE SUBSTANCES, BUT LITTLE KNOWN. A. ACIDS. Usnic, Cetraric, Lichenstearic acids 429 TABLE OF CONTENTS. XV PAGE Vulpic, Meconic acids ...... 480 Clielidonic acid . . . . . . .431 B. BASES^ ALKALOIDS). Conine, Conydrine 432 Nicotine 434 Sparteine 435 Opium-bases 435 Morphine, Oxymorpkine, Apomorpliine . . 437 Narcotine, Cotarnine ...... 439 Codeine, Thebaine, Papaverine, Narceine, etc. . 440 Bases of Cinchona-bark 441 Quinine 442 Ciuchonine 443 Quinidine, Cinchonidine, Quinicine, Cinchonicine 444 Bases of the Strychnos-species .... 445 Strychine, Brncine ....... 445 Bases of the Veratrum-species .... 446 Veratrine, Jervine 446 Bases of Berberis vulgaris 447 Berberine, Oxyacanthine 447 Theobromine ........ 448 Caffeine, Caffeidine 448 Piperine, Piperidine ...... 450 Sinapine ......... 450 Harmaline, Harmine 451 Cocaine, Ecgonine, Hygrine 451 Atropine, Physostigmine 452 Hyoscyamine, Emetine, Aconitine, Colchicine . 453 Chinolin-bases, Cyanin ...... 454 C. COLORING MATTERS, BITTER PRINCIPLES, ETC. Aloin, Athamantin ...... 454 Antiarin, Brasilin, Cantharidin, Carotin, Cartha- min 456 Chlorophyl, Columbin, Curcumin .... 457 Gentianin, Haematoxylin, Helenin . . . 458 Laserpitin, Peucedanin, Picrotoxin, Porissic acid . 459 D. ETHEREAL OILS. Oil of turpentine . 462 Tcrpine, Terpinol, Terebic acid, Terebentilic acid 463 Oils isomeric with oil of turpentine . . . 465 Other ethereal oils 465 E. CAMPHOR. Japan camphor ....... 466 Campholic, Camphoric, Camphoronic, Camphocar- bonic acids 468 Borneo Camphor (Borneol) 469 Mentha Camphor (Menthol) 470 F. RESINS. 1. Resins proper. Colophony ........ 471 XVI TABLE OF CONTENTS. Sylvic acid (Abiotic acid), Pimaric acid, Copaiba resin 472 Elemi, Betulin, Lactucone, Copal, Dammara-resin, Mastic 473 Olibanum, Sandarac, Gum-lac, Gum-benzoin, Guaiacum 474 Acaroid resin, Dragons blood, Amber . . . 475 2. Caoutchouc, Gutta Percha ..... 475 3. Gum-Resins ........ 476 4. Balsams ........... 476 VII. BILIARY COMPOUNDS. Glycocholic acid 477 Cholic acid, Dyslisin 478 Taurocholic acid 479 Litliofellic acid, Cliolesterin 480 Biliary coloring matters ..... 481 Bilirubin, Biliverdin, Bilifuscin .... 482 Biliprasin, Bilihumin ...... 483 VIII. PROTEIN COMPOUNDS. Albumen 486 Casein 487 Legumin 488 Fibrin 489 Fibrinogenous and fibrinoplastic substance . . 489 Globulin 490 Vegetable fibrin, Glutin 490 Myosin ......... 491 Syntonin (Parapeptone) 491 ANIMAL CHEMISTRY. BLOOD 493 Hsematoglobulin (Haemoglobin) .... 494 Hsematin 495 Hsemin, Haematoidin 496 Respiration 498 CHYLE 499 LYMPH 500 SALIVA . .500 GASTRIC JUICE 501 BILE 501 SKIN AND ITS SECRETIONS, HORNY TISSUE . . . 503 Hair, Sebaceous matter, Perspiration . . . 504 MUSCLES . 505 TABLE OF CONTENTS. XV11 PAGE BONES 506 Fish-scales, Teeth 507 TISSUES YIELDING GELATIN 508 Glutin, Chondrin 508 Silk, Fibroin, Silk-gelatin 511 FAT 511 Mucus 511 TRANSUDATES OP SEROUS MEMBRANES .... 512 THE EYE 512 THE NERVOUS SYSTEM 513 THE EGG .515 SEMEN 516 MILK 517 URINE 518 EXCREMENTS ... ... 522 CONSTITUTION OF CHEMICAL COMPOUNDS. IT is noticed that certain elements combine with each other in only one proportion, forming thus but one kind of compounds. If we take, for instance, hydrogen and chlo rine, and allow them to combine under the most varied conditions, the result is always hydrochloric acid, and this always contains 35.5 parts by weight of chlorine to 1 part by weight of hydrogen. The same is true of a number of other elements, as bromine, iodine, potassium, sodium, etc. Further, we notice that in the case of other elements, as oxygen and sulphur, nitrogen and phosphorus, carbon and silicium, a greater variety presents itself in their combina tions, not only with each other, but with the elements of the first class referred to. Oxygen combines with hydro gen in two proportions, forming water and hydrogen per oxide ; nitrogen combines with oxygen in five proportions, forming nitrous oxide, hyponitric acid, nitrogen binoxide, nitrous anhydride, and nitric anhydride. This distinction, between elements that combine with each other only in one proportion, and those which combine with each other and all other elements in more than one proportion, is fundamental and characteristic. The recognition of this distinction led to the acceptation of the hypothesis of the valence of elements. This hypothesis may be stated as follows : Every atom of an element has an inherent power of holding in combina tion a certain number of other atoms of known combining power. The simplest examples of this principle, we find in the first class of elements mentioned above ; they com bine with each other in only one proportion, i. e., each atom can retain in combination only one other atom of any kind, and its combining power, as well as that of the atom with which it is united, represents the unit of this power. The atoms of such elements are said to possess one affinity; and the elements are called monovalent. In order to determine which elements are monovalent, XX CONSTITUTION OF CHEMICAL COMPOUNDS. we have to subject the formulae and nature of their com pounds, as far as they are known, to the most careful study. We thus find, in the first place, that hydrogen, chlorine, bromine, iodine, etc., are monovalent. Having once established this fact, knowing which elements are monovalent, we have a basis upon which we can work to determine the valence of other elements. Here again the determination of the empirical formulae of the compounds, of the elements to be investigated, with monovalent ele ments must be the first step in the inquiry. If we take oxygen, for example, we find that its simplest compound with hydrogen is water, and by the aid of familiar means we determine its formula to be H20, i. e., it consists of two atoms of hydrogen united with one atom of oxygen. Hence we see that in this case, the atom of oxygen exhibits a combining power, twice as great as that of hydrogen, and, not finding any fact to conflict with this, we say that oxygen is a bivalent element — its free atom possesses two free affinities. In a similar manner we find that sulphur, selenium, tellurium, etc., are also bivalent. Proceeding further, nitrogen, phosphorus, arsenic, and other elements are found to possess three times the com bining power of the monovalent elements ; their simplest compounds with hydrogen are NH3, PH3, AsH3, etc. Ele ments of this class are called trwalent. Carbon, silicium, etc., are tetravalent, or the uncombined atoms of these elements possess four free affinities. Their simplest hydrogen compounds are CH4, SiH4, etc. . In this way all the elements have been classified into groups, the individual members of which are said to be monovalerit, bivalent, triualent, tetravalent, or pentavalent. The elements are designated by the names monads, dyads, triads, tetrads, pentads, etc. This subdivision is dependent merely upon the combining powers of the elements, and tells us merely that the atoms of the elements of each group can unite with, or hold in combination, a certain number (indicated by the name) of monovalent atoms, such as hydrogen, chlorine, etc. When we say an element is monovalent, bivalent, trivalent, etc., we intend merely to say that each one of its atoms possesses the power of combin ing with one, two, three, etc., monovalent atoms or atomic units ; that each one of its atoms in the free state possesses one, two, or three free affinities. Now compounds are formed by virtue of the mutual ac- CONSTITUTION OF CHEMICAL COMPOUNDS. XXI tion of these free affinities upon each other ; and, the com pounds once formed, the affinities are no \onger free. Upon this mutual neutralization or saturation of free affinities are based oftr fundamental ideas in regard to the constitu tion of chemical compounds, or chemical structure. The compounds of the elements with hydrogen alone are very simple. We have hydrochloric acid, for instance, consist ing of one atom of hydrogen united with one atom of chtorine ; and the molecule of the compound is represented by the formula. H.C1 ; and so also for hydrobromic acid, CH H.Br., etc. For water we have H.O.H or O j H which sig nifies that each of the free affinities of the bivalent oxy gen atom is saturated by a hydrogen atom ; for ammonia .H (H we have N.H or N \ H ; for marsh gas, CH4, we have •H (H CH TT TT I T-T "C* or C 4 5 These formulae indicate the constitution H. -H ^ of the compounds, i. e., the arrangement of the atoms in the molecule. By the expression "arrangement of the atoms in the molecule," however, we do not intend to go so far as to refer to the actual relative position of the atoms in space, as our present knowledge will not permit conclu sions of any value in regard to this point. We only mean to give an account of the employment of the affinities of the atoms, which are the essential causes of the formation of the molecules. In the case of hydrochloric acid, for instance, we mean that the one free affinity originally pos sessed by the hydrogen-atom, and that possessed by the chlorine-atom, as inherent, characteristic powers, have been mutually satisfied, and, ceasing to be free affinities, now perform a function in holding together the two atoms, in order to form the molecule of the compound. It may be here mentioned that the so-called free affinities are in almost all cases never free except for an infinitesimally short space of time. An atom of hydrogen or of chlorine does not exist in a free condition, but, if nothing else be present with which it can combine, it combines with another atom of the same kind, forming a molecule of the element instead of a molecule of a compound. The mole cule of hydrogen, or of chlorine, has the same chemical XX11 CONSTITUTION OF CHEMICAL COMPOUNDS. constitution as hydrochloric acid, i. e., it consists of one monovalent atom united with another monovalent atom, thus H.H and C1.C1 ; and, in order that the compound H.C1 may be formed, it is necessary that the union of atoms already existing be broken up ; which is accom plished by virtue of the stronger affinity of the hydrogen- atom for the chlorine-atom, than of the hydrogen-atom for hydrogen-atom, or the chlorine-atom for chlorine-atom. Thus the affinities, as stated, are not free, but the instant they become free they are taken up, neutralized, saturated by those of other atoms present. In the simple cases which we have considered, viz., hy- •H drochloric acid H.C1, water H.O.H, ammonia N-H and TT TT marsh gas TT!C!TT the constitution of the compounds is •"• -"-? plainly indicated by the formula?. By replacing one or all of the elements in the above formula; by other elements of equal valence, we have the formulae of a number of known compounds :— H.C1 similar to II.Br, Na.Cl, K.Br, etc. II.O.II » K.O.II, Cl.O.II, C1.0.C1, II.S.H, etc. .H N-H •H TT TT xi •/->!* in. ct -^/J.^^.A^- v_y * . ^-^ • --^ .1. •»_/ A • ,^ • >_/ A •^.1.^1 ••\_/A f\4- s\ But by far the greater number of chemical compounds are more complicated in constitution, and may be looked upon as formed by the replacement of one or all of the elements in the above formula; by atomic groups, which have the same valence as the replaced atoms. The four fundamental formulae, inasmuch as they illustrate the func tions of the elements of different valence, may be conveni ently employed for the purpose of comparison with more complicated formulae with the object of rendering the ex planation of the latter more simple. If we take any of the fundamental formulae, and divide them at any part, we obtain two residues of equal valence. For instance, if we divide H.C1, we obtain II and Cl, both monovalent ; if we divide H.O.H, we obtain H and OH, and these are both monovalent, for, as can be readily seen, the group OH requires a monovalent atom or group in .K .H .Cl .H N-H P-H P-C1 As-H etc. •H, •H, •Cl, •H, Cl H H-C-H, Cl .Cl ci.c.ci C1.-.C1 Ci;Sl-H, CONSTITUTION OF CHEMICAL COMPOUNDS. XX111 order that it may become saturated, and this is what we .H understand by a monovalent group. If we divide N*H •H, we obtain H and NH2, or H2 and NH ; by the former division there are left two monovalent, by the latter two TT TT bivalent factors. And so in the case of TT'^'TT if we divide ±i* *xi ; this formula, the following cases are possible : H and CH3, H2 and CH2, H3 and CH, leaving in the first case two monovalent, in the second, two bivalent, and in the third, two trivalent factors. This principle may be carried out further in connection with other and more complicated for mulae, and so are obtained the formulae of a great variety of these so-called residues ; in most cases, however, the division made, and the residues resulting, may be com pared to the simpler forms described. We speak of a water-residue, OH, which, on account of the exceedingly important part it plays in the constitution of chemical compounds, has received a distinct name, hydroxyl ; the ammonia-residue. Nil2, is called amide; the residue, Nil, is called imide ; the residue, CH3, of marsh gas, is called methyl ; the residue, CII2, methylene, etc. etc. If we now operate with the groups mentioned instead of with atoms alone, we shall find that we are able to build up a larger number of formulae representing compounds, as follows : — II. TT Still further complications are introduced when, instead of compounds consisting of atoms of different valence, we have atoms of the same element, or of different elements of the same valence, united together, forming chains. Ex amples of the first kind are met with particularly in the case of carbon. If two carbon atoms unite in the simplest manner possible, we have a group *C*C', which must have .H .Oil .T:0 .CH3 .Oil .CH3 N'H similar toN • H, i -OH, N-H P-OII P-CH3 •H H, -H, •OH, •CH3, etc. TT TT !C|j_£ similar to TT! n.NH2 H.^.OH ( ^ .TT TT. ^ .TT •H, H H, ):C:H, N;C.OE 0:C:gg5etc. xxiv CONSTITUTION OF CHEMICAL COMPOUNDS. six free affinities ; if three atoms unite, •C'OO the result- * 5 ing group must have eight free affinities, etc.; and, as this chain combination may be continued indefinitely, and the free affinities may be saturated by the greatest variety of groups, it is evident that the number of compounds, the possibility of whose existence is thus indicated, is un limited. The atoms of oxygen also possess this property of uniting with each other to form chains, as we see in the compounds : — H.O.O.H, Cl.O.O.H, Cl.O.O.O.H, Cl.O.O.O.O.H, Br.O.O.O.H, etc. In these cases the oxygen-atoms, which with one of their affinities are united with hydrogen, impart to this hydro gen-atom. characteristic properties ; and, whenever this kind of combination is found, we say, for convenience sake, the compound contains hydrox}^. Examples of compounds formed by the chain-combina tion of different elements of the same valence are the fol lowing: H.O.S.O.O.H, H.O.O.S.O.O.H, in which we have sulphur and oxygen, forming a continuous chain. Having thus seen the various methods of combination of atoms, let us briefly illustrate the applications of these forms to the characteristic classes of compounds. In the first place, chemists have long recognized the existence of two classes of compounds, bases and acids, the representative members of which have, in certain re spects, opposite or complementary properties. The larger number of acids, as well as bases, contain hydrogen and oxygen ; and either all or a part of the hydrogen-atoms contained in them are united with oxygen. To the pre sence of these hydrogen-atoms or of the hydroxyl groups (see above), of which they form a part, are due the proper ties which distinguish the compounds as acids or bases. Examples of acids and bases are : — C1.0.H=C1(OH), K.O.II=K(OH). H.O.O.S.O.O.H = S02(OH)2, H.O.Ca.O.H = Ca(OH)2. 0:C.O.H = IICO(OH), H-C-C-O.H = C2IP(OII). CONSTITUTION OF CHEMICAL COMPOUNDS. XXV Acids are usually derived from the so-called metalloids ; bases from the metals. When acids act upon bases, salts are formed, water being given off, thus : — H.O.O.S.O.O.H and K.O.H give H.O.O.S.O.O.K and H.O.H. H.O.O.S.O.O.H and 2(K.O.H) give K.O.O.S.O.O.K and 2(H.O.H). Now, if we examine these formulae, we see that the salt may be considered either as the base, in which the original h}Tdrogen is replaced by the acid-residue, or as the acid, in which the original hydrogen is replaced by the base residue or metal. As the latter is the simpler view, it is the one usually held, though be it remembered, that it is imma terial, for the constitution of the salt, which of the two views is held. Compounds similar to salts in their constitution are anhydrides and metallic oxides. In the former two acid- residues, in the latter two base-residues, are emplo3red in the formation. O:N.O.H -f- 0:N.OJI = 0:N.O.(N:0) -f II.O.H, K.O.H + K.O.H = K.O.K -f H.O.H, H.O.Ca.O.H -{- H.O.Ca.O.H = Ca'^'Ca -f 2(H.O.H), H.O.O.S.O.O.H -f H.O.O.S.O.O.H = s;£;°;£;s + 2(H.O.H). It is, however, probable that in such cases as the two latter, the product splits up into two molecules, and the union of the atoms takes place in a different manner in consequence : — (0*0), s;g;°;g;s = a( s ;°;o The compounds of carbon resemble those of other ele ments, but, owing to certain properties of the element, variations are met with in this connection that require special notice. For one group of carbon-compounds, marsh gas, CH4, is the mother substance. From this, other substances con taining only carbon and hydrogen can be obtained, thus : — C ( H I H.C. V H XXVI CONSTITUTION OF CHEMICAL COMPOUNDS. H H H.C.H 4- ci.ci = H.C.CI + ii.ci. H H II ^ H H 01 I + 2Na = H-c-C-H + 2Na.Cl, etc. J H H Each one of the compounds obtained in this way, as well as marsh gas itself, may be looked upon as a compound of one or more hydrogen atoms, with a residue or residues of corresponding valence; and each one of these residues can and does play the part of an element. Marsh gas, when divided as above, leaves, as we have seen, the residues H H H.C.H (methyl), .C.H (methylene), .C.H, and .0., which are respectively mono-, bi-, tri- and tetravalent. Now, in the formation of the hydrocarbons (substances containing only hydrogen and carbon) from marsh gas, these four residues are the "elements," which are employed, and, by careful examination, we see that here an infinite variety presents itself. If we take the hydrocarbon C*H10 = HHHH H.C.C.C.C.H, we see that it consists of 2CH3 and 2CH2 ; HHHII but these atoms can be arranged in another way, and the composition CJII10 still be retained : — HUH ' c* H- • -H H-C-C-C-H; H- -H H in this case we have 3CH3 and 1CH. This principle can be carried out further, showing the possibility of a very large number of compounds of the same composition, but different constitution. This difference in constitution gives rise to a difference in the properties of the compounds. In the hydrocarbons we can replace hydrogen by other elements or groups, and thus obtain the other possible compounds. The replacement by monovalent elements re quires no explanation, as the constitution of the resulting CONSTITUTION" OF CHEMICAL COMPOUNDS. XXV11 compounds is exactly the same as that of the hydrocarbon itself. Just as marsh gas may be considered as the mother- substance of a whole group of carbon-compounds, so, by re placing its hydrogen-atoms by various groups, we obtain compounds, each of which may, in turn, be looked upon as the mother-substance of a subordinate group. It has already been shown that the water-residue, hydroxyl, OH, plays an important part in the structure of the two classes of compounds known as acids and bases. If, for a hydro gen-atom of marsh gas, we substitute OH, we obtain a H compound H.^.OH = CH3(OH). This possesses the pro- H perties of the bases in general, corresponding to the sim pler base K.O.H. We have in this case only CH3, instead of the element K. Here, too, the hydrogen-atom, which is in combination with oxygen, imparts to the compound its characteristic properties, whereas the other hydrogen- atoms present exhibit only those other general properties which are met with in connection with the hydrogen-atoms of other groups of carbon-compounds. One or all of these latter can be replaced by other elements or groups, and the compound still retains the properties originally im parted to it by the hydroxyl group. We can, for instance, replace one of these atoms by CH3, thus obtaining a com- HH pound, H-C-C-O.H = C2H5(OH). This in every way re- HH sembles the body from which it is derived. We can, further, in this compound replace one or more hydrogen- atoms by elements or groups, without disturbing the hy- droxyl-group. Let us again employ the group GIF. We find that two products are formed, dependent upon the hydrogen-atoms replaced : — HUH H|HH II 1. H.r " " C C^OOO.H, and 2. II-C • OO'H, H'HH ii H and, just as in the case of the hydrocarbon C4H10, the two products differ from each other in properties as well as in constitution. XXV111 CONSTITUTION OF CHEMICAL COMPOUNDS. According to this method we can build up an indefinite number of compounds, all containing hydroxyl, and all exhibiting certain common properties owing to the pre sence of this group. Although these compounds strictly belong to the general heading bases, they have, as a class, received a distinct name to designate some properties which the bases do not possess in common with them. They are called alcohols. The acids of carbon-compounds have an equally simple constitution. Let us start again with CH4. Replacing one atom by OH and two by 0, we obtain a compound OrCJQ TT This is formic acid. Here we have an oxidized carbon-atom, and in combination wtih it a water-residue. Again the hydrogen of the hydroxyl is the characteristic ingredient of the compound, but its characterizing powers have been imparted to it not alone by the fact that it is in combination with oxygen, but that this group is in its turn in combination with an oxidized carbon-atom. Organic acids all contain the group 0:0.0. H, which may be looked upon as a residue of formic acid. It is monovalent, and can take the place of hydrogen in the most varied com pounds. It has received the name carboxyl. The con sideration of organic acids may be still further simplified by comparing them with certain derivatives of sulphuric acid. When sulphuric acid, and a number of other acids containing one hj^droxyl-group, are allowed to act upon a compound containing replaceable l^drogen-atoms, one of the hydroxyl groups of the acid is given off in company with one of the hydrogen-atoms of the other compound in the form of water, and the two residues unite, thus: — ( OTT C6H6 -f SO2 \ : = C6H5.S02.OH + H20. Benzene. Sulphuric acid. The resulting compound may be called a substituted sulphuric acid, one of its hydroxyls having been replaced by a monovalent group. Now carbonic acid resembles sulphuric acid in the fact that it contains 2(OH), and, although the acid itself is unknown to us, we can, under certain circumstances, induce a substitution similar to that noticed in connection with sulphuric acid, and thus obtain substituted carbonic acids, which are nothing but the so- called organic acids : — CONSTITUTION OF CHEMICAL COMPOUNDS. XXIX C6H6 -f CO;^ = C6H5.CO.OH -f H20. or, C6H5.H -f °:C; = 0:C;J6 + H20. When acids and bases, in general terms, act upon each other, salts are formed, water being eliminated. Just so when alcohols and organic acids act upon each other, bodies, similar to salts, are formed, water being elimi nated : — H.CO.OH -f C2H5.OH = H.CO.O.C2H5 -f H20. Salts were defined as acids, in which the hydrogen of the hydroxyl-group is replaced by a base-residue. In this case we have the hydrogen of the hydroxyl-group of the carboxyl replaced by an alcohol residue, and the resulting compound has received the name ether. The name ether is applied to all similar compounds, it being, as is clear, but a special form of the salt. In regard to anhydrides the remarks made above are here equally applicable. The carbon-compounds, which are formed like metallic oxides, and which correspond to them, have also been called ethers, though the same differences between them and the ethers mentioned may be found, that are met with between metallic oxides and salts. K.O.H -f K.O.H = K.O.K -f H20, > .C2H5.O.H + C2H5.O.H = C2H5.O.C2II5 -f H20.j Among carbon-compounds there are other series, which do not occur among inorganic compounds, the character of which is dependent upon the peculiar properties of carbon. If in marsh gas, CH4, we replace two hydrogen- TT atoms by one 0, we obtain the body O:C.'TT which occupies ' TT OTT a position intermediate between that of jj.'Cij^- and ' Tliese bodies consist of two hydrogen-atoms united by the bivalent group C:0, which has been called carbonyl. Now either one or both of these hydrogen- atoms may be replaced by alcohol-residues, as CH3, C2H5, etc. If only one be replaced, we obtain the compounds pTT3 P2TT5 known as aldehydes, as 0:C j/J ' 0:0;;; ' etc. If, how- n, -Ti, ever, both be replaced, we obtain compounds of a some- XXX CONSTITUTION OF CHEMICAL COMPOUNDS, what different character. These have been designated as PJT3 p'2TT5 p2TT5 acetones or ketones, as 0:C;^g3 O.-C.^jp O.-C^gs etc. Aldehydes are, hence, compounds which consist of an alcohol-residue and a hydrogen-atom united by means of the group CO: and acetones consist of two alcohol-residues united by the group CO. It will thus be seen that the jj body 0:C.'jj may be considered as the simplest representa tive of both classes of compounds. In addition to the various classes of compounds, there are others, but they are all variations on these principal classes, and demand here no special explanation. We have, for instance, compounds which partake of the pro perties of both acids and bases, acids and alcohols, alde hydes and acids, aldehydes and alcohols, etc. etc., but with the aid of the few principles laid down these will be readily understood. We have, further, instances, especially among carbon-compounds, in which atoms of the same kind are united with each other by means of more than one affinitjr, and also those in which each carbon-atom of the compound is united with two other carbon-atoms, on the one hand with one, on the other with two affinities. etc. etc.; the constitution of such compounds can, how ever, be easily comprehended by the application of the fundamental principles. The main question which now presents itself is: What grounds have we for the acceptation of these fundamental principles ? It can only be answered, they have been proposed and accepted as affording the simplest explana tion of innumerable investigations concerning the proper ties of chemical compounds. At present no facts are known that conflict with their acceptation. They are by no means established beyond a doubt, but, as they simplify known facts, and have been exceeding^ fruitful in widen ing the field of observation, they are worthy of our most careful study. It would lead too far in this place to recall the indi vidual investigations and the methods of reasoning which have led to the acceptation of our present ideas concern ing the constitution of chemical compounds. In order to draw our conclusions we must know the methods of forma tion, the decompositions, and all the varied changes which individual compounds or groups of compounds undergo. CONSTITUTION OF CHEMICAL COMPOUNDS. XXXI A simple example may suffice to illustrate the rationale of the process. Let us take ordinary alcohol. We can first establish the formula by means of analysis and the deter mination of«the specific gravity of its vapor. This we find to be C2H60. This formula is the expression of a fact and a hypothesis. The fact expressed is that alcohol con sists of 52.17 per cent, carbon, 13.04 per cent, hydrogen, and 34.78 per cent, oxygen. The hypothesis of which it is an expression is that the molecules of all chemical com pounds in the form of vapor have the same volume as a molecule of hydrogen. This hypothesis, when applied, tells us the weights of the atoms contained in the mole cule of alcohol and the weight of the molecule of alcohol, and hence, further, the number of atoms of carbon, hydro gen, and oxygen contained in the molecule under considera tion. We know that hydrogen is monovalent, oxygen biva lent, and carbon tetravalcnt. It now remains to decide how those atoms are united — what the constitution of alcohol is? If we take marsh gas, CH4, which, according to our ideas, as we have seen, can only have the constitu- TT TT tion jjiC.'jj we can produce from it (see above) the hydro- HH carbon H.C.C.H = C2II6; if we now replace one of the HH hydrogen-atoms of this compound by chlorine, we have HH the compound H.C.C.C1 = C2H5C1, and experience shows HH us that only one compound of this composition can re sult, it being immaterial which one of the hydrogen- atoms is replaced. If we, further, allow the substance K.O.II, in regard to the constitution of which, according to the principles already laid down, there can be no ques tion, to act upon this compound, two products are formed, thus : — HH HH H.C.C.Cl + K.O.II = H.C.C.OH + KC1. HH HH The water-residue, the hydroxyl group, before in com bination with K, has changed places with Cl. The result ing compound, C2IP(OH), is ordinary alcohol, and we XXX11 CONSTITUTION OF CHEMICAL COMPOUNDS. have thus from one point of view determined its constitu tion. Again, by the action of certain reagents we find that an atom of ox}Tgen and an atom of hydrogen are given off, and their place is taken by one atom of chlorine, thus showing that the hydrogen and oxygen were present in the compound in the form of a monovalent group, or as h}rdroxyl, which is the only form that satisfies these con ditions. These and other similar facts are looked upon as proofs of the constitution of alcohol. It is in work of this kind that chemists are at present largely engaged, and the results achieved are already of great magnitude. The constitution of a large number of substances occurring in nature has been discovered, and the discovery of their constitution has in many cases led directly to the artificial preparation (synthesis) of the sub stances. Although this cannot be considered the highest aim of the science of chemistry, yet the cultivation of this field promises rich reward, direct and indirect, and its development will place us a step nearer that state in which all chemical phenomena can be dealt with as other physical phenomena are now dealt with, viz., as subject to mathe matical laws. CHEMISTRY OF ORGANIC COMPOUNDS. INTRODUCTION. ORGANIC CHEMISTRY is the chemistry of the com pounds of carbon. It includes those compounds of carbon which have had their origin in the organs of plants and animals, as well as those which have been produced exterior to the living organism. Most organic compounds are solid, partially crys talline, partially amorphous bodies; many are liquids; only a few are gaseous at ordinary temperatures. All of them are destroyed when heated above their melt ing or boiling point without access of air ; a very large number cannot even be melted nor volatilized without undergoing decomposition. The melting point and boiling point are very characteristic properties for those bodies, which are not readily decomposed at higher temperatures. The difference in the boiling points of organic compounds is very frequently made use of for the purpose of separating them from each other, and preparing them in a pure condition from a mixture (partial distillation). Another very important property of those organic bodies, which are volatile without decomposition, is their specific gravity in the form of gas or vapor (vapor density). Experience has shown, that the molecules (the smallest quantity that can exist in a free condi tion) of the various chemical compounds in the form of gas or vapor possess the same volume, and that this volume is the same as that of two atoms (one molecule) of hydrogen. 2 14 INTRODUCTION. The proportion of the molecular weight to the specific gravity of the vapor (molecular weight divided by the specific gravity) is, therefore, for all compounds the same, and is represented hy the constant number 28.9. This conformity yields an important and frequently the only means of determining the molecular weight of an organic compound. This is obtained by multi plying the specific gravity found by the number 28.9. Carbon is the characterizing element of all organic compounds. In most of these compounds it is in com bination with hydrogen and oxygen, in very many together with nitrogen, sulphur, etc. Furthermore, nearly all other elements can be made constituents of carbon compounds. The fact that so great a number and variety of carbon compounds exist is principally due to the tendency, possessed by the atoms of carbon more than by the atoms of any other element, to unite with each other in chains. Carbon is tetravalent in all its compounds. "When two or more carbon atoms unite with each other, a portion of the affinities of each atom is used in hold ing the atoms together, so that two atoms of carbon have always less than eight free affinities, three always less than twelve. In most cases the union of several atoms of carbon takes place in such a manner that each of them loses one of its four affinities. Hence, two atoms of carbon have six, three atoms of carbon eight, or in general terms x carbon atoms have 2#-f 2 free affinities. The valence of any group of atoms containing carbon may be found by subtracting the sum of the affinities of the other atoms present from the affinities of the carbon atoms. The group methyl CIP must be mono- valent, inasmuch as three of the four affinities of the carbon atom are saturated by the affinities of the three monovalent hydrogen atoms. Carbonic oxide CO must be bivalent, because but two of the four affini ties of the carbon atom are saturated by the bivalent oxygen atom. A similar reflection shows us that ethy- lene C2H4 must be bivalent, that acetylene C2IP must INTRODUCTION". 15 be tetravalent, for in the first case four of the six affini ties of the two carbon atoms are saturated by hydrogen, in the latter only two. Compounds, in which all the affinities of the carbon atoms thus united are saturated by other elements, are called saturated ; compounds which possess free affini ties, non-saturated. Experience has shown that only such non-saturated carbon compounds can exist in an isolated condition, in which two, four, or in general terms an even num ber of affinities, are unsaturated. Atomic groups, in which an odd number of affinities are unsaturated, cannot be isolated. It is, however, questionable whether, with the excep tion of carbonic oxide CO, non-saturated compounds of carbon are really capable of existence. In the so- called non-saturated compounds the carbon atoms are probably united with each other with more than one affinity. Ethylene C2H4 may be regarded as the satu rated compound of a group of two carbon atoms, which are united with each other by means of two affinities, ( CII2 as •< || It is not positive proof of the contrary ( CH2. that this body conducts itself in most reactions as a non-saturated compound, and, for instance, unites with the greatest ease with two atoms of a monovalent element or monovalent group, as in this reaction the double union of the carbon atoms can be broken up and the simple union, quite sufficing for the suste nance of the atoms in their position, re-established. According to this view the carbon atoms in acetylene C2II2 must be united with each other by means of three of their free affinities each. In a large number of compounds, especially the so- called aromatic bodies, we are compelled to admit that the union of the carbon atoms takes place in a manner different from that mentioned above ; that, for the purpose of holding together the single atoms of carbon, more than one of the affinities of each of the .carbon atoms is employed. Benzol C6IP, for instance, accord- 16 INTRODUCTION. ing to the above method of consideration, should have eight free affinities ; in most reactions, however, it conducts itself as a saturated compound. It is frequently the case that two organic bodies contain the same elements in the same proportion by weight, and still have entirely different physical and chemical properties. In general such bodies are called isomeric. For this relation there may be two different causes, viz. :— 1. A dissimilarity of constitution, i. c., a dissimi larity in the method of grouping or joining of the atoms in the two bodies, as, for instance, in ethyl for mate, methyl acetate, and in propionic acid. All three of these compounds have the formula C3II602. In ethyl formate, however, the atoms are grouped together according to the formula CHO.O.C2!!5, or further reduced CHO.O. CIP.CIP, whereas in methyl ace tate the method of grouping is C3IPO.O.CIP or CIP.CO.O.CIP, and in propionic acid C3IF.O.OH or CIP.CIP.CO.OH. Ammonium cyanate CKO.NH4 and ( NIP urea CO \ \\ bear a similar relation to each ( NH2 other. In the latter case the change in the arrange ment of the atoms from the first manner of grouping to the second takes place spontaneously at the ordinary temperature. Such bodies are called metameric or isomeric in the narrower application of the word. Or, 2. A different molecular weight, as, for instance, acetic aldehyde and butyric acid, which both contain the same percentages of their constituents. The mole cular weight of aldehyde C2II40 is, however, only half as large as that of butyric acid C4H802. According to the same principle acetic acid C2H402, and grape- sugar C6H1206, acetylene C2H2, and benzol C6H6, and many other compounds, are isomeric. Such bodies are called ^polymeric. Compounds which contain the same elements in the same proportions by weight, have the same molecular INTRODUCTION. 17 weight, and show no essentially different chemical pro perties, and yet conduct themselves somewhat differ ently in connection with certain physical properties, especially in the action on polarized light, are said to be physically isoineric. By the expression homologous bodies, are understood such bodies as conduct themselves in their chemical properties in a similar manner, and differ in their com position by the group CH2, or a multiple of it. We are, for instance, acquainted with a series of compounds which, in their conduct, show the greatest similarity to ordinary alcohol, and of which each succeeding member differs in its composition from the preceding by the group CH2, as may be seen in the following schedule : — CH40 .... Wood-spirits, methyl alcohol, C2H60 .... Spirits of wine, ethyl alcohol, C3H80 .... Propyl alcohol, C4H100 .... Butyl alcohol, C5H120 .... Fusel-oil, amyl alcohol, etc. Another series, of which acetic acid is the principal representative, runs parallel to this : — CH202 Formic acid, C2IF02 Acetic acid, C3H602 Propionic acid, C4H802 Butyric acid, C5H1002 Valeric acid, etc. For several of these homologous series, as, for instance, for the two mentioned, experience has shown that the following law exists : The boiling point of a compound is 19-20° higher if it contains CH2 more than another member of the series. The boiling point of ethyl alcohol is, for instance, 78°; that of normal amyl alcohol, which differs from ethyl alcohol by 3 x CH2, should, according to this law, be 3 x 19° higher. The observed boiling point is 137°. In connection with other homologous series, a simi lar conformity is observed, but the difference in the boiling points effected by the addition of every CH2 is not the same. With the hydrocarbons, which are 18 INTRODUCTION. homologous with benzol CftHft, viz.: toluol C7H8, xylol CSH10, and cumol C9H12, for instance, the difference is 28-29°. This conformity is, however, only observed in the case of those bodies which, being homologous according to their empirical composition, are also of an analogous constitution. Conditions dependent upon isomerism can at times entirely withdraw it from observation. While with ethyl alcohol C2HC0, boiling point 78°, normal propyl alcohol, boiling point 97-98°, normal butyl alcohol, boiling point 115-116°, complete regularity takes place, we observe no regularity in comparing the three following dissimilarly constituted alcohols with each other: — • Ethyl alcohol .... C2II60 boiling point 78°, Isopropyl alcohol . . . C3IIrtO boiling point 85°, Tertiary butyl alcohol . C4IIll)0 boiling point 82°. Organic bodies undergo the most varied changes when subjected to the action of high heat. Frequently the action is such that hydrogen and oxygen are removed from the body in the form of water, or car bon and oxygen in the form of carbonic acid, and the other elements of the compound remain united as a new organic body ; for instance: — C4H6O = C4II403 + IPO Succinic acid. Succiaic anhydride. (C2H302)2Ca <= C3IPO + C03Ca Calcium acetate. Acetone. Calcium carbonate. Or one organic body is separated into two new ones under the influence of heat, or there is formed at the same time a larger number of new organic compounds, which, in their turn, are often destroyed at the moment of their formation, thus giving rise to a complicated mixture of products, generally ending in leaving behind a residue of carbon. These products are different, according as the heat is more or less strong, slower or more rapid. The products of decomposition of bodies free of nitrogen are frequently acid, from the forma- INTRODUCTION. 19 tion of acetic acid; of those which contain nitrogen, they are mostly alkaline, from the formation of ammonia and other bases. Many organic substances, especially such as contain nitrogen, are decomposed when exposed to the influ ence of air and water at ordinary temperatures, their elements being rearranged during the process to form simpler substances. This kind of decomposition is called putrefaction. Putrefaction occurs only under certain conditions. It can only take place in the pre sence of water, and access of atmospheric air is neces sary to its commencement. Once begun, however, it continues without access of air. Everywhere in the air are present microscopical germs of vegetable and animal organisms. "When these fall on a soil favor able to their growth they are developed quickly, they multiply with great rapidity, and in consequence of the vital process and the dying off of these organisms, that species of decomposition of organic compounds takes place which is called putrefaction. The air loses its power to start the process of putrefaction when pre viously passed through a strongly heated tube, or a dense cotton stopper, or even only through a tube which has a large number of curves, as by these means the germs, which are present in the atmosphere, are either destroyed or held back. Further, putrefaction occurs only within certain limits of temperature, most readily between 20° and 30°. Below 0° and above 100° it does not take place. If the oxygen of the air takes part in the decompo sition, and thus a simultaneous oxidation takes place, the decomposition is called decay. The last products of decaying organic substances are water, carbonic acid, and ammonia. A phenomenon very similar to putrefaction is fer mentation. This will be treated of more in detail in connection with alcohol. Organic compounds can be changed in a variety of ways under the influence of many inorganic bodies. Free oxygen acts on but a very few organic bodies at the ordinary temperature ; it acts, however, more 20 INTRODUCTION. energetically in statu nascendi, or in the presence of certain substances, particularly of spongy platinum. When it acts at all, it is either added directly to the compound, or the hydrogen contained in the com pound is oxidized to form water, or both of these changes take place together. At times a more mate rial decomposition takes place. At a red heat, all or ganic substances burn in oxygen, forming carbonic acid, water, and nitrogen. Hydrogen, especially in statu nascendi, likewise trans forms very many organic compounds, either a direct addition of hydrogen, or an elimination of oxygen, or both at the same time taking place. In most cases in which hydrogen acts upon compounds containing chlo rine, bromine, or iodine, these elements are eliminated and replaced by hydrogen. Hydriodic acid and sul phuretted hydrogen act similarly to free hydrogen. At times, bodies containing iodine or sulphur result, but generally the iodine or sulphur is set free, and merely the hydrogen acts. Chlorine and bromine act very energetically upon organic bodies. Non-saturated organic compounds (those in which the carbon atoms are united by means of more than one of each of their four affinities), usu ally combine directly with these elements, and take up as many atoms as are sufficient to produce saturated bodies, the simple union of the carbon atoms being re established. In this way are formed from ethylene, CH2 CH'Cl C2H4 = || , the compounds C2H4CP = I and CH2 CIPC1 CH2Br C2H4Br2= I . With saturated compounds, how- CH2Br ever, the action generally takes place in such a man ner, that a certain number of atoms of hydrogen are eliminated, and replaced in the compound by an equal number of atoms of chlorine or bromine ; for instance:— C2H402 + 201 = CWCIO2 + C1H Acetic acid. Chloracetic acid. INTRODUCTION. 21 This kind of action is called substitution, and the newly -formed body a substitution-product of the ori ginal body. Iodine, in other respects so similar to chlorine and bromine, when alone acts never, or at least only exceptionally, in the manner described, as hydriodic acid is formed at the same time, and this has the tendency to cause a reverse substitution, i.e. a displacement of the iodine in organic compounds, con taining iodine, by hydrogen. If, however, a body be added with the iodine which has the property of removing the hydriodic acid as soon as formed, for instance iodic acid, substitution-products containing iodine can in many cases be obtained. An addition of small quantities of iodine aids materially the substi tuting action of chlorine upon organic compounds. In the presence of water, chlorine sometimes acts as an oxidizing agent. Organic compounds containing chlo rine likewise result, as a rule, by the action of hydro chloric acid or the chlorine compounds of phosphorus. Concentrated nitric acid acts in most cases in a simi lar manner to chlorine. A certain number of hydro gen atoms is eliminated, and for each of them the monovalent group NO2 (hyponitric acid) enters the compound ; for example : — C6H6 -f E"02.OH = C6H5.K02 + IPO. Benzol. Nitrobeuzol. Compounds resulting in this way are called nitro- compounds, or nitro-substitution-products. The forma tion of these bodies is very much aided by mixing the concentrated nitric acid with twice its volume of con centrated sulphuric acid. Nitric acid acts frequently, especially by continued boiling, only as an oxidizing agent. Concentrated sulphuric acid acts upon a great many organic bodies similarly to nitric acid. One or more hydrogen atoms of the compound are displaced by the monovalent group SO2. OH ; for example : — C6H6 + SO2 =C6H5.S02.OH + H20. Benzol. SulpUobenzolic acid. 22 INTRODUCTION. Bodies formed in this way are called sulpho-com- pounds, or, as they all possess the character of acids, sulpho-adds. Frequently, however, the action of concentrated sul phuric acid consists in the elimination of the elements of water from organic compounds, the latter being completely destroyed (carbonized), or converted into others containing less hydrogen and oxygen ; for ex ample: — C2H5.OH = C2H4 -f H20. Alcohol. Ethylene. When ammonia acts upon organic compounds, espe cially those which contain chlorine, bromine, or iodine, bodies containing nitrogen are formed as a rule, the halogens being eliminated and replaced by the group NIP ; for example : — C2IPC10 + 2NIP = C2IP(NIP)02 + NIPC1. Chloracetic acid. Arnidoacetic acid. The new compounds which result in this way are called amides. They are also formed by the action of hydrogen in statu nascendi (from tin and hydrochloric acid), or of sulphuretted hydrogen upon nitro-com- pounds, the group NO2 contained in the latter being transformed into NH2; for example: — C6IP.N02 + 6H = C6IP.KEP + 2IPO. Nitrobenzol. Anilin. The elementary composition of organic bodies can be determined with the greatest exactitude. The ana lysis of the ordinary ones consists in the oxidation of the carbon to carbonic acid, and of the hydrogen to water, and the calculation, from the quantity of these products of combustion, of the quantity of carbon and hydrogen in the compound. Nitrogen is separated as nitrogen and measured, or it is transformed into am monia. Oxygen is calculated indirectly by loss. The most common method of estimating carbon and hydrogen consists in submitting an accurately weighed quantity of the substance to be analyzed, with a large INTRODU-CTION. 23 excess of perfectly dry copper oxide or lead chromate, to a red heat, finally employing a current of pure oxy gen. The water formed during the process is taken up by a tube filled with calcium chloride, the carbonic acid by a small apparatus which is filled with a solu tion of potassium hydroxide, and, to secure absolute safety, is joined to a small tube containing pieces of solid potassium hydroxide. The gain in weight of these three pieces shows the quantity of water and car bonic acid. The conversion of nitrogen into ammonia is accom plished by heating the body strongly with a large excess of a dry mixture of sodium hydroxide and cal cium hydroxide. The ammonia formed is either taken up by hydrochloric acid and weighed as ammonium chloroplatinate, or by dilute sulphuric acid of a known strength, and the quantity of acid which remains free afterwards estimated by means of a standard test-solu tion of sodium hydroxide. This subtracted from the quantity of acid employed shows how much of the acid has been neutralized by ammonia, from which the quantity formed and the nitrogen contained there in may be easily calculated. Nitrogen is not, however, given off in all cases by heating with soda-lime. This applies especially to such cases in which the nitrogen is in close combination with the oxygen, as for instance in nitro-compounds. In analyzing such substances, the nitrogen is set free by heating the substance with an excess of finely pow dered copper oxide, and passing the escaping gases over metallic copper for the purpose of destroying^the oxides of nitrogen. This operation is carried out in a long tube, from which the air has been previously com pletely removed by means of carbonic acid. The mix ture of carbonic acid and nitrogen is collected in a graduated tube over mercury, the carbonic acid ab sorbed by caustic potassa, the volume of nitrogen which has remained unabsorbed, measured and its weight calculated according to the formula . 0.001256, _ - 1 + 0.00367* 760 24: INTRODUCTION. in which V represents the volume of gas, t its tem perature, B the pressure under which the gas stands (height of barometer), expressed in millimetres, /the tension of water vapor at the temperature £, and 0.001256 the weight of I cc. of nitrogen at 0°, and 760 mm. pressure. When an organic compound contains chlorine, bro mine, iodine, or sulphur, it must in most cases be tho roughly decomposed, before these can be detected by ordinary reagents and estimated. The estimation of the halogens is accomplished by igniting the substance with pure lime, free from water ; the estimation of sul phur by heating with nitric acid in sealed tubes, or igniting with a mixture of sodium carbonate and po tassium nitrate. Chlorine, bromine, and iodine can in many cases be detected in the ordinary manner, and estimated by previously treating the substance with hydrogen in statu nascendi (from sodium-amalgam and water). As an example of the method of calculating an ele mentary analysis, that of acetic acid may be taken. 0.234 grm. of acetic acid were ignited with copper oxide. The gain in weight of the calcium chloride tube amounted to 0.1405 grm.; that of the potassa bulbs and tube 0.3432 grm. From 0.234 grm. acetic acid were hence produced 0.1405 grm. of water, and 0.3432 grm. carbonic acid, and these contain 0.0156 grm. hydrogen, and 0.0936 grm. carbon. These num bers show 40.00 per cent, of carbon, and 6.67 per cent, of hydrogen. As acetic acid only contains carbon, hydrogen, and oxygen, its composition expressed in percentages is — C = 40.00 per cent. H = 6.67 " 0 = 53.33 " In order to find the atomic proportion from these numbers, we must divide them by the respective atomic weights of the elements. C = 40.00 - 12 = 3.33 H= 6.67- 1 = 6.67 0 = 53.33 16 = 3.33 INTRODUCTION. 25 The elements in acetic acid hence stand to each other in the atomic proportion of 3.33 : 6.67 : 3.33, or, 1:2:1. The chemical formula of the acid could hence be ex pressed by CH20, but, of course, with exactly the same right, we might express it by C2II402, or C6H120°, for all these formulae show the same percentages of the elements. Simply the elementary analysis is not suffi cient to determine which of these formulae is the cor rect one ; an estimation of the molecular weight must be united with it. With an acid this is simple if we know its basicity. We know that, for the purpose of forming a neutral salt, one molecule of acetic acid gives up one atom of hydrogen, and takes up in its place one atom of a monovalent metal. Hence, in order to find the molecular weight of acetic acid, we need only determine the amount of metal contained in one of its salts. 0.412 grrn. silver acetate on being ignited leave a residue of 0.2665 grm. metallic silver. This represents 64.7 per cent. In 100 parts of silver acetate are hence contained Organic substance .... 35.3 Silver 64.7 The molecular weight of the organic substance in silver acetate can now be found by means of the fol lowing proportion :— 64.7: 35.3 :: 108*:s Eesult = 59 Free acetic acid contains one atom more of hydro gen, therefore the molecular weight of the free acid is 60. The simplest formula, agreeing with the results of the analysis, has the molecular weight 30. This must hence be doubled, and the composition must be expressed by the formula C21TO2. When basic bodies are under investigation, a neutral * Atomic weight of silver. 26 INTRODUCTION. salt is also prepared for the estimation of the molecular weight, and from the quantity of acid contained in this salt the molecular weight of the base is calculated in a similar manner. The molecular weight cannot, however, in all cases be determined by this method — only when experiments have shown how many atoms of a monovalent element an acid, or how many molecules of a monobasic acid a base, needs to form a neutral salt. If the substance is volatile without decomposition, the molecular weight can be found more simply by an estimation of the specific gravity of its vapor. The specific gravity of acetic acid vapor, for instance, was found to be 2.08 at 300°. This number, multi plied by the constant number 28.9 (see ante, p. 14), gives as a result for the molecular weight of acetic acid the number 60.1, hence, taken together with the results of the analysis, the formula C2H402. The processes, more intimately connected with the formation of the primitive organic compounds in the living organism of plants and animals, are almost entirely unknown to us. "We only know with cer tainty that all organic material is originally formed in plants, that for this purpose plants make use of the elements of existing compounds particularly of carbonic acid, water, ammonia, and the inorganic acids of nitro gen, and that this process of formation takes place only under the influence of sunlight and of certain inorganic salts, which are absorbed from the soil ; the manner in which this takes place is, however, up to the present, inexplicable. The animal organism, on the other hand, receives its constituents in the food in the form of organic compounds already existing. A great many of the organic compounds occurring in nature can be produced artificially from the elements, but in by far the most cases the conditions and the chemical processes are entirely different from those through the instrumentality of which the formation occurs in nature. I. MARSH GAS DERIVATIVES (FATTY BODIES). FIRST GROUP. A. HYDROCARBONS, Cn H2n+2 (MARSH GAS SERIES). COMPOUNDS consisting merely of carbon and hydro gen are called hydrocarbons. The simplest compound of this kind is marsh gas CH4, in which the four affin ities of the carbon are saturated with four hydrogen atoms. Marsh gas is the first member of an homologous series of compounds, which have for their general for mula CnH2w+2. All facts as yet known justify the conclusion that each of the four hydrogen atoms in marsh gas has exactly the same value, and that, as far as the properties of compounds are concerned, which are produced by the displacement of hydrogen atoms in marsh gas by means of other elements or groups of atoms, it is immaterial which of the four hydrogen atoms are displaced. Assuming this to be the case, we see that for the first three members of this series, CH4, C2H6, and C3II8, but one manner of constitution is possible, viz.: CH4,— CH3.CH3andCH3.CH2.CH3. There can hence exist only one modification of each of these three hydrocarbons. Isomeric compounds are not pos sible. Of the fourth member, C4H10, there are two different modifications possible: CH3.CH2.CII2.CH3and CH3.CH 3; of the fifth member, C5H12, there are three modifications possible ; of the sixth member, five, etc. 28 HYDROCARBONS. 1. Marsh Gas (Fire Damp, Methyl Hydride), CH4. Occurrence and Formation. Together with the homo logous hydrocarbons, and mixed with carbonic acid and nitrogen, it issues in many localities from the earth ; frequently collects in mines and coal-beds. Is formed in the process of putrefaction under water and in the destructive distillation of a great many organic bodies, and is hence contained in ordinary coal gas. It is further formed when a mixture of the vapor of car bon bisulphide with sulphydric acid is conducted over ignited metals ; from ethylene at a red heat ; and is most readily obtained in a pure state by heating 2 parts of crystallized sodium acetate with 2 parts of potassium hydroxide and 3 parts of lime. Properties. Inodorous, inflammable gas, insoluble in water, of specific gravity 0.559. Mixed with oxygen or air it explodes with great violence when ignited ; also when mixed with chlorine it forms a gas, which explodes violently when exposed to direct sunlight. In dispersed sunlight chlorine acts upon it in another manner, displacing its hydrogen and forming the com pounds, CIPCl, CH2C12, CHOP and CC14 (treated of in connection with methyl alcohol). 2. Ethyl Hydride, C2H6. Is contained in a state of -solution in crude petroleum. Is produced from the first substitution-products of marsh gas (methyl chloride CIPCl, methyl iodide CIPI) by the action of sodium or zinc ; by the decom- rition of a concentrated solution of sodium acetate means of an electrical current ; by the action of water on zinc ethyl, or by heating ethyl iodide with water and zinc in sealed tubes to 180°. Colorless, almost inodorous gas. Burns with a slightly lumi nous flame. Is but slightly absorbed by water, more by alcohol. Chlorine displaces its hydrogen, forming successively the compounds C2IPC1, C2H4CP, C2IPCP, C2!!^!4, C2IICP, and C2CP (see Ethyl Chloride). HYDROCARBONS. 29 3. Propyl Hydride ( Trityl Hydride], C3H8. In petroleum. Is formed like ethyl hydride, and can be obtained most readily, though not free from hydrogen, by the action of hydrogen in statu nascendi (from zinc and hydrochloric acid) on propyl iodide or isopropyl iodide. Colorless gas ; liquid below — 17°. 10 4. Butyl Hydride (Tetryl Hydride), C4H In petroleum. The normal hydrocarbon diethyl CH3.CH2.CH2.CH3 is produced by the action of zinc or sodium on ethyl iodide. Colorless gas ; liquid at +1°. Pseudobutyl hydride (Trimethylformene), CH3. CH QTT3 is isomeric with diethyl. It is obtained from the corresponding iodide (see tertiary butyl alco hol) by the action of zinc and water. Colorless gas ; condensable at — 17°. 5. Amyl Hydride, C5H12. The normal hydrocarbon CH3.CH2.CH2.CH2.CH3 is contained in petroleum, together with the following compound ; also in products of distillation of cannel and boghead coal.— Mobile liquid ; boils at 37°— 39°. / PTT3 The hydrocarbon CH3.CH2.CH j ^3 is contained in large quantity in American petroleum. It is formed by heating the iodide C5H]1I from ordinary amyl alcohol, with zinc and water to 142°; by distil ling ordinary amyl alcohol over zinc chloride. (In both reactions other hydrocarbons are formed at the same time, particularly amy lene C5H10.) Colorless liquid ; boils at 30° ; does not solidify at — 24° ; specific gravity 0.626. The third hydrocarbon (tetramethylformene) CIP 1 ^ I CH3 *s Pr°duce(l by the action of zinc methyl on the iodide obtained from tertiary butyl 3* 30 HYDROCARBONS. alcohol. — Colorless, mobile liquid. Boiling point 9°.5. Solidifies at — 20°, forming crystals, which resemble sublimed sal-ammoniac. The higher members of this series form the principal ingredients of American petroleum and of the oils (solar oil, photogene) obtained by the distillation of peat, bituminous slates, lignite and certain varieties of anthracite. The hydrocarbons, which are obtained from these sources by means of partial distillation, are mostly mixtures of isomeric compounds. By means of transforming these mixtures into the corresponding alcohols and oxidizing the latter, the chemical consti tution of the principal ingredients has been discovered. The accompanying hydrocarbons, however, which occur in but very small quantity, are not well investigated. Others have been prepared artificially by means of reactions, that permit of a conclusion in regard to their constitution. 6. Hexyl Hydride (Hexan), C6II14. There are three methods known for the preparation of this hydrocarbon ; by partial distillation of Ameri can petroleum ; by the action of tin and hydrochloric acid on the iodide of secondary butyl alcohol ; by the ac tion of sodium on an ethereal solution of propyl iodide. The first product boils at 70° ; the second and third at 71.5°. The two latter have the specific gravity 0.663. These products are probably all identical and represent the normal hydrocarbon CH3.CH2.CH2.CH2.CII2.CH3. Ethyl-isobutyl, C6H14 = CIP.CIP.CH2.CH By the action of sodium in a mixture of ethyl iodide and isobutyl iodide. Boiling point, 62°; specific gravity, 0.7011. PTTs } ( PTT3 Di-isopropyl, OTI" = £|a [ CH. OH J £g,; By the action of sodium on an ethereal solution of isopropyl iodide. Boiling point, 58° ; specific gravity, 0.67. HYDROCARBONS. 31 7. Normal Heptyl Hydride (Heptan), C7II16 = CH3.CH2. CIF.CIP.CIP.CH'.CII3. Is contained in the light oil of cannel coal-tar and in large quantity in petroleum. Can be obtained from these sources by partial distillation. Boiling point, 99° ; specific gravity, 0.699. Ethyl-amyl, C7H16=CIP.CH2.CH2.CH2.CH. By the decomposition of a mixture of ethyl and amyl iodides (the latter from ordinary amyl alcohol) with sodium. Boiling point, 90.5; specific gravity, 0.6819 at 17°. Dimethyldiethylformene, C7H16 chloride. Boiling point, 86-87°; specific gravity, 0.711 at 0°. 8. Normal Odyl Hydride (Octan),C*Hl* = CIP. CH2. CIP. CIP.CIP.CIP.CIP.CH3. The hydrocarbons obtained by the action of sodium on butyl iodide, from methylhexyl carbinol by reduc tion, from sebasic acid and from octyl alcohol, all appear to be normal octyl hydride. Boiling point, 123-125°; specific gravity at 17°, 0.7032. In regard to the constitution of the remaining dis covered hydrocarbons nothing is as yet known. Boiling point. Specific Gravity. Nonyl hydride, C9II20 . . 136-138° 0.741 Decatyl hydride, C10H22 . . 158-162° 0.757 Undecyl hydride, C11!!24 . . 180-182° 0.766 Lauryl hydride, C12H26 . . 198-200° 0.778 Cocinyl hydride, C13H28 . . 218-220° 0.796 Myristyl hydride, C14IP° . . 236-240° 0.809 Benyl hydride, C15H32 . . 258-262° 0.825 Falrnityl hydride, C16!!34 . . 280° \0 9 32 MONATOMIC ALCOHOLS. Paraffin. The portions of petroleum or of the oils obtained by the distillation of peat, bitumen, etc., which boil above 300°, solidify wholly or partially on cooling, forming, when purified, a colorless, translucent mass, called paraffin. Paraffin is not a distinct chem ical body, but a mixture of several solid hydrocarbons, homologous with marsh gas, which, up to the present, have not been separated. The melting point of com mercial paraffin varies from 45° to 65°. B. MONATOMIC ALCOHOLS, CWH2W+20. A large class of organic compounds has been desig nated by the name alcohols. These are formed by the displacement of one or more atoms of hydrogen in the hydrocarbons by the same number of hydroxyl atoms (OH). These bodies possess the common property of readily taking up acid radicles in the place of the hy drogen of the hydroxyl group, thus forming compounds, analogous to inorganic salts, called ethers. According to the number of hydroxyl atoms con tained in tfiem, alcohols are divided into monatomic, diatomic, triatomic, etc. The monatomic alcohols, which are derived from the hydrocarbons of the marsh-gas series, have the general formula OH2"+20 or C^H'^.OH. Only one mona tomic alcohol can be derived from marsh gas and ethyl hydride each. These two alcohols have the constitu tional formulse CH3.OH, and CIP.CIP.OII. With the third member C3IPO, however, the case is different. Here, according as in the hydrocarbon GH3.CH2.CH3 an atom of hydrogen of one of the terminal carbon atoms, or of the central one is displaced by OH, two isomeric alcohols must result, which have respectively the constitutional formula CIP. CIP.CIP.OII, and CIP.CH.OH.CH3. A similar method of consideration shows that four isomeric modifications of the fourth member C4H100 are possible, of the fifth, eight, etc. The conduct of the alcohols in a chemical point of METHYL ALCOHOL. 33 view, especially under the influence of oxidizing agents, is dependent upon their constitution. They are divided into primary, secondary, and tertiary alcohols. Primary alcohols contain the group CH2.OH. Un der the influence of oxidizing agents they are at first converted into aldehydes by the transformation of the group CH2.OH into CHO, and then, by further oxida tion of the group CHO to COOH, into acids contain ing the same number of carbon atoms. Secondary alcohols contain the group CH.OH. "When oxidized, they are at first converted into ace tones, the group CH.OH being changed to CO. These acetones, when further oxidized, are resolved into simpler compounds, yielding acids with a smaller num ber of carbon atoms. Tertiary alcohols contain the group C.OH. They are decomposed by oxidation without previous forma tion of aldehydes or acetones, and yield acids with a smaller number of carbon atoms. Normal alcohols are the primary alcohols of nor mal hydrocarbons. 1. Methyl Alcohol (Wood Spirit), CH40=CH3.OII. Formation and Occurrence. By the destructive dis tillation of cellulose, hence contained in wood vine gar obtained by distilling wood. The volatile oil of Gaultheria procumbens is the methyl ether of salicylic acid. Pure methyl alcohol may be obtained by distil ling this oil with a solution of potassa. Preparation. From wood vinegar by distilling with calcium hydroxide ; only practicable on a large scale. The volatile distillate which at first goes over (wood spirit) contains the methyl alcohol, still, how ever, containing impurities in the form of other vola tile products. After distilling again over quicklime, it is placed in contact with calcium chloride, and the whole distilled on a water bath, by which process the volatile impurities distil over, and the methyl alcohol remains behind in combination with calcium chloride. By mixing with water and distilling, these are sepa- 34 METHYL ALCOHOL. rated, and by means of repeated distillations over quicklime, the alcohol is purified. Or, volatile methyl oxalate is prepared from com mercial wood spirit by mixing the wood spirit gradu ally with its own weight of concentrated sulphuric acid and distilling the brown mixture over two parts by weight of finely powdered acid potassium oxalate. At first a combustible liquid passes over, which, on be ing evaporated gently, leaves the oxalic ether behind, then the principal part of the ether passes over and congeals in a crystalline form. By pressing and allow ing it to stand over sulphuric acid, or by continued fusing, it is obtained pure. By boiling with water or caustic potassa, the alcohol is obtained from the ether. Properties. A limpid, colorless liquid, of a pecu liar odor, similar to that of spirits of wine, and a pungent taste; specific gravity, 0.798; boiling point, 60-65°; combustible; miscible with water, alcohol, and ether. Combines with anhydrous baryta, and with calcium chloride, forming crystalline compounds which are easily decomposed by water. Potassium and sodium are dissolved by it, the action being accompanied by an evolution of hydrogen, and the formation of potassium and sodium methylate, CH3KO, readily crystallizing compounds. DERIVATIVES OF METHYL ALCOHOL. These are perfectly analogous to the derivatives of ethyl alcohol, and are formed from methyl alcohol in the same manner as those from ethyl alcohol. As the corresponding ethyl compounds are of greater im portance and generally better investigated, they will be treated of more in detail in the following section, and only a few of the more important methyl com pounds will be here described. Methyl chloride, CIPCl. Is formed by the action of chlorine on marsh gas, and of hydrochloric acid on methyl alcohol. Colorless gas, with an ethereal odor ; condensable at — 22°. DERIVATIVES OF METHYL ALCOHOL. 35 Methylene chloride, CH2C12. Is produced by the action of chlorine on methyl chloride or methylene iodide, and by treating chloroform with zinc and am monia. — Colorless liquid of specific gravity 1.36 at 0° ; boiling point, 40° ; insoluble in water. Chloroform, CHC13. Produced by the action of chlorine on the preceding compounds, and in many other ways, particularly by the action of calcium hypo- chlorite on alcohol, wood spirit, acetone, and several other organic bodies. It is prepared most expediently by distilling 3 parts of alcohol, 100 parts of water, and 50 parts of calcium hypochlorite. It is purified by shaking successively with water and sulphuric acid and subsequent distillation. Colorless liquid, not miscible with water, with a sweetish ethereal taste and odor; specific gravity, 1.48. Boiling point, 62° ; not inflammable ; dissolves iodine, the solution taking a bluish-purple color. Its vapor on being inhaled causes unconsciousness and insensi bility. With an alcoholic solution of potassa it forms potassium chloride and potassium formate ; with sodium ethylate, a colorless ether, orthoformic ether CH(O.C2H5)3, which boils at 146°. Heated with aque ous or alcoholic ammonia to 180° it yields ammonium cyanide and chloride. If potassa is present this decom position takes place at 100°. Carbon tetrachloride, CC14. Is obtained most readily by the action of chlorine on chloroform in di rect sunlight. — Colorless liquid, of a pleasant odor, boil ing at 77° ; specific gravity, 1.6 ; below —25°, solid and crystalline; acts upon the organism analogously ^ to chloroform; yields potassium carbonate and chloride when heated with an alcoholic solution of potassa. Methyl bromide, CH3Br. Is obtained by saturat ing methyl alcohol with hydrobromic acid, or better, by~ mixing 6 parts of methyl alcohol with 1 part of amorphous phosphorus, carefully adding 6 parts of bromine, at the same time cooling the mixture, and 36 DERIVATIVES OF METHYL ALCOHOL. afterward gently heating the whole. — Liquid, of a leeky odor, boiling at 13° ; specific gravity, 1.66. Brompfonn, CHBr3. Is produced by the action of bromine on a solution of potassa in wood spirit. — Colorless liquid, boiling at 150-152°; congealing at — 9° ; of specific gravity 2.9. Carbon tetrabrpmide, CBr4. Is obtained by heat ing carbon bisulphide or bromoform with bromine in the presence of iodine or antimony bromide (SbBr3) in sealed tubes to 150-160°. — Colorless, lustrous plates. Fusing point, 91°. Insoluble in water, easily soluble in alcohol and ether. It is decomposed when heated in an alcoholic solution. Methyl iodide, CIPI. Is prepared in the same manner as the bromide. — Colorless liquid of an ethereal odor. Boils at 43° ; specific gravity, 2.2. Methylene iodide, CH2!3. Is produced by the action of sodium ethylate on iodoform, by heating iodoform alone or with iodine, and can be prepared most readily by heating chloroform or iodoform for several hours with very concentrated hydriodic acid to 125-130°. — Yellow liquid, of specific gravity 3.34. Congeals at a low temperature, forming lustrous plates, which fuse at +4°. Boils at 180°, undergoing partial decomposition. Iodoform, CHI3. Is formed, when iodine, together with caustic alkalies, acts on alcohol, aldehyde, acetone, and a great many other organic bodies. — Yellow scales, which fuse at 119°. Can be distilled with the vapors of water without undergoing decomposition. Readily soluble in alcohol and ether. Nitroform, CH(]TO2)3. The ammonium compound of this body C(NH4) (NO2)3, a yellow, crystalline sub stance, soluble in water and alcohol, is produced when trinitroacetonitrile (see fulminuric acid) is treated with DERIVATIVES OF METHYL ALCOHOL. 37 water or alcohol. By agitating with sulphuric acid, free nitroforrn is obtained from this. — Colorless, cubical crystals. 'Fusing point, 15°; easily soluble in water. Strong acid. When rapidly heated it is decomposed with explosion. Nitrocarbon, C(ISr02)4. Is produced from nitro- form by heating with a mixture of concentrated sul phuric acid and fuming nitric acid. — White crystalline mass, fusing at about 13°, and boiling at 126°. Not inflammable. Insoluble in water; soluble in alcohol and ether. Nitrochloroform (Chloropicrm), C(ITO2)C13. Is formed when alcohol or wood-spirit is distilled with sodium chloride, saltpetre and sulphuric acid, by the distillation of a number of nitro-compounds with cal cium hypochlorite or hydrochloric acid and potas sium chlorate. Further, by heating chloroform with nitric acid (containing hyponitric acid) in sealed tubes to 90-100° for 12 hours. Is most readily prepared by adding 45 parts of calcium hypochlorite, mixed with water so as to form a thick pasty mass, to a saturated aqueous solution of 4J parts of picric acid at 30°. The reaction begins immediately and spontaneously, and the greater part of the chloro- picrin distils over. — Colorless oil, not combustible; boiling at 112° ; specific gravity, 1.66. When heated with acetic acid and iron filings, it yields methylamine; heated with sodium ethylate, it yields orthocarbonic ether C(O.C2H5)4, a liquid which boils at 158-159°. A compound very similar to chloroform, Marignac's oil C(N02)2C12, is produced by the distillation of naph thalene chloride with nitric acid. — Colorless liquid; explodes when heated alone ; can be distilled, however, with vapors of water. Nitrobromoform (Bromopicrin), C(N02)Br3. Is prepared, like chloropicrin, by distilling picric acid with calcium hypobromite (lime-water containing bro mine). — Colorless, prismatic crystals, which melt at 4 88 DERIVATIVES OF METHYL ALCOHOL. 10°, forming a liquid of specific gravity 2.8. Can only be distilled in a vacuum without decomposition. Acetonitrile (Methyl cyanide), Is obtained by gently heating acetamide with phos phoric anhydride or phosphorus pentasulphide ; and by distilling a mixture of potassium methylsulphate with potassium cyanide. — Colorless liquid, boiling at 82°. Combines with two atoms of bromine, with hydrobromic and hydriodie acids, and with several metallic chlorides. Is decomposed by boiling with potassa, yielding ammonia and potassium acetate, and gives, with hydrogen in statu nascendi, ethylamine. For the substitution-products of acetonitrile, see ful- minic acid. Methyl carbylamine, CZIPE"=CH3.]STC (isomeric with acetonitrile). Is formed by the action of methyla- mine on chloroform in the presence of potassa; by heating one molecule of methyl iodide with two mole cules of silver cyanide to 130-140°, and distilling the resulting crystalline compound C2IKN" -f AgGN" with half its weight of potassium cyanide and a little water. Is formed in small quantity, together with acetonitrile, by the distillation of a mixture of potas sium methylsulphate with potassium cyanide. — Color less liquid, possessing an exceedingly strong odor. Soluble in ten parts of water. Boiling point, 58-59°. Combines with thoroughly dried hydrochloric acid gas; is decomposed by dilute hydrochloric acid, how ever, and by being heated with water to 180°, yielding methylamine and formic acid. Methylether, (CH3)20, is formed, but with difficulty, by distilling methyl alcohol with four times its weight of concentrated sulphuric acid. — Colorless gas, of ethereal odor, congealing at — 21°; combustible, ex ploding violently with chlorine; specific gravity, 1.617. Water absorbs thirty-seven times its volume of the gas. Combines with sulphuric anhydride, forming methyl sulphate. , DERIVATIVES OF METHYL ALCOHOL. 39 Methyl nitrate, CIRO.NO2. Results in small quantity when a mixture of wood-spirit with salt petre and sulphuric acid is subjected to distillation. — Colorless liquid, boiling at 66°. Methyl sulphate, (CH3.0)2S02, is formed by distilling wood-spirit with eight to ten times its weight of con centrated sulphuric acid. — Colorless liquid, possessing the odor of garlic, of specific gravity 1.324; boiling point, 188°. Is decomposed by heating with water, yielding methyl alcohol and methylsulphuric acid. Methylsulphuric acid, CH3.0. S02.OII, is formed by mixing one part of methyl alcohol with two parts of concentrated sulphuric acid. Crystallizes in color less needles, when carefully evaporated ; forms easily soluble salts with bases. The potassium salt, crystal lizing in deliquescent plates, yields by distillation methyl sulphate. Methylsulphurous acid (sulphomethylic acid), CH3.S02.OH. The potassium salt, CH3.S02.OK, is pro duced by heating methyl iodide with neutral potas sium sulphite to 100-120°. The free acid is a syrupy liquid. Trichlormethylsulphurous acid, CC13.S02.OH. The barium salt, (CCP.S03)2Ba, is obtained by digest- Ing trichlomethyl sulphochloride with baryta water. The acid, set free from this salt by means of sulphuric acid, crystallizes in small, colorless, very deliquescent prisms. Very strong acid. Trichlormethyl sulphochloride, CC13.S02C1. Is formed by the action of hydrochloric acid and black oxide of manganese, or of hydrochloric acid and potas sium bichromate on carbon bisulphide. An addition of nitric acid aids the reaction. — Colorless, crystalline mass ; insoluble in water ; easily soluble in alcohol and ether. Melting-point, 135° ; boiling-point, 170° ; also volatile with the vapor of water without t decomposi tion. ^f*~~ 40 DERIVATIVES OF METHYL ALCOHOL. Methylamine, CHAlsTIP. Gas, of ammoniacal odor ; liquid below 0° ; water absorbs more than 1000 times its volume of the gas. The solution is strongly alka line, smells like ammonia, and acts on solutions of metallic salts like ammonia, but does not, however, re- dissolve the precipitated hydroxides of nickel, cobalt, and cadmium, when added in excess. It forms neu tral, easily soluble salts with acids. Dimethylamine, (CH3)2HK. Inflammable gas ; li quid below -f 8a; strongly alkaline. Trimethylamine, (CH3)3]Sr. Is formed in Chenopo- dium vulvaria, in the blossoms of Crat&gus oxyacantha, and several other plants; is contained in herring brine, in liver oil, coal-tar oil, and bone oil. At ordinary temperatures it is gaseous; below 4-9°, a clear liquid, of a peculiar odor somewhat resembling that of ammo nia ; in water and alcohol very easily soluble. Strong base. The compounds of methyl with phosphorus and the metals bear the strongest resemblance to the cor responding ethyl compounds, which will be treated of later; hence, only the methyl compounds of arsenic, which are better investigated than the ethyl com pounds, will be here treated of. Arsendimethyl (Cacodyl), tilling dry potassium acetate with arsenious acid is obtained a liquid (alkarsin), which contains cacodyl together with the products of its oxidation. Treated with concentrated hydrochloric acid, this liquid yields cacodyl chloride, and this chloride treated with zinc filings in an atmosphere of carbonic anhydride at 100° yields pure cacodyl, the zinc chloride having been dissolved out with water. — Clear liquid, of a disgust ing odor ; congeals at — 6° ; boils at 170° ; but slightly soluble in water, easily soluble in alcohol and ether. In contact with the air it gives off fumes and takes DERIVATIVES OF METHYL ALCOHOL. 41 fire ; its vapor is very poisonous ; it combines directly with oxygen, sulphur, and chlorine. Cacodyl chloride, (CH3)2AsCl. Liquid, boiling at 100° ; heavier than water ; unites with metallic chlo rides. The iodide and bromide are similar to the chlo ride. The cyanide forms large prisms, fusing at 30°, boiling at 140°. Exceedingly poisonous. Cacodyl oxide, [(CH3)2As]20. Is formed by slow oxidation of cacodyl, simultaneously with cacodylic acid, and can be separated from the latter by distilla tion. Liquid, boiling at 150°, of disagreeable odor. It does not give off fumes in contact with the air, and does not take fire ; is oxidized slowly, however, forming cacodylic acid. It combines with 2HgCl2, yielding a crystalline compound. Cacodyl sulphide, [(CIP)2AspS. By distilling cacodyl chloride with potassium or barium sulphhy- drate. — Colorless liquid, of a disagreeable odor; insolu ble in water, easily soluble in alcohol and ether. Yields cacodyl chloride and hydrosulphuric acid when treated with hydrochloric acid. Cacodyl disulphide, (CH3)4As2S2, is formed by dis solving sulphur in cacodyl or cacodyl sulphide. — Large colorless crystals, fusing at 50° ; not volatile without decomposition. Cacodylic acid, (CH3)2As.OH. Is produced by slow oxidation of cacodyl, and by the action of mer cury oxide on cacodyl under water (or on the crude liquid alkarsin). — Large, colorless, deliquescent prisms, which fuse at 200° ; are inodorous and -not poisonous. Phosphorous acid reduces it, forming cacodyl. Cacodyl trichloride, (CH3)2AsCl3. Is formed by the action of phosphorus pentachloride (under ether) on cacodylic acid, or when chlorine is conducted upon the surface of a solution of cacodyl in carbon bisul- 4* 42 ETHYL ALCOHOL. phide. — Crystallizes in transparent prisms, or large laminae. Heated up to 40-50° it is resolved into me thyl chloride and Arsen-monomethyldichloride,(CH3)AsCl2. This is also formed by the action of dry hydrochloric acid gas on cacodylic acid. — Colorless, heavy liquid, boiling at 133° ; easily soluble in water ; does not give off fumes in contact with the air. It takes up two atoms of chlorine, but the resulting crystalline compound is decomposed even below 0° into methyl chloride and arsenic trichloride. On being treated with hydrosul- phuric acid, it yields crystals of arsen-monomethyl sul phide (CH3)AsS, which fuse at 110°. Arsen-monomethyl oxide, (CH3)AsO. Is formed by the action of potassium carbonate on the dichloride under water. — Crystals fusing at 95° ; not volatile alone without decomposition, readily with vapors of water ; soluble in water, alcohol, and ether. Arsen-monomethylic acid, (CH3)As(OH)2. Is formed when the dichloride is treated under water with silver oxide. — Large crystalline laminse, soluble in water and alcohol ; bibasic acid ; forms crystalline salts. 2. Ethyl Alcohol (Spirits of Wine). C2IPO = CIP.CIP.OJ formation. By the fermentation of sugar. "When the clear juice of a plant containing sugar is left to itself at the ordinary summer temperature, it soon begins to grow turbid, and small bubbles of car bonic anhydride appear in it, which gradually increase in number, at the same rate that the liquid, accom panied by a simultaneous and spontaneous increase in warmth, shows signs of a more or less marked internal motion (fermentation). After a time this phenome non ceases, the juice is then no longer sweet, its sugar has disappeared, and the liquid now contains alcohol ETHYL ALCOHOL. 43 instead of sugar. The turbidness has settled in the form of an ill-looking, grayish mass, which is called yeast. A solution of pure sugar in water does not undergo this change alone. If, however, a small quantity of yeast be added to it, the phenomena observed in con nection with the plant-juice make their appearance, though more slowly than in the former case. Cane- sugar, grape-sugar, and fruit-sugar, according to all appearances, conduct themselves in a similar manner. Grape-sugar and fruit-sugar are in reality, however, the only varieties capable of fermentation ; cane-sugar only undergoes fermentation after having been previ ously converted into these varieties. From one mole cule of grape-sugar result two molecules of alcohol, and two molecules of carbonic anhydride ; but in addition to these are always formed small quantities of succinic acid and glycerin. Yeast consists of microscopical vesicles (yeast-cells), the walls of which are formed by an elastic membrane consisting of cellulose. — Their contents are, in the young cells, a liquid, but in the older ones, a thick, granular, nitrogenous mass. The germs of the yeast-cells come from the air. Hence, contact of the plant-juice with the air is essen tial to the beginning of fermentation ; once begun, how ever, fermentation continues regularly even though the air be excluded. The germs, which have fallen from the air into the solution, develop when they meet with the substances necessary to their growth. But, in addition to the saccharine solution, nitrogenous sub stances and inorganic salts are essential. For this reason albuminous substances aid fermentation mate rially, but they are not, as was supposed for a long time, the real ferment which causes fermentation. As these substances are not present in a pure solution of sugar, the germs cannot develop in it. They are contained in plant-juices, however, and hence in these the development and rapid multiplication of the cells by means of the formation of buds begin immediately. The splitting up of sugar into alcohol and carbonic 44 ETHYL ALCOHOL. anhydride stands in the closest relation to the growth of these vegetable organisms in the saccharine solution. It has been proven with certainty, that the formation of alcohol and carbonic anhydride only takes place in the interior of the plant cells, but, regarding the de tails of this process and the character of the chemical reaction, nothing is positively known. Fermentation only takes place between 3-35°, it progresses most rapidly at 25-30°. The character of the ferment (the variety of vegetable organism) that is undergoing development in the saccharine solution, exerts the most marked influence upon the products of the fermentation. Under certain circumstances, which appear to be unfavorable to the development of yeast- cells, the germs of another ferment are developed, and now entirely different products result (see Lactic Acid). Yeast loses its efficacy by being thoroughly dried, by being heated up to 60°, by being immersed in alco hol, and by being acted upon by acids and alkalies. Various substances, particularly the volatile oil of mustard, sulphurous, nitrous, and arsenious acids, mer cury chloride, prevent the beginning of fermentation, when added in exceedingly small quantity to a fer mentable liquid. Starch is not fermentable, but, as it can be readily converted into sugar, alcohol can also be obtained from substances containing starch, such as potatoes, grain, etc. Preparation. By partial distillation of a fermented liquid, the alcohol goes over still mixed with more or less water. Such a mixture containing between 30 and 40 per cent, of alcohol is brandy. Subjected again to distillation, it is separated into water, which remains behind, and an alcohol containing less water (spirits of wine), which distils over. The last portions of water cannot be removed from this by means of distillation, but only by means of desiccating agents, such as fused calcium chloride, fused potassa, quicklime, etc., most efficiently, however, by means of anhydrous baryta, which is brought in contact with the alcohol, and the latter afterward distilled off from it. Properties. Colorless, thin liquid; in a perfectly DERIVATIVES OF ETHYL ALCOHOL. 45 pure condition and free from water, almost inodorous. Specific gravity, 0.78945 at + 20°, 0.80625 at 0°. Does not solidify even at 100°. Boiling point, 78°. Easily inflammable, burning with a flame, which has a weak light and does not soot. Attracts moisture from the air, and is miscible with water in all proportions with the accompaniment of heat and contraction of the volume of the mixture. The greatest contraction takes place when one molecule of alcohol is mixed with three molecules of water. 100 volumes of this mixture contain 53.939 volumes of alcohol and 49.836 volumes of water, hence the contraction amounts to 3.775 volumes. "With an increase of the amount of water contained in it the boiling point is elevated and the specific gravity increased. Like water, it is a solvent for a great many sub stances ; it combines, also, with salts, forming crystal line compounds. Decompositions. By means of oxidizing agents (black oxide of manganese and sulphuric acid, chromic acid, etc.) and oxygen in the presence of spongy platinum or certain organic substances, it is converted into aldehyde and acetic acid. "When heated with nitric acid a violent reaction takes place, and a large number of products result. Mixed with sulphuric acid there result, according to the proportions of the two and the temperature, either ethylsulphuric acid, ether, or ethy- lene (C2H4). Potassium and sodium are dissolved by it, hydrogen being evolved, and potassium and sodium ethylate C2H5. OK being formed. DERIVATIVES OF ETHYL ALCOHOL. Ethyl chloride, C2IFC1. Absolute alcohol is satu rated with dried hydrochloric acid gas, the liquid heated to boiling after standing for twenty-four hours, the evolved ethyl chloride passed through water of the temperature of 25° for the purpose of cleansing it, and then condensed in a vessel which is cooled at least down to 0°. It is formed by the action of chlorine on 46 DERIVATIVES OF ETHYL ALCOHOL. ethyl hydride. — Colorless, very mobile liquid, of a pleasant odor; specific gravity, 0.874; boiling point, 12°, hence at the ordinary temperature gaseous. Burns with a green-bordered flame. But slightly soluble in water. *" It is converted into alcohol, with formation of hydrochloric acid or potassium chloride, when heated for a long time with water at 100° ; more rapidly with an alcoholic solution of potassa. With chlorine, ethyl chloride yields a series of sub stitution-products. Ethylidene chloride, COTCla=CHf.CHC?. Is the first product of the action of chlorine on ethyl chloride. Is also produced by the action of phosphorus pentachloride on aldehyde. — Colorless liquid, boiling at 58-59°, of specific gravity 1.198. Further action of chlorine, finally with the aid of heat and direct sunlight, produces the liquid compounds C2IPC13, boiling point, 75°; C2H2C14, boiling point, 102° ; C2HCP, boiling point, 158° ; and the final pro duct Carbon trichloride, C2C16. Colorless crystals of a camphorous odor. Fusing point, 160° ; boiling point, 182°. But slightly soluble in water, readily in alcohol and ether. Ethyl bromide, C2H5Br. 1 part of red phosphorus is put into 6 parts of alcohol and 6 parts of bromine added, the vessel being kept cool. After a time the mixture is distilled. The distillate is shaken with caustic soda, the oil which separates is freed of water and rectified. — Colorless, heavy liquid, boiling at 40°, of specific gravity 1.47. Bromine acts upon this com pound, displacing its hydrogen, forming thus ethylidene bromide (ethyl bromobromide) C2H4Br2 = CHACIIBr2 (colorless liquid, boiling at 110°) and higher substitu tion-products. \- Ethyl iodide, C2II5I, is prepared in the same man ner as bromine from 1 part of red phosphorus, 5 parts DERIVATIVES OF ETHYL ALCOHOL. 47 of alcohol, and 10 parts of iodine.— Very similar to the bromide. Boiling point, 72°; specific gravity, 1.975. Propionitrile (Ethyl cyanide), C3H5F = C2H5.C^, is prepared by distilling a mixture of potassium cyanide and potassium ethylsulphate, or of ammo nium propionate and phosphoric andydride. — Colorless liquid, specific gravity, 0.787 ; boiling point, 98° ; in a pure condition possessing a pleasant odor ; does not mix with water. Combines directly with bromine, with hydrochloric, hydrobromic, and hydriodic acids, with phosphorus terchloride, and several metallic sub- chlorides. Heated with caustic potassa it is trans formed into ammonia and potassium propionate; hydrogen in statu nascendi converts it into propyla- mine. When allowed to drop gradually on potassium a violent reaction and the formation of potassium cyanide and volatile products ensue, and it is trans formed into cyanethine, C9H15E"3, which is polymeric with ethyl cyanide. This substance crystallizes in colorless and inodorous laminse, is difficultly soluble in water, and possesses strong basic properties. Ethylcarbylamine, C3H5^" = C2H5.NC (isomeric with propionitrile), is produced with a violent reaction when an alcoholic solution of ethylamine is poured upon caustic potassa, or when silver cyanide is heated with ethyl iodide. It is also formed in small quantity, as a secondary product, in the preparation of propio nitrile from potassium ethylsulphate. — Oily liquid, lighter than water, of an unendurable, garlic-like odor. Boiling point, 79°. Unites with silver cyanide, form ing a crystalline compound ; is with great difficulty decomposed by means of potassa, easily by hydro chloric acid, yielding ethylamine and formic acid, the elements of water being assimilated for the purpose. Ethylether, (C2H5)20. Is formed by the action of sulphuric acid, phosphoric acid, or anhydrous zinc subchloride and a few similar metallic chlorides on 48 DERIVATIVES OF ETHYL ALCOHOL. alcohol at a temperature of 140° ; by means of the double decomposition of sodium ethylate C2H5.ONa and ethyl iodide C2IFI. For its preparation a mixture of 9 parts of concentrated sulphuric acid and 5 parts of 85-90 per cent, alcohol is heated to boiling, i.e. up to 140°, in a retort connected with a good condensing apparatus. During the operation just as much alcohol is allowed to flow into the retort, through a tube passing to the bottom of the retort, as liquid distils off. The distillate consists of ether and water. The formation of the ether in this reaction takes place in two phases. At first, from one molecule of alcohol and one molecule of sulphuric acid, water and ethyl- sulphuric acid are formed ; the latter then acts on a second molecule of alcohol, the result being ether and sulphuric acid. Hence a small quantity of sulphuric acid can transform a large (theoretically an unlimited) amount of alcohol into ether. Ether prepared in this way contains alcohol, which has distilled over unchanged, especially when the too rapid addition of alcohol to the mixture caused the temperature to sink much below 140°; it also often contains sulphurous acid, when, the addition of the alcohol having been too slow, the temperature in the retort has risen much above 140°. Both impurities may be removed by shaking the distillate with water containing an alkali and rectifying the ether, after separating from the water, over calcium chloride or quicklime. Ether can be obtained perfectly anhy drous and free from alcohol by being allowed to stand for some time in contact with metallic sodium. Colorless, limpid liquid, strongly refracting, of a peculiar penetrating odor and taste. Specific gravity at + 20° = 0.713, at 0° = 0.736. Very volatile, boil ing at 35°.5. At —31° congeals, forming a crystalline mass. Easily inflammable, burning with a luminous, sooty flame. Mixed with air in the form of vapor it is exceedingly explosive. Inhaled as vapor it causes unconsciousness and insensibility. Does not mix with water; ether, however, does dissolve some water g'g DERIVATIVES OF ETHYL ALCOHOL. 49 and water some ether TV Mixes with alcohol in all proportions. Chlorine acts very energetically on ether, yielding substitution-products: C4IPC10 = CH3.CHC1.0.C2H5, boiling point 97-98° ; C41FC120 = CH2C1.CHC1.0.C2H5, colorless liquid, boiling at 140-147°; C41FC140, heavy, yellow liquid with a fennel-like odor; C4C1100, color less crystals, fusing at 69°. Concentrated sulphuric acid forms ethylsulphuric acid; sulphuric anhydride forms ethyl sulphate together with other products. Heated with water and a little sulphuric acid to 150- 180°, it is reconverted into alcohol. Ethyl-methylether (ethyl-methyl oxide), C2H5.0. CH3, is formed by the double decomposition of sodium ethylate and methyl iodide. — Liquid, boiling at -f 11°. Compound ethers. Alcohol combines with acids to form ethers, water being eliminated. These may be considered as salts, in which the atomic group C2IP (ethyl) takes the part of a metal. Monobasic acids can form only one kind of ethers, and this is a neutral substance ; bibasic acids, as for instance sulphu ric acid S04H2, can take up one or two atoms of ethyl. In the first case there is formed an acid ether, a so- called ether acid, which conducts itself as a monobasic acid ; in the latter case, however, a neutral ether is the result. Tribasic acids, finally, as for instance phosphoric acid POH3, yield three different ethers, of which one is a bibasic, the second a monobasic acid, and the third a neutral compound. By boiling with alkalies the ethers are decomposed into alcohol and acids. The ethers of most of the weaker acids can only be produced by the simultaneous action of sulphuric or hydrochloric acid. Ethyl nitrate, C2H5.O.E"02. 15 grm. of urea nitrate are added to a mixture of 80 grm. of nitric acid free of hydrochloric acid, of specific gravity 1.4, which has been previously heated with a little urea, and the 5 50 DERIVATIVES OF ETHYL ALCOHOL. liquid distilled off down to one-eighth of the original volume. The distillate is agitated with water; the ether, which is precipitated, is separated from the water, desiccated by means of calcium chloride, and rectified on a water bath. Without the presence of the urea, a violent reaction takes place and the acid and the alcohol are thorough ly decomposed, forming nitrous ether together with many other products. — Colorless liquid, of pleasant odor ; of specific gravity, 1.132 at 0° ; boiling point, 87.° Does not mix with water; burns with a white flame; its vapor explodes when heated above the boiling point. Ethyl nitrite, C2H5.N02, is formed when nitrous anhydride is mixed with well-cooled aqueous alcohol, in which case the ether separates immediately ; or by conducting the acid in a gaseous form into the alcohol and condensing the gaseous ether that passes over by cooling. Is prepared most easily by adding a solution of potassium nitrate to a mixture of alcohol and sul phuric acid, or by pouring this mixture upon the dry salt. — Pale yellow, very thin liquid, of an agreeable fruity odor; specific gravity, 0.947; boiling point, 16°. 5; does not mix with water; decomposes when kept for any length of time. Ethyl sulphate, (C2H5.0)2S02, is formed when the vapor of sulphuric anhydride is conducted into well- cooled ether, or, better, when absolute alcohol or ether is added drop by drop to sulphuryl oxichloride (S02.C1.0H). — Colorless, thick liquid, undergoes de composition at 130-140°. ^ Ethylsulphuric acid (Sulphovinic acid), C2H5.0. S02.OII, is formed when 1 part of alcohol and 2 parts of sulphuric acid are mixed together. "When the mix ture has cooled, it is diluted with water, neutralized with barium carbonate, and the dissolved barium ethylsulphate filtered off. The solution is then care fully evaporated, and the ethylsulphuric acid obtained in a free state by precipitating the barium with the DERIVATIVES OF ETHYL ALCOHOL. 51 exact amount of sulphuric acid required. The acid can, however, only be concentrated in a vacuum at the ordinary temperature. It forms a thick, very strongly acid liquid. The watery solution is resolved, by heat ing, into alcohol and sulphuric acid. Its salts are soluble in water, the alkaline salts also in alcohol. The barium ,saft (C2IP.S04)2Ba-f 21PO forms large lami nated crystals. Ethyl sulphite, (C2IP)2S03, is formed by the action of sulphur chloride S2C12 or chlorothionyl SOC12 on alcohol. — Liquid, boiling at 160° ; of specific gravity, 1.106 ; of a peppermint odor ; is decomposed gradually by water. "An ether isomeric with this, ethylsulphonic ether (C2H5)2S03, is produced by the action of sodium ethylate on ethylsulphonchloride. — Colorless liquid; boiling at 207-208° ; of specific gravity, 1.1712. Ethylsulphurous acid, C2H5.S02.OH, is formed by the oxidation of mcrcaptan, ethyl sulphide, and ethyl sulphocyanide by means of nitric acid ; by the action of zinc ethyl on sulphurous acid or sulphuric anhydride. The potassium salt is formed by boiling ethyl iodide with a concentrated solution of potassium sulphite. — Crystalline, very deliquescent mass, much more stable than ethylsulphuric acid. Its solution can be evaporated on a water bath. By oxidation it is con verted into ethylsulphuric acid. Its salts are all easily soluble and are decomposed only at a high tem perature. The lead salt (C2II5S03)2Pb forms colorless laminae, soluble in alcohol and water. Ethylsulphonchloride, C2IPS02C1. Is produced by the action of phosphorus pentachloride on potassium ethylsulphite. — Colorless liquid, boiling at 173°. 5. Ethyl phosphate, (C2H5.0)3PO, is formed by the action of phosphoric anhydride on absolute alcohol in the presence of ether; by heating silver phosphate with ethyl iodide ; and by heating lead diethylphos- 52 DERIVATIVES OF ETHYL ALCOHOL. phate to 200°. Is prepared most readily by the action of phosphorus oxichloride on sodium ethylate. — Clear, transparent liquid ; soluble in water, alcohol and ether. Boiling point, 211°; specific gravity, 1.072 (at 12°). Is decomposed slowly by water. Diethylphosphoric acid, (C2H5.0)2PO.OH, is formed when phosphoric anhydride is allowed to slowly absorb the vapor of alcohol. By neutralizing the liquid, diluted with water, with lead carbonate, the soluble lead salt [(C2H5)2PO]2Pb is obtained, which crystallizes in needles. The free acid decomposes by evaporation. Monobasic acid. Ethylphosphoric acid, C2H5.O.PO(OH)2, is formed by heating a mixture of syrupy phosphoric acid and alcohol. — Strongly acid, thick liquid. Its aqueous solution does not undergo decomposition by boiling. Bibasic acid. The barium salt C2H5.P04Ba crystallizes in prisms, and is soluble in water. Ethylphosphoric chloride, C2H5.O.POC12. Is pro duced by conducting chlorine into a mixture of 1 molecule of PCI3 and 2 molecules of alcohol. — Liquid, boiling at 167°. Ethyl phosphite, (C2H5.0)3P, is produced when sodium ethylate and phosphorus terchlorideare brought together; and by the action of phosphorus cyanide on alcohol. Boiling point, 191°; specific gravity, 1.075. By the action of phosphorus terchloride on alcohol is produced ethylphosphorous chloride C2H5.O.PC12. — Color less liquid ; specific gravity, 1.316 ; boiling point, 117°. Is resolved rapidly by water into hydrochloric acid, phosphorous acid, and alcohol. Yields with bromine ethyl bromide and PCPBrO. Ethyl arsenate, (C2H5.0)3AsO, is formed when silver arsenate is heated with ethyl iodide to 120°. — Color less liquid ; boils with slight decomposition at 235- DERIVATIVES OF ETHYL ALCOHOL. 63 238° ; specific gravity, 1.3264 at 0°. Mixes with water and is decomposed by it. Ethyl arsenite, (C2H5.0)3As, is produced by the action of methyl iodide on silver arsenite; by heating silicic ether with arsenious acid to 220°.— Colorless liquid; boiling point, 166-168°; specific gravity, 1.224 at 0°. Decomposed immediately by water, arsenious acid being precipitated. Ethyl borate, (C2H5.0)3B, is formed when 2 parts of anhydrous borax are heated with 3 parts of potassium ethylsulphate ; by the action of boron chloride on absolute alcohol ; and by continued heating of boracic anhydride with absolute alcohol at 110-120°. Liquid ; boiling point, 120° ; specific gravity at 0° = 0.887. Decomposed rapidly by water. Ethyl silicate, (C2TI5)4Si, is obtained by distilling a mixture of silicium chloride and absolute alcohol. — Colorless liquid; boiling point, 165-168°; specific gravity, 0.933 at 20°. Insoluble in water ; is, however, slowly decomposed by it, silicic acid being thrown down. If the alcohol used in the preparation be not entirely free of water, a small quantity of an ether, (C2H5)6Si207, is formed at the same time. This boils at 230-240°. — By heating silicic ether with silicium chloride, fluid ethyl-silicic chlorides are formed, as follows: (C2IP.O)3SiCl, boiling point, 155-157°; (C2H5.0)2SiCl2, boiling point, 136-138° ; C2H5.OSiCl3, boiling point, 104°. When these chlorides are allowed to act' upon different alcohols, compound silicic ethers are formed; for instance, diethyldimethyl silicate, ' boiling P°int' 143-147°; triethylmcthyl sili- )3Si, boiling point, 155-157°; ethyltri- O2TT5O methyl silicate, /^fpQxs Si, boiling point, 133-135°. The ethers with organic acids will be treated of in connection with the latter. 64 DERIVATIVES OF ETHYL ALCOHOL. Ethyl sulphhydrate(Mercaptan),C2H6S=C2H5.SH, is produced by distilling a mixture of concentrated solutions of potassium ethylsulphate and potassium sulphhydrate. — Very thin, colorless liquid, of an ex ceedingly nauseous smell ; specific gravity, 0.831 ; boil ing point, 36°. Does not mix with water; easily in flammable. It dissolves potassium and sodium, hydrogen being evolved, and, on evaporating, granular compounds potassium and sodium mercaptide, C2H5.SK and C2H5.SNa, are left behind. With a number of metallic oxides, it forms water and similar metallic compounds, the action being accompanied by an evolution of heat. Mercury mercaptide, (C2H5.S)2Hg, crystallizes from alcohol in colorless shining laminee, fuses at 85-87°, and is decomposed by sulphuretted hydrogen, yielding mercury sulphide and mercaptan ; hence used as a means of purification for crude mercaptan. When mercaptan is mixed with an alcoholic solution of cor rosive sublimate, there results a diificultly soluble precipitate, C2H5.S.HgCl. Ethyl sulphide, (C2H5)2S, is best prepared by con ducting ethyl chloride into an alcoholic solution of potassium sulphide and then distilling. It is precipi tated from the distillate by means of water. — Colorless, thin liquid of an exceedingly disagreeable smell ; spe cific gravity, 0.825 ; boiling point, 91°. Combines with several metallic chlorides. Mercury chloride causes a precipitate from an alcoholic solution (C2H5)2S.IIgCl2 ; platinum chloride precipitates 2 [(C2H5)2S].PtCl4. On being oxidized with dilute nitric acid, it is converted into sulphethyl oxide (C2IP)2SO. Thick liquid, not volatile without decomposition. Treated with fuming nitric acid diethylsulphon (C2H5)2S02 is produced. Large, thin plates, which fuse at 70°, begin to sublime below 100°, and boil at 248° without decomposition. Easily soluble in alcohol and water. Hydrogen in statu nas- cendi (zinc and sulphuric acid) reconverts it into ethyl sulphide. DERIVATIVES OF ETHYL ALCOHOL. 55 Ethyl sulphide, when heated, combines readily with ethyl iodide, forming triethyl sulphiodide (C2H5)3SI, a crystalline substance, easily soluble in water and alco hol, which, when treated with silver oxide and water, yields triethyl sulphhydroxide (C2H5)3S.OH. Indistinct deliquescent crystals. Strong base, combines with acids forming well characterized, easily soluble salts. Ethyl bisulphide, (C2H5)2S2, is produced when ethyl chloride is conducted into an alcoholic solution of potas sium bisulphide, and by the action of iodine on sodium mercaptide. — Liquid, boiling at 151°. When shaken with dilute nitric acid, it yields ethyl disulphoxide (C2H5)S202, a liquid, which cannot be distilled without decomposition. The corresponding selenium and tellurium com pounds are produced in a similar manner to the sul phur compounds, potassium selenide or telluride being employed instead of the sulphide. Selenmercaptan, C2H6Se. Colorless, thin liquid, with an insupportable odor ; with mercury oxide it also yields a mercaptide. — Ethyl selenide (C2H5)2Se. Pale yellow liquid, with an exceedingly repulsive odor, heavier than water. Is oxidized by nitric acid, the action being accompanied by an evolution of nitrogen binoxide; from the resulting solution hydrochloric acid precipitates ethyl chloroselenide (C2H5)2SeCl2, a pale yellow, heavy oil. Ethyl telluride, (C2H5)2Te. Eeddish-yellow liquid, heavier than water, of insupportable odor. Is dissolved by nitric acid as tellurethyloxide nitrate. From this solution hydrochloric acid precipitates an oily, color less substance, tellurethyl chloride (G2W)^QG\2\ hydriodic acid, an orange-yellow, powdery substance, tellur ethyl iodide (C2H5)2TeI2. Aqueous ammonia decomposes the chloride, forming ammonium chloride and an oxichlo- ride (C2H5)2TeCl2 -f (C2IP)2TeO, which crystallizes in colorless and inodorous prisms. The iodide conducts itself in a similar manner. 66 DERIVATIVES OF ETHYL ALCOHOL. Ethylamine, C2IR^"H2. Ethyl bromide and aqueous ammonia combine gradually at the ordinary temperature, more rapidly when heated in sealed tubes to 100°, forming ethylamine hydrobromate (bromethyl- ammonium). Ethyl iodide and bromide act in the same way. By this reaction, however, small quanti ties of di- and triethylamine are formed at the same time.* It is obtained in a pure condition b}^ distilling ethyl cyanate or cyanurate with potassa ; the distillate, being neutralized by hydrochloric acid, yields, on evaporation, ethylamine hydrochlorate. Ethylamine nitrate is produced when ethyl nitrate is heated with an alcoholic solution of ammonia ; ethylamine sulphate by treating acetonitrile (see p. 38) with zinc and sul phuric acid. By gently heating one of these salts with caustic potassa, ethylamine is set free ; it evolves in gaseous form, is passed through a tube containing pieces of caustic potassa, for the purpose of drying it, and then conducted into a vessel cooled below 0°. This liquid (boiling point, 18°) smells almost exactly like ammonia ; specific gravity, 0.696 ; inflammable ; mixes with water; a caustic alkali ; a more powerful base than ammonia. Its solution precipitates metallic salts the same as ammonia, redissolves precipitated alumina, however, when added in excess. Nitrous acid decomposes it, alcohol, nitrogen, and water being formed. Ethylamine hydrochlorate, OTFKHCl, forms large, deliquescent, tabular crystals, soluble in alcohol. With platinum chloride it gives a yellow compound (C2H7JSr.IICl)2PtCl4. Diethylamine, (C2H5)2I^H. Ethylamine in an aqueous solution combines in a short time with ethyl bromide, forming diethylamine hydrobromate, from which the free base can be obtained by means of potassa. — A liquid, easily inflammable, boiling at 57°, * On the separation of these three bases from each other, see Diethyl Oxamid in connection with Oxalic Acid. DERIVATIVES OF ETHYL ALCOHOL. 57 miscible with water. Strong base. The hydrochlorate (C2H5)2NH.HC1, when distilled with a concentrated solution of" potassium nitrite, yields nitrosodiethyline (C2H5)2M).N, a liquid boiling at 177°, which is^decom- posed by hydrochloric acid, forming nitrogen binoxide and diethylamine hydrochlorate. Triethylamine, (C2IP)3K Is formed from diethyl amine in the same way that this is formed from ethyl- amine.— Colorless, light, strongly alkaline liquid, but slightly soluble in water. Boiling point, 89°. The hydrochlorate, when heated in concentrated solution with potassium nitrite, yields nitrosodiethyline, the same as diethylamine. Tetrethylammonium. Triethylamine and ethyl iodide combine slowly at the ordinary temperature, rapidly at 100°, forming tetrethylammonium iodide (C2IP)4M. Colorless crystals, easily soluble in water and alcohol. Is resolved into ethyl iodide and triethyl- amine by heating. Is converted into a triiodide (C2IP)4NP, of a dark violet color, when treated with an alcoholic solution of iodine. Silver oxide precipi tates silver iodide from the aqueous solution of the iodide, and the filtered solution, when carefully eva porated, leaves behind fine, deliquescent crystals of tetrethylammonium hydroxide (C2H5)4.N".OH. This is not volatile, but at 100° breaks up into triethylamine, ethylene, and water. Its watery solution conducts itself almost like caustic potassa, takes up^ carbonic anhydride from the air; has a very caustic action, saponifies fats, and causes the same precipitates as potassa in solutions of metallic salts. Ethylphosphine, C2IPP=C2IP.PH2. Is produced, together with some diethylphosphine, when^ iodophos- phonium is allowed to act upon ethyl iodide in the presence of a metallic oxide. To prepare it 1 part of zinc white, 4 parts of iodophosphonium, and 4 parts of ethyl iodide are heated to 150° in sealed tubes. The 58 DERIVATIVES OF ETHYL ALCOHOL. product of the reaction is then brought into an ap paratus filled with hydrogen, and water, which has been boiled and allowed to cool, slowly added. The ethyl phosphine is by this means set free and then condensed in a spiral tube surrounded by ice. The distillate dried by means of caustic potassa is pure ethylphos- phine. — Mobile, colorless, transparent liquid, insoluble in water; refracts light strongly; lighter than water; boils at 25° ; entirely without action upon vegetable colors ; exceedingly disagreeable odor. Takes fire when brought together with bromine, chlorine, and fuming nitric acid. Combines with sulphur and carbon bisul phide, forming liquid compounds. It combines with hydrochloric, -bromic, and -iodic acids, forming salts. Ethylphosphine hydriodate (C2H5)H2P.HI forms white, four-sided plates, which can be sublimed in an atmosphere of hydrogen at the temperature of boiling water. Is soluble "" in water, undergoing complete decomposition ; soluble in alcohol with partial decomposition ; insoluble in ether ; slightly soluble but without decomposition in concentrated hydriodic acid. The addition of ether to this solution causes the salt to separate in crystalline form. Oxid ized by means of nitric acid it yields ethylphosphinic add (C2H5).PO.(OH)2. This is a solid body, that fuses at 44°. It is a bibasic acid. Diethylphosphine, C4H11P=(C2H5)2.PH. Is pro duced together with ethylphosphine in the preparation of the latter. To obtain it from the mixture, after having treated the product of the reaction with water in order to set the ethylphosphine free, a strong solu tion of caustic soda is added to the mixture in the flask, which still must be kept filled with hydrogen. The diethylphosphine is thus set free and condensed by means of an ordinary apparatus. The liquid dried with caustic potassa is diethylphosphine in a chemi cally pure condition. — Colorless, transparent, perfectly neutral liquid, insoluble in water, lighter than it, refracts light strongly. Boils at 85°. Penetrating odor, not at all similar to that of ethylphosphine. DEEIVATIVES OF ETHYL ALCOHOL. 59 Takes up oxygen very rapidly, and occasionally takes fire in contact with the air. Combines with sulphur and carbon bisulphide, forming liquid compounds. Dis solves readily in all acids. The salts crystallize with difficulty, with the exception of the hydriodate. The salts are not decomposed by water. Oxidized by means of nitric acid, it yields diethylphosphinic acid (C2IF)2PO.OH, a liquid. Triethylphosphine, (C2H5)3P,is formed, when phos phorus terchloride is added drop by drop to an ethereal solution of zinc ethyl and the resulting viscid com pound of zinc chloride with the phosphorus base dis tilled with potassa. Is most readily obtained by heating 1 molecule of iodophosphonium, PII4I, with 3 molecules of absolute alcohol for eight hours in sealed tubes at 180°. On the addition of caustic soda to the solution, it is precipitated. — Colorless, strongly refracting liquid, which possesses an almost narcotic odor (in a dilute condition like hyacinthes), perfectly insoluble in water, mixes with alcohol and ether in every proportion ; specific gravity, 0.812 ; boiling point, 127°. 5. Combines slowly with acids forming very easily soluble salts, which crystallize badly. In contact with the air it forms triethylphos- phivie oxide (C2II5)3PO, this being accompanied by an increase in temperature and an assimilation of oxy gen. It crystallizes in needles, is exceedingly deli quescent, and boils at 240°. Sulphur is also dissolved by the free base, forming triethylphosphine sulphide (C2H5)3PS. This crystallizes from water in long, bril liant, white needles, which fuse at 94°. Phosphethylium iodide, (C2H5)4PI. Is produced when an ethereal solution of triethylphosphine is mixed with ethyl iodide ; is also formed in the pre paration of triethylphosphine from iodophosphonium and alcohol, and crystallizes from the liquid after the addition of caustic soda and evaporation. — Crystals, easily soluble in water. Is not decomposed by caustic 60 DERIVATIVES OF ETHYL ALCOHOL. potassa ; when treated with silver oxide, gives silver iodide and Phosphethylium hydroxide, (C2IP)4P.OH. Crys talline, very deliquescent, strong base ; takes up car bonic anhydride from the air with avidity and forms very deliquescent salts with acids. Is decomposed at a high temperature into ethyl hydride and triethyl- phosphine oxide. Triethylarsine, (C2H5)3As, is formed, together with the following compound, when sodium arsenide, mixed with sand for the purpose of lessening the violence of the reaction, is distilled with ethyl iodide in a vessel filled with carbonic anhydride. By careful distillation of the oil which passes over, in an atmos phere of carbonic anhydride, triethylarsine distils over first. — Colorless liquid, strongly refracting, of exceedingly disagreeable odor; specific gravity, 1.151 ; begins to boil at 140° ; gives off fumes in contact with the air, but takes fire only when heated. Combines with oxygen, forming triethylarsine oxide (C2H5)3AsO, a colorless, oily liquid ; with sulphur forming triethyl arsine sulphide (C2H5)3AsS, a beautifully crystallizing compound. It combines with ethyl iodide, forming crystals of arsenethylium iodide (C2IP)4AsI, and this gives with silver oxide arsenethylium hydroxide (C2H5)4As.OH, a white, alkaline, deliquescent mass. Arsendiethyl (Ethylcacodyl) SI^Ai } * Yel~ lowish liquid, of a very disagreeable odor. Takes fire spontaneously in contact with the air; boils at 190°; is heavier than water. Combines with oxygen, sul phur, chlorine, etc., with evolution of heat. Conducts itself perfectly analogously to the methyl compound (P. 40). Triethylstibine (Stibethyl), (C2IP)3Sb, is produced when potassium antimonide is distilled with ethyl iodide in a current of carbonic anhydride. Colorless, DERIVATIVES OF ETHYL ALCOHOL. 61 very thin liquid, of a disagreeable odor like that of onions; specific gravity, 1.824; boiling point, 158°; gives off fumes in contact with the air, takes fire and burns with a white flame. When air is allowed entrance to it very slowly, it is oxidized, forming triethylstibine oxide (C2H5)3SbO, a viscid, uncrystalline base, easily soluble in water ; forms with acids crystallizing salts. From the solutions of these salts hydrochloric acid precipitates a chloride (02IP)3SbCl2, in the form of a colorless, thick liquid. Triethylstibine combines with sulphur, forming triethylstibine sulphide (C2H5)3SbS, crystals with a silvery lustre. Ethyl iodide combines with triethylstibine at 100°, forming Stibethylmm iodide, (C2H5)4SbL— Large transpa rent prisms, easily soluble in alcohol, but slightly soluble in ether. Silver oxide converts it into stib- ethylium hydroxide (C2IF)4Sb.OH, a colorless, oleaginous liquid, which conducts itself like the analogous arsenic compound. Triethylborine (Borethyl), (C2H5)3B, is formed by the action of ethyl borate on zinc ethyl. — Colorless, very mobile liquid ; specific gravity, 0.6961 ; boiling point, 95° ; its vapor excites to tears. It combines with ammonia with great avidity. In contact with the air and in oxygen it is oxidized, forming triethyl- borine oxide (C2H5)3B02, a colorless liquid, boiling at 125°, which breaks up into alcohol and (C2H5)H2B02 in contact with water. Triethylbismuthine, (C2IP)3Bi, is formed from bis muth-potassium and ethyl iodide. — Heavy, unvolatile liquid, of a very disagreeable odor. It is extracted from the mass by means of ether. It fumes in the air and takes fire spontaneously. It conducts itself like triethylstibine ; its compounds, however, are less stable. Zincethyl, (C2H5)2Zn, is formed by the action of zinc on an ethereal solution of ethyl iodide at 150° (if sieved zinc-filings or a small amount of zincethyl 6 62 DERIVATIVES OF ETHYL ALCOHOL. be added, the reaction takes place at a lower tempera ture), or by gently heating equal parts of ethyl iodide and zinc-sodium in an atmosphere of carbonic anhy dride. When the reaction ceases, the zincethyl iodide C2H5.ZnI is decomposed by means of heat, and the zinc- ethyl distilled off. — Colorless liquid ; specific gravity, 1.18 ; boiling point, 118°. It takes fire in the air and burns with a white flame. When its solution in ether is slowly oxidized, it is transformed into zinc ethylate (C2H50)2Zn, a white, solid body. Sulphur converts it, in an ethereal solution, into zinc mercaptide (C2H5S)2Zn. Water decomposes zincethyl instanta neously, forming zinc hydroxide and ethyl hydride. Sodium and potassium are dissolved by an excess of zincethyl, zinc being thrown down: when this solu tion is cooled or the excess of zincethyl evaporated in an atmosphere of hydrogen, a crystalline compound of zincethyl with sodium- or potassiumethyl separates. From these compounds the potassium or sodium com pounds can be isolated. Mercury ethyl, (C2H5)2Hg, is produced by the distil lation of mercury chloride or subchloride with an excess of zincethyl. Can be best prepared by bring ing sodium-amalgam and ethyl iodide or bromine together and adding acetic ether ( ^ the weight of the bromide or iodide). The mixture is alternately shaken and cooled and finally subjected to distillation. The distillate is again treated with sodium-amalgam, water added, the oily liquid, which separates, shaken at first with an alcoholic solution of potassa for the purpose of decomposing the acetic ether, then with water, finally desiccated by means of calcium chloride and rectified. — Heavy, colorless liquid, boiling at 159° ; specific gravity, 2.44. — Exceedingly poisonous. Insoluble in water, but slightly soluble in alcohol, easily in ether. When heated with zinc at 100° it is converted into zincethyl. By boiling its alcoholic solu tion with corrosive sublimate there is formed a crys talline precipitate of mercuryethyl chloride C2H5HgCl. The corresponding iodide C2H5IIgI is formed slowly DERIVATIVES OF ETHYL ALCOHOL. 63 from mercury and ethyl iodide in dispersed light. Both compounds form iridescent scales; of an un pleasant odor, volatile without decomposition. The iodide is decomposed by silver oxide, forming silver iodide and mercuryeihyl "hydroxide C2II5.Hg.OH. An oleaginous, almost colorless, strongly akaline liquid, easily soluble in alcohol and water. The solution pre cipitates solutions of metallic salts the same as potassa, and expels ammonia from its salts. With acids it yields crystallizing salts. Aluminiumethyl, (C2H5)3A1, is produced by heat ing mercuryethyl with aluminium-filings at 100°". — Colorless liquid, boils at 194°, does not congeal at — 18°. Gives off fumes in the air and in thin layers takes fire spontaneously. Is decomposed by water, with explosion. Leadtetrethyl, (C2H5)4Pb, is formed from zincethyl and lead chloride, metallic lead being thrown down. —Colorless, oily liquid, boiling at 198-202°, under going at the same time partial decomposition. Does not combine with, oxygen, chlorine, or iodine. Leadtriethyl (Methplumbethyl), (C2H5)6Pb2, is pro duced by bringing together ethyl iodide and an alloy of lead and sodium (Pb^N~a3) an evolution of heat accompanying the reaction. When the reaction is ended, the substance is extracted with ether. — Thin, yellowish oil, not volatile without decomposition; insoluble in water ; specific gravity, 1.471. Is decom posed when exposed to the light or boiled for some time with water, lead being thrown down. With iodine it yields a very unstable iodide (C2H5)3PbI. The corresponding chlorine compound (C2H5)3PbCl is formed in long needles of a silken lustre by the action of hydrochloric acid gas on leadtetrethyl, the reaction being accompanied by an escape of ethyl hydride. Both compounds give, with water and silver oxide, leadtriethyl hydroxide (C2H5)3Pb.OH. Colorless, thick liquid, but slightly soluble in water, strong 64 DERIVATIVES OF ETHYL ALCOHOL. base, saponifies fats, expels ammonia from its salts, precipitates solutions of metallic salts, and forms with acids neutral crystalline salts. Tindiethyl, (C2H5)2Sn, is formed, together with tin- triethyl, when ethyl iodide is brought together with an alloy of 1 part of sodium and 4 parts of tin. — Yel low, oily liquid, not volatile without decomposition ; unites with oxygen, chlorine, bromine, and iodine. Tindiethyl iodide (C2H5)2SnI2 is formed when tin and ethyl iodide are heated together. It forms needly crys tals, which fuse at 44°. 5 and boil at 245°, are soluble ?n ether and hot alcohol, only with difficulty soluble in water. Zinc precipitates tindiethyl from its solu tions. Alkalies precipitate tindiethyl oxide (C2IP)2SnO; white, amorphous powder; insoluble in water, alcohol, and ether; soluble in an excess of caustic soda or potassa ; combines with acids, forming crystalline salts. Tintetrethyl, (C2H5)4Sn, is formed by heating tindi ethyl and distilling tindiethyl iodide with zincethyl. — Colorless liquid, of specific gravity 1.187 ; boiling point, 181°. Does not unite with oxygen, chlorine, or iodine. Tintriethyl, (C2H5)6Sn2.— Thin liquid, boiling at 265-270°, but not entirely without decomposition ; specific gravity, 1.4115. It absorbs oxygen and yields with it an oxide (C2II5)6Sn20, volatile without decom position, the hydrate of which is a strong base, con sisting of colorless prisms fusing at 66° and boiling at 271°, forming with acids crystalline salts. The iodide (C2IP)3SnI is formed by direct union of tintriethyl with iodine, by continued heating of ethyl iodide with zinc-sodium (containing 2 per cent, sodium), and, together with ethyl iodide, by the action of iodine on tintetrethyl. A liquid boiling at 231° ; specific gravity, 1.83. The further action of iodine resolves it into tindiethyl iodide and ethyl iodide. — The chloride (C2IP)3SnCl is formed, together with ethyl hydride, by the action of hydrochloric acid on tin PROPYL ALCOHOLS. 65 tetrethyl. A liquid of pungent odor, congealing at 0°, boiling at 208-210°. Siliciumethyl, (C2H5)4Si, is formed by heating silicium chloride with zincethyl to 160°. — Colorless liquid, boiling at 153°, lighter than water and insolu ble in it. Yields with chlorine a liquid C8H19ClSi, boiling at 180-190°. 3. Propyl Alcohols. C3H80 = C3H7.OH. Of the alcohols, which have the formula C3H80, there are two isomeric modifications possible, as was shown at p. 32. Both are known. 1. Normal propyl alcohol, CIF.CH2.CII2.OH. Is formed in the preparation of ethyl alcohol by fer mentation, together with some of the other alcohols of this series, and is contained in the secondary products, which boil at a higher temperature (fusel-oil). It can be isolated from these by means of partial distillation, but only with difficulty can it thus be obtained in a pure condition. To prepare the pure alcohol, that portion of fusel-oil that boils between 85-110° is treated with amorphous phosphorus and bromine (see ethyl bromide, p. 46), and thus converted into bro mides. These are then separated by partial distilla tion, the portion that boils at 71° decomposed with silver acetate or potassium acetate, and the ether thus formed decomposed by means of caustic potassa. It is also produced by the action of hydrogen in statu nascendi on propionic aldehyde, by the action of sodium-amalgam on propionic anhydride, and together with ethyl alcohol and other bodies by heating allyl alcohol with caustic potassa. Colorless liquid, of a pleasant odor, of specific gravity 0.8205 at 0° ; boiling point, 97° ; mixes with water, but not with a concentrated solution of calcium chloride. Under the influence of oxydizing agents it yields propionic aldehyde and propionic acid. 6* 66 PEOPYL ALCOHOLS. The derivatives of propyl alcohol are prepared in the same manner as those of ethyl alcohol, and con duct themselves analogously. Propyl chloride, C3H7C1. Colorless liquid, boiling at 52°. Propyl bromide, C3H7Br. Liquid ; boiling point, 71°. Propyl iodide. C3H7I. Liquid; boiling point, 102°. Propylether, (C3H7)20. Very mobile liquid, boil- ing at 85-86°. Propylamine, C3H7.KH2. By the action of hydro gen in statu nascendi (zinc and hydrochloric acid) on propionitrile (p. 47), and by the distillation of propyl eyanate with caustic potassa. — Clear, strongly refract ing liquid, possessing an ammoniacal odor. Boiling point, 49-50°. Mixes with water. Burns with a luminous flame. Strong base. The hydrocMorate, C3H7.NH2.HC1, is deliquescent, also very easily soluble in alcohol. With platinum chloride it yields a double salt (C3H7.KH2.HCl)2PtCl4, which is pretty easily solu ble in hot water and in alcohol, and crystallizes in large, gold-colored, klinorhombic plates. 2. Secondary propyl alcohol (Pseudopropyl alcohol), CH3.CH.01LCH3. Is formed by the action of hydrogen in statu nascendi (from water and sodium- amalgam) on acetone. — Colorless liquid, miscible with water in all proportions. Boiling point, 85°; specific gravity, 0.791 at 15°. Combines with calcium chlo ride, forming a solid compound. By oxidation it is at first reconverted into acetone and then yields acetic and formic acids. Pseudopropyl iodide, C3II7I, is produced by the direct union of propylene with hydriodic acid, and by BUTYL ALCOHOLS. 67 heating pseudopropyl alcohol, propylene alcohol, ally! iodide, or glycerin with the same acid.— Is prepared most readily by the simultaneous action of iodine and phosphorus on glycerin. — Colorless liquid, boiling at 89° ; specific gravity, 1.7 at 15°. "When heated with potassium cyanide, it is converted into pseudopropyl cyanide (pseudobutyronitrile), C4!!7^. At the same time is formed a small quantity of the isomeric com pound pseiulopropykartylamine, C3H7.NC, which boils at 87°. Pseudopropyl chloride, C3H7C1, and pseudopro pyl bromide, C3H7Br, are very similar to the iodide, and are obtained from the alcohol in the same way as the corresponding ethyl compounds. The former boils at 36-38°; the latter at 60-63°. Pseudopropylether, (C3H7)20, is formed, together with pseudopropyl alcohol and propylene, by heating the iodide with silver oxide and water. — A liquid not miscible with water. Boiling point, 60-62°. Pseudopropylamine, C3H7.MI2. Colorless, very mobile liquid, of ammoniacal odor. Boiling point, 32° ; specific gravity, 0.69. 4. Butyl Alcohols. C4H100 = C4II9.OH. The existence of four different alcohols of the for mula C4H100 is possible— two primary, one secondary, and one tertiary. These are all known. 1. Normal butyl alcohol, CH3.CH2.CH2.CH2.OH. Is obtained by the action of hydrogen in statu nas- cendi (sodium-amalgam and very dilute sulphuric acid) on butyric aldehyde, or by the action of sodium-amal gam on a mixture of butyric acid and buty ryl chloride, and treatment of the product, chiefly consisting of butyl butyrate, with caustic potassa. — Colorless liquid of agreeable odor ; specific gravity, 0.826 ; boiling 68 BUTYL ALCOHOLS. point, 115-116°. But slightly soluble in water. Yields butyric acid by oxidation. Butyl chloride, C4H9C1. Clear liquid. Boiling point, 77.6°; specific gravity, 0.8874 at 20°.— The bromide, C4II9Br, boils at 100.4° ; specific gravity, 1.2792 at 20°.— The iodide, C4H9I, boils at 129.6°; specific gravity, 1.6136 at 20°. Butyl cyanide, C4H9.CK Liquid, boiling at 140.4°, of exceedingly disagreeable odor. Specific gravity, 0.8164 at 0°. Butyl-ethylether, C4H9.O.C2H5. Liquid, boiling at 91.7°; specific gravity at 20°, 0.7512. Butylamine, C4H9.N"H2. Clear liquid, possessing a strongly ammoniacal odor, fumes in contact with the air, very hygroscopic. Mixes with water in all propor tions. Boils at 75.5° ; specific gravity, 0.7558 at 0°.— "With hydrochloric acid and platinum chloride it yields a double salt, (C4II9.OTI2.HCl)2PtCl4, which crystallizes in gold-colored laminae, but slightly soluble in cold water, more readily in hot water and in alcohol. 2. Isobutyl alcohol, ^ 1 CH.CH2.OH. Is often contained in fusel-oil, and is obtained from this like propyl alcohol. — Colorless liquid of specific gravity 0.805. Boiling point, 108-109°. Soluble in 10 parts of water, and is precipitated from this solution by soluble salts. By oxidation it is converted into isobu- tyric acid. Isobutyl chloride, C4II9C1. Colorless liquid, boil ing at 64-68°.— The bromide, C4H9Br, boils at 92° ; the iodide, C4H9I, at 121°. 3. Secondary butyl alcohol (butylene hydrate), CH3.CH2.CII.OH.CIP. The iodide corresponding to this alcohol is obtained by distilling erythrite with A MYL ALCOHOLS. 69 concentrated hydriodic acid. From this the alcohol is obtained by heating with silver oxide and water. — Colorless liquid, rather easily soluble in water, is pre cipitated from this solution by means of potassium carbonate. Of a strong, penetrating odor. Boiling point, 96-98°; specific gravity, 0.85 at 0°. When heated to 240-250° it is resolved into butylene and water. By oxidation it is at first converted into ethyl- methylketone, and then into acetic acid. The iodide, C4H9I, boils at 117-118°. 4. Tertiary butyl alcohol (Pseudobutyl alcohol, ( CH3 trimethylcarbinol), CH3.C.OI1 •[ Qjp Is contained in small quantity in commercial butyl alcohol of fermen tation. — Can easily be prepared from isobutyl alcohol. Isobutyl iodide, when heated with an alcoholic solu tion of potassa, yields a hydrocarbon, C4II8 (isobuty- lene), which combines directly with hydriodic acid, forming pseudobutyl iodide. By means of silver oxide and water the alcohol is prepared from this. The alcohol can be obtained still more readily by conduct ing the isobutylene into concentrated sulphuric acid, and, after diluting with water, subjecting to distil lation. "When acetyl chloride (1 vol.) is poured very slowly into an excess (about 4 vols.) of zjncethyl, kept at 0°, there separates from the mixture after a time, large, transparent prisms of C2IPO.C1 + 2 [(CH3)2Zn], which, in contact with water, are imme diately decomposed, forming zinc oxide, zinc chloride, marsh gas, and pseudobutyl alcohol. — Colorless, thick liquid, which, when thoroughly free of water, congeals at 20-25° in a crystalline form, and boils at about 82°. Yields by oxidation carbonic, acetic, and propionic acids.— Pseudobutyl chloride, C4IPC1, boils at 50-51°. The iodide, C4H9I, at 98-99°. 5. Amyl Alcohols. isomeric exist, viz Eight isomeric alcohols of this composition can dst, viz. : 4 primary, 3 secondary, and 1 tertiary. Of 70 AMYL ALCOHOLS. these, five are known, as follows : 2 primary, 2 secondary, and the tertiary. PRIMARY AMYL ALCOHOLS. 1. Normal amyl alcohol, CH3.CH2.CH2.CH2.CH2. OH. Is obtained from the aldehyde of normal valeric acid by the action of hydrogen in statu nascendi, in the same manner as normal butyl alcohol. — Colorless liquid ; insoluble in water; boiling point, 137°. By oxidation it yields normal valeric acid. Amyl chloride, C5HUC1, boils at 106.6° ; specific gravity at 0° = 0.9013.— The bromide C5HnBr boils at 128.7°, specific gravity at 0° = 1.246.— The iodide C5HnI boils at 155.4° ; specific gravity at 0° = 1.5435. —Amyl acetate C5Hn.O.C2H30 boils at 148.4° ; specific gravity at 0° = 0.8963. 2. Amyl alcohol of fermentation, CH3 1 CH. CH2.CH2.OH. Is the principal constituent of fusel- oil, and is prepared from this by means of partial distillation. — Colorless liquid, boiling at 130-131°; specific gravity, 0.825 ; of an unpleasant odor and acrid taste, but slightly soluble in water. By oxidation it yields ordinary valeric acid. Its derivatives are pre pared like those of ethyl alcohol, and thoroughly resemble them in their chemical conduct. The chloride C5H]1C1 is a liquid, boiling at 102°. The iodide C5HnI boils at 147° ; the bromide C5HnBr, at 119°. Amylether, (C5IIn)20, is a liquid, boiling at 170°. SECONDARY AMYL ALCOHOLS. 3. Isoamyl alcohol, CH3.CII2.CH2.CH.OH.CH3. Is produced from methyl-propylketone by the action of hydrogen in statu nascendi. The iodide is formed by the direct combination of ethylallyl (see amylene) HEXYL ALCOHOLS. 71 with hydriodic acid, and the alcohol obtained from this in the same way that normal propyl alcohol is obtained from propyl bromide (p. 65). — Colorless liquid, insoluble in water, of specific gravity, 0.8205 ; boiling point, 120°. By oxidation it yields first methyl-propylketone, then acetic and propionic acids. The iodide C5HnI is a liquid, boiling at 146° ; of specific gravity, 1.537 at 0°. 4. Amylenehydrate, CH.CH.OH.CH3. Amylene C5H10, which results from the action of zinc chloride on amyl alcohol, combines with hydriodic acid, forming the iodide C5HnI, boiling at 128-130°, which, when treated with silver oxide yields the alcohol. — A liquid, boiling at 105-108°. Does not combine with sulphuric acid, but is decomposed by it, yielding water, amylene, and substances polymeric with it. Furnishes by oxidation carbonic and acetic acids ; acetones are formed as intermediary products. 5. Tertiary amyl alcohol (Pseudoamyl alcohol, Ethyldimethylcarbinol), ^ I C.OH.CH2.CH3. Is pre pared, like pseudobutyl alcohol, from propionyl chlo ride and zincmethyl. — A liquid, boiling at about 100°. Yields acetic acid by oxidation. Congeals at — 30°, forming a mass of small needles. — The iodide C5HnI is a heavy liquid. 6. Hexyl Alcohols (Caproyl Alcohols). C6H140 = C6H13.OH. 1. Primary hexyl alcohol. Is contained in fusel- oil obtained from grape skins. Hexyl hydride from petroleum (p. 30) yields the chloride C6H13C1, from which hexyl acetate may be obtained by heating with potassium or silver acetate. This when boiled with potassa gives hexyl alcohol, a liquid boiling at 150-155°.— The iodide boils at 172-175°. 72 HEXYL ALCOHOLS. That portion of the volatile oil of Heradeum gigan- teum, which boils at 201-206°, consists partially of hexyl butyrate. The alcohol, prepared from this ether by means of saponification, boils at 156.6°. — The iodide boils at 179.5°. This alcohol, as well as the preceding one, yields an acid C6H1202 by oxidation, and is probably the normal alcohol. It is not decided whether these two alcohols are identical or not. 2. Secondary hexyl alcohol (js-Hexyl alcohol), CH3.CH2.CH2.CH2.CILOH.CH3. When mannite is dis tilled with concentrated hydriodic acid, there results an iodide, C6H13I, boiling at 167.5°. This yields the alcohol when heated with silver oxide and water. —A liquid, boiling at 137° ; of specific gravity, 0.8327 at 0°. Its conduct towards sulphuric acid is similar to that of amylenehydrate. Yields by oxidation carbonic, acetic, and butyric acids ; as an intermediary product, methyl-butylketone. The chloride of the same alcohol (C6H13C1, boiling point, 125-126°) appears to be formed together with the chloride of the primary alcohol by the action of chlorine on the hexyl hydride from petroleum. In addition to these there are three tertiary hexyl alcohols known : — 3. Dimethylpropylcarbinol, ^ 1 C.OH.CH2. CH2.CH3. From butyryl chloride and zincmethyl like pseudobutyl alcohol. — Boiling point, 115°. By oxi dation it yields acetic and propionic acids. 4. Diethylmethylcarbinol, QEPCIP 1 a°ILCH3- From acetyl chloride and zincethyl. — Boiling point, 120°. Yields by oxidation only acetic acid. 5. Dimethylpseudopropylcarbinol, Q^ 1 C. OII.CII j Qjp Is obtained by the action of isobutyryl chloride on zincmethyl. — Colorless liquid, that con- HEPTYL ALCOHOLS.— OCTYL ALCOHOLS. 73 geals at — 35°, forming a white crystalline mass. Boiling point, 112-113° ; specific gravity at 0°, 0.8364. Yields by oxidation acetone, and by further oxidation of this, acetic acid. 7. Heptyl Alcohols ((Enanthyl Alcohols). C7H160 = C7II15.OH. 1. Primary heptyl alcohol. Is contained in the fusel-oil from grape skins, and is prepared from heptyl hydride (obtained from petroleum) in the same way as hexyl alcohol. Is also formed by the action of hydro gen in stain nascendi on cenanthylic aldehyde. — Color less liquid, insoluble in water, boiling at 164-165°.— The chloride, C7H15C1, obtained from heptyl hydride by the action of chlorine, boils at 146-149°. It^is not positively known whether these alcohols, obtained from different materials, are identical. 2. Secondary heptyl alcohol, CH.OH. Is produced by the action of hydrogen on butyrone.— Liquid that boils at 149-150° ; but slightly soluble in water ; soluble in all proportions in alcohol ; specific gravity at 25° = 0.814.— The iodide, OH15!, boils at^lSO0, but not without undergoing partial de composition. 3. Triethylcarbinol (Tertiary heptyl alcohol),C7H160 = C2H5.C.OH | g^ Is produced by the action of propionyl chloride on zincethyl. — Colorless liquid, of an odor similar to camphor; boiling point, 140-142° ; specific gravity, 0.8593 at 0°. Yields by oxidation acetic and propionic (?) acids. 8. Octyl Alcohols (Capryl Alcohols). C8II180 = C8II17.OH. Primary octyl alcohol. That portion of the vol atile oil of Heradeum spondylium which boils at 206- 7 74 OCTYL ALCOHOLS. 208° is the acetic ether of this alcohol. By decom posing this with caustic potassa the alcohol is obtained. — Colorless liquid, insoluble in water ; specific gravity, 0.83 ; boiling point, 190-192°. The chloride, C8H17C1, boils at 180°; the bromide, C8H17Br, at 198-200° ; the iodide, C8H17I, at 220-222°. Secondary octyl alcohol (Methylhexylcarbinol), C6H13.CH.OILCH3. Is formed by the distillation of castor oil with alkaline hydrates, and can be prepared from octyl hydride (obtained from petroleum) in the same way as hexyl alcohol. — Oil boiling at 181°. Yields by oxidation at first methyl-hexylketone and then acetic and caproic acids. The chloride, C8H17C1, boils at 175°. Tertiary octyl alcohol (Propyldiethylcarbinol), :* 1 C.OH.C3H7. Prepared from butyryl chloride (u 11 j and zincethyl in the same way as pseudobutyl alcohol. — A liquid, boiling between 145-155°. 9. Nonyl alcohol, C9H200, a liquid, boiling at about 200°, and 10. Decatyl alcohol, C10H220, a liquid, boiling ^ at 210-215°, have been prepared from the corresponding hydrocarbons of petroleum in the same way as hexyl alcohol. They have not been subjected to closer study. 11. Cetyl alcohol, C16H340. A compound ether of this alcohol is the principal constituent of spermaceti. By boiling this with an alcoholic solution of potassa the alcohol is obtained. — White crystalline mass, fusing at 50°, volatile without decomposition. 12. Ceryl alcohol, C27II560. In Chinese wax and in opium wax in the form of ceryl cerotate and palmitate. FATTY ACIDS. 75 Prepared from this by boiling with an alcoholic solu tion of potassa. — A wax-like mass, fusing at 79°. 13. Myricyl alcohol, C30H620. Is contained in Car- nauba wax (from the leaves of Copernica cerifera) and as myricyl palmitate in beeswax. Separated by means of caustic potassa, it forms a crystalline mass, fusing at 85°. C. MONOBASIC, MONATOMIC ACIDS, CWH2W02 (FATTY ACIDS). The acids of this series are formed in general terms by oxidizing the primary alcohols, the group CIP.OH being hereby converted into CO.OII (carboxyl), and by heating the alcoholic cyanides (nitriles) with caustic potassa, the cyanogen group (GN) being transformed into COOH, and nitrogen in the form of ammonia being given off. The first member of the series is the hydro gen compound of carboxyl H.CO.OH ; the homologous members, C2ETO2 - CIP.COOH, C3IP02=C2IP.CO.OH, etc., must be considered as derivatives of the marsh gas hydrocarbons, formed by the displacement of an atom of hydrogen by the monovalent group, COOH. In regard to the isomeric compounds that are possible in connection with the individual members of the series, the remarks made under the head of alcohols are here equally applicable. Each hydrocarbon can yield just as many monobasic acids (carboxyl-deriva- tives) of different constitution, as it can form mona- tomic alcohols (hydroxyl-derivatives). Hence only one acid of the composition of each of the three first members of the series can exist. Of the fourth member, C4H802=C3H7. COOH, two differently consti tuted varieties are possible, CH3.CH2. CIP.COOII and CH.CO.OH; of the fifth member, C5H1002 = C4IP.CO.OH, four varieties are possible; of the sixth member, C6H1202 ^ C'IP.CO.OII, eight, etc. 76 FORMIC ACID. 1. Formic Acid. CIPO2 = H.CO.OH. Occurrence. In ants, in common nettles, in pine needles. Formation, (a) From carbonic oxide; potassium hydroxide unites with it when heated for some time at 100°, forming potassium formate ; (b) from carbonic anhydride ; potassium spread out on a basin under a bell-jar inserted in lukewarm water and kept constantly filled with carbonic anhydride is converted into a mix ture of potassium formate and bicarbonate ; it, in fact, always results in small quantities whenever hydrogen in stain nascendi and carbonic anhydride in a state of transmission come together, as, for instance, by the action of sodium-amalgam on a concentrated solution of ammonium carbonate, by tha addition of a mixture of zinc and zinc carbonate to hot caustic potassa ; (c) from methyl alcohol by means of oxidation ; (d) from prussic acid by treating with alkalies or dilute acids ; (e) from oxalic acid, by heating, or by the action of sunlight upon an aqueous solution of the acid contain ing a salt of uranium ; (/) from chloroform, iodoform, and bromoform by treatment with alcoholic potassa ; (^7) from a large number of organic substances, starch, sugar, tartaric acid, etc., by distillation with dilute sul phuric acid and black oxide of manganese or potassium chromate. Preparation. By distilling ants with water. — Most practicably by treating crystallized oxalic acid with glycerin, from which the water has been separated as thoroughly as possible. The reaction commences at 70° and is in full progress at 90°. Carbonic anhydride escapes, and a very dilute formic acid distils over. When the evolution of carbonic anhydride begins to grow less active, a fresh quantity of oxalic acid is added and heat again applied. A more concentrated acid now goes over, and, by continued addition of oxalic acid, an acid containing 56 per cent, is finally obtained. — For the purpose of obtaining the acid in an anhydrous con dition, the lead or copper salt is prepared, dried, and FORMIC ACID. 77 decomposed with sulphuretted hydrogen: the acid, which is by this means set free, is distilled off and rectified ove* dried lead or copper formate. Or ^ anhy drous oxalic acid is dissolved in 70 per cent, formic acid (obtained by carefully heating glycerin with dried oxalic acid) by the aid of gentle heat, the solution allowed to cool, poured off from the oxalic acid that crystallizes out, and rectified. Properties. Colorless liquid of a pungent odor, crys tallizing below 0° ; specific gravity, 1.223 at 0° ; boiling point, 99°; fusing point, -f 1°. Acts as a vesicant. Decompositions. Concentrated sulphuric acid resolves it into water and carbonic oxide. Heated with mercury or silver oxide, it is converted into water and carbonic acid, the oxides being reduced. All formates are soluble in water. The salts of the alkalies are deliquescent in the air. Ammonium formate, CH02.KH4, is decomposed when heated up to 110, forming prussic acid and water. Barium formate, (CH02)2Ba, crystallizes in prisms, which are not changed by contact with air. Lead formate, (CH02)2Pb. Lustrous, difficultly soluble needles.— Copper formate (CH02)2Cu + 4II20. Large, blue, transparent crystals. When heated yields formic acid of 82 per cent. — Silver formate CH02Ag. White crystals, which are decomposed when heated, yielding carbonic anhydride, silver, and formic acid. — Mercury formate (CH02)2Hg conducts itself in a similar manner; when heated it is, however, at first converted into the difficultly soluble salt of the suboxide, carbonic anhydride being evolved. Methyl formate, HCO.O.CII3. By the distillation of sodium formate with methyl sulphate. — Colorless liquid of pleasant odor, boiling at 36°. Ethyl formate, HCO.O.C2!!5. By the distillation of 7 parts dried sodium formate with a mixture of 10 parts sulphuric acid and 6 parts 90 per cent, alcohol. 7* 78 ACETIC ACID. More readily by heating a mixture of glycerin with oxalic acid and alcohol, in an apparatus in which the vapors are condensed and returned to the flask. When the evolution of carbonic anhydride has ceased, the ether, which has been* formed, is distilled off. — Color less, spicy-smelling liquid, soluble in 10 parts of water ; boils at 55°. 4 Amyl formate, IICO.O.C5!!12, obtained like the ethyl ether. — A fluid, boiling at 112°, having a fruity odor. Formylamide, IICO.OT!2, is formed when ethyl formate, which has been saturated with ammonia, is heated for several days at 100° ; and by heating 2 parts dry ammonium formate with 1 part of urea up to 140°. Is formed also, together with ether products, by the destructive distillation of ammonium formate, and by heating formates with ammonium chloride. — Colorless liquid, boiling at 192-195°. Can only be distilled in a vacuum without decomposition. 2. Acetic Acid. C2II402 = CH3.CO.OH. Formation and preparation. By the decay of a great many organic bodies ; by the destructive distilla tion of wood, sugar, starch, tartaric acid, and numerous other substances. — From alcohol under the influence of oxidizing agents or such substances as cause its oxida tion in contact with the air. Sodiummethyl combines with carbonic anhydride, forming sodium acetate. Alcohol, in contact with black powdered platinum, is converted into concentrated acetic acid, an elevation of temperature and absorption of oxygen from the air accompanying the action. Certain organic substances act in a similar manner to platinum; through their agency dilute alcohol, at a temperature of 20-40°, is caused to absorb oxygen from the air and is tranformed into acetic acid. Hence the power of every fermented liquid, i. e. vegetable juice containing alcohol, to become ACETIC ACID. 79 acid when left in contact with the air. In this manner vinegar is formed, which is a mixture of acetic acid with a great deal of water and small quantities of acci dental foreign substances. It is obtained by allowing wine, beer, fermented fruit juices, particularly after the addition of a small quantity of vinegar, to acidify spontaneously, in vessels which permit the access of air and are kept warm. Or by a similar acidifying of fermented beer wort, or ot mixtures of brandy arid water with honey and a fer ment. This takes place most readily in the German process for the manufacture of vinegar (Schnellessigfa- brikation); in which the liquid to be acidified is ex posed to the air in such a manner that as much surface as possible may be presented to its action. This is effected by allowing the liquid to flow slowly through a high cask filled with -beech shavings, the sides of the cask being furnished with air holes. The shavings must be previously steeped in vinegar. By distilling vinegar the acetic acid can be freed from the foreign substances with which it is mixed, but the water cannot be removed by this means. The anhydrous acid is obtained by distilling 5 parts anhydrous sodium acetate with 6 parts concentrated sulphuric acid, or also by distilling an intimate mixture of equal parts of anhydrous lead acetate and fused potassium bisulphate. A large quantity of acetic acid is obtained by the destructive distillation of wood (wood vinegar). The watery distillate is saturated with sodium carbonate, evaporated, the dried sodium salt heated for a length of time at 230-250° for the purpose of destroying any organic impurities which may be present, dissolved in water, filtered, evaporated and the heating repeated if necessary. Properties. Colorless liquid of a penetrating and pleasant acid odor, of a sharp acid taste, caustic ; specific gravity, 1.056 at 15.5° ; fumes slightly in the air ; boils at +119° ; its vapor is inflammable and burns with a blue flame. It crystallizes in lustrous, transpa rent tablets, which fuse at +17°. Miscible with water in all proportions. At first the specific gravity 80 ACETIC ACID. of this mixture increases. The acid containing 77-80 per cent, has the highest specific gravity, 1.0754 at 15.5°. Then it decreases, and an acid of 50 per cent, has about the same specific gravity as the anhydrous acid. When the acid contains water, it does not crys tallize even at 0°. Potassium acetate, C2H302K. A white, very deli quescent salt, also soluble in alcohol. From a solution of this salt in concentrated acetic acid is deposited, on evaporating, a salt, C2H302K -1- C2H402, in laminae, pos sessing a mother-of-pearl lustre. This salt fuses at 148°, and at 200° is resolved into acetic acid 'and potas sium acetate.— Sodium acetate, C2IL*02Nsi+ZK20. Clear, prismatic, easily soluble crystals. — Ammonium acetate, C2H302.KH4. White salt. Its solution loses ammonia w^hen evaporated. Subjected to dry distillation, it yields acetamide. Barium acetate, (C2H302)2Ba, crystalline, easily soluble salt. Iron acetate. The salt of the suboxide, (C2H302)2Fe, forms green, easily soluble prisms. The salt of the oxide does not crystallize ; it forms a deep red solution, from which all the iron is precipitated as a basic salt by boiling. Lead acetate, (C2H302)2Pb ± 3H20. Sugar of lead. Is prepared on the large scale by dissolving ground litharge in distilled acetic acid. — Colorless, lustrous prisms of a disagreeable, sweet taste ; poisonous. Easily soluble in water and also in alcohol. Fuses at 75° in its water of crystallization, loses this at 100° and con geals. At a high temperature it fuses again and loses one-third of its acetic acid, which escapes as carbonic anhydride and acetone. The solidified residue is a basic salt, which at a still higher temperature decom poses, yielding lead oxide, carbonic anhydride and acetone. Basic salts can also be obtained by digesting a solution of sugar of lead with lead oxide. It com- ACETIC ACID. 81 bines with lead chloride, iodide, and bromide, forming easily soluble compounds. Copper acetate, (C2H302)2Cu+IPO. Dark green, untransparent, rhombohedral crystals. Difficultly solu ble in water. Crystallizes at a low temperature with 5 molecules of water in transparent, blue crystals, which are converted, at 30°, into crystalline aggregates of a green salt. Verdigris, a mixture of several basic salts, is obtained by the action of vinegar or acid grape skins on sheet-copper. Blue or bluish-green, fine, crys talline mass, only partially soluble in water. Copper acetate combines directly with other acetates and also with salts of other acids. Schweinfurt green is such a compound with copper arsenite. Silver acetate. C2H302Ag. Lustrous, pliant needles or laminae, difficultly soluble in water. Methyl acetate, C2H3O.O.CIP. Is present in crude wood-spirit ; and is obtained by distilling acetates with methyl alcohol and sulphuric acid. — A liquid of plea sant odor, soluble in water and alcohol ; boiling at 55°. Treated with chlorine, there is formed a series of liquid substitution-products, which crystallize with water.* Bromine does not act upon it at ordinary temperatures ; at 150°, however, are formed methyl bromide, acetic acid, mono- and dibromacetic acids. Towards sodium it conducts itself the same as the ethyl ether. Ethyl acetate (Acetic ether), C2II3O.O.C2H5. By distilling 10 parts of sodium acetate with a mixture of 15 parts of sulphuric acid, and 6 parts of alcohol. — Thin liquid, very pleasant, refreshing odor ; specific grav ity, 0.905 at 17°;boils at 72.1°; very inflammable. Soluble in 11 parts of water ; is converted, however, by it into acetic acid and alcohol. It conducts itself towards bromine and chlorine the same as the methyl ether. — * The same compounds are formed by the action of chlorine on citrio acid and several other organic compounds. They were formerly con sidered as chlorinated acetones. 82 ACETIC ACID. Sodium is dissolved by it, giving rise to the formation of sodium ethylate and of a compound, C6H9NaO3 (so dium ethyldiacetate or sodium acetonecarbonic ether), which is decomposed into sodium carbonate, carbonic anhydride, alcohol, and acetone by the boiling of its watery solution, and yields a colorless compound, boil ing at 181°, C6H1003 (acetyl-acetic ether, ethyl-acetone carbonate, ethyl-diacetic acid), on being heated in a current of dry carbonic anr^dride or hydrochloric acid gas. By the successive action of an excess of sodium and ethyl iodide on acetic ether, there result, in addi tion to the ethyl compound, C6H903.C2H5 (boiling point, 198°), corresponding to the above sodium compound, the ethyl ethers of diethyldiacetic add (diethacetone carbonic acid), C8H1303.C2IF (boiling point, 210-212°), of butyric add, C4IF02.C2H5 (boiling point, 119°), and of dietkylacetic add, C6IIn02.C2II5 (boiling point, 151° ; isomeric with ethyl caproate). — Analogous products result by. the successive action of sodium and the iodides of other alcohol radicles. Amyl acetate, C2H302.C5Hn. A liquid, boiling at 140°, with a fruity odor. Monochloraeetic acid, C2H3C102 = CIPC1.CO.OH, results from the action of chlorine on concentrated acetic acid, particularly in the presence of iodine, and by the decomposition of chlorinated acetyl chloride (which see) with water. — Rhombic plates or prisms, fusing at 62°; boiling at 185-187°. Yields glycolic acid by boiling with the alkalies in aqueous solutions or with silver oxide and water ; by heating with am monia, glycocol. The potassium salt, C2H2C102.E: + 1JH20, crystallizes in laminae ; the silver salt, C2H2C102Ag, in small scales of a mother-of-pearl lustre. Ethyl monochloracetate, C2H2C10.0.C2H5. A so lution of chloracetic acid in absolute alcohol is saturated with hydrochloric acid gas, then heated gently for some ACETIC ACID. 83 time on a water-bath, the ether precipitated with water and purified by means of distillation.— Colorless liquid, boiling at 143.5°, but slightly soluble in water. Dichloracetic acid, C2H2C1202 - CHCRCO.OH is formed by the further action of chlorine on monochlor- acetic acid in the presence of iodine.— A liquid, boil ing at 195°, forming, when perfectly pure, rhombohe dral crystals. Ethyl dichloracetate, C2HC12O.O.C2H*, is obtained by conducting dried hydrochloric acid gas into a solu tion of the acid in absolute alcohol ; is also formed by heating carbon chloride, C2C14, with sodium ethylate.— Heavy liquid, boiling at 153-158°. Is decomposed when kept for any length of time, or when agitated with caus tic soda, forming oxalic acid and hydrochloric acid. Trichloracetic acid, C2HC1302, is formed by the action of an excess of chlorine on acetic acid in direct sunlight ; by the decomposition of trichloracetyl chloride by water, and by the action of chlorine in direct sun light on carbon chloride, C2C14, in presence of water ; and is prepared most readily by the oxidation of chloral with fuming nitric acid.— Colorless, rhombohedral crys tals, deliquescent; fuses at 46°; toils at 195-200°. Combines with bases forming crystalline salts. "When boiled with ammonia, it is resolved into chloro form and potassium carbonate, potassium formate, and potassium chloride. Mono- and Dibromacetic acids, C2H3Br02 and OTPBr^O*, are formed when acetic acid or acetic ether is heated with bromine in sealed tubes at 180°. Mono- bromacetic acid forms deliquescent rhombohedral crys tals, and boils at 208° ; dibromacetic acid, a crystalline mass, fusing at 45-50° and boiling at 232-234°. The salts of both acids are somewhat unstable. Ethyl mono- bromacetate is a colorless liquid, boiling at 159° with partial decomposition. Its vapor attacks the eyes vio lently.— Tribromacetic acid, OTEtBrK)2, results by the 84 ACE TIC ACID. action of water on tribromacetyl bromide (which see). —Crystals, which fuse at 130°, and boil at 245°. lodoacetic acid, C2H3I02. Is produced when a mixture of acetic anhydride, iodine, and iodic acid is heated to boiling (140°), a violent reaction taking place. — Ethyl bromacetate is decomposed by potassium iodide, forming potassium bromide and ethyl iodoace- tate, and this, when heated with baryta water, gives barium iodoacetate, which, treated with sulphuric acid, yields the acid. — Colorless plates, which fuse at 82° with partial decomposition. When heated with hydri- odic acid, it is reconverted into acetic acid. Most of its salts are decomposed, when merely boiled with water. — Diiodoacetic acid, C2H2I202, is obtained in a similar manner. Cyanacetic acid, C3H3M)2 = CH2(CN"),CO.OH. Monochloracetic acid (5 parts) is boiled with potassium cyanide (6 parts) and water (24 parts) until the smell of prussic acid can no longer be detected ; the liquid is then neutralized exactly with sulphuric acid, evaporated down to a small volume, filtered, supersaturated with sulphuric acid, and by agitating with ether the cyan- acetic acid extracted. The crude acid, that remains behind after the evaporation of the ether, can be puri fied by conversion into its lead salt and decomposition of this with sulphuretted hydrogen. — Colorless, crys talline mass. Its salts, with the exception of the silver and mercury salts, are easily soluble in water. Amidoacetic acid (Ghjcin, Glycocol}, C2H5]TO2 = CH2(OTI2)CO.OIL Is produced from chlor- and brom- acetic acids by heating with ammonia, Hippuric acid (which see), when boiled with acids or alkalies, is re solved into glycocol and benzoic acid. Glycocholic acid (which see), treated in the same manner, yields glycocol and chplic acid. It is produced further by boiling glue with sulphuric acid or potassa. — It is prepared most practicably by boiling hippuric acid for an hour with four times its weight of concentrated hydrochloric ACETIC ACID. 85 acid, allowing to cool, filtering the benzoic acid off, and evaporating the filtrate. Grlycocol hydrochlorate remains behind. To an aqueous solution of this, lead or silver oxide is added, the lead or silver chloride filtered off, and, after the removal of any lead which may remain dissolved, by means of sulphuretted hydrogen, the solution is evaporated to crystallization. Large c^stals, stable in the air, soluble in 4 parts of water, but little in alcohol. Fuses at 170° ; not volatile without decomposition. The watery solution possesses an acid reaction. It combines with bases, acids, and salts. The copper salt (C2H4K02)2Cu + IPO, prepared by dissolving copper oxide in a hot solution of glycocol, separates on cooling in needles of a deep-blue color. — The silver salt C2H4]Nr02.Ag is obtained by allowing a solution of glycocol, which is saturated with silver oxide, to evaporate slowly over sulphuric acid. Ethyl ether of glycocol, CH2(OTI2).CO.O.C2H5. The hydriodate of this ether is obtained by heating an alcoholic solution of glycocol with ethyl iodide at 115- 120°. — Clear, rhombic crystals, soluble in water, alcohol, and ether. Silver oxide removes the hydriodic acid from this compound, but the free ether decomposes, when its solution is evaporated, yielding glycocol and alcohol. Glycocol combines with hydrochloric acid, forming two crystallizing salts, C2H5N02.HC1 and 2(C2H5N02). HCL— Glycocol ^nitrate CWNO.IINO3 crystallizes in prisms. In addition to these there are a number of crystal lizing compounds with chlorides, sulphates, and nitrates known. Heated with dry caustic baryta, glycocol yields car bonic anhydride and methylamine. When its aqueous solution is treated with nitrous acid, glycolic acid is produced. Methylglycocol (Sarcosine), C3H7N02 = CH2 (NH.CH3).CO.OH. Is produced by the action of methyl- 8 86 ACETIC ACID. amine on chloracetic acid; by the evaporation of a solution of creatine (which see) with barium hydroxide ; and by heating caffeine for several hours with barium hydroxide. — Colorless, rhombic prisms, easily soluble in water, less in alcohol, fuses somewhat above 100°, and sublimes undecomposed. Yields salts with acids and with bases. Ethylglycocol, CH2(NH.C2H5).CO.OH (isomeric with the ethyl ether of glycocol), is formed from ethyl- amine and monochloracetic acid. — Small, laminated crystals, which deliquesce in the air, become brown at 150-160°, and fuse at a higher temperature, undergoing decomposition. Like glycocol, it combines with acids, bases, and satis.— Diethylglycocol C2H3pST(C2H5)2]02 is obtained from monochloracetic acid by the action of diethylamine. — Deliquescent crystals, which sublime under 100°. Acetylglycocol (Aceturic acid), CH2(NH.C2H30). CO.OH, results by the action of acetyl chloride on glycocol silver. — Small, white needles, soluble in water and alcohol, which turn brown at 130°. Monobasic acid; forms easily soluble salts. In the preparation of glycocol from monochloracetic acid and ammonia, there are formed as secondary pro ducts: Diglycolamidic acid C4H7N04 and triglycolamidic acid C6H9]N~06. Both compounds crystallize well and unite with bases and acids. {SO2 OH CO OH is formed by the action of sulphuric anhydride on acetic acid with the aid of heat. Its salts with the alkalies are produced by heating monochloracetic acid with concentrated solu tions of alkaline sulphites. — Colorless, deliquescent prisms ; fusing point, 62°. Bibasic acid. — The barium salt CH2 £Q'o Ba + H20 crystallizes in laminse.— When heated with sulphuric acid, it is converted into disulphometholic acid and carbonic anhydride. ACETIC ACID. 87 Thiacetic acid, C2H4OS = CEP.CO.SH, is produced by distilling concentrated acetic acid with phosphorus tersulphide or pentasulphide. — Colorless liquid, which turns yellow when left for any length of time ; smells of acetid acid and sulphuretted hydrogen ; boils at 93° ; and is soluble in water and in alcohol. Its salts are soluble in water. The lead salt, (C2H3O.S)2Pb, forms colorless needles, which are decomposed easily, sulphur being thrown down. Acetic anhydride, (C2H30)20, is obtained by dis tilling 3 parts anhydrous sodium acetate and 1 part phosphorus oxichloride; or, better, by distilling equal parts by weight of acetyl chloride and anhydrous sodium acetate. — Colorless liquid, boiling at 138°, heavier than water, decomposed rapidly by it, forming acetic acid. With hydrochloric acid it yields acetic acid and acetyl chloride; with chlorine, monochlor- acetic acid and acetyl chloride. Bromine acts the same as chlorine. Phosphorus sulphide converts it into thiacetic anhydride (C2H30)2S, a yellowish liquid, boiling at 121°. Acetyl hyperoxide, (C2H30)202, is obtained by adding barium peroxide to an ethereal solution of acetic anhydride. After distilling off the ether at a very low temperature, washing with water and potas sium carbonate, it remains as a thick, consistent liquid. Is rapidly decomposed in sunlight; explodes when gently heated, like nitrogen chloride. Powerful oxi dizing agent, decolorizes indigo, separates iodine from potassium iodide, and converts potassium ferrocyanide into the ferricyanide. Acetyl chloride, C2H3O.C1 = CHACOCl, is formed when dry hydrochloric acid gas is allowed to act upon acetic acid in the presence of phosphoric anhydride ; by the action of phosphorus terchloride, pentachloride, or oxichloride on acetic acid or dry acetates. Is most readily prepared by carefully distilling a mixture of 9 ACETIC ACID. parts acetic acid and 6 parts phosphorus tcrchloride on a water-bath. — Colorless liquid, boiling at 55° ; is de composed by water, forming acetic and hydrochloric acids. Dry chlorine gas converts it, in sunlight or in the presence of iodine, into substitution-products: C2H2C10.C1 (boiling point, 106°), C2IIC12O.C1 and C2CPO.C1 (boiling point, 118°). The same substances are produced by heating mono-, di-, or trichloracetic acids with phosphorus terchloride. Acetyl bromide, C2H3O.Br, is produced by the action of phosphorus bromide on acetic acid. — Colorless liquid, boiling at 81°. Yields with bromine liquid sub stitution-products : OTPBrO.Br (boiling point, 149- 151°), C2HBr2O.Br (boiling point, 194°), C2BiO.Br (boiling point, 220-225°). Acetyl iodide, C2H3O.I, is obtained by the action of iodine and phosphorus on acetic anhydride. — Liciuid, boiling at 108°. Acetyl cyanide, C2IPO.Cy, is formed by heating the chloride with silver cyanide. — Liquid, boiling at 93°. Conducts itself towards water like the chloride. By being preserved in imperfectly closed vessels and by treating with solid potassium hydroxide or sodium hydroxide it is converted into a polymeric crystalline compound (C2II3O)2Cy2, which fuses at 69° and boils at 208-209°. Acetamide, C2H3O.KE2 = CIRCO.OTI2, is formed by distilling ammonium acetate and by decomposing acetic ether by means of ammonia. The latter forma tion takes place slowly without the aid of heat, rapidly when the substances are heated to 120-130°.— Colorless crystals, easily soluble in water and alcohol ; fuses at 78° ; boils at 222°. Combines with metals (C2H4^0)2Hg and with acids (C2H5NO.IICL), forming unstable com pounds. Chloracetamide, CIPCl.CO.OTI2. Is produced from ethyl chloracetate and ammonia at the ordinary PROPIOJSTIC ACID. 89 temperature. — Colorless, thick prisms; fusing point, 119.5°. Amidoacetamide, CH2(^H2)CO.ISrH2. The hydro- chlorate is formed by heating ethyl chloracetate with an excess of an alcoholic solution of ammonia to 60- 70°, the free compound by heating glycocol with alco holic ammonia to 155-156°. — White mass, very easily soluble in ammonia; strongly alkaline; undergoes a partial spontaneous decomposition into glycocol and ammonia, when its aqueous solution is allowed to evaporate in contact with the air. Takes up carbonic anhydride from the air. It is hence difficult to obtain it in a free condition.— The hydfochlorate C2H6N2O.HC1 consists of easily soluble prisms. Diaeetamide, (CH3.CO)2ML Is formed, together with other bodies, by heating acetamide in a current of dry hydrochloric acid, and by heating acetonitrile with concentrated acetic acid up to 200°. — Colorless crystals, easily soluble in water; fusing point, 59°; boiling point, 210-215°. Triacetamide, (CIP.CO)3]^. Is formed when aceto nitrile is heated for a long time with acetic anhydride to 200°. — Small, colorless crystals; fusing point, 78- 79°. 3. Propionic Add. C3H602 == CHACH2.CO.OH. Formation and preparation. In small quantity, to gether with acetic acid, by the dry distillation of wood. From metacetone (see cane-sugar) and other acetones by oxidation. From sugar by the action of concen trated potassa. Sodium ethylate combines with car bonic anhydride, forming sodium propionate. Carbonic oxide and sodium alcoholate unite, forming sodium propionate. — Is prepared most practicably by boiling propionitrile (see p. 47) for a long time with an alco- 90 PROriONIC ACID. liolic solution of potassa, evaporating, and distilling the residue with sulphuric acid. Properties. Colorless, clear liquid, with an odor resembling that of acetic acid; specific gravity, 0.992 at 18°; boiling point, 139°. Mixes with water in all proportions, can be separated from this solution by means of calcium chloride. Its salts are all soluble in water. The silver salt, C3II502Ag, crystallizes in small needles, which are difficultly soluble in cold water. Ethyl propionate, C3IFO.O.C2H5. Is prepared like acetic ether. — Colorless liquid, boiling at 100°. Substitution-products of propionic acid. Of each of the simple substitution-products, formed by the displacement of one hydrogen atom by a monovalent element or a monovalent group, two varieties can exist. Their difference results from the difference in position of the substituted hydrogen atoms ; it being in the one case in the group CH3, in the other in the centre group CH2. The direct action of chlorine, etc., appears only to cause the substitution of hydrogen, that is in com bination with the central carbon atom. a-Chlorpropionic acid, C3H5C102 = CIP.CHCl.CO. OH. Is prepared by the decomposition of lactyl chloride (see Lactic Acid) with water. — Colorless liquid, boiling at 186° ; specific gravity, 1.28.— The ethyl ether of this acid C3H5C10.0.C2H5 is obtained by bringing lactyl chloride together with alcohol, and by the action of phosphorus terchloride on lactic ether. — Licmid, boilino- at 144°. /3-Chlorpropionic acid, C3H5C102=CII2C1.CH2.CO, OIL The crystalline chloride of this acid (C3H5O.C10.C1) is formed by the action of 3 molecules phosphorus pentachloride on lead gly cerate or glyceric acid. Yields with alcohol ethyl $-chlorpropionate C3H5C10.0.C2IP, a liquid that boils at 150-160°. From this is obtained the free acid by treating with baryta water, and decom- PROPIONIC AG'ID. 91 posing the salt formed by means of sulphuric acid. Can also be prepared by boiling iodopropionic acid with chlorine water. — Fibrous, fascicular crystals, which fuse at 65°. The ethers of the two acids when boiled with potassium cyanide yield two different cyanpro- pionic acids. a-Brompropionic acid, CH3.CHBr.CO.OH, is pro duced together with dibrompropionic acid by heating propionic acid with bromine in sealed tubes ; also by heating lactic acid with concentrated hydrobromic acid. It is a liquid, boiling at 202°, congealing at — 17°.— Dibrompropionic acid, C^KBr'O2, is also formed by the oxidation of allylalcohol bromide. — Colorless crystals that fuse at 65° and boil at 227°. 0-Brompropionic acid, CIPBr.CIP.CO.OII. Is ob tained by heating j3-iodopropionic acid with bromine and water. — Colorless crystals, fusing at 61.5°. a-Iodopropionic acid, CH3.CHLCO.OH. Obtained by the action of phosphorus iodide upon lactic acid. — Thick oil, scarcely soluble in water. /3-Iodopropionic acid, CH2I.CII2.Cp.OH. Is formed by treating glyccric acid with hydriodic acid (phos phorus iodide and water). — Colorless crystal-plates, easily soluble in hot water ; fusing point, 82°. Yields propionic acid, when heated to 180b with hydriodic acid. a-Amidopropionic acid (Alanin), C3II7^02=CH3. CH(OTI2).CO.OH. Is produced by heating a-chlorpro- pionic acid or ethyl a-chlorpropionate with an aqueous solution of ammonia. Can be most readily prepared by boiling an aqueous solution of aldehyde-ammonia (2 parts) for a long time with hydrocyanic acid (1 part anhydrous) and an excess of hydrochloric acid. Sal- ammoniac is separated from the concentrated solution by means of alcohol, and, from the alanin hydrochlorate in solution, the alanin is obtained in the same manner as glycocol (p. 85) is obtained from its hydrochlorate. 92 BUTYRIC ACIDS. • — Hard, fascicular needles, soluble in 5 parts cold water, more easily in hot water and alcohol. When carefully heated it sublimes ; when rapidly heated it decomposes, yielding ethylamine and carbonic anhydride. It com bines, like glycocol, with bases, acids, and salts. /3-Amidopropionic acid, CH2(OTI2)CH2.CO.OH. Is obtained, like afanin, from 0-iodopropionic acid. — Color less, transparent, oblique rhombic prisms. Easily solu ble in water, but slightly in absolute alcohol. When heated it fuses and decomposes, carbon being deposited. When very carefully heated to 170° it sublimes par tially in needles. The remaining derivatives of propionic acid are pre pared in the same manner as the corresponding deriva tives of acetic acid. Propionyl chloride, C3IPO.C1. Liquid. Boiling point, 80°. Propionyl bromide, C3II5O.Br. Liquid. Boiling point, 96-98°. Propionyl iodide, C3IPO.I. Liquid. Boiling point, 127-128°. Propionylamide, C3IPO.NH2. Colorless prisms, fusing at 75-76°. 4. Butyric Acids. C4H802=C3H7.CO.OII. Theoretically there are two acids of this composition possible (p. 75). Both are known. 1. Normal butyric acid (butyric acid of fermen tation), CH3.CH2.CH2.CO.OH. Is contained in a great many animal juices, and in the form of the glycerin ether in butter. — Is produced by the oxidation of nor mal butyl alcohol and, in small quantity together with acetic acid and other acids, by the dry distillation of BUTYRIC ACIDS. 93 wood. Its ethyl ether is produced together with other substances by the successive action of sodium and ethyl iodide on acetic ether (p. 82). — Most readily obtained by the fermentation of sugar. 3 kilogrammes cane-sugar and 15 grm. tartaric acid are dissolved in 13 kilogrammes boiling water and allowed to stand for a few days ; then about 120 grm. rotten cheese, suspended in 4 kilo grammes sour milk, and 1 J kilogrammes chalk, are added, and the whole allowed to remain unmolested in some place, where the temperature is kept at 30-35°. In ten days the mass becomes pulpy from the presence of calcium lactate, which has separated ; at a later period hydrogen is evolved together with carbonic anhydride, the mass again becomes a thin liquid, and in the course of five or six weeks the fermentation is completed. Now the same volume of water and 4 kilogrammes crystal lized sodium -carbonate are added, the calcium carbo nate filtered off, the filtrate evaporated to about 5 kilo grammes, and then mixed with 2} kilogrammes sul phuric acid previously diluted with water. The prin cipal amount of butyric acid separates as an oily layer. It is removed, desiccated by means of calcium, chloride and then rectified. By distilling the residual solution of the salt, the dissolved acid can be obtained from this. Colorless liquid, boiling at 157° ; specific gravity, 0.988 at 0° ; mixes with water in every proportion; is, however, thrown down from its watery solution by easily soluble salts. It is not acted upon by potassium bichromate and sulphuric acid ; by continued oxidizing with nitric acid, a small portion is converted into suc- cinic acid. Its salts are soluble in water. Calcium butyrate, (C4IF02)2Ca, is less soluble in hot water than in cold. A solution, saturated at the ordinary temperature, on being heated, throws down nearly all the dissolved salt, in the form of lustrous laminae. Silver butyrate, C4H702Ag, crystallizes from hot water in microscopic prisms. 94 BUTYRIC ACIDS. Ethyl butyrate, pleasant odor, boili C4IFO.O.C2H5. Colorless liquid of ing at 119°. Butyroacetic acid, C°H1204, a remarkable com pound of butyric with acetic acid, is produced by the fermentation of crude calcium tartrate. It forms salts, but the free acid, when subjected to partial distillation, is decomposed into equal molecules of butyric and acetic acids. Substitution-products. Of each substitution-pro duct, in which one hydrogen atom is replaced by a monovalent group, there are three modifications possi ble. Up to the present, but few of them have been prepared, and their constitution is not well known. Monochlorbutyric acid, C4H7C102. By the action of chlorine on butyric acid in the presence of iodine. — Fine, pliant needles. Easily soluble in hot water. Fuses at 98-99°, and sublimes at 80°. A non-crystalline, viscid acid, isomeric with this, is produced by the decomposition of chlorbutyryl chloride with water. Monobrombutyric acid, C4H7Br02 (a liquid, which does not congeal at — 15° ; boiling at about 217°, not, however, without undergoing decomposition), and dibromhutyric acid (colorless, long, thin prisms, fusing at 45-48°) are produced by heating butyric acid with bromine. Amidobutyric acid, C4H7(lsrH2)02. From mono- brombutyric acid and ammonia. — Small laminae or needles, easily soluble in water, difficultly in alcohol, insoluble in ether. pTT3 \ 2. Isobutyric acid, Qjp [ CH.CO.OH. Is contained in the Carob bean (the fruit of Ceratonia siliqua). Is obtained from pseudopropyl cyanide (p. 67) by heating with alkalies and by the oxidation of isobutyl alcohol VALERIC ACIDS. 95 . ). — A liquid very similar to butyric acid ; is, how ever, more difficultly soluble in water (in 3 parts at the ordinary temperature) ; boils at 153-154°. Calcium isobutyrate, (C4H702)2Ca + 5H20, crystal lizes in long prisms, and is much more easily soluble in hot than in cold water. Silver isobutyrate, C4H702Ag, crystallizes from hot water in lustrous laminse. Monobromisobutyric acid, C4H7Br02 = CH3 j- CBr.CO.OH. By heating isobutyric acid with bro mine to 140°. — Colorless crystals, fusing at 45°, not volatile without decomposition. Becomes oily on being mixed with water; over sulphuric acid in a vacuum, it congeals again. But slightly soluble in cold water, soluble in every proportion in hot water. 5. Valeric Acids. = C4H9.CO.OH. Of the four acids of this composition, which are theoretically possible, only two are well known. 1. Normal valeric acid, CIP.CH2.CH2.CH2.CO.OH. Is prepared from butyl cyanide like propionic acid. Is also obtained by the oxidation of the mixture of alcohols from the amyl hydrides of petroleum.— Color less liquid, with an odor like that of butyric acid. Boiling point, 184-185°; specific gravity at 0°, 0.9577. The barium salt (C5H902)2Ba crystallizes in small anhydrous laminse. 2. Ordinary valeric acid (Isopropylacetic acid), CH.CH2.CO.OH. Is contained in the root of Valeriana and Angelica qfficinalis and of Athamanta oreoselinum ; in the berries and bark of Viburnum 96 VALERIC ACIDS. opulus ; in the oil of Delphinum globiceps. — Is produced by the oxidation of amyl alcohol ; by warming isobutyl cyanide with potassa ; the ethyl ether is produced by the successive action of sodium and isopropyl iodide on acetic ether. It is produced further by the oxida tion of fats and of leucine ; by the putrefaction of albu minoid substances (hence contained in old cheese). — To prepare it, valerian roots are distilled with water. — More practicably from ferment amyl alcohol. To 5 parts potassium bichromate and 4 parts water in a retort, which is united with a condensing apparatus in such a manner that the condensed vapors are returned to it, is gradually added a mixture of 1 part amyl alcohol and 4 parts concentrated sulphuric acid. At first the liquid becomes heated spontaneously, afterward it is kept at the boiling temperature, until oily streaks (of valeric aldehyde) are no longer observable in the neck of the retort, then distilled off. The distillate is neutralized with sodium carbonate, the amyl valerate, which separates, drawn or distilled off, and the dried salt decomposed with £ its weight of sulphuric acid, previously diluted with J its weight of water. The valeric acid, which separates, is drawn off, desiccated and rec tified. — Colorless liquid, with a peculiar, pungent, acid odor; specific gravity, 0.9468; boiling point, 171-172°. Soluble in 30 parts of water. Can be separated from this solution by means of easily soluble salts. The valerates of the alkalies are deliquescent salts. Barium valerate, (C5H902)2Ba, easily soluble, lus trous prisms of the triclinic system, or laminse. — Zinc valerate, (C5Il902)2Zn, separates, on the evaporation of its solution, in the form of lustrous scales. — Silver valerate, C5H902Ag, white precipitate, crystallizing from boiling water. Methyl valerate, C5IPO.O.CIP. Liquid, boiling at 115° ; insoluble in water. The ethyl ether, C5H9O.O. C2H5, boils at 133° ; the amyl ether, C5II9O.O.C5Hn, boils at 188°. CAPEOIC ACIDS. 97 The derivatives of valeric acid are perfectly analo gous to those of acetic and propionic acid. Amidovaleric acid (Butalanin), C5HlljN"02, occurs in the spleen, and in the pancreas of the ox. Is formed by heating bromvaleric acid with ammonia. — Colorless laminae; easily soluble in water. "When carefully heated, sublimable without decomposition, without previous fusion. Combines, like glycocol, with bases and acids. The valeric acid from valerian root, as well as that obtained by oxidation of amyl alcohol and of leucine from different albuminoid substances, appears almost always to consist of two acids in varying proportions, one of which is the optically inactive isobutylformic (isopropylacetic) acid, while the other is optically active. The barium salt of the latter is distinguished by being more easily soluble and by crystallizing less readily. The optically active valeric acid (probably methylethyl- acetic acid) boils, at the most, 1 to 1.5° lower than the inactive acid ; its specific gravity is higher, 0.9505 at 0°. Its power to act upon polarized light is completely removed by heating it with a few drops of concentrated sulphuric acid. 6. Caproic Acids. C6H1202=C5Hn.CO.OII. Of the eight acids of this composition, whose exist ence is indicated by the theory, four are known. 1. Normal caproic acid, CIP.CH2.CH2.CII2.CH2. CO.OII. Is prepared by treating normal amyl cyanide with alcoholic potassa. — Clear liquid, of a sharp, acid taste ; does not mix with water ; boiling point, 204.5- 205°; specific gravity, 0.9499 at 0°. The caproic acid, obtained by oxidation of the mixture of alcohols from the hexyl hydrides of petro leum and mamiite, is probably also normal caproic acid. 98 CAPROIC ACIDS. 2. Ordinary caproic acid (Isobutylacetic acid), Qg3 1 CH.CH2.CH2.CO.OH. Occurs, sometimes in a free state, sometimes in the form of the glycerin ether, in a number of plants (for instance, in the blossoms of Saty- rium hircinum, in the fruit of Gingko biloba, in cocoa-nut oil), further in butter and many other fats ; and results from the oxidation of fats and a number of albumi noid bodies. It is most readily obtained by boiling amyl cyanide with an alcoholic solution of potassa. Colorless liquid, but slightly soluble in water, with a sudorific odor; congealing at +5° ; boiling at 195- 198°. Leucine (Amidocaproic acid), C6H13N02, is exten sively distributed throughout the animal organism, is formed by the putrefaction of urine, glue, and protein substances, and by boiling them with dilute sulphuric acid. Eesults from valeric aldehyde, the same as ala- nine (p. 91) from acetic aldehyde. — Lustrous, colorless crystalline laminae; fuses at 170° ; sublimes when very carefully heated ; when rapidly heated, it is decomposed, yielding carbonic anhydride and amylamine. Soluble in 27 parts cold water ; but slightly in cold alcohol, more easily in hot alcohol. 3. Isocaproic acid, CH3 \ CH.CH j CQ QH is ob tained by heating the cyanide corresponding to amy- lenehydrate (p. 71) with potassa. — An oil but slightly soluble in water. Q2TT5 ) 4. Pseudo caproic acid (Diethylacetic acid), C2jp \ CH.CO.OH. The ether of this acid (boiling point, 151°) is produced from acetic ether by the action of sodium and ethyl iodide (p. 82). The acid separated from this is liquid. The remaining acids of this series have been but very slightly investigated in regard to their constitution. (ENANTHYLIC ACID, ETC. 99 Of most of them but one modification is as yet known ; but whether the acids of the same composition of dif ferent origins are really identical or not, is a question still to be answered, as the researches on the subject have not the necessary exactness. 7. (Enanihylic acid, C7H1402. Is produced by the ox idation of a number of fats, especially castor oil, and by oxidation of the mixture of alcohols prepared from the heptyl hydrides of petroleum. It is obtained most conveniently by the oxidation of its aldehyde (p. 108). — Liquid, of an agreeable, aromatic odor, but slightly soluble in water, boiling at 219-222°. 8. Caprylic add, C8H1602. In the fusel-oil of wine. As the glycerin ether in butter and other fats. Is produced by the oxidation of primary octyl alcohol. — Crystallizes in fine needles or laminae ; fuses at 16-17°; boils at 232-234°. 9. Pelargonic add, C9H1802. In the volatile oil of Pelargonium roseum. Results from the oxidation of oleic acid and oil of rue. — Crystalline mass ; fusing at 7°; boiling at 248-250°. An acid called nonylie add, probably identical with the preceding compound, is obtained from the cyanide of the alcohol derived from the volatile oil of Heradeum spondylium and other species of Heradeum. Fusing point, 253-254° ; specific gravity, 0.9065 at 17°. 10. Capric acid, C10H2002. In the fusel-oil of wine. As the glycerin ether in a number of fats (butter, cocoa-nut oil). — Crystalline mass, of a sudorific odor ; fusing at 30° ; boiling at 268-270°. 11. Laurie acid, C12H2402. In the form of the gly cerin ether in the fruit of Lauris nobilis, in pichurim beans, in cocoa-nut oil. — Needles of a silky lustre; fusing point, 43.6°. 12. Myristic add, C14H2802. In nutmeg-butter and in spermaceti. — Crystalline scales ; fusing at 53.8°. 100 PALMITIC ACID, ETC. 13. Palmitic ^ add, C16II3202. Palmitic and stearic acids, in the form of glycerin compounds, constitute the principal ingredients of most solid fats. It is present in large quantity, and partially in a free condition, in palm oil.^ In order to prepare it from fats, these are heated with caustic potassa (saponified), the soap (potas sium palmitate and stearate) precipitated from the solu tion and decomposed by hydrochloric acid. The acids are now dissolved in alcohol, and separated from each other by means of partial precipitation with magnesium acetate. If only 4 of the amount of the magnesium salt necessary for complete precipitation is added, magne sium stearate falls down almost free of the palmitate ; the succeeding precipitations contain the stearate mixed with palmitate ; the last precipitations are almost pure magnesium palmitate. The precipitates are now de composed separately by hydrochloric acid, and the free acids treated a few times more in the same manner. Fine white needles, which congeal after fusion in the form of a scaly, crystalline mass. Fusing point, 62°. 14. Margaric acid, C17H3402. Probably does not occur in nature. That which was formerly designated as such has proven to be a mixture of palmitic and stearic acids. ^ It is prepared artificially by boiling cetyl cya nide with caustic potassa. It resembles palmitic acid. 15. Stearic add, C18II3602. On the occurrence and preparation see Palmitic Acid. Crystallizes from alco hol in laminae; fuses at 69.2°, and congeals in crystal line scales. 16. Arachidic add, C20H4002, is contained in oil of earth-nut and in the fruit kernels of Nephelium lappa- ceum. 17. Bertie acid, C22I14402. In the oil expressed from the nuts of Moringa mix Behen. 18. Hydnic add, C25IP°02. In the anal glands of Micena striata. FORMIC ALDEHYDE. 101 19. Cerotic acid, C27IP402. In beeswax as a free acid. As ceryl ether in Chinese wax. 20. Melissic acid, C39H6002. Results from heating myricyl alcohol with soda-lime. Has not been detected in nature. D. ALDEHYDES, CnH2riO. Aldehydes are compounds which occupy an inter mediate position between the primary alcohols and the acids. They contain two atoms of hydrogen less than the alcohols, and one atom of oxygen less than the acids. They are produced by careful oxidation of the primary alcohols, the group CIP.OH being hereby transformed into the group CHO, which is com mon to all aldehydes. Hence, the aldehydes can also be considered as derivatives of the hydrocarbons, formed by the displacement of a hydrogen-atom by the monovalent group CHO. By the action of hydro gen in statu nascendi, they are reconverted into the primary alcohols ; under the influence of oxidizing agents, they are readily changed to acids. They pos sess strong reducing properties. 1. Formic Aldehyde (Methyl Aldehyde). 20 = H.CHO. Formation. Is produced when the vapors of methyl alcohol, together with air, are conducted over a plati num spiral, which at first is heated. The spiral be comes red and continues so during the operation. Is further formed by subjecting glycolic acid, calcium formate, or glycolate to dry distillation ; by treating methylene iodide (see p. 36) with silver oxide or silver oxalate. Properties. It appears that it can only exist at a high temperature in the form of gas. At the ordinary temperature, several (probably three) molecules com bine, forming a white, indistinctly crystalline mass, oxymethylene C3H603, which sublimes below 100°, fuses 102 ACETIC ALDEHYDE. at 152°, and at a somewhat higher temperature is con verted into gas. The specific gravity of the vapor is 1.06, corresponding to the simpler formula CH20. F9rmylsulphaldehyde, C3H6S3. When the liquid obtained by oxidizing methyl alcohol, or when pure oxymethylene, is saturated with sulphuretted hydro gen, a substance, having an alliaceous odor, separates, which dissolves, when the liquid is heated with half its volume of concentrated hydrochloric acid, and crystallizes out on cooling. Is also produced by the action of hydrogen in statu nascendi (zinc and hydro chloric acid) on carbon bisulphide, sulphocyanic acid, ethyl and allyl mustard-oils ; and by treating methy- lene iodide with an alcoholic solution of sodium sul phide. — Fine, needly crystals, which fuse at 218°, and are volatile without decomposition. Difficultly soluble in boiling water, more readily in alcohol and ether. Combines wTith silver nitrate, mercury chloride, and platinum chloride, forming crystalline compounds. Hexamethyleneamine, (CH2)6K4. Is formed when ammonia is conducted over oxymethylene, at first at the ordinary temperature and finally with the aid of gentle heat. — Clear, colorless, lustrous, rhombohedric crystals. Sublimable when very carefully heated. Easily soluble in water and boiling alcohol, but slightly soluble in cold alcohol and in ether. Has an alkaline reaction, and yields salts with acids. The hydrochlorate, C6II12N4.HC1, crystallizes in long, colorless needles, which are easily soluble in water. 2. Acetic Aldehyde. C2H40 = CIP.CIIO. Preparation. By imperfect oxidation of alcohol. 2 parts of alcohol are distilled with 3 parts manga nese peroxide, 3 parts sulphuric acid, and 2 parts water until that which passes over begins to have an acid reaction. The distillate is rectified over calcium chlo ride, then mixed with an equal volume of ether, and ACETIC ALDEHYDE. 103 saturated with dry ammonia. Or a mixture of 4 parts sulphuric acid, 12 parts water, and 3 parts alcohol is poured upon 3 parts potassium bichromate, care being taken to cool the vessel in which the reaction takes place; the vapors, freed of water as well as possible, are token up by ether and saturated with ammonia. The crystalline ammonia compound, when distilled with sulphuric acid, yields pure aldehyde, which can be obtained free of water by rectifying again over calcium chloride. Properties. Colorless liquid, of a suffocating odor ; specific gravity, 0.807 at 0°; boiling point, 21\|° mixes with water, alcohol, and ether in every propor tion. Acts as a powerful reducing agent ; from a silver solution it separates the metal, which forms a beauti ful specular coating on the sides of the vessel. Com bines Avith the bisulphites of the alkalies, forming crystallizing compounds. Phosphorus pentachloridc converts it into ethylidene chloride (p. 64). It unites with hydrogen in statu nascendi, forming ethyl alcohol and butylene glycol (which see). All oxidizing agents convert it into acetic acid. Alkalies decompose it, forming resinous bodies. Polymeric aldehydes. Small quantities of various substances (chlorcarbonic oxide, hydrochloric acid, sul phurous acid, zinc chloride, a drop of concentrated sulphuric acid) cause aldehyde to become transformed into polymeric compounds of entirely different pro perties. At the ordinary temperature paraldehyde Q6JJ12Q3 is produced. This is a colorless liquid, boiling at 124°, but slightly soluble in water ; congeals at a low temperature and fuses again at 10.5°. — At a tem perature below 0°, metaldehyde is principally formed. This is a white, finely crystallizing body, which, with out previously fusing, sublimes at 112-115°, at the same time being partially decomposed into aldehyde. "When heated in fused tubes to 112-115°, it is com pletely reconverted into aldehyde. Both of these com pounds, when distilled with dilute sulphuric acid, hydrochloric acid, etc., are reconverted into aldehyde; 104 ACETIC ALDEHYDE. and, with phosphorus chloride, hydrochloric acid, etc., they yield the same products as alhehyde. {OTT NH2 Is formed when aldehyde, either alone or in ethereal solution, is brought together with dry ammonia. — Colorless, lus trous rhombohedrons. Fusing point, 70-80° ; easily soluble in water ; more difficultly soluble in alcohol ; insoluble in ether. Hydracetamide, C6H12^"2 = (CH3.CH)3]Sr2. Is formed when a solution of aldehyde in alcoholic ammonia is allowed to stand for some time. — Amorphous, easily soluble powder. Diatomic base. When boiled with water or dilute acids, it is resolved into ammonia and oxytrialdine C6HnNO, an amorphous, brown substance, possessing basic properties. {OTT Q-^- Is pro duced by the direct combination of aldehyde with anhydrous hydrocyanic acid. — Colorless liquid ; soluble in water and alcohol in all proportions ; boiling point, 183° ; is, however, partially resolved at this temperature into hydrocyanic acid and aldehyde. Concentrated hydrochloric acid decomposes it at the ordinary tem perature, forming ammonium chloride and lactic acid. Aldehyde-acetate, CIP.CHJ Q'OTPO Is formed by direct union of aldehyde with acetic anhydride at 180°. — Colorless liquid, boiling at 169°. Does not mix with water. Acetal, C6H1402 » GEP.CH j 0-gEP Is produced by the slow oxidation of alcohol (hence contained in crude spirits of wine), and is a secondary product in the preparation of aldehyde ; and can be prepared by heating alcohol with aldehyde to 100° ; or by double ACETIC ALDEHYDE. 105 decomposition of ethylidene bromide (p. 46) and sodium ethylate. — Clear liquid, boiling at 104°. Is converted by oxidation into aldehyde and acetic acid ; by con centrated hydrochloric acid into ethyl chloride. Dichloracetal, CHC12.CH(O.C2H5)2 (colorless liquid, boiling at 180°) and trichloracetal CC13.CH(O.C2H5)2 (lustrous needles; fusing point, 72°; boiling point, 230°) are formed by the action of chlorine on ethyl alcohol. The former is also produced by the action of chlorine on acetal. Monobrpmacetal, CH2Br.CH(O.C2H5)2. Is formed by the action of bromine on acetal. — Colorless liquid that boils at 170° without undergoing decomposition. Dimethyl-acetal, C4IW = CH3.CH j g;^ Is contained in crude wood-spirit. Is produced by the action of black oxide of manganese and sulphuric acid on a mixture of ethyl and methyl alcohols; and by heating aldehyde with methyl alcohol to 100°. — Color less liquid, boiling at 64°. Ethylidene oxichloride, C4H8C120=(CH3.CHC1)20 (isomeric with the second substitution-product resulting from ethylether, p. 49), is obtained by the action of hydrochloric acid on aldehyde. — Colorless liquid, boil ing at 116-117°, which, when heated with water, yields aldehyde and hydrochloric acid. Dichloraldehyde, CIICP.CIIO. Is obtained by distilling dichloracetal with concentrated sulphuric acid. — Colorless liquid, boiling at 88-90°. Insoluble in water. When preserved it is gradually transformed into a solid, polymeric substance, which, at 120°, is re converted into the original body. Yields dichloracetic acid by oxidation. Trichloraldehyde (Chloral), CCP.CHO. Difficult to prepare directly from aldehyde. Is obtained by 106 ACETIC ALDEHYDE. thoroughly saturating ethyl alcohol with dry chlorine, and distilling the crystalline product after the addition of concentrated sulphuric acid. — Colorless liquid, of a penetrating odor ; specific gravity, 1.502, boils at 94.4°. "When kept for a time it is changed to a solid polymeric body, from which it can be regenerated by heating. Like aldehyde it combines with ammonia and the bisulphites of the alkalies. Yields trichloracetic acid by oxidation, dichloracetic acid by treatment with silver oxide and water, and is resolved into chloro form and formic acid by treatment with alkalies in aqueous solutions. When taken internally in small quantities it causes sleep. Combines with water, form ing chloral-hydrate C2HC130 4- H20, a substance that crystallizes well (fusing point, 46° ; boiling point, 96- 98° ; insoluble in water); with alcohol forming chloral- alcoholate C2HC130 + C2H60. Colorless crystals ; fusing point, 56°; boiling point, 114-115°. This compound is the final product of the action of chlorine on alcohol. Dibromaldehyde, CHBr2.CHO. By bringing bro mine and aldehyde together carefully. — Colorless, long needles, of a penetrating odor, exciting to tears. Tribromaldehyde (Bromal), CBr3.CHO. Is prepared in the same manner as chloral, and resembles it in every respect. Sulphaldehyde, C6H12S3 = (CH3.CHS)3. When sul phuretted hydrogen is conducted into an aqueous solution of aldehyde, an oil C2H4S + C2H40, of a disa greeable odor, congealing at — 8°, is precipitated, which, when distilled, or, better, when treated with hydro chloric acid, yields sulphaldehyde. — White needles, insoluble in water, easily soluble in alcohol and ether. Begins to sublime at 45°. AXJ.cixu.xxic;, v J-J- J-T >o , uijBttu.il/jco iiuiii a, wa/teij' cuiu- tion of aldehyde-ammonia when sulphuretted hydrogen is conducted into it. — Large, colorless crystals, fusing ACETIC ALDEHYDE, ETC. 107 at 43°, which are decomposed by keeping. It is a base, and yields crystallizing salts with acids. The remaining aldehydes of this series are prepared either by carefully oxidizing the corresponding alco hols with potassium bichromate and dilute sulphuric acid, the apparatus being so arranged that the aldehyde formed may distil over immediately ; or by subjecting an intimate mixture of the calcium salt of the corre sponding acid with calcium formate to dry distillation. To purify them and separate them from foreign sub stances, they are shaken with a concentrated solution of potassium or sodium bisulphite. The aldehydes combine with these substances, forming crystalline compounds, which are difficultly soluble in cold water. These are then pressed, washed with alcohol, or recrys- tallized from a little warm water, and, finally, decom posed by distillation with a solution of an excess of sodium carbonate, the pure aldehyde now passing over. The most important aldehydes are the following: — 3. Propionic aldehyde, C3H60 = CIP.CIP.CHO. A liquid, possessing a suffocating odor, very similar to acetic aldehyde. Specific gravity, 0.8327 ; boiling point. 49.5°. 4. Butyric aldehyde, C4IFO = CH3.CH2.CH2.CHO. Colorless liquid ; specific gravity, 0.834 at 0° ; boiling point, 75° ; soluble in 27 parts water. Chlorbutyric aldehyde, C4H7C10. Is produced by di rect combination of crotonic aldehyde (which see) with hydrochloric acid gas. — Colorless needles ; fusing point, 96-97° ; insoluble in water, scarcely soluble in alcohol. Isobutyric aldehyde, C4H80 = £jjp } CH.CHO. Color less liquid ; specific gravity, 0.8226 at 0° ; boiling point, 62°. 5. Normal valeric aldehyde, C5H100 = CH3.CIP.CH2. CIF.CIIO. A liquid, boiling at 102°. 108 KETONES. Ordinary valeric aldehyde, C5II100 = CH.CIP. CIIO. Colorless liquid, of a pleasant, fruity, slightly suffocating odor ; specific gravity, 0.822 at 0° ; boiling point, 92.5°. 6. Caproic aldehyde, C6H120. Liquid of a disagree able odor; boiling point, 121°. 7. CEnanthylic aldehyde (ocnanthol), C7H140. Is most readily obtained by dry distillation of castor oil. The aldehyde is separated from the distillate by the process above described. — Liquid, of an unpleasant odor ; spe cific gravity, 0.827 ; boiling point, 152°. 8. Palmitic aldehyde, C16II*20. From cetylic alcohol. — "White, indistinctly crystalline mass ; fusing point, 46-47°. E. KETONES (ACETONES). Ketones are compounds, which consist of two monovalent hydrocarbon groups, held together by the bivalent group (CO). They stand in close relation to the aldehydes, and can be considered as aldehydes, in which the hydrogen-atom of the group COI1 is re placed by a monovalent residue of hydrocarbon. They are produced by careful oxidation of the secondary alcohols, the group CH.OII, common to these alcohols, being hereby converted into CO, by a loss of two hydrogen atoms ; further, by subjecting the salts of the fatty acids to dry distillation, by the action of zinc methyl, zinc ethyl, etc., on acetyl chloride and the homologous chlorides, etc. — Most of them form crystallizing compounds with the bisulphides of the alkalies. Nascent hydrogen converts them into secon dary alcohols (the group CO being changed to CH.OII). —"When oxidized with potassium bichromate and sul phuric acid, they are resolved into simpler compounds, in the following manner. One of the hydrocarbon residues (where the residues are different, that which ACETONE. 109 has the largest number of carbon-atoms) is oxidized, yielding the fatty acid with the same number of carbon- atoms, while the other residue remains in combination with the CO and, together with this, is converted into the corresponding acid. Thus dimethylketone CERCO.CH3 yields formic and acetic acids; ethylmethylketone CH3.CO.C2H5, only acetic acid; ethylbutylketone C2H5.CO.C4H9, propionic and butyric acids, etc. 1. Acetone (Dimethylketone). C3H60 = CTP.CO.CEP. Formation and preparation. By the action of zinc- methyl on acetyl chloride; by the destructive dis tillation of acetates; by the oxidation of isopropyl alcohol and propylene ; by boiling the substance (p. 82) obtained from acetic ether by means of sodium with water; by heating monobrompropylene with mercury acetate and glacial acetic acid for several days at 100°; by heating citric acid; by distillation of wood (hence contained in crude wood spirit), and sugar or gum, mixed with lime. — Is prepared most expediently by distilling calcium acetate or a mixture of lead acetate with lime. — It is obtained on the large scale, as a secondary product in the manufacture of anilin with acetic acid and iron. Properties. Clear liquid, of a pleasant odor, miscible with water, alcohol, and ether; specific gravity, 0.814; boils at 58°. Acetone combines, like aldehyde, with the bisul phites, forming crystallizing compounds. Nascent hydrogen converts it into isopropyl alcohol with an accompanying formation of pinacone (s. hexylene alcohol)^ Concentrated sulphuric acid, alkalies, and caustic lime eliminate water from acetone, and convert it into mesityl oxide C6H100 (colorless liquid, boiling at 130°), phoron C9II140 (slightly colored crystals ; fusing point, 28° ; boiling point, 196°), and mesitylene C9H12 (s. Aromatic Compounds). 10 110 PKOPIONE. Methylchloracetol (Acetone-chloride), C3H6C12 = CH3.CC12-CH3. Is produced by the action of phos phorus chloride on acetone. — Colorless liquid, boiling at 69°. Treated with alcoholic potassa or ammonia, it is converted into monochlorpropylene C3H5C1. Methylbromacetol (Acetone-bromide), C3H6Br2 = CH3.CBr2.CH3. By the action of phosphorus bromide or phosphorus chlorobromide (PCl3Br2) on acetone. — Colorless liquid, boiling at 113-116°; specific gravity, 1.815 at 0°. Monochloracetone, C3H5C1O. Is produced when an electric current is conducted through a mixture of ace tone and hydrochloric acid ; and by the action of hypo- chlorous acid on monochlor- or monobrompropylene. — Colorless liquid, exciting to tears; boiling point, 119°. Dichloracetone, C3H4C120. Is produced by satu rating acetone with chlorine. — A liquid, boiling at 120°. With phosphorus chloride it yields Dichloracetone chloride, C3H4C14. Heavy liquid, boiling at 153°. By the action of bromine and chlorine-iodide on acetone, there are produced bromine and iodine substi tution-products. Sulphacetone, C6H12S2. Is produced by the action of phosphorus trisulphide on acetone. — Yellowish liquid, of a very unpleasant odor ; boiling point, 183- 185°. Does not mix with water. 2. Propione (Diethylketone). C5H100 = C2H5.CO.C2H5. Formation and preparation. By destructive distil lation of propionates; or by the action of zincethyl on propionyl chloride ; further, by bringing together sodium ethylate and carbonic oxide; by oxidizing diethoxalic acid with potassium bichromate and dilute METHYLETHYLKETONE, ETC. Ill sulphuric acid ; and by heating the same acid with concentrated hydrochloric acid to 130-150°. Properties, Colorless, pleasant smelling liquid, of specific gravity, 0.815 ; boiling point, 101°. Oxidized with potassium, bichromate, and dilute sulphuric acid, it yields acetic and propionic acids. 3. Methylethylketone, C4H80 = CH3.CO.C2H5. By the oxidation of secondary butyl alcohol (p. 68). By the action of zincethyl on acetyl chloride. In small quan tity in the preparation of acetone on a large scale. From ethyl-methyl acetone carbonate (obtained by the successive action of sodium and methyl iodide on acetic ether) by heating with potassa ley. — Colorless liquid, boiling at 81°; of 0.8125 specific gravity. Combines with alkaline bisulphites. 4. Methylpropylketone, C5H10O = CH3.CO.C3H7. Is produced by the distillation of a mixture of calcium buty rate" and acetate; as a secondary product by the distillation of calcium butyrate and by the oxidation of isoamyl alcohol (p. 71). By the oxidation of the mixture of alcohols from the heptyl hydrides of petro leum. — Colorless liquid; boils at 102-105°; specific gravity, 0.807. 5. Ethylpropylketone,V«W*Q = C2IP.CO.C3II7. By the distillation of calcium butyrate ; by the action of butyl chloride on zincethyl. — Boiling point, 126° ; specific gravity, 0.818 at 17.5°. 6. Dipropylketone (Butyrone), C7H140= C3H7.CO.C3H7. Is formed as the principal product by the distillation of calcium butyrate. — Boiling point, 144°; specific gravity at 20°, 0.82. 7. Methylbutylketone, C9II120 = CH3.CO.C4H9. By the oxidation of secondary hexyl alcohol ; by the oxi dation of the mixture of alcohols obtained from the hexyl hydrides of petroleum. — Boiling point, 127° ; specific gravity, 0.8298. 112 ETHYLENE SEKIES. 8. Methylamylketone, C7H140 = CH3.CO.C5Hn. By the oxidation of the mixture of alcohols obtained from the heptyl hydrides of petroleum. — Boiling point, 150-152°. 9. Methylhexylketone, C8H160 = CH3.CO.C6H13. By the oxidation of secondary octyl alcohol ; and by the distillation of a mixture of calcium oenanthylate and acetate.— Boiling point, 171°; specific gravity, 0.818. 10. Methylnonylketone, CnH220 = CH3.CO.C9H19. Forms the principal constituent of oil of rue (from Euta graveolens)-, and is produced by the distillation of a mixture of calcium caprate and acetate. — Colorless liquid, with a peculiar, bluish fluorescence. Boiling point, 225-226° ; specific gravity, 0.8268 ; congeals at -f 6°, forming a laminated crystal In :e mass, which fuses again at 15°. SECOND GROUP. A. HYDROCARBONS, Cnll2n (ETHYLENE SERIES). The hydrocarbons of this series differ from those of the marsh gas series in containing two hydrogen atoms less. They may be considered as non-saturated com pounds ; it is, however, more probable that two of the carbon atoms contained in them are united by means of so-called double-union. A characteristic property of these hydrocarbons is that of combining directly with two monovalent atoms (Cl2, Br2, 12, HI, etc.), and thus yielding Compounds which may be looked upon as substitution-products of the hydrocarbons of the marsh gas series, and are either identical or isomeric with the products obtained from the latter. The first member of this series CH2 is not known, and is apparently not capable of existence. ETHYLENE SERIES. 113 1. Ethylene (Elayl, Olefiant Gas). C2H4=CH2:CH2. Formation and preparation. By the destructive dis tillation of the salts of a great many fatty acids ; by distillation of fats, resins, wood, of anthracite coal, and a large number of other organic bodies. Prepared most easily by heating a mixture of 1 part alcohol and 4 parts concentrated sulphuric acid, to which has been added sand enough to form a thick pulp, in order to prevent foaming. The gas, which is cooled, is con ducted through soda ley and sulphuric acid, in order to free it of carbonic and sulphurous anhydrides, alco hol and ether vapors. Properties. Colorless gas ; specific gravity, 0.978 ; not congealing above — 110° ; burns with a luminous flame, and is absorbed but little by water. When con ducted through an ignited tube, it is decomposed into carbon, marsh gas, hydrogen, and acetylene. It com bines with sulphuric anhydride to form carbyl sul phate ; English sulphuric acid absorbs it very slowly, forming ethylsulphuric acid. Hydrochloric, hydro- bromic, and hydriodic acids combine slowly with it, forming ethyl chloride, bromide, and iodide. A solu tion of platinum chloride in hydrochloric acid absorbs it slowly and, on the addition of potassium chloride, lemon-colored crystals of C2H4.PtCl2.KCl + H20 are deposited. Ethylene chloride (Elayl chloride), C2H4C12 = CII2C1.CH2C1, is formed from ethylene and chlorine by direct combination. In order to prepare it, ethylene gas is conducted into a gently heated chlorine mixture and the chloride finally "distilled off. — Colorless liquid, of an ethereal odor ; of specific gravity 1.271 at 0° ; boiling point, 85°. When boiled with alcoholic po- tassa, it is converted into chlor ethylene, C2IPC1, water and potassium chloride being formed at the same time. A gas condensable at --18°. Chlorine acts upon ethylene chloride, yielding substitution-products, and, according to the length of time occupied in the action, 10* 114 ETHYLENE SERIES. one, two, three, or all the hydrogen atoms can be re placed by chlorine. These chlorinated products con duct themselves towards alcoholic potassa like ethylene chloride ; a molecule of hydrochloric is given off, and in this way are formed the two series : — C2H4C12 ; boiling point, 85° C2H3C13 " " 115° C2H2C14 " " 137° C2HC15 " " 158° C2C16 " " 182° And C2H3C1 " « —18° C2H2C12 " " 37° C2HCP " " 87-90° C2C14 " " 117° The first three members are different from the sub stitution-products (p. 46) obtained from ethyl hydride or ethyl chloride by the action of chlorine; for the fourth and fifth members there is but one kind of constitution possible. Ethylene bromide, C2H4Br2, a colorless liquid, boiling at 129°, congealing at a temperature below + 9°, is formed by conducting ethylene into bromine under water. It conducts itself towards an excess of bromine and towards an alcoholic solution of potassa like the chloride. In this way are obtained the two series :— C2H4Br2 ; boiling point, 129° OTPBr8 " " 186.5° C2H2Br4, liquid ) . ,. ,.„ ,, .., C2HBr5 no distillable without And C2Br r5 } . V 6 fS^d f decomposition. C2H3Br ; boiling point, 23-24° OTPBr2 " « 88° CPHBr3 " " 130° C2Br4 ; fusing point, 50° Ethylene iodide, C2H4I2, is produced by conduct ing ethylene gas over iodine in sunlight at an elevated ETHYLENE SERIES. 115 temperature. Can be most easily prepared by conduct ing the gas into an alcoholic solution of iodine, to which is added an excess of iodine. — Colorless crys tals, fusing at 73°, which, when kept in a dark place, slowly turn yellow. Exposed to the light, this dis coloration takes place rapidly. Sublimable; above 80°, however, it is resolved into iodine and ethylene. Ethylene nitrite, C2II4(^T02)2. Is produced by direct combination of ethylene with hyponitric acid. — Four-sided prisms, which fuse at 37.5°. Chlornitrocarbon, C2C14(N02)2. By heating carbon chloride C2C14 with hyponitric acid in sealed tubes to 110-120°.— Colorless, crystalline mass. At 140° it is resolved into C2C14 and hyponitric acid. Ethylene cyanide, C4H4^2 = C2H4(C£T)2. Is ob tained by heating ethylene chloride, or better, bromide, in an alcoholic solution with potassium cyanide. — Crystalline mass, fusing at about 37°. * Not volatile, without undergoing decomposition. Heated with an alcoholic solution of potassa, it yields ammonia and potassium succinate ; it combines with nascent hydro gen, forming butylene diamine C4H8(NH2)2. 2. Propylenc. C3H6 « CH3.CH:CH2. Is produced together with the homologous hydrocar bons from a large number of organic bodies, when these are distilled either alone or mixed with lime. It can be obtained pure by heating glycerin with phos phorus iodide, or by heating the allyl iodide C3H5I, which is formed simultaneously with it, with mercury or zinc and fuming hydrochloric acid ; or, most readily, by heating isopropyl iodide with an alcoholic solution of potassa on a water-bath. It is also produced together with ethyl bromide by the action of zincethyl on bromoform. — Colorless gas, with an odor similar to that of ethylene ; condensable by pressure, but is still 116 ETHYLENE SERIES. gaseous at — 40°. It is but slightly absorbed by water, more easily by alcohol (12 volumes). It con ducts itself like ethylene, and combines, like this gas, directly with chlorine, bromine, and iodine. It com bines with hydriodic acid, forming isopropyl iodide. By agitating it with concentrated sulphuric acid, a sulpho-acid is formed, which, when distilled with water, yields isopropyl alcohol. Propylene chloride, C3H6C12 = CH3.CHC1.CH2C1 (isomeric with methylchloracetol, p. 110), is also pro duced by the action of chlorine on propyl hydride. — Colorless liquid, boiling at 93-98°. Monochlorpropylene, C3H5C1 = CH3.CC1:CH2. Is produced from propylene chloride, and also from the isomeric methylchloracetol by the action of alcoholic potassa. — Liquid, boiling at 23°. Propylene bromide, C3H6Br2. Is also obtained by allowing bromine to act upon isopropyl bromide ; and, together with the following compound, by the action of hydrobromic acid on allyl alcohol. — Colorless liquid, boiling at 142°. Trimethylene bromide, C3H6Br2 = CHXBr.CH2. CH2Br. A liquid, boiling at 160-163°: specific suavity, 2.0177 at 0°. Monobrompropylene, C3H5Br. Liquid; boils at 56.5°. 3. Butylenes. C4H8. There are three butylenes of different constitution known. 1. Butvlene (Methylallyl), CH3.CH2.CH:CH2. Is obtained by decomposing a mixture of allyl iodide and methyl iodide with sodium. — Colorless liquid, boiling ETHYLENE SERIES. 117 between — 4 and +8°. Combines with hydriodic acid, forming secondary butyl iodide (p. 69). The 'bromide, CH3.CH2.CHBr.CH2Br, boils at 156- 159°. 2. Isobutylene, C:CH2- Is Produced by the action of alcoholic potassa on the iodides of isobutyl alcohol and tertiary butyl alcohol ; by the decomposi tion of am}7! alcohol at red heat; and by the electrol ysis of potassium valerate. — Boiling point — 6°. Unites with hydriodic acid, forming tertiary butyl iodide. Is absorbed by sulphuric acid, a sulpho-acid being formed, which yields tertiary butyl alcohol (p. 69), when subjected to distillation with water. The bromide, 3 CBr.CtPBr, boils at 160°. 3. Pseudobutylene, CIP.CILCH.CH3. Is obtained by the action of alcoholic potassa, silver oxide and water, or silver acetate on secondary butyl iodide ;_ and by heating secondary butyl alcohol to 250°. — Boiling point, +3° ; congeals as a crystalline mass when cooled down to a very low temperature. Combines with hydriodic acid, regenerating secondary butyl iodide. The bromide, CH3 CHBr.CHBr.CH3, boils at 159°. A fourth butylene, the constitution of which is not well known, results from the action of zincethyl on monobromethylene. It boils at — 5° ; yields a bromide that boils at 166°; and, as it seems, combines with hydriodic acid, forming isobutyl iodide. 4. Amylenes. C5II10. 1. Ethylallyl, C5H10 = CH3.CH2.CH2.CH:CH2. Is obtained by the action of zincethyl on allyl iodide. — • Colorless liquid, boiling at 37°. Combines with hydri odic acid, forming isoamyl iodide (p. 71); with bro mine yielding a bromide, C5H10Bi^, that boils at about 175°. 118 ETHYLENE SERIES. 2. Amylene, C5H10 = £j*** 1 CH.CH:CH2. Is pro duced, together with diamylene, triamylene, and small quantities of other hydrocarbons, by the distillation of amyl alcohol of fermentation over zinc chloride. — Colorless liquid ; boiling point, 35° ; specific gravity, 0.663 at 0°. — When shaken with concentrated sul phuric acid, it is converted into polymeric compounds (diamylene, triamylene); combines with hydriodic acid, forming the iodide of amylenehydrate (p. 71.) Amylene bromide, C^Br2. Colorless liquid, boiling at 170-180°, not, however, without a slight decomposition. 3. Isoamylene, C5II10 = ^ 1 C:CH.CH3 or CIP CH2 ) CH3 I ^C^-2- ^s f°rme(l from tertiary amyl iodide by the action of very concentrated alcoholic potassa. —Colorless liquid, that boils at 35°. Unites with hydriodic acid, forming tertiary amyl iodide. Other isomeric hydrocarbons are produced by the action of sodium on chlorinated amyl chloride (alpha- amylene, boiling point, 28-30°) and by the action of zincethyl 011 chloroform. 5. Hexylene, C6H12. Is produced from the iodide of secondary hexyl alcohol (p. 72) by boiling with alco holic potassa, — Colorless liquid, boiling at 68-70°. Combines with hydriodic acid regenerating secondary hexyl iodide. It is not known exactly, whether the hexylene, ob tained in the same manner from the iodide of the primary alcohol, and also boiling at 68-70°, is identical with that mentioned, or not. Another hexylene (alpha- hexylene, boiling point, 68-71°) is obtained by the action of sodium on bichlorinated hexyl hydride (from petroleum). ALLYL ALCOHOL. 119 The remaining hydrocarbons of this series — Hepty- lene C7H14, boiling point, 94-96° ; octylene C8H16, boiling point, 118-120°; nonylene C9H18, boiling point, 140°; decatylene C10H20, boiling point, 158-160°— are obtained in the same manner by treating the alcohol chlorides or iodides with alcoholic potassa, or like diamylene C10H20, boiling point, 150-153° ; dihexylene C12H24, and triamylene C15H30, etc., by polymerisation of the simpler hydrocarbons by means of sulphuric acid. B. MONATOMIC ALCOHOLS, CnH2nO. The alcohols of this series bear the same relation to the hydrocarbons of the ethylene series, as the alcohols Qnjpn+2Q |.)ear £O ^e hydrocarbons of the marsh gas series. There is at present but one alcohol belonging to this group well known. Allyl Alcohol. C3H60 = CH2:CH.CH2.OH. Formation and preparation. Four parts glycerin are heated slowly with one part crystallized oxalic acid (an addition of quarter to half per cent, ammonium chloride is advantageous) to 220-230°, finally to 260°. At first an aqueous solution of formic acid passes over, afterward allyl alcohol. The receiver is changed when the temperature of the mixture has reached 195° ; that which passes over from 195-260° is redistilled, the operation being continued until potassium car bonate precipitates no oil drops from a specimen of the distillate. The allyl alcohol is then precipitated from the whole distillate with potassium carbonate, purified by treatment with powdered potassium hy droxide, freed of water, by means of barium hydroxide, and rectified. — Or allyl iodide is transformed into allyl oxalate by digestion with silver oxalate ; this is then decomposed by means of dry ammonia gas and the alcohol distilled oft'. — It is also produced by the action of sodium on dichlorhydrine (see Glycerin). 120 ALLYL ALCOHOL. Properties. Colorless liquid of a pungent odor; specific gravity, 0.858 at 0°; boiling point, 96-97°; congeals at — 50°. Mixes with water in all propor tions. Combines with two atoms of chlorine or bromine without elimination of hydrogen ; does not combine with hydrogen. Heated with potassium hydroxide to 100-150°, it yields propyl alcohol, ethyl alcohol, formic acid, and other products. Allyl chloride, C3H5C1 = CH2:CH.CH2C1 (isomeric with monochlorpropylene). By allowing hydrochloric acid or phosphorus terchloride to act upon ally! alcohol ; by bringing an alcoholic solution of allyl iodide together with mercury chloride ; and by heating allyl oxalate with an alcoholic solution of calcium chloride to 100°. — Colorless liquid, boiling at 46° ; specific gravity, 0.954 at 0°. Allyl bromide, C3H5Br. Colorless liquid ; boiling point, 70-71° ; specific gravity, 1.461 at 0°. Allyl iodide, C3H5I. Prepared from allyl alcohol, like ethyl iodide from ethyl alcohol (p. 46). Most expediently by adding 6 parts phosphorus gradually to a mixture of 15 parts glycerin and 10 parts iodine. After the reaction, which is frequently very violent, is finished, the substance is distilled off, the distillate washed with water. and caustic soda, delrydrated and rectified ; that portion which passes over between 98- 103° is pure allyl iodide. — Colorless liquid, of an un pleasant, leeky odor ; boiling at 101° ; specific gravity, 1.789. — When its alcoholic solution is shaken with mercury, mercurallyl iodide C3II5IIIg is formed. Color less laminre, difficultly soluble in alcohol; when dis tilled with iodine, yields allyl iodide ; when treated with hydrochloric or hydriodic acids, yields propylene. Hydriodic acid converts allyl iodide into isopropyl iodide. Allyl cyanide, C4H5^ = C3H5.dST, is contained in the mustard-oil of commerce, and is prepared from ALLYL ALCOHOL. 121 this by distilling repeatedly with water. (On its pre paration from mustard-seed, see Glucosides, Myronic Acid.) — Colorless liquid, of an agreeable, leeky odor, boiling at 117-118°. By the action of silver cyanide on allyl iodide, a compound is formed, which is isomeric with allyl cyanide. Allylether, (C3IP)20, results from the action of allyl iodide on silver or mercury oxide, and from the decomposition of potassium ally late by means of allyl iodide. — Colorless liquid, insoluble in water, boiling at 82°. A body of the same composition (allyl oxide), which is perhaps identical with allylether, occurs in crude oil of garlic. The compound ethers of allyl alcohol are formed by the action of allyl iodide on the silver salts of the respective acids. Allyl formate, CHO.O.C3!!5, is formed as a second ary product in the preparation of formic acid from oxalic acid and glycerin (p. 76). — Liquid, of a sharp odor; specific gravity, 0.932 ; boiling point, 81-83°. Allyl acetate, C2H3O.O.C3H5. A liquid, with a penetrating odor, boiling at 98-100°. Allyl valerate, C5II9O.O.C3Ii5, boils at 162°. Allyl sulphide (oil of garlic), (C3H5)2S. By the dis tillation of garlic (bulbs of Allium sativum) with water, a heavy, yellow oil is obtained, which contains allyl sulphide as its principal ingredient. By repeated recti fication, finally over potassium, it is obtained in a free condition. It is further contained in the leaves of Alliaria officinalis, and in the seeds and green portions of a great many other plants of the cruciferous order. — It can be prepared artificially by the action of an alcoholic solution of potassium sulphide on allyl iodide. — Colorless oil, of a repulsive odor, which boils at 140°. Gives a crystalline precipitate of (C3H5)2S + 2AglXT03 with an alcoholic solution of sil- 11 122 ACRYLIC ACID. ver acetate. This precipitate crystallizes from alcohol in needles. Allyl-mercaptan, C3H5.SH, is formed from allyl iodide and an alcoholic solution of potassium sulphy- drate. — A liquid, boiling at 90°, very similar to ethyl- mercaptan. Allylamine, C3H5.NH2. Is produced when allyl mustard-oil is treated with zinc and hydrochloric acid, or, better, with concentrated sulphuric acid. — Liquid, boiling at 58°. — By the action of ammonia on allyl iodide, the principal product formed is tetrallylammo- nium iodide (C3H5)4NI, a crystalline body, which, when heated with silver oxide, yields tetrallylammonium hydroxide (C3H5)4E".OH, a strongly alkaline liquid. C. MONOBASIC MONATOMIC ACIDS, OH2W~202. 1. Acrylic Acid. C3H402 = CH2:CH.CO.OH. Formation and preparation. Is produced from its aldehyde, acrolein, when the latter, mixed with 3 parts IPO, is left for a few days in contact with silver oxide. The liquid is then heated to boiling, sodium carbonate added until it shows an alkaline^ react ion, evaporated to dryness, the residue decomposed with dilute sulphuric acid, and filtered. By distilling the filtrate the pure acid is obtained still containing water. Can be prepared in any quantity from allyl alcohol. The alcohol is combined with bromine, the resulting alcohol oxidized, and the dibrompropionic acid thus obtained, freed of bromine by the action of zinc-dust and water. Can only be obtained free of water by the decomposition of its silver or lead salt by means of sulphuretted hydrogen. It is also produced by heat ing 0-iodopropionic acid with alcoholic potassa or with milk of lirne. Properties. Clear liquid, boiling above 100° ; has an odor similar to that of acetic acid; miscible with water in all proportions. Oxidizing agents resolve it into CKOTONIC ACID. 123 acetic and formic acids. Treated with sodium amal gam and water, it is converted into propionic acid. ^ It combines with two atoms of bromine, without elimina tion of hydrogen, forming an exceedingly unstable acid. Its salts are all easily soluble in water, with the exception of the silver salt CBIl302Ag.—Lead acrylate, (C3H302)2Pb, crystallizes in thin needles of a silky lustre. 2. Crotonic Add. C4H602 = C3H5.CO.OH. There are three isomeric acids of this composition known. 1, Crotonic acid, CII2:CH.CH2.CO.OH. Is pro duced by the oxidation of its aldehyde (p. 129); from allyl cyanide by boiling with caustic potassa; and by the destructive distillation of j3-oxybutyric acid. — Fine, fleecy needles or large plates, which fuse at 72° and boil at 180-182°. Nascent hydrogen converts it into butyric acid, fusing potassium hydroxide into acetic acid. Monochlorcrotonic acid, C4H5C102. Is produced by the action of zinc and hydrochloric acid on tri- chlorcrotonic acid, and, together with another acid, when phosphorus chloride is allowed to act on acetyl- acetic ether (p. 82) and the product then treated with water. — Colorless crystals, easily soluble in water; fusing point, 94-95°. Tr ichor crotonic acid, C4H3C1302. Is formed by the action of cold concentrated nitric acid on tri- chlorcrotonic aldehyde (p. 129). — Colorless, radiating needles ; fusing point, 44° ; soluble in 25 parts water. Monobromcrotonic acid, C4H5Br02, is formed by boiling citradibrompyroracemic acid (see Pyroracemic Acid) with watery solutions of the alkalies. — Long, flat needles, but slightly soluble in cold water. Fusing point, 65° ; boiling point, 228-230° ; combines directly 124 ANGELIC ACID. with 1 molecule bromine; and is converted into butyric acid by the action of sodium amalgam and water. 2. Isocrotonic acid, CIRCILCH.CO.OH. Is ob tained by the action of sodium amalgam on chloriso- crotonic acid. — Colorless liquid: boils at 172°; does not congeal at — 15°. Chlorisocrotonic acid, C4H5C102. Is formed from acetylacetic ether together with chlorcrotonic acid. — Colorless crystals, difficultly soluble in water. Sub limes at the ordinary temperature. Fusing point, 59.5° ; boiling point, 195°. 3, Methacrylic acid, CH2:C j QQ QJJ The ether of this acid, C4IPO.O.C2H5, is produced by the action of phosphorus terchloride on ethyl isoxybutyrate. — The free acid is liquid, does not congeal at 0°, and is resolved into formic and propionic acids by fusing with caustic potassa. 3. Angelic Acid. C5H802 = C4H7.CO.OH. Occurrence and preparation. In the roots of Angelica archangelica. In order to prepare the acid from these, they are boiled with lime, filtered, the filtrate decom posed by sulphuric acid, and distilled ; the distillate saturated with sodium carbonate, evaporated to dry- ness, and the residue again distilled with sulphuric acid. Acetic, valeric, and angelic acids pass over; by means of cooling, the latter separates from the mixture in crystalline form. It is also produced by the action of caustic potassa on the essential oil of chamomile (volatile oil of Anthemis nobilis), which appears to con tain an ether of angelic acid ; and by heating laserpi- tium and peucedaniii with an alcoholic solution of potassa. Properties. Colorless needles, fusing at 45°, but HYDROSORBIC ACID. 125 slightly soluble in cold water, more easily in hot water and in alcohol ; boiling point, 191°. Sodium amalgam produces no change in the acid in aqueous solution, but when it is heated for a long time with hydriodic aeid and a little amorphous phosphorus at 180-200°, it is completely converted into valeric acid. Fusing caustic potassa resolves it into acetic and pro- pionic acids. — Combines directly with bromine, form ing the dibromide C5H8J3r202. Crystals fusing at 76°. This dibromide is converted into angelic acid by the action of sodium amalgam and water. Methylcrotonic acid, C5H802 (isomeric with angelic acid), is produced from isoxyvaleric acid in the same manner as methacrylic acid. — Colorless needles, fusing at 62° ; conducts itself towards fusing potassa the same as angelic acid. 4. HydrosorUc Acid. 2 = C5H9.CO.OH. Is produced by the action of sodium amalgam and water on sorbic acid. — Colorless liquid, of a sweaty odor, but slightly soluble in water ; specific gravity, 0.969 ; boiling point, 201°. Does not congeal at —18° ; melting potassa resolves it into butyric and carbonic acids. The following acids are isomeric: — Pyroterebic acid, C6H1002. Is produced by the destructive distillation of terebic acid (see Oil of Tur pentine). — Oily liquid, boiling at 210°. Is broken up by means of fusing potassa, yielding acetic and butyric acids. Ethylcrotonic acid, C6II1002, is produced from ethyl diethoxalate the same as methacrylic acid ; also by heating ethyl diethoxalate for several hours with concentrated hydrochloric acid at 130-150°. — Quad ratic prisms, fusing at 41.5°. Conducts itself towards potassa the same as pyroterebic acid. 11* 126 CIMICIC ACID, ETC. 5. Cimidc Add. C14H27.CO.OII. Occurs in a leaf bug, Ehapigaster punctipennis. Yellowish, crystalline mass. Fusing point, 44°. 6. Hyiiogceic Add. Ci6H3002 = C15H29.CO.OH. In the form of the glycerin ether in ground-nut oil (the oil of the fruit of Arachis hypogcea). — Colorless, needly crystals, fusing at 33°, which become yellow in the air. Combines with bromine to form the dibro- mide C16H30Br202 (solid, uncrystalline mass, fusing at 29°), which, when treated with alcoholic potassa at 100° yields monobromliypogcEic add C16H29Br02. — When carefully heated with nitric acid, hypogseic acid is converted into an acid of the same composition, gaidic add. Crystals, fusing at 39°. 7. Okie Add (Ela'ic Add). Contained in nearly all fats as glycerin ethers (elain) ; in the largest proportion in the liquid fats, for instance, olive oil, oil of almonds, whale and seal oils. —In order to prepare it from these, the liquid fat is digested with lead oxide, the lead salts washed, and from these the lead oleate extracted with ether, and the ethereal solution decomposed with hydrochloric acid. The solution, poured off from lead chloride, leaves impure oleic acid behind when evaporated. It is dissolved in ammonia, barium oleate precipitated by adding barium chloride, and the salt, after having been repeatedly recrystallized from alcohol, is decom posed by means of tartaric acid. Colorless oil, congeals at 4° and fuses at 14° ; inodor ous and tasteless. Alone, it cannot be distilled, the distillation can, however, be effected by means of over heated vapor of water at 250°. In a pure condition pretty stable ; in an impure condition it takes up ERUCIC ACID. 127 oxygen rapidly from the air, turns yellow, and then emits a rancid odor. ^ Fusing potassa decomposes it into palmitic and acetic acids. Of its salts only those of the alkalies (soaps) are soluble in water; these are, however, separated from their solutions by easily soluble salts. The lead salt, (C^HWyPb, forms the principal ingredient of ordi nary lead-plaster. Oleic acid combines directly with bromine, forming a liquid dibromide, C18H34Br202, which, when treated with alcoholic potassa, at the ordinary temperature, is converted into crystalline monobromoleic acid C18H33 BrO2, difficult to prepare in a pure condition. By treatment with nitrous acid, pleic acid is con verted into elaid'ic acid, which is isomeric with it. This crystallizes in laminae, which fuse at 44-45°, and yield a crystalline dibromide with bromine; fusing point, 27°. 8. Erucic Add. Q22JJ42Q2 == C21H41.CO.OH. Is contained in mustard-oil and in rape-seed oil in the form of the glycerin ether.— Rape-seed oil is de composed with litharge; the resulting lead-plaster, after being repeatedly extracted with ether, leaves behind pure lead erucate, which, when decomposed with hydrochloric acid, yields pure erucic acid.— Long, thin needles, insoluble in water, easily soluble in alcohol and ether; fusing point, 33-34°. Unites with bromine to form the dibromide, U* Br202, which crystallizes in verrucose crystals, fuses at 42-43°, and yields monobromerudc add C22H41Br02 (fusing point, 33-34°), when treated with alcoholic potassa at the ordinary temperature. "When carefully heated with dilute nitric acid to 60- 70°, erucic acid is converted into brassidic add, which is isomeric with it. This acid crystallizes in white, lustrous laminae, fusing at 60°, and yields a dibromide (fusing point, 54°) with bromine. 128 ACROLEIN. Linoleic acid (C16H2802?), in linseed oil, and ridnic add, C18H3403, in castor oil, are similar to, but not homologous with, oleic acid. Both are contained in the oils as glycerin compounds, and are prepared by saponifying the oils and decomposing the alkali salts with hydrochloric acid. Ricinic acid can be purified by dissolving its lead salt in ether. It is an almost colorless liquid, congealing at 0° ; not volatile without decomposition. Like oleic acid, it is transformed into an isomeric, crystalline acid, ridnelaidic add, fusing at 50°. Conducts itself towards bromine like oleic acid. D. ALDEHYDES, CnII2n~20. 1. Acrolein. C3H40 = CH2:CH.CHO. Formation and preparation. From allyl alcohol by careful oxidation ; by the distillation of glycerin and the fats. Can be most readily prepared by distilling 1 part glycerin with 2 parts potassium bisulphate. Properties. Colorless liquid, the vapor of which attacks the eyes and nose violently. Boiling point, 52°. Lighter than water and but slightly soluble in it. When kept it becomes changed, sometimes in a very short time, into a white, amorphous substance. It forms no crystallizing compounds with alkaline bisulphites ; with nascent hydrogen it yields allyl alco hol. Alkalies convert it into a resinous mass. It combines directly with hydrochloric acid, forming C3H5C10 (colorless needles, fusing at 32°, insoluble in water), which, when subjected to distillation, are con verted into acrolein and hydrochloric acid. Metacrolein (polymeric acrolein, probably C9H1203) is formed when the compound of acrolein with hydro chloric acid is distilled with caustic potassa. — Colorless crystals ; fusing point, 50° ; boiling point, 170° ; insolu ble in water, easily soluble in alcohol and ether. When distilled it is partially reconverted into acrolein. CROTONIC ALDEHYDE. 129 Acrolein chloride, C3H4C12 = CH2:CH.CHC12. Is produced, together with the isomeric dichlorglycide, (see Glycerin), by the action of phosphorus pentachlo- ride on acrolein or metacrolein. — Colorless liquid, boil ing at 84°. Acrolein-ammonia, C6HXN"0. Is produced when the vapor of acrolein is conducted into ammonia, and when an alcoholic solution of acrolein is mixed with alcoholic ammonia. — Yellowish-white mass, which, when dried, becomes brownish-red. Combines with acids, forming amorphous salts. "When subjected to dry distillation it is resolved into water and picoline. 2. Crotonic Aldehyde. C4H60 = CH2:CH.CH2.CHO. Formation. Is produced from acetic aldehyde (p. 103), when this is heated for some time at 100° with watery solutions of potassium formate or acetate, or with a little zinc chloride. Properties. Colorless liquid, of an exceedingly pun gent odor. Boiling point, 103-105°. In contact with the air, and under the influence of oxidizing agents, it is converted into crotonic acid. — Phosphorus chloride converts it into a fluid chloride C4H6C12, boiling at 125-126°. It combines with hydrochloric acid directly, forming chlorbutyric aldehyde (p. 107). Trichlorcrotonic aldehyde (Crotonchloral), C4H3C130. Is formed when acetic aldehyde, either alone or dissolved in carbon tetrachloride, is saturated with chlorine. — Colorless, oily liquid ; boiling point, 163-165°. Combines with water, forming a hydrate C4H3C130 + H20, which crystallizes in colorless, very thin laminse, fusing at 78°. Caustic potassa decom poses it without the aid of heat, forming potassium formate and chloride, and dichlorallylene C3II2C12. Ni tric acid oxidizes it, forming trichlorcrotonic acid. Crotonal-ammonia (Oxytetraldin), C8H13NO. Is produced when an alcoholic solution of acetic aldehyde- 130 PYRIUINE BASES. ammonia is heated to 90-100°. — Amorphous brown mass, very much like acrolein-ammonia. Combines, like the latter, with acids, yielding amorphous salts ; and is resolved by heat into water and collidine. Pyridine bases, CME2n-5£T. "When acrolein-ammo nia and crotonal-ammonia are heated, there result liquid bases, picoline and collidine, which belong to an homo logous series, the single members of which are formed by the dry distillation of anthracite coal, peat, and particularly of bones. They are extracted from the distillation-products (coal-tar, bone-oil) by treating with dilute sulphuric acid ; set free again by means of alkalies; and separated from each other by means of fractional distillation. 1. Pyridine, C5H5]Sr. Colorless liquid, of a penetrat ing odor. Boiling point, 116.7° ; specific gravity, 0.986 at 0°. Soluble in water. Strong base. — The hydro- chlorate C5IKN".HC1 is deliquescent, and gives with pla tinum chloride a yellow double salt (C5H5KHCl)2PtCl4, which is difficultly soluble in water. In the presence of metallic sodium, pyridine is changed, gradually at the ordinary temperature, more rapidly when heated, into a polymeric base, dipyridine C10H10N2, which crystallizes in colorless needles, fuses at 108°, and sublimes without decomposition. 2. Picoline, C6H7N. Is formed by the distillation- of acrolein-ammonia and also when tribromhydrine is heated for several days with alcoholic ammonia to 250°. — Colorless liquid, mixes with water ; specific gravity, 0.96 ; boiling point, 135°. Strong base. Is converted into a polymeric base by sodium, the same as pyridine. 3. Lutidine, C7HXN". Colorless liquid ; specific gravity, 0.946 ; boiling point, 155.5°. More easily soluble in cold water than in hot. ACETYLENE SEKIES. 131 4. Collidine (Aldehydine), C8HnK Is obtained by heating an alcoholic solution of acetic aldehyde- ammonia to 120-130°, or of ethylidene chloride (p. 46) with alcoholic or aqueous ammonia to 160°. — Colorless, liquid, but slightly soluble in water ; specific gravity, 0.944 ; boiling point, 176°. In addition to these the following bases have been separated from coal-tar, but not carefullv investigated : Parvoline C9!!13^ boiling point, 188° ; corindine C10H15^", boiling point, 211° ; rubidine CnH17N, boiling point, 230°, and vindine C12H1{% boiling point, 251°. THIRD GROUP. A. HYDROCARBONS, CwH2n~2 (ACETYLENE SERIES). The hydrocarbons of this series differ from those of the ethylene series, in that they contain two hydrogen atoms less ; and are produced from these when their bromides are heated in sealed tubes with alcoholic potassa. They contain either two carbon atoms united by triple union (acetylene CHiCH) or twice two car bon atoms united by double union (diallyl CH2:CH. CH2CH2.CH:CH2). 1. Acetylene. C2H2. Formation and preparation. Is formed directly from its elements under the influence of an electric flame, which is produced in a current of pure hydrogen be tween points of purified carbon ; is also formed by the decomposition of carbon-calcium with water; by the action of heat on ethylene and marsh gas (hence con tained in coal-gas) ; by the decomposition of the latter by electrical sparks ; by imperfect combustion of a great many organic bodies ; by heating ethylene bromide or monobromethylene with alcoholic potassa ; and in many other ways. 132 ACETYLENE SERIES. Properties. Colorless gas ; somewhat soluble in water ; of a characteristic unpleasant odor; burns with a very luminous flame. — It is absorbed in large quantity by an ammoniacal solution of copper subchloride; the resulting red precipitate, which is exceedingly explo sive and evolves pure acetylene gas when hydrochloric acid is poured upon it, is cuprosoacetyl oxide (C2CuH)20. In an ammoniacal solution of silver, it produces a white precipitate with similar properties. By the aid of this property acetylene can be separated from other gases and prepared in a pure condition. — By the action of nascent hydrogen (when the copper compound is brought in contact with zinc and ammonia) it is trans formed into ethylene. Acetylene dichloride, C2H2C12. Cannot be pre pared by direct action. Acetylene detonates when brought in contact with chlorine gas. Acetylene is entirely absorbed by antimony chloride (SbCP), large crystalline laminae C2H2.SbCl5 being formed, which, when heated, are resolved into antimony terchloride (SbCl3) and acetylene dichloride. Colorless liquid; boiling point, 55°. Is decomposed when heated to 360°, yielding carbon and hydrochloric acid; when heated with alcoholic potassa to 100°, it yields potas sium chloride and acetate. Acetylene tetrachloride, C2H2C14. Is formed when the compound C2H2.SbCl5 is distilled with an excess of antimony chloride. — Colorless liquid, boiling at 147°. Acetylene unites directly with bromine, forming C2II2Br2 and C2H2Br4. Both compounds are liquids.— When heated with iodine to 100°, it yields a crystal line iodide C2H2I2, fusing at about 70°. It combines with hydriodic acid, forming liquid compounds: C2II3I, boiling point, 62°, and C2H4I2, boiling point, 182°. The latter compound is isomeric with ethylene iodide. 2. Allylene, C3H4, is produced by the action of sodium ethylate on monochlor- or rnonobrornpropylene, and by ACETYLENE SERIES. 133 the action of sodium on dichloracetone chloride (p. 110). — Gaseous; produces a yellow precipitate in an ammoniacal solution of copper subchloride; a white precipitate (C3H3Ag) in an ammoniacal solution of silver. Conducts itself towards bromine, iodine, and hydriodic acid like acetylene. By the action of alcoholic potassa on monobrompro- pylene bromide, tribrom- or trichlorhydrine (see Gly cerin), dichlorglycid, allylenbromide, and some other similar compounds, is produced propagylic ether C3H3. O.C2H5, a liquid boiling at 72°, which causes a yellow precipitate in a solution of copper subchloride; in solutions of silver, a white crystalline precipitate of C3H2Ag.O.C2H5 or C6IPAg2.02.(C2H5)2. 3. Crotonylene, C4H6. From monobrombutylene with alcoholic potassa at 100°. — Liquid, boiling at 18°. 4. Valerylene, C5H8. From monobromamylene, like crotonylene. — Liquid; boiling point, 45°. Gives no precipitates in solutions of copper subchloride or of silver. Propylacetylene (isomeric with valerylene), C5H8. From methylpropylketone chloride (CH3.CC12.C3H7) with alcoholic potassa. — A liquid boiling at 50°, which gives a yellow precipitate in an ammoniacal solution of copper subchloride, and a white precipitate in a silver solution. 5. Hexoylene, C6H10. From monobromhexylene. Boil ing point, 76-80°. Diallyl, C6H10 (isomeric with the preceding com pound). Is formed by the action of sodium on allyl iodide, and by the distillation of mercurallyl iodide (p. 120). Liquid, boiling at 59°. The hydrocarbons, with a larger number of carbon atoms, are produced in a similar manner. Alcoholic derivatives of these hydrocarbons are not known. 12 134 SOEBIC ACID — PALMITOLIC ACID. B. MONOBASIC, MONATOMIC ACIDS, CnH27l~402. The acids of this series are formed, like the hydrocarbons, by heating the dibromides of the acids OH27l-202 with alcoholic potassa. 1. Sorbic Acid. C6H802 == C5H7.CO.OH. Occurrence and preparation. Together with malic acid in the juice of the unripe berries of the moun tain-ash. If this is subjected to distillation after being partially neutralized with milk of lime, impure sorbic acid passes over with the vapors of water in the form of a yellow oil. The pure acid is obtained from this by heating gently with potassa or with concentrated sulphuric acid, or by boiling with concentrated hydro chloric acid. * Properties. Long, colorless needles, inodorous, almost insoluble in cold water, more easily soluble in hot water and alcohol ; fuses at 134.5° ; cannot be distilled alone without decomposition, readily with water vapor. Barium sorbate, (C6H702)2Ba. Laminae of a silvery lustre, easily soluble in water, scarcely more in boiling than in cold water. — Silver sorbate C6H702Ag. White, insoluble, scarcely crystalline precipitate. Ethyl sorbate, C6H7O.O.C2H5. Liquid, of a plea sant, aromatic odor, boiling at 195.5° ; lighter than water. Sorbic acid combines with nascent hydrogen, form ing hydrosorbic acid (p. 125); with bromine forming a tetrabromide C6H8Br402, which crystallizes well, fuses at 178-179°, and is but slightly soluble in water. 2. Palmitolic Acid. = C15H27.CO.OH. Results from heating the dibromide of hypogceic acid or gaidic acid with alcoholic potassa to 170°. — STEAROLIC ACID — BEHENOLIC ACID. 135 Fine needles, of a silvery lustre, insoluble in water, easily soluble in alcohol and ether. Fusing point, 42°. Combines directly with 1 and with 2 molecules of bromine, but not with hydrogen. Palmitoxylic acid, C16H2804, is formed, together with suberic acid and suberic aldehyde, by the action of fuming nitric acid on palmitolic acid. — Crystalline laminae, insoluble in water, easily soluble in alcohol and ether. Fusing point, 67°; monobasic acid. 3. Stearolic Acid. C18II3202 = C17H31.CO.OH. Is produced, like the preceding acid, from the di- bromide of oleic acid or ela'idic acid. — Long, colorless prisms. Fusing point, 48° ; can be distilled, almost entirely without decomposition ; insoluble in water, but slightly in cold alcohol, easily soluble in ether and hot alcohol. — Yields salts that crystallize well. Is not changed by the action of nascent hydrogen ; combines, however, with bromine, forming a liquid dibromide C18II32Br202, and a crystalline tetrabromide C18H32Br402, fusing at about 70°. Stearoxylic acid, C13H3204, produced like palmi- toxylic acid. — Lustrous laminee ; fusing point, 86°. Very similar to palmitoxylic acid. 4. Behenolic Add. = C21H39.CO.OH. Is produced from the dibromide of erucic acid by heating it with alcoholic potassa to 140-150°, and from the dibromide of brassinic acid by heating with alcoholic potassa to 210-220°. — "White, lustrous, fasci- cular needles. Fusing point, 57.5°. Conducts itself towards hydrogen and bromine, the same as stearolic acid. Behenoxylic acid, C22H4004. Lustrous scales; fusing point, 90-91°. 136 GLYCOLS. FOURTH GROUP. A. DIATOMIC ALCOHOLS, CnII2n+202 (GLYCOLS). The diatomic alcohols are derived from the hydro carbons of the marsh gas series by the replacement of two hydrogen atoms by means of two hydroxyl-groups. They are formed from the chlorides, bromides, and iodides of the hydrocarbons CnH2n by the exchange of the chlorine, bromine, or iodine atoms for hydroxyl. The first member of this series, methylene alcohol CH2(OH)2, is not known and can probably not exist. Methylene iodide (p. 36), when treated with silver acetate, yields, besides silver iodide, methylene acetate CH2 '* a li(luid' that boils at 170°* If> how" ever, the attempt is made to isolate the alcohol from this ether by means of heating with water or alkalies, formic aldehyde (oxymethylene) is obtained instead. It appears to be a general fact, that such diatomic alco hols as contain both hydroxyl groups in combination with the same carbon atom, cannot exist. Two dia tomic alcohols can theoretically be derived from ethyl hydride CIP.CIR, viz., £jp OH and CH3-CH j OH Only the first of these can, however, be isolated ; the second, the acetic ether CH3.CH 'SJS of which can readily be prepared (p. 104), is resolved into aldehyde and water when the attempt is made to iso late it. 1. Ethylene Alcohol (Ethylglycol). Preparation. Ethylene bromide is boiled for a few hours with potassium acetate and alcohol, then dis tilled ; that portion of the distillate boiling between 140- 200° (which consists mainly of monacetic glycol ether), GLYCOLS. 137 is separated from the rest and decomposed with potas sium or barium hydroxide. Properties. Colorless, inodorous, somewhat viscid liquid, of specific gravity 1.125; boiling point, 197.5°; mixes with" water and alcohol. — Sodium dissolves in it, hydrogen being evolved and sodium-glycol C2H4 Sa a crystalline mass, resulting, which, heated up ( CXNTa to 190° with sodium, yields di sodium-glycol C2H4 -j Q^a> JO C2H5 OH (a liquid of a pleasant odor) and dieihylglycol ether C2H4 1 o'c?H« (a liquid boilin£ at 128-5°> insoluble in water, isomeric with acetal) are formed by heating with ethyl iodide. Oxidizing agents convert ethylene alcohol into gly- colic acid and oxalic acid. Ethylene chlorhydrine (Glycol hydroclorate), C2H5C1O = CII2C1.CH2.OH, is formed by the direct union of ethylene with an aqueous solution of hypo- chlorous acid, or when ethyl alcohol is saturated with hydrochloric acid and then heated. — A liquid, boiling at 128°. When heated with potassium iodide, yields glycol iodohydrine C2H4LOH, a heavy undistillable liquid ; when heated with potassium cyanide, glycol cyanhydrine C2H4Cy.OH, a yellow syrup, which, treated with potassa, yields paralactic acid, together with some ordinary lactic acid. OH* Ethylene oxide (Glycol ether), C2H40 = QHa>O (isomeric with acetic aldehyde). Is produced by the action of potassium hydroxide on glycol chlorhydrine. —Colorless liquid, boiling at 13.5° ; specific gravity at 0°, 0.898 ; mixes with water in all proportions ; does not enter into combination with the bisulphites of the alkalies. It possesses basic properties; combines directly with acids to form ethylene ethers ; and preci- 12* 138 GLYCOLS. pitates the hydroxides from solutions of metallic salts. It unites with water, when heated with it to 100° in sealed tubes, forming ethylene alcohol ; with the lat ter, forming diethylene alcohol C4H1003=CH2.OILCH2.O. CIP.CH2.OH (a liquid, boiling at 250°) and triethylene al cohol C6H1404= CH2.OII.CII2.b.CH2.CH2.O.CH2.CH2.OII (boiling point, 285-289°). — Is converted into ethyl alcohol by nascent hydrogen (from sodium-amalgam and water). Ethylene sulphydrate (Glycolmercaptan), C2H4 (SH)2, is formed by the action of ethylene chloride or bromide on an alcoholic solution of potassium sulph ydrate. — Colorless oil, of a penetrating odor. It forms salts with metallic oxides, like ethylmercaptan. — Ethylene chlorhydrine gives a similar compound with potassium sulphydrate, ethylene monosulphydrate Ethylene sulphide, By the action of ethylene chloride or bromide on an alcoholic solution of potas sium sulphide, a crystalline substance, diethylene sul phide (C2H4)2S2 is formed, together with an amorphous yellow powder C2H4S, which is prepared most readily by double decomposition of mercurio-glycolmercaptan C2H4.S2Hg with ethylene bromide at 150°.— Fuses at 111°, and boils undecomposed at 200°. It unites directly with chlorine, bromine, iodine, with oxygen and several salts. Amorphous ethylene sulphide is converted into diethylene sulphide by being heated alone or with car bon bisulphide. Ethylene monacetate, C2H4 j Q g2 IPO Ethylene bromide (1 part) is heated on a water-bath for a length of time with potassium acetate (1 part) and alcohol (2 parts) in a flask connected with an inverted condensing apparatus. It is separated and purified by means of distillation.— A liquid, boiling at 182°, mixes with water and alcohol. Hydrochloric acid gas decora- GLYCOLS. 139 poses it at 100°, yielding water and glycolchloracetin C2II4CLO.C2H30, a liquid, boiling at 145°. ( 0 C2II30 Ethylene diacetate, C2II4 j Q'QSJJSQ is formed by mixing dry silver acetate with ethylene iodide. — A liquid, boiling at 186°, soluble in 7 parts water. Ethyleneamine bases. By the action of ethylene bromide on an alcoholic solution of ammonia, the crys talline hydrobromates of the three bases: Ethylene- diamine C2H4(^"H2)2, diethylenediamine (C2H4)2(NH)2, and triethylenediamine (C2H4)3N2, are formed. These can be separated from each other by means of crystallization. From these salts the volatile bases can be set free by means of silver oxide or by distillation with potassa. They are liquid. Ethylenediamine, which can also be. produced by conducting cyanogen into a mixture of tin and hydrochloric acid, boils at 123°. Its formula is C2IF(NH2)2 + H20, and it does not give off the water even by repeated distillation over caustic baryta. Diethylenediamine boils at 1.70° ; triethylenediamine boils at 210°. Oxethylamine bases. When ethylene oxide is heated with aqueous ammonia, heat is evolved, and a mixture of three bases is formed: Oxethylamine CIP.OH (C2H4.OH)KH2 = -CH2 ^-jp (isomeric with aldehyde- ammonia), dioxethylamine (C2H4.OH)2OTJ, and triox- ethylamine (C2H4.OH)3K Their hydrochlorates are also produced when ethylene chlorhydrine is heated with aqueous ammonia to 100°. The difference in the solubility of the hydrochlorates and the platinum double salts of the three bases in alcohol affords a means of separation. They are of a syrupy consistence, easily soluble in water, strongly alkaline, and yield crystallizing salts. Similar bases of more complicated constitution are formed by the union of ethylene oxide or ethylene 140 GLYCOLS. chlorhydrine with organic bases. The most important of these is — Trimethyloxethylammonium hydroxide (Bili- neurine, choline, sinkaline), 95H15N02 - C2H4.OII. (CH3)3N.OH. Is contained in bile; is produced from sinapine (see Alkaloids) by gently heating with barium or potassium hydroxide ; and can be most readily pre pared by mixing a concentrated solution of tri m ethyl- am ine with ethylene oxide. The chloride C2H4.OH. (CIF)3KC1 is produced by the direct union of ethylene chlorhydrine and trimethylamine. — The free base is colorless, crystalline, very easily soluble in water, and possesses very strong basic properties. Its solution in hydrochloric acid, when treated with platinum chlo ride and absolute alcohol, gives a yellow precipitate (C5H14^"O.Cl)2PtCl4, which crystallizes from water in hexagonal plates ; with gold chloride a yellow crystal line precipitate OH^lTO.Cl + AuCl3.— Hydriodic acid converts it into trimethyliodethylammonium iodide C2H4I (CH3)3M, a substance that crystallizes well and is diffi cultly soluble in cold water. When treated in aqueous solution with silver oxide, the latter compound is con verted into trimethylvinylammonium hydroxide (neurine) C2IP(CH3)3KOH. This is a very easily soluble base, which is also formed by boiling the substance of brain (lecithine, protagon) with baryta water. Sulphogly colic aci&^lycolsufyhuricacid), C2II6SO = PIT2' O SO2 OTT *s f°rmed- ^7 heating equal mole cules of ethylene alcohol and concentrated sulphuric acid to 150°. The barium salt (C2IPS05)2Ba is very easily soluble in water and crystallizes with difficulty. 2 OTT Isethionic acid, C2IISS04 = Qjp'gQi QJJ (isomeric with ethylsulphuric acid), is formed when sulphuric anhydride is conducted into well-cooled alcohol or GLYCOLS. 141 ether, and at the end of the reaction the mass diluted with four times its volume of water and then boiled for a few hours. By neutralizing the liquid with barium carbonate, the soluble barium salt is prepared. Is also forrfled by mixing barium ethylsulphate with sulphuric anhydride, evaporating the excess of the anhydride and boiling for a long time with water. The sodium salt is formed by direct union of ethylene oxide with sodium bisulphite, and by treating ethylene chlorhydrine with a concentrated solution of sodium sulphite. — The free acid can be evaporated to a syrup ; decomposes, however, when further evaporated. Mono basic acid. Its salts crystallize well and are very stable. — The potassium salt, when distilled with phos phorus chloride, yields isethion chloride (chlorethyl sul- pho-chloride) CH2C1.CH2.S02C1, a liquid, boiling at 200°, which when heated with water is decomposed into Morcthylsulphurous add CH2C1.CH2.S02.OH and water. Taurin (Amidoisethionic acid), C2H7E"S03 = CIP.KII2 CH2 SO2 OH Occurs free and in combination with cholic acid, as taurocholic acid, in the animal organism, in bile, in the contents of the alimentary canal, in the lung tissue, in the kidneys. Can be best prepared by evaporating bile to which has been added hydrochloric acid, removing the resinous substance which is thrown down, and mechanically separating the crystals of taurin and sodium chloride, which make their appear ance on cooling. Is produced artificially by heating ammonium isethionate to 210°, and by heating silver chlorethylsulphite with aqueous ammonia to 100°. — Large, clear crystals, easily soluble in hot water, but slightly in cold water, insoluble in alcohol. It fuses, and decomposes at 'a high temperature. It does not yield well characterized compounds with bases nor with acids. CH2.S02.OH Disulphetholic acid, C2H6S206 142 GLYCOLS, produced by the action of fuming sulphuric acid on ethyl cyanide or propionamide; by the oxidation of ethylene sulphydrate with nitric acid; the sodium salt is formed by heating ethylene bromide with a concen trated solution of sodium sulphite. — Easily soluble crystals; fusing point, 94°. Bibasic, very stable acid. Carbyl sulphate (ethionic anhydride). C2H4S206 = CH2 SO2 OIF 0 SO2^ ^' *s f°rme(^ by the Direct union of ethylene with sulphuric anhydride. — Colorless crystals, fusing at 80°; deliquesces in the air, and combines with water, forming CH2.O.S02.OH Ethionic acid, C2H6S207 = ^ SQ2 QH This acid is formed particularly when sulphuric anhydride is conducted into alcohol, which is cooled by means of ice. — Bibasic acid, which is resolved into isethioiiic acid and sulphuric acid when its aqueous solution is evaporated. Its salts are also decomposed by boiling their aqueous solutions. 2. Propylene Alcohol (Propylglycol). Q3H802 = C3H6(OH)2. Taking for granted that alcohols, which contain two hydroxyl groups in combination with the same carbon atom, cannot exist, there are only two diatomic alcohols C3H802 possible, viz. : CH2(OH).CII2.CII2(OH) and CH2(OH).CH(OH).CtP. The first is a primary alcohol, the second half primary, half secondary. Only the second alcohol is known as yet. Preparation. From propylene bromide in the same manner as ethylene alcohol from ethylene bromide. Properties. Colorless, viscid liquid ; specific gravity, 1.051 at 0°; boiling point, 188-189°; mixes with alcohol and water in all proportions. When heated with concentrated hydriodic acid, it is converted into isopropyl alcohol and isopropyl iodide. GLYCOLS. 143 Propylene chlorhydrine, C3H6C1.0H, is prepared like the analogous ethylene compound. — Colorless liquid, boiling at 127°. "When carefully ozidized it is converted into monochloracetone (p. 110). Propylene bromhydrine, C3H6Br.OH. Colorless liquid, boiling at 145-148°. Propylene oxide, C3H6.0. Liquid, boiling at 35°. Combines with nascent hydrogen, forming isopropyl alcohol. 3. Butylene alcohol (Tetrylene alcohol), C4H1002 = C4H8(OH)2, prepared from butylene (obtained from amyl alcohol), is a colorless, inodorous, thick liquid, of specific gravity 1.048 at 0° ; boiling point, 183-184° ; mixes with water and alcohol in all proportions. A substance isomeric with this is — Butyleneglycol, C4H1002= CH3.CH.OH.OH2.CH2.CH. Formed in small quantity, together with ethyl alcohol, by treating aldehyde, very much diluted with water, with sodium-amalgam, in a weakly acid solution. — Clear, viscid liquid, of a sweet, slightly pungent taste; boiling point, 203.5-204°. When oxidized, it yields carbonic, acetic, and oxalic acids, and crotonic alde hyde, the latter in very small quantity. 4. Amylene alcohol, C5H1202 = C5H10(OH)2. Fromamy- lene bromide. — Colorless liquid; does not mix with water ; specific gravity, 0.987 ; boiling point, 177°. 5. Hexylene alcohol, C6II1402 = C6H12(OH)2. From hexylene bromide. — Colorless liquid ; mixes with water; specific gravity, 0.967 ; boiling point, 207°. The two following compounds are isomeric with this — Diallylhydrate, C6H1402 = C6H12(OH)2. The iodide of this alcohol C6H12I2, a thick liquid that does not boil without undergoing decomposition, is produced 144 GLYCOLS. by direct union of diallyl (p. 133) with hydriodic acid. The alcohol is obtained from this in the same manner as ethylene alcohol. It boils at 212-215°. Pinacone, C6H"02 = ®j? | C(OH).C(OH) j ^ Is formed, together with isopropyl alcohol, by the action of sodium-amalgam on acetone containing water. — Colorless, fine crystalline mass. Fusing point, 35-38°. Boiling point, 171-172°. Combines with water, form ing a hydrate C6H1402 + 6H20, which crystallizes from water in large quadratic plates, fusing at 42°, and, when heated with dilute sulphuric acid or hydrochloric acid, or with concentrated acetic acid, is converted into pinacoline C6H120, a colorless liquid, boiling at 105° ; insoluble in water. 6. Octylene alcohol, C8H1802 = C8H16(OH)2. From octylene bromide. — Colorless liquid, does not mix with water; specific gravity, 0.932; boiling point, 235-240°. B. MONOBASIC, DIATOMIC ACIDS, CnIl2nO\ The primary diatomic alcohols, when subjected to oxidation, conduct themselves like the monatomic alcohols. The groups CH2.OH, contained in them, are oxidized, forming carboxyl : — CH2.OH CH2.OH CO.OH. CIP.OH CO.OH CO.OH. Ethylene alcohol. Glycolic acid. Oxalic acid. In this way are produced two series of acids. The acids of the first series are still half alcoholic in their character, and must hence play the part of monatomic alcohols and at the same time of monobasic acids. They stand in close relation to the fatty acids, and can be easily prepared from them by replacing hydrogen in the latter by hydroxyl. Of each acid of this series GLYCOLIC ACID. 145 there can exist just as many isomeric modifications, as of the monochlorine- or monobromine-substitution-pro- ducts of the corresponding fatty acid ; of the first member only one; of the second two, CH2(OH).CH2.CO. OH and CIRCH j etc' .Oil, 1. Gly colic Acid (Oxy acetic Acid). Occurrence. In unripe grapes. Formation and preparation. By heating potassium chlor- or bromacetate with water, or by the addition of silver oxide to a hot aqueous solution of chlor- or bromacetic acid ; by the action of nascent hydrogen (from zinc and sulphuric acid) on oxalic acid or oxalic ether ; by treating glycocol with nitrous acid ; and by careful oxidation of ethylene alcohol. — Can be most readily obtained by slow oxidation of ethyl alcohol. A mixture of 500 grms. alcohol and 440 grms. nitric acid is allowed to stand in cylinders, which are imper fectly closed, until small gas bubbles begin to appear in the liquid: the cylinders are then placed in water of 20°. In a few days the action is completed. The solution is now evaporated in small portions to a syrupy consistence, dissolved in water, neutralized with chalk and allowed to crystallize. The calcium glycolate. thus obtained, must be again dissolved and boiled for some time with milk of lime, for the pur pose of decomposing any secondary products which may be present (glyoxal, glyoxylic acid). The solution is treated with oxalic acid in order to set the acid free, the filtrate from calcium oxalate almost neutralized with lead carbonate, and the solution of the lead salt evaporated to crystallization. From the solution of this salt, the lead is removed by means of sulphuretted hydrogen or, still better, sulphuric acid, which is added in not quite sufficient quantity to complete the decomposition, the filtrate evaporated and the gly colic acid extracted by means of anhydrous ether. 13 146 GLYCOLIC ACID. Properties. Deliquescent crystals ; easily soluble in water, alcohol, and ether; fuses at 78-79°. When subjected to distillation, it undergoes decomposition, yielding formic aldehyde (oxymethylene, p. 101). The calcium salt (C2H303)2Ca forms fine, needly crys tals, difficultly soluble in cold water ; the silver salt C2H303Ag + JH20, lustrous crystals, also difficultly soluble. Glycolic acid is acetic acid in which one atom of hydrogen is replaced by hydroxyl. The hydrogen of this OH cannot be replaced by metals by treatment with bases, but easily by alcohol and acid radicals. A number of such compounds, for instance, methylglycolic acid CH2(O.CII3)CO.OH (from sodium chloracetate and sodium methylate ; colorless, thick liquid, boiling at 198°), ethylglycolic acid CH2.(O.C2H5).CO.OH (liquid, boiling at 206-207°), are known ; and^all these com pounds, like gly colic acid, are monobasic acids. CH2.0. CH2 Diglycolic acid, OH605 + H2C = co.OHCO.OH. Is produced as a secondary product in the preparation of glycolic acid from monochloracetic acid and by the oxidation of diethylene alcohol (p. 138).— Large, color less, monoclinic crystals. Easily soluble in water and alcohol. Fuses below 150° ; bibasic acid ; isomeric with malic acid. Glycolid (Glycolic anhydride), C2H202 = CH2| QQ^> is formed by heating glycolic acid, or potassium chloracetate ; or by heating tartronic acid to 180°. — White, amorphous powder ; is converted into glycolic acid by boiling with water or alkalies; by heating with ammonia, into glycolamide C2H5N02 = CHXOH.CO.NH2 (isomeric with glycocol).— Colorless crystals, fusing at 120°. OXYPROPIONIC ACIDS. 147 2. Oxypropionic Acids. Both of the acids, possible according to the theory, are known. 1. Lactic acid (Ethylidenelactic acid) = CH3. iOTT CO OH *s Pr°duced by the souring of milk by fermentation of the sugar of milk contained in it. In the same way it is formed from cane-sugar, grape- sugar, gum, starch, when these are left for some time in contact with water and old cheese or similar protein substances at a temperature of 20-50° (lactic fermenta tion). It is hence contained in large quantity in acidi fied vegetable juices (for instance, in beet juice, in saurkraut), and its presence has also been proven in animal liquids, particularly in the gastric juice. — It is produced from a-chlor- or a-brompropionic acid, and from alanin in the same manner as the homologous glycolic acid is prepared from chloracetic acid and glycocol; further, by the action of hydrochloric acid on aldehyde hydrocyanate (see p. 104), and of nascent hydrogen on pyroracemic acid. Most practically prepared in the following manner : 3 kilogrammes cane-sugar and 15 gr. tartaric acid are dissolved in 17 litres boiling water and allowed to stand several days ; 100 grms. old cheese, suspended in 4000 grms. sour milk, and 1200 grms. zinc white are then added, and the temperature retained as nearly as rsible at 40-45° during the period of fermentation, eight to ten days the fermentation is ended. The whole mass is now heated to boiling, filtered, evaporated, and allowed to crystallize. The separated* zinc lactate is crystallized again from hot water, then * The fermentation is prevented by any large amount of free acid, and hence ceases as soon as this is formed, long before all the sugar is decomposed. This can, however, be avoided by neutralizing the acid, from time to time, by means of a base, or by adding a base at the com mencement. 148 OXYPROPIONIC ACIDS. dissolved in boiling waler and decomposed with sul phuretted hydrogen. The liquid filtered from zinc sulphide is evaporated 011 a water-bath. The acid thus obtained still contains mannite, as an impurity. It is separated from this by dissolving the residue in a little water and agitating with ether in which mannite is insoluble, and, after the separation of the two liquids, evaporating the ethereal solution. Colorless, syrupy liquid, of 1.215 specific gravity ; mixes with water, alcohol, and ether in all proportions. Not volatile without decomposition. Is decomposed by distillation into water, aldehyde, carbonic oxide, and lactide. When heated with dilute sulphuric acid to 130°, it is decomposed into aldehyde and formic acid. It is reduced by means of hydriodic acid, most readily by distillation with phosphorus iodide and a little water, to propionic acid. Heated with hydrobromic acid it is transformed into brompropionic acid. By oxidation with chromic acid, acetic and formic acids are formed. The lactates of the alkalies do not crystallize. Calcium lactate, (C3H503)2Ca + 5IPO. White needles in verrucose combinations. Very easily solu ble in hot water and alcohol, more difiicultly in cold water (9 J parts). Zinc lactate, (C3H503)2Zn + 3IPO. Lustrous needles, or small crystals, in crusty formations, soluble in 6 parts hot and 58 parts cold water. Insoluble in alcohol. Iron lactate, (C3H503)2Fe 4- 3H20. Can be prepared, like the zinc salt, directly from milk whey and iron filings; crystallizes in fine prisms, united together, forming an almost colorless crust ; is difiicultly soluble, and in solution undergoes a change in the air. !OTT CO 0 C2IP results ing lactic acid with alcohol to 170°. — Neutral liquid, boiling at 156°, which, in contact with water, is rapidly decomposed into lactic acid and alcohol. OXYPROPIONIC ACIDS. 149 Potassium and sodium are dissolved in it with evolu tion of hydrogen, and by the action of ethyl iodide on the resulting compounds are formed Ethyl ethyllactate (lactic-diethylether), C2H* ( O O2TT5 ) CO O T2H5 ^is *s a^so Pro^llced by the decomposi tion of chlorpropionic ether with sodium ethylate. — Colorless liquid, insoluble in water, boiling at 126.5°. Treated with caustic potassa, only one atom of ethyl is replaced by potassium, and there is formed a potas sium salt of Jo P2TT5 caon. This is a strong acid and isomeric with ethyl lactate. "When lactic acid is heated for a long time at 140- 145°, it is converted into dilactic add C6H1005, a yellow, amorphous substance, which, when boiled with alka lies and acids, is reconverted into lactic acid. Lactide (lactic anhydride), C3H402 = CIP.CH j ^Q>> The distillate from lactic acid is evaporated at 100°; the residue washed with cold absolute alcohol and crystallized from hot alcohol. — Ixhombic plates, fusing at 107°, but slightly soluble in water, slowly uniting with it to form lactic acid. Trichlorlactic acid, CCP.CH j ^aoil. When hydrocyanic acid is allowed to act upon chloral, the ( OTT crystallizing compound CCRCH j ^ is obtained, which yields the acid when digested with moderately concentrated hydrochloric acid. — Crystalline mass, con sisting of small prisms ; fusing point, 105-110° ; yields crystallizing salts. Lactyl chloride, C3H4C120 = CIP.CHCl.CO.Cl, is formed by the distillation of zinc lactate with double its 150 OXYPKOPIONIC ACIDS. weight of phosphorus chloride ; phosphorus oxichloride is formed at the same time, and, for the separation of the two products, no means have been devised up to the present. K~ot distillable without partial decomposi tion. Is decomposed by water, yielding hydrochloric acid and a-chlorpropionic acid; by alcohol, yielding hydrochloric acid and ethyl a-chlorpropionate ; when heated with alkalies, it yields lactic acid ; and in con tact with zinc and water, propionic acid. {OTT CO KIP *s f°rmec^ kv heating alaiiine in a current of hydrochloric acid gas at 180- 200°. — Colorless, transparent needles or laminae ; fusing point, 275 ; easily soluble in water and alcohol. 2. Sarcolactic acid (Paralactic acid, ethylene- CIP.OII lactic acid), AT™ nr\ QTT 1S contained in the juice of flesh and in animal secretions, at times also in urine, probably together with ordinary lactic acid. It is produced by boiling ethylene cyanhydrine (p. 137) with alkalies, and, together with some acrylic acid, by boiling /3-iodopropionic acid with milk of lime. — To prepare it, baryta water is added to an aqueous extract of chopped meat, the whole then boiled, filtered, and evaporated. Sulphuric acid is added to the syrupy residue, and the lactic acid extracted by means of ether. — The free acid is very similar to lactic acid of fermentation, but the corresponding salts of the two acids present differences in the degree of their solu bility and in the amount of water of crystallization contained in them. The calcium salt is less soluble in water than that of ordinary lactic acid, and crystal lizes with 4 molecules of water. The zinc salt contains only two molecules of water, is much more easily soluble in water (in five to six parts of cold water), and also easily soluble in alcohol. — Oxidized by means of chromic acid, sarcolactic acid is converted into malonic acid. Heated up to 130-140°, and the OXYBUTYRIC ACIDS — OXYVALERIC ACIDS. 151 residue dissolved in water, it is converted into ordinary lactic acid. 3. Oxybutyric Acids. ( HTT p4TT8n3 P3TT6 ) VLL 1 I CO.OH. 1. a-Oxybutyric acid. From monobrombutyric acid by boiling with barium hydroxide. — Colorless, stel late needles or flat prisms ; fusing point, 43-44°. When carefully heated it can be sublimed. Deliquescent in the air. 2. p-Oxybutyric acid, CH3.CH(OH).CH2.CO.OH. Is produced by the action of hydrogen (sodium-amal gam and water) on ethyl acetylacetate (p. 82) and by boiling propylene cyanhydrine with caustic potassa. — Colorless, syrupy, very deliquescent liquid. 3. Oxyisobutyric acid, ^ } C(OH).CO.OH. Is produced by boiling bromisobutyric acid with barium hydroxide; by the action of cyanhydric and hydro chloric acids on acetone (acetonic acid) ; by the action of dilute nitric acid on amylene alcohol (butyllactinic acid) ; by heating methyl oxalate with methyl iodide and zinc, and then treating the product with water (dimethoxalic acid). — Colorless prisms, easily soluble in water. Fusing point, 79°. Sublimes in long needles even at 50°, when carefully heated. When carefully oxidized with potassium bichromate and dilute sul phuric acid, it yields acetone, together with carbonic and acetic acids. • 4. Oxyvaleric Acids. P5TT10O3 P4T-T8 j OH. L | CO.OH. 1. Oxyvaleric acid. From bromvaleric acid in a hot aqueous solution by treatment with silver oxide. Its ether is formed when ethyl oxalate is heated with isopropyl iodide and zinc, and the product treated 152 OXYCAPROIC ACIDS. with water. — Large, colorless, very easily soluble plates. Fusing point, 80°. Sublimes even below 100°. 2. Isoxy valeric acid (Ethometb oxalic acid). The ether, boiling at 165°, is produced by heating ethyl oxalate with a mixture of methyl iodide and ethyl iodide and zinc, and afterwards treating the product with water. The free acid, separated from the ether, forms colorless, easily soluble crystals, fusing at 63°. 5. Oxycaproic Adds. UH CO.OH. PSTTIO j I 1. Leucic Acid. Is produced by the action of nitrous acid on leucine (p. 98). — Colorless, easily solu ble needles ; fusing point, 73°. 2. Isoleucic acid. (Diethoxalic acid). Is obtained, like isoxyvaleric acid, by heating ethyl oxalate with ethyl iodide and zinc. — Colorless, easily soluble crys tals ; fusing point, 74.5° ; sublimes at 50°. When care fully oxidized it gives propione (p. 110) ; also yields propione, together with ethylcrotonic acid (p. 125), when heated with concentrated hydrochloric acid. C. BIBASIC, DIATOMIC ACIDS, CnH2w~204. The acids of this series are derived from the hydro carbons of the marsh gas series by the replacement of two hydrogen atoms in the latter by two carboxyl groups ; or from the fatty acids by the replacement of one hydrogen atom by the carboxyl group CO.OH. They are produced by the complete oxidation of the primary diatomic alcohols containing twice the group CH2.OH ; by heating the dicyan-substitution-products of the marsh gas hydrocarbons (cyanides of the hydro carbons CnH2n) and the monocyan-substitution-products of the fatty acids with caustic potassa. OXALIC ACID. 153 1. Oxalic Acid. CO.OH. Occurrence. Very widely distributed in nature ; in the form of the acid potassium salt in the different varieties of Oxalis ; in the form of the calcium salt in a number of plants ; in urine (some of the urinary cal culi consist entirely of this salt) ; in the form of the ammonium salt in guano. Formation. By the action of finely divided sodium on dry carbonic anhydride at 350-360° ; by heating sodium formate; by the decomposition of cyanogen with water ; by the heating of cellulose (paper, linen) with potassium hydroxide ; the most important method of formation is, however, by the oxidation of a great many organic substances with nitric acid, hyperman- ganic acid, etc. Preparation. The expressed juice of oxalis plants is precipitated by means of a solution of sugar of lead, the precipitate decomposed with sulphuric acid or sul phuretted hydrogen, and the filtrate evaporated to crystallization. — Or 1 part sugar or starch is heated with 8 parts of nitric acid (specific gravity, 1.38) until action has ceased, and the solution then evaporated to dryness. — On the large scale it is also produced by heating sawdust with caustic potassa or soda. Properties. Colorless prisms, soluble in 15 parts water, more easily soluble in alcohol. It contains 2 molecules water of crj^stallization, which are given off at 100°. When carefully heated up to 150°, the efflo- resced crystals can be completely sublimed ; when rapidly heated, it is partially resolved into carbonic anhydride, carbonic oxide, formic acid, and water. Oxidizing agents transform it into carbonic anhydride and water. Sulphuric acid resolves it into water, car bonic anhydride, and carbonic oxide. Nascent hydrogen (zinc and hydrochloric acid) converts it into glycolic acid (p. 145) and acetic acid. Strong, bibasic acid. Its salts, with the exception of 154 OXALIC ACID. those of the alkalies, are very difficultly soluble in water, but soluble in mineral acids. Potassium oxalate. The neutral salt C204K2 + H20 forms easily soluble crystals, which effloresce at an ele vated temperature. The acid salt C2OHK is difficultly soluble in cold water. A still more acid salt C204HK + C2H204 + 2H20 is the salt-of-sorrel of commerce. Ammonium oxalate. The neutral salt C204(NH4)2 + H20, long prismatic crystals, easily soluble in cold water, is decomposed at a high temperature, forming oxamide, carbonic anhydride, carbonic oxide, ammonia, and hydrocyanic acid. The acid salt C204H(lsrH4) + H20, prisms, more difficultly soluble than the neutral salt ; when heated, yields oxamic acid. Calcium oxalate, C204Ca+H20. A crystalline powder, insoluble in water. "When allowed to crystal lize slowly, it combines with three molecules of water of crj^stallization. It can only be obtained in an anhy drous state by heating it above 200°, and it then re- absorbs one molecule very rapidly, when exposed to the air. Lead oxalate, C204Pb. White precipitate, insolu ble in water. — Silver oxalate C204Ag2. White powder, insoluble in water. Detonates when heated. Methyl oxalate, C204(CH3)2, is produced by the distillation of acid potassium oxalate (2 parts) with a mixture of methyl alcohol (1 part) and concentrated sulphuric acid (1 part). — Colorless, rhomboidal plates, of a weak odor, fusing point, 51° ; boiling point, 162° ; soluble in water and alcohol ; is decomposed, however, by water, particularly rapidly with the aid of heat, yielding oxalic acid and methyl alcohol. With aqueous ammonia, it yields oxamide and methyl alcohol ; with dry ammonia, methyl oxamate. The ethers of oxyiso- butyric acid (p. 151) and isoleucic acid (p. 152) are formed by the action of zinc on a mixture of this ether OXALIC ACID. 155 with methyl or ethyl iodide, and subsequent addition of water. — The acid methyl ether, methyloxalic add C2O.H.CH3, is contained in the mother-liquor from the neutral ether. When in a free state, it decomposes easily. Ethyl oxalate (Oxalic ether), C204(C2H5)2, is formed like methyl oxalate ; is prepared most readily in the following manner : A mixture of 3 parts oxalic acid, dehydrated at 100°, and 2 parts absolute alcohol, in a tubulated retort, is heated slowly in an oil-bath until the thermometer shows 125-130° ; in the mean time the vapor of 2 parts absolute alcohol is conducted upon the bottom of the retort in an uninterrupted current. The product is then distilled, and that portion which boils at 182-186° collected separately. — Colorless liquid with a slight odor ; specific gravity, 1.0824 ; boiling point, 186° ; does not mix with water. Conducts itself towards water and ammonia, and zinc and the alco holic iodides, like the methyl ether. Its solution in absolute alcohol gives a crystalline precipitate with an alcoholic solution of potassa. This is the potassium salt of ethyloxalic acid C204.H.C2H5, which, in a free state, is readily decomposed. Ethyloxy-oxalylchloride, C4H503C1= C202<°|C2]EI5 Is formed by the action of phosphorus oxichloride on potassium ethyloxalate. — Colorless, clear, mobile liquid, of a suffocating odor; boils at 140°; specific gravity at 16°, 1.216 ; fumes in contact with air, and is con verted into oxalic acid. CO.NH2 Oxamide, C2H4N202 = ^Q ^H2 is formed by the decomposition of oxalic ether with ammonia ; by con ducting cyanogen into strong hydrochloric acid ; further from cyanogen and water in the presence of a very small quantity of aldehyde ; and, in small quantity, by mixing hydrocyanic acid with manganese super- oxide and a little sulphuric acid. — White powder or 156 OXALIC ACID. long entangled needles ; inodorous and tasteless ; insol uble in cold water, slightly in hot water; partially sublimable without decomposition. Heated in closed vessels up to 200° with water, it is converted into neutral ammonium oxalate. .. Dietnyloxamide, ibr(mamlin C6H3Br2.NH2. Flat needles. Fusing point, 19^0.— Tribromanilin C6H2Br3.KE2. Long, colorless needles. Fusing point, 117° ; boiling point, 300°. Orthoiodanilin, C6H4I.NH2. Colorless needles, which fuse at 60°. The hydriodate is produced when anilin is mixed with powdered iodine. lodanilin hydrochlorate C6H4I(NH2).HC1, prepared from this with hydrochloric acid, crystallizes in laminae, which are difficultly soluble in water, and still more difficultly in hydrochloric acid. — A second iodanilin, prepared from the nitroiodobenzene of fusing point 34°, forms lamime of a silvery lustre. Fusing point, 25°. Orthonitranilin, C6H4(N02)^H2. Cannot be prepared directly from anilin. Is produced by boiling nitra- cetanilide and other anilides with caustic potassa. — Yellow needles or plates. In water very difficultly, in alcohol easily soluble. Fusing point, 141°. Sublim- able. "Weak base. — Metanitranilin is formed by the action of alcoholic ammonia on metabromnitroben- zene. — Dark, yellow, long, fine needles ; fusing point, 66°. Weak base. — Paranitranilin is formed oy con ducting sulphuretted hydrogen into a warm alcoholic solution of paradinitrobenzene, to which has been added ammonia. — Long, yellow needles, which fuse at 108°. Easily sublimable. But slightly soluble in water, but more readily than the preceding compound ; in alcohol easily soluble. Weak base. The hydro- chlorate is decomposed even by water. Dinitranilin, C6H8(F02)2.NH2. By heating dinitro- chlorbenzene with alcoholic ammonia. — Bright-yellow prisms. Fusing point, 175°.— Trinitranilin C6H2(N02)3. Nil2. From trinitrochlorbenzene with aqueous or alco- BENZENE. 261 holic ammonia. — Long, furrowed needles. Fusing point, 179-180°. Ethylanilin, C6H5.KH.C2H5. Anilin combines di rectly with ethyl bromide, slowly at the ordinary temperature, rapidly by the aid of heat, forming ethyl- anilin hydrobromate, a crystalline substance, from which the base can be separated by means of potassa. — Color less liquid ; becomes brown in contact with the air ; boils at 240° ; and forms with acids, crystallizing, easily soluble salts. Diethylanilin, C6H5.]ST(C2H5)2. The hydrobromate of this base is produced by direct combination of ethyl- anilin with ethyl bromide. — Colorless oil ; does not turn brown ; boils at 213°. /Iphenylammonium. The iodide, C6IP.N (C2IF)3I, is formed by heating diethylanilin with ethyl- iodide at 100°, for a long time. Silver oxide produces from this the hydroxide C6H5.N"(C2II5)3.OH, which is strongly alkaline ; easily soluble in water ; and is resolved into diethylanilin, ethylene, and water by distillation. „ , .—Cry: talline base, fusing at 57°. A large number of analogous bases can be prepared in the same manner, by allowing the bromides of other alcoholic radicles to act on anilin. When aiiilin is- heated with amyl bromide, for instance, amylanilin C6H5.im.C5H11, is produced; this yields, with ethyl bromide, amylethylanilin C6H5.N j ^jp and, finally, if methyl iodide is allowed to act upon this, the iodide of an ammonium is produced, in which each hydrogen atom is displaced by a different radicle (phenylamyl- ( C5!!11 , ethylmethylammonium iodide C6ll5^ •! C2H5I ). A CH3 ' 262 BENZENE. great many such compounds have been prepared and carefully investigated. Diphenylamine, (C6H5)2NH. Is produced by heat ing anilin with anilin hydrochlorate, and by distilling anilin-blue (see Anilin Colors). — Crystals, that fuse at 45°, and distill, without decomposition, at 310°. Is colored deep blue by nitric acid. Weak base. The salts are decomposed by water. The hydrogen of the NH2 in anilin can also be dis placed by acid radicles. The compounds formed in this way, which are called anilides, may also be con sidered as the amides of the acids, in which hydrogen is displaced by phenyl. There are a great many such compounds known. The following may serve as ex amples : — Formanilide (Phenylformamide), C6H5.FH.CHO, is produced by digesting ethyl formate with anilin, and by heating equal molecules of oxalic acid and anilin rapidly; in the latter cases secondary products are formed. — Prisms, fusing point, 46° ; easily soluble in hot water, alcohol, and ether. In an aqueous solution it gives a precipitate of sodiumformanilide, C6II5.OTsTa. CIIO, with concentrated soda-ley, which is again re solved into formanilide and sodium hydroxide by means of water. When distilled with concentrated hydro chloric acid, formanilide yields benzonitrile (p. 256). Acetanilide (Phenylacetamide), C6IF.OTI.C2H30, is .produced by mixing anilin with acetic anhydride or acetyl chloride, and also by heating equal molecules of glacial acetic acid and anilin together for an hour.— Colorless, shiny, lamellar crystals, that fuse at 112-113°, and volatilize without decomposition at 295°. But slightly soluble in cold water, more readily in hot water and in alcohol. Treated with soda-ley it yields acetic acid and anilin. CO.IsriI.C6H5 Oxanilide (Diphenyloxamide), _ , is formed by heating anilin oxalate to 160-180°, and, together BENZENE. 263 with monophenyloxamide, AQ ^-jp by evaporating a solution of anilin cyanide (p. 265) with hydrochloric acid. — Shiny crystals, that fuse at 245°, and are sub- limable. CO.NH.C6!!5 Oxamlic acid (Phenyloxamic acid), QQQJJ is produced by heating anilin with an excess of oxalic acid. — Crystalline scales, easily soluble in hot water, but slightly in cold. Has a strong acid reaction. Monobasic acid. Phenylcarbamide (Phenylurea), COJ produced like ethylurea (p. 230) by the decomposition of phenol cyanate with ammonia ; by the mixing of potassium cyanate with anilin sulphate ; by the slow action of the vapor of cyanic acid on anilin, etc. — Color less, needle-shaped crystals, difficultly soluble in cold water, easily in hot water, in alcohol and ether. Is de composed by heat, yielding ammonia, cyanuric acid, and Diphenylurea (Carbanilide), CO(NILC6H5)2, which is also produced by bringing together phenol cyanate with water or anilin ; by heating 1 part urea with 3 parts anilin at 150-170° ; and, together with formanilide, by heating oxanilide. — Needles of a silken lustre, sparingly soluble in water, easily soluble in alcohol ; fuses at 205°. Volatile without decomposition. Phenylcarbamic acid (Carbanilic acid), ( Nil C6IP CO j QJJ ' Not known in an isolated condition. Its ethyl ether is produced by the action of ethyl chlor- carbonate on anilin. It forms colorless needles, that fuse at 52°. Treated with concentrated potassa-ley, or heated with anilin, it yields diphenylurea. {Nil C61I5 ^-jp Is pro duced by the action of ammonia on phenyl mustard-oil ; 264 BENZENE. and by heating ammonium sulphocyanate with anilin for a long time. Diphenylsulphocarbamide (Sulphocarbanilide), CS (NIL C6H5)2. Is produced by bringing together carbon bisulphide with anilin, slowly at the ordinary tempera ture, rapidly by heating a mixture of carbon bisulphide, anilin, and alcohol. — Colorless laminae. Fusing point, 140°. Insoluble in water, easily soluble in alcohol and ether. Phenyl Mustard-oil, CS:KC6IF. Is produced from diphenylsulphocarbamide by distilling it with phosphoric anhydride ; by heating with concentrated hydrochloric acid, the vessel being connected with an inverted condenser ; and by mixing its alcoholic solution with an alcoholic solution of iodine. — Color less liquid, with an odor very similar to that of mus tard-oil. Boiling point, 222°. Combines directly with ammonia, forming phenylsulphocarbarnide ; with anilin forming diphenylsulphocarbamide ; with al cohol at 110-115°, forming phenylxanthogenamide, CS \ ^ p2TT5 which is also formed by heating phenyl- sulphocarbamide for a long time with alcohol at 140- 150°. Colorless crystals ; fusing point, 65°. Phenylcyanamide (Cyananilide), CKOTI.OTP, is produced by conducting dry cyanogen chloride into an ethereal solution of anilin; and by digesting a solution of phenylsulphocarbamide with lead oxide. — Colorless, long needles, arranged concentrically. Fusing point, 36-37°! Difficultly soluble in water, easily solu ble in alcohol and ether. Without basic properties. Is spontaneously transformed, even at the ordinary temperature, into the polymeric compound, triphenyl- melamine C3II3(C6H5)3]^6, which crystallizes in prisms, fusing at 162-163°. Diphenylguanidine, C13H13^T3 = CMII3(C6H5)2. Is produced from diphenylsulphocarbamide when its solution in alcoholic ammonia is treated with lead oxide. — Long, flattened needles. Fusing point, 147°. BENZENE. 265 M on atomic TDRSG. A base isomeric with this, p-diphe- nylguanidine (melanilin), is produced, in the forrn^ of the hydrochlorate, by conducting cyanogen chloride into pure anilin ; and by heating an alcoholic solution of phenylcyanamide with anilin hydrochlorate. — Color less, crystalline laminae. Fusing point, 131°. Sparingly soluble in water, more easily soluble in alcohol than the o-base. i/"\TTT p,6TT5\2 KC'H» Is produced by heating diphenylurea; by heating diphenylsulphocarbamide, either alone or with copper, at 150-160°, or with anilin up to the boiling point of the latter. Is prepared most readily by dissolving 1 molecule diphenylsulphocarbamide and 1 molecule anilin in alcohol, and adding lead oxide, or mercury oxide, or an alcoholic solution of iodine to the boiling liquid. The hydrochlorate is also formed by melting diphenylsulphocarbamide with lead chloride or mer cury chloride. — Long, colorless, shiny, rhombic prisms. Fusing point, 143°. Almost insoluble in water even at the boiling temperature, easily soluble in hot alco hol. Monatomic base. Heated with carbon bisul phide at 160-170°, it is converted into phenyl mustard- oil and diphenylsulphocarbamide. The hydrochlorate of a base isomeric with the preceding, viz.: p-triphenylguanidine (Carbotriphenyl- triaminej is formed by heating anilin with carbon tetrachloride for a long time at 170-180°. The free base crystallizes in colorless, four-sided plates, that are insoluble in water, difficultly soluble in ether, more easily in alcohol. Anilin cyanide, (MF^= (C'HTC)f (CN)2. Is pro duced by the direct combination of anilin and cyano gen, when an alcoholic solution of anilin is saturated with cyanogen. — Shiny crystalline laminae ; insoluble in water, difficultly soluble in alcohol. Fusing point, 210°. Diatomic base. 266 BENZENE. Orthodiamidobenzene (Orthophenylendiamine), C6II4(NH2)2, is produced by the reduction of orthoni- tranilin with iron-filings and acetic acid, or hydriodic acid. — Colorless crystals. Easily soluble in water. Melts at 140°, and boils at 267°. Paradiamidobenzene (Paraphenylendiamine), C6H4(N"H2)2. Is produced by the reduction of dinitro- benzene, or of the paranitranilin obtained from this. — Crystalline mass, which undergoes a change in contact with the air. Easily soluble in water. Fuses at 63°, and boils at 287°. Diatomic base. — The hydrochlorate, C6II4(^H2)22HC1, crystallizes in fine needles. Diazobenzene, C6tHN"(?), is obtained by the decom position of diazobenzene potassa (see below) with acetic acid. — Thick, yellow, very unstable oil. Diazobenzene nitrate, C6H4N2.HM)3. A current of nitrous acid is conducted into anilin nitrate, to which is added a quantity of water insufficient for its solution, until caustic potassa no longer causes a pre cipitate of anilin. The salt is deposited in crystals, which are increased in quantity by the addition of alcohol and ether. — Long, colorless needles, very easily soluble in water, but sparingly in alcohol, insoluble in ether and benzene. Explodes with great violence when heated or struck with a hammer. Is decom posed in a moist atmosphere, and, when boiled with water, yields nitrogen, nitric acid, and phenol. Diazobenzene sulphate, C6H4N2.H2S04, is obtained from anilin sulphate, like the preceding compound ; is prepared, however, most readily by treating the latter with dilute sulphuric acid. — Colorless prisms. Deto nates at 100°. Conducts itself towards solvents and by boiling with water like the nitrate ; by boiling with absolute alcohol it is converted into benzene, nitrogen being evolved, and the alcohol is oxidized to BENZENE. 267 aldehyde ; treated with hydriodic acid it yields nitro gen, sulphuric acid, and iodobenzene. Diazobenzene hydrobromate, C6H4N2.HBr, is formed by mixing an ethereal solution of diazoamido- benzene with bromine. — Colorless very unstable laminae. When a watery solution of the nitfate is mixed with a solution of bromine in hydrobromic acid, diazoben- zene perbromide, C6H4N2.HBr.Br2, is produced. Large, yellow lamellae, insoluble in water and ether, difficultly soluble in alcohol. Heated either alone or with alco hol it yields monobrombenzene. Diazobenzene potassa, C6H4N2.KOH. Is pro duced by the addition of very concentrated potassa-ley to the nitrate ; and can be separated from the saltpetre, that is formed at the same time, by dissolving in alco hol. — Colorless laminae of a mother-of-pearl lustre, easily soluble in water and alcohol, insoluble in ether. Detonates when heated. A freshly-prepared aqueous solution gives with silver nitrate a grayish-white, very explosive precipitate of diazobenzene silver-oxide, C6H4l$r2.AgOH. Diazo-amidobenzene, C12HnIsT3 is produced by mixing an aqueous solution of diazo benzene nitrate with anilin ; by conducting nitrous acid into a cooled alcoholic solution of anilin, and by pouring a cooled, slightly alkaline solution of sodium nitrite gradually on anilin hydrochlorate. — Golden- yellow, shiny lamellae. Fuses at 91°, and detonates when strongly heated. Insoluble in water, easily soluble in ether, benzene, and hot alcohol, less readily in cold alcohol. Nitrous acid, containing nitric acid, converts it into diazobenzene nitrate ; concentrated hydrochloric acid into anilin hydrochlorate, phenol, and nitrogen. Biazobenzenimide, C6H5N3, is produced by treat ing diazobenzene-perbromide with aqueous ammonia. — Slightly yellow-colored oil, volatile with water 268 BENZENE. vapor. Nascent hydrogen converts it into anilin and ammonia. Diazochlor-, Diazobrom-, Diazoiodo-, and Dia- zonitrobenzene-compounds are formed by the action of nitrous acid on the substitution-products of anilin. They conduct themselves in every respect like the diazo-compounds described. Azobenzene, C12H10N2, is produced from nitroben zene by the action of sodium-amalgam, alcoholic potassa or acetic acid, and a great deal of iron ; from anilin hydrochlorate by oxidation with potassium hypermanganate. — Large, red crystals, fusing at 66.5°. Distills without decomposition at 293°. Insoluble in water, easily soluble in alcohol and ether. — Combines with bromine, without elimination of hydrogen, form ing golden-yellow needles of C12H10Br2S"2, which fuse at 205°. Nitric acid converts azobenzene into nitro- substitution-products. Amido-azobenzene, C12HnN3 = C12H9.NH2.]Sr2 (Amidodiphenylimide), is produced from the isomeric compound diazoamidobenzene, when the latter is al lowed to stand for several days with alcohol and some salt of anilin. It is hence formed together with diazo amidobenzene, and under certain circumstances exclu sively by treating anilin with nitrous acid. It is also formed by the oxidation of anilin with sodium stannate, or bromine vapor. — Yellow, rhombic prisms. Almost insoluble in water, easily soluble in alcohol and ether. Fuses at 127.4°. Monatomic base. — Is the principal constituent of the dye known as anilin-yellow. Azoxybenzene, C12H10N20, is produced from nitro benzene, like azobenzene and usually both are formed together. — Long, yellow needles, insoluble in water, easily soluble in alcohol and ether. Fuses at 36°, and yields by distillation, anilin and azobenzene. — Treated with reducing substances, it is converted into azoben zene and hydrazobenzene. BENZENE, 269 Hydrazobenzene, C12H12N2, is formed by treating azobenzene or azoxybenzene with hydrosulph uric acid, ammonium sulphide, or sodium-amalgam. — Crystallizes in plates, that fuse at 131°. Almost insoluble in water, easily soluble in alcohol and ether. It is re solved by heating into azobenzene and anilin, and, when treated with oxidizing substances, is very readily converted into azobenzene. It does not combine with acids, is converted by them, however, into an isomeric body, benzidine. Sulphobenzolic acid, C6IP.S02.OH+ 1 JH20. Ben zene is shaken with weak fuming sulphuric acid, until it is dissolved, the solution is diluted with water, neu tralized with barium or lead carbonate, and the metal afterward removed from the solutions of the easily soluble salts by means of sulphuric acid or hydrosul- phuric acid. Is also produced from sulphanilic acid by replacement of the OTP group by hydrogen.— Small, colorless, four-sided plates, easily soluble in water and alcohol, deliquescent. Barium sulphobenzolate, (C6H5.S03)2Ba+H20. Plates of a mother-of-pearl lustre, easily soluble in water. Ethyl sulphobenzolate, C6IP.S02.O.C2IP, crystal lizes in fine, colorless needles. Sulphobenzolchloride, C6H5.S02C1, is thrown down, when sodium sulphobenzolate is intimately mixed with phosphorus pentachloride, the mass gently heated, and then thrown into water. — Colorless oil of specific gravity 1.371 ; boils at 246-247°, at the same time undergoing partial decomposition. Crystallizes below 0°, in large rhombic crystals. Boiling water decomposes it slowly, forming sulphobenzolic acid and hydrochloric acid. Treated with ammonia or ammo nium carbonate, it yields sulphobenzolamide, C6IP.S02. NIP, colorless laminae, fusing at 149°. 270 BENZENE. Chlor-, Brom-, lodo-, Nitro-, and Amidosulpho- benzolic acid, are produced by dissolving the mono- substitution-products of benzene in weak fuming sul phuric acid. They all belong to the para-series. Benzenesulphurous acid, C6H5.S02IL The sodium salt is produced by treating an ethereal solution of sulphobenzolchloride with sodium-amalgam. Hydro chloric acid separates the free acid from this. — Large, colorless prisms of a high lustre. Difficultly soluble in cold water, easily soluble in hot water, alcohol, and ether. Fuses at 68-69°, and is decomposed at a higher temperature. With chlorine or bromine it yields sul- phobenzolchoride or bromide ; and, in contact with the air, is transformed slowly into sulphobenzolic acid, rapidly by means of oxidizing agents. Monobasic acid. Paradisulphobenzolic acid, C6H4(S02.OH)2, is formed by heating sulphobenzolic acid or benzonitrile with fuming sulphuric acid. The barium salt, C6II4. S206Ba-flJH20, forms easily soluble microscopic crys tals. Paradisulphobenzolchloride, C6H4(S02C1)2. Is produced by the action of phosphorus pentachloride on sodium paradisulphobenzolate. — Large, colorless crys tals. Fusing point, 62°. Diphenyl, C12IF°. Is formed when sodium is al lowed to act upon a solution of monobrombenzene in ether or benzene. Is also produced when benzene- vapor is passed through an ignited tube ; by heating- potassium benzoate with phenol potassium; and in small quantity, together with benzene, by heating ben- zoic acid with lime. — Large, colorless, crystalline laminse, insoluble in water, easily soluble in hot alco hol. Fuses at 70.5°, and boils at 239-240°. BENZENE. 271 Dibromdiphenyl, C12H8Br2, is produced by the ac tion of bromine on diphenyl under water. — Large, colorless prisms, that fuse at 164°, and can be distilled without decomposition. Insoluble in cold alcohol, diffi cultly soluble in boiling alcohol, easily in benzene. Dinitrodiphenyl, C12H8(N02)2, is formed by pour ing cold fuming nitric acid on diphenyl. — Fine, color less needles, difficultly soluble in alcohol. Fuses at 213°. — A compound of the same composition, isodini- trodiphenyl, is formed at the same time with dinitrodi- phenyl ; it is more easily soluble in alcohol, and forms large colorless crystals that fuse at 93.5°. Diamidodiphenyl (Benzidine), C'2H8(OTI2)2. Is obtained by the reduction of dinitrodiphenyl with am monium sulphide or tin and hydrochloric acid. Is further formed by the treatment of the isomeric hy- drazobenzene (p. 269) with acids ; by heating azoben- zene with concentrated hydrochloric acid at 115°; by treating monobromanilin with sodium ; and, together with anilin, by conducting sulphuretted hydrogen into an alcoholic solution of nitrobenzene in the presence of copper or lead. — Colorless laminae of a silvery lustre, fusing at 118°, but slightly soluble in cold water, more readily in hot water, and easily in alcohol. Sublimable, but undergoing partial decomposition. — Benzidine sul phate, C12H12N2.H2S04, is almost insoluble in water and alcohol. Carbazol, C12H9ISr (probably Imidodiphenyl CCH4 \ O6II4 ( •^"•B-)* -^s obtained as a secondary product in the process for the purification of crude anthracene on the large scale. Can be artificially prepared by con ducting the vapor of anilin or diphenylamine through red-hot tubes. — Crystals, that resemble those of anthra cene ; fusing point, 238° ; boiling point, 338°. — By the action ofliydriodic acid on carbazol, there is formed a base carbazolin, C12H15N, that crystallizes in large, white needles, fuses at 96°, and boils at 286°. 272 BENZENE. Disulphodiphenylicacid, C12H8(S02.OH)2, is form ed by dissolving diphenyl in concentrated sulphuric acid. Long, colorless prisms, that fuse at 72.5°. Very easily soluble in water. The potassium salt, C12H8.S206K2 + 2 JH20, crystallizes in large, colorless prisms, moder ately difficultly soluble in cold water. The barium and lead salts are insoluble in water. Diphenylbenzene, C18II14 = C6H4 j g^ Is pro duced like diphenyl by the action of sodium on a mix ture of mono- and dibrombenzene. — Colorless, crystal line mass. Fusing point, 205° ; boiling point, 400°. Mercuryphenyl, (C6H5)2Hg. Is produced, when, to a solution of monobrombenzene in benzene, sodium- amalgam is added, and the whole then heated for a few hours in connection with an inverted condenser ; the formation takes place particularly easily in the presence of a little acetic ether. (See Mercury ethyl, p. 62). — Colorless, rhombic prisms, that become yellow in contact with the air. Fusing point, 120°. Insolu ble in water, easily soluble in chloroform, carbon bisul phide, and benzene, more difficultly in ether and boil ing alcohol. "When carefully heated, it can be par tially sublimed without decomposition ; it is, however, partially resolved into mercury, benzene, diphenyl, and carbon. Treated with two molecules chlorine, bromine, or iodine, it is resolved into monochlor-, brom-, or iodobenzene, and mercury chloride, bromide, or iodide ; treated with only one molecule of the halogenes, or heated with mercury chloride, bromide, or iodide and alcohol at 110°, it is converted into mercurymono- phenyl chloride, C6H5.IIg.Cl (rhombic plates, fusing point, 250°), bromide, C6H5.Hg.Br (rhombic plates, fusing point, 275-276°), and iodide, C6H5.Hg.I (rhombic plates, fusing point, 265-266°). Hydrogen, sodium, and alkaline sulphides regenerate mercury phenyl from these compounds. — "When the chloride is heated with TOLUENE. 273 moist silver oxide mercurymonophenyl hydroxide, C6H5. Hg.OH, is produced. This crystallizes in small, white, rhombic prisms, and is a stronger base than ammonia. Tin triethylphenyl, C6IF(C2H5)3Sn. Is o by treating a solution of monobrombenzene a obtained and tin- triethyl iodide in ether with sodium. — Colorless liquid, of a not unpleasant odor ; boiling point, 254° ; easily soluble in ether and absolute alcohol, difficultly in dilute alcohol, insoluble in water. It possesses a strong refracting power ; specific gravity at 0°, 1.2689 ; burns with a luminous flame, leaving a residue of metallic tin. la reduced by silver nitrate to diphenyl. Hydro chloric acid decomposes it, yielding tintriethyl chloride and benzene. 2. Toluene (Methylbenzene, Toluol). C7H8 = C6H5.CIP. Preparation. From light oil by partial distillation. By distilling a mixture of toluic acid with an excess of lime. By treating a mixture of monobrombenzene and ethyl iodide with an excess of sodium, the mix ture being diluted with ether and kept well cooled. It is also produced by the dry distillation of tolu- balsam and many resins. Properties. Colorless liquid of an odor resembling that of benzene ; specific gravity, 0.88 ; boiling point, 111°. — Oxidized with dilute nitric acid or chromic acid, it is converted into benzoic acid. Substitution-products of Toluene. According as the subtituting chlorine, bromine, and iodine take the place of hydrogen in the benzene residue, or in the methyl, compounds of the same composition but of entirely different properties are formed. Chlorine, etc., that has entered the benzene residue, is held as tena ciously in combination as in chlorbenzene ; that which has entered the methyl-group, on the other hand, can be replaced by other monovalent elements or atomic 274 TOLUENE. groups with the greatest ease. — When chlorine or bromine is allowed to act on toluene that is kept well cooled or to which is added iodine, substitution takes place only in the benzene residue; at boiling temperature, and in the absence of iodine, on the con trary, the hydrogen of the methyl is replaced. Of the substitution-products of the first class there are, fur ther, certain isomeric modifications possible, the differ ence of which depends upon the different relative posi tions of the substituting atoms with reference to each other, and with reference to the methyl-group already present in the molecule (See p. 252). The entrance of one atom of chlorine into toluene can accordingly give rise to the formation of four different compounds, C6IF.CH2C1; and three modifications of C6H4C1.CH3. The direct action of chlorine, bromine, or nitric acid causes chiefly the formation of compounds belonging to the para-series (1 : 4) ; but, together with these, small quantities of ortho- or meta-compounds are also formed. Both the latter are obtained in a pure condition by treating the substitution-products of the amido-deriva- tives (toluidins) with nitrous acid, thus converting them into diazo-compounds, and then decomposing the sulphates of the diazo-compounds by boiling with abso lute alcohol (See diazobenzenesulphate, p. 266). — The conduct of the monosubtitution-products by oxidation with potassium bichromate and dilute sulphuric acid is very characteristic. The compounds, in which the substitution has taken place in the methyl, are by this means, like toluene itself, converted into benzoic acid : of the other compounds, those belonging to the meta- and para-series are oxidized directly to meta- and para- substitution-products of benzoic acid (by simple oxi dation of the group, CH3 to CO.OH) ; the ortho-com pounds on the contrary are completely burnt up with out yielding an aromatic acid. Ortho-, Meta-, andParachlortoluene, C6II4C1.CH3, are very stable liquids, boiling at 156-158°. — Benzyl chloride C6H5.CH2C1, a liquid boiling at 176°. TOLUENE. 275 Dichlortdluene, C6II3C12.CH3, liquid; boiling point, lQ6°.—CMorbenzyl chloride, C6H4C1.CH2C1, liquid ; boil ing point, 213-214°. — Benzol chloride (Chlorobenzol), C6H5.CIIC12, is also formed by the action of phosphorus pentachloride on oil of bitter almonds. Liquid, boil ing at 206°. Trichlortoluene, C6H2C13.CH3. Colorless crystals; fusing point, 76°; boiling point, 235°. — Dichlorbenzyl chloride, C6H3C12.CH2C1. Liquid, boiling at 241°.— Chlorbenzal chloride, C6H4C1.CHC12. Liquid; boiling point, %&k°.—Benzotrichloride, C6H5.CC13, is also formed by heating benzoyl chloride with phosphorus pentachlo ride. Liquid ; boiling point, 213-214°. Tetrachlortoluene, C6IIC14.CH3; fusing point, 91- 92°; boiling point, 271°. — Trichlorbenzyl chloride, C6II2C13.CH2C1. Liquid ; boiling point, 273°.— Dichlor- benzal chloride, C6IPC12.CHC12. Liquid; boiling point, 257°.— Chlorbe?izotrichloride,C6ll*C\.CGl3. Liquid; boil ing point, 245°. Pentachlortoluene, C6C15.CH3; fusing point, 218° ; boiling point, 301°.— Tetrachlorbenzyl chloride, C6IIC14. ClPCl. Liquid; boiling point, 296°.— Trichlorbenzal chloride C6H2CRCHC12 Liquid; solidifies below 0°; boiling point, 28Q-2Sl°.—Dichlorbenzotrichloride, C6II3 CRCC13. Liquid; boiling point, 273°. Pentachlorbenzyl chloride, C6C15.CH2C1. Fusing point, 103; boiling point, 325-327°. — Tetrachlorbenzal .ctonWe,C6HC!4.CHCl2. Liquid; boiling point, 305-306°. — Trichlorbenzotrichloride, C6H2C13.CC13. Fusing point, 82° ; boiling point, 307-308°. Pentachlorbenzal chloride, C'CP.CIICl2. Fusing point, 109°; boiling point, 334°. — Tetrachlorbenzotri- chloride, C6HC14.CC13. Fusing point, 104°; boiling point, 316°. When the attempt is made to replace the last hydro gen-atom in toluene, the molecule breaks up, and per- chlorbenzene is formed. 276 TOLUENE. Bromine substitution-products. Parabromto- luene, C6II4Br.CH3 (colorless crystals; fusing point, 28.5° ; boiling point, 181°), and Dibromtoluene (col orless needles; fusing point, 107-108°; boiling point, 245°) are produced by the action of bromine on toluene without the aid of heat.— Orthobromtoluene,C6TL4'Br.CIL3. From diazoorthobromtoluene sulphate with absolute alcohol. Liquid, boiling at 182-183°. — Metabromto- luene C6H4Br.CH3, from diazometabromtoluene sul phate with absolute alcohol. Liquid, boiling at 182°. Yields, with bromine, a liquid, dibromtoluene, boiling at 238-239°, that does not congeal at —20°.— Benzyl bromide, C6H5.CH2Br, is obtained by the action of bro mine on boiling toluene ; and by the decomposition of benzyl alcohol by means of hydrobromic acid. Color less liquid ; gives off fumes in contact with the air and excites to tears; boiling point, 198-199°. — Benzol bro mide, C6II5.CHBr2, is produced by the action of phos phorus pentabromide on oil of bitter almonds. A liquid that cannot be distilled without suffering par tial decomposition. Paraiodotoluene, C6II4I.CH3 (laminae; fusing point, 35° ; boiling point, 211.5°), and Orthoiodoto- luene (a liquid, boiling at 201°) are produced by the action of hydriodic acid on the diazotoluene sulphates, prepared from the corresponding toluidins. Benzyl iodide, C61P.CH2I (colorless crystals, fusing at 24°, not volatile without decomposition), is produced by the action of hydriodic acid on benzyl chloride at the ordinary temperature. Benzyl cyanide, C6H5.CII2.CE", is obtained by boiling benzyl chloride with alcohol and potassium cyanide ; and by distilling potassium benzylsulphate, with potassium cyanide. — Colorless liquid, boiling at 229°. Paranitrotoluene, C6H4(^02).CIP, and Orthoni- trotoluene are produced by treating toluene with fuming nitric acid. The former forms almost color- TOLUENE. 277 less prisms (fusing point, 54° ; boiling point, 236°) ; the latter, a liquid boiling at 222-223°.— Metanitroto- luene is produced by boiling diazonitrotoluene sulphate (from metanitro-paratoluidin) with absolute alcohol. Crystalline; fusing point, 16°; boiling point, 230-231°. Dinitrotoluene, C6H3(^"02)2.CH3. Is produced from toluene, para- and orthonitrotoluene by treating with nitric-sulphuric acid. — Long, almost colorless needles ; fusing point, 71°. — An isomeric dinitrotoluene (needles, fusing point, 60°) is produced from metanitrotoluene by the same treatment. Trinitrotoluene, C6H2(]TO2)3.CIP. Almost color less needles, but sparingly soluble in cold alcohol. Fusing point, 82°. Amidotoluene (Toluidins), C6H4(^H2).CH3. The three modifications are prepared from the three iso meric nitrotoluenes, like anilin from nitrobenzene. The commercial crude toluidin is a mixture of ortho- and paratoluidin. Orthp toluidin (Pseudotoluidin). Colorless liquid, of specific gravity 1.00. Boiling point, 197°. But slightly soluble in water. Does not congeal at — 20°. — Gives, with acetyl chloride, an acettoluide^ C€H4 (ISrH.C2H3O).CH3, that crystallizes in needles, and fuses at 107°. Metatoluidin. Colorless liquid, of specific gravity 0.998. Boiling point, 197°. Does not congeal at — 13°. "With acetyl chloride it gives an acettoluide, that crystallizes in fascicles and fuses at 65.5°. Paratoluidin. Large, colorless crystals ; fusing point, 45° ; boiling point, 198°. With acetyl chloride, it gives an acettoluide that crystallizes well, and fuses at 145°. 24 278 TOLUENE. Benzylamine, C6H5.CH2.lSrH2. Is produced by the action of nascent hydrogen (zinc and sulphuric acid) on benzonitrile (p. 256) ; and in small quantity, together with di- and tribenzylamine, by heating benzyl chlo ride with alcoholic ammonia at 100°. — Clear liquid; boiling point, 183°. Miscible with water, alcohol, and ether in all proportions. From its aqueous solution it is separated by caustic potassa. Attracts carbonic anhy dride from the &\?.-—Dibenzylamine (C6H5.CH2)2NH. Colorless, thick oil, insoluble in water, easily soluble in ether and alcohol.— Tribenzylamine (C6H5.CH2)3K Col orless laminae or needles. Fusing point, 91°. Insolu ble in water, difficultly soluble in cold alcohol, easily in hot alcohol and in ether. The hydrochl orate is decomposed when heated in a current of dry hydro chloric acid gas, yielding benzyl chloride and dibenzyl- amine hydrochlorate. Benzylphosphine, C6H5.CH2.PH2. Two molecules benzylchloride, two molecules phosphonium iodide, and one molecule zinc oxide are heated together for six hours at 160°, and the product then distilled with water vapor. Benzylphosphine and dibenzylphosphine pass over. By means of distillation the benzylphos- phine can be prepared from the mixture in a pure condition. — Clear liquid, insoluble in water, easily soluble in ether and alcohol; boiling point, 180°; be comes oxidized in contact with the air, and gives off fumes.— Dibenzylphosphine (C6H5.CH2)2PH. Crystal lized from alcohol, it forms stellate or fascicular needles, of a high lustre ; insoluble in water, difficultly in cold alcohol, more easily in boiling alcohol; fusing point, 205°. Diamidotoluene (Toluylenediamine), C6H3(NH2)2 CH3, is produced by the reduction of dinitrotoluene. — Long needles ; fusing point, 99° ; boiling point, 280°. Difficultly soluble in cold water, easily in hot water, in alcohol, and ether. Anilin-dyes. Rosanilin, C20H19N3 = C6H4(C7H6)2 K3H3. The salts of rosanilin are produced by heating TOLUENE. 279 a mixture of anilin and toluidin (commercial anilin) with different oxidizing substances (tin chloride, mer cury chloride, mercury nitrate, arsenic acid, etc.). The free base is obtained most readily by adding an excess of ammonia to a hot saturated solution of the acetate. It separates, partially, immediately in the form of a reddish crystalline precipitate. The hot solution, fil tered off from this, deposits on cooling another portion of the base in the form of colorless needles or plates, containing one molecule of water. These turn red rapidly in contact with the air without changing their weight. But slightly soluble in water, somewhat more easily in alcohol, insoluble in ether. ISTot volatile without decomposition. Triatomic base. Tri-acid rosanilin hydro chlorate, C20H19N3. 3HC1, is obtained by dissolving the monacid salt in hot concentrated hydrochloric acid. Brown needles. By treatment with water or by heating, it is very easily converted into the monacid salt. — Monacid rosanilin hydrochlorate, C20H19mHCl (Fuchsine), is produced by heating anilin with metallic chlorides. Rhombic plates of a beautiful metallic green color and bright lustre. Sparingly soluble in water, still less in saline solutions, easily and with an intensely red color in alcohol. Monacid rosanilin nitrate (Azaleine), C20!!19!^8. HITO3, is obtained by heating anilin with mercury nitrate or other nitrates. It resembles the monacid hydrochlorate. Rosanilin acetate, C20H19K3.C2H402, crystallizes in large, very beautifully developed crystals of a metallic green color. More easily soluble in water than the hydrochlorate and nitrate. Triethylrosanilin, C20H16(C2H5)3m The salts of this base are obtained by heating rosanilin or salts of rosanilin with ethyl iodide and alcohol. They dissolve readily, imparting to the solutions a beautiful violet 280 TOLUENE. color, and are (especially the hydrochlorate, which forms a semi-crystalline mass of a golden-yellow lus tre), very highly valued dyes (anilin-violet, Hofmann's violet). Triphenylrosanilin, C20H16(C6H5)3m The salts are produced by heating rosanilin salts with an excess of anilin at 180°. The free base is a whitish, almost amorphous mass, that turns blue rapidly in contact with the air. — Triphenylrosanilin hydrochlorate (anilin- blue), C20H16(C6H5)3IST3.HC1, is a bluish-brown, indis tinctly crystalline powder; insoluble in water and ether; difficultly soluble in alcohol. The alcoholic solution has a splendid deep blue color. Excellent dye. — Subjected to destructive distillation, it yields diphenylamine (p. 262). If, in the preparation of anilin-blue, less anilin is employed, or the heating is not long enough continued, there are produced reddish-violet and bluish-violet dyes, which consist of the salts of mono- or diphenyl- rosanilin. Leucanilin, C20H2rN"3, is produced by the action of zinc and hydrochloric acid, or ammonium sulphide on salts of rosanilin. — White powder, difficultly soluble in water ; turns a pale red color in contact with the air. Triatomic base. Yields colorless salts, and is very easily reconverted into rosanilin by oxidizing agents. Chrysanilin, C20H17N3, is formed as a secondary product in the preparation of rosanilin hydrochlorate. Amorphous powder, but slightly soluble in water, easily soluble in alcohol ; looks like freshly precipita ted lead chromate. Dyes silk and wool golden yellow. — Chrysanilin nitrate, C20H17K3.HN"03, crystallizes in ruby-red needles, that are exceedingly difficultly solu ble in water. Cold concentrated nitric acid converts it into the salt, C20H17N3.2(H^"03), which forms crystals resembling potassium ferricyanide, easily decompos able by water. TOLUENE. 281 Anilin-green (Iodine-green), C20H16(CH3)3K(CH3)2I2 + H20, is prepared by heating 1 part of rosanilin ace tate, 2 parts of methyl iodide, and 2 parts of methyl alcohol in closed vessels at 100°. The mass is distilled for the purpose of removing volatile products, and the residue exhausted with water, with an addition of common salt, by which means the green dye is dis solved, and a violet dye remains undissolved. Pure iodine-green crystallizes in prisms with a green metal lic lustre, resembling that of cantharides. — The anilin- green of commerce consists chiefly of the picrate, pre pared by adding picric acid directly to the solution obtained. Mauveine, C2rH24Isr4. The sulphate (anilin-purple, anileine, indisine, violine), (C27H24^4)2.H2S04, is produced by mixing a dilute solution of anilin sulphate (con taining toluidin) with a dilute solution of potassium bichromate. The base, separated from this by means of potassa, is a crystalline, almost black, glistening powder, that dissolves in alcohol, forming a violet so lution, which turns purple on the addition of acids. Very stable monatomic base. Decomposes ammonium salts. The salts crystallize and have a green metallic lustre. Anilin-brown is obtained by heating anilin-violet or anilin-blue, with anilin hydrochlorate at 240°. Aldehyde-green is prepared by heating rosanilin sul phate, sulphuric acid, and aldehyde together, and treat ing the resulting blue dye with sodium hyposulphite. Sulphotoluenic acid, C6H4 j gj^'oH is formed in two isomeric modifications (para- and ortho-), when toluene is dissolved in weak fuming sulphuric acid. There is a very large number of varieties of the sub stitution-products of these acids known. 24* 282 TOLUENE. Sulphobenzylic acid, C6H5.CH2.S02.OH. The po tassium salt of this acid is produced by heating benzyl chloride with a concentrated solution of potassium sulphite. Benzylbenzene, C13H12 = C6IP.CH2.C6H5. Is pro duced by the action of zinc-dust on a mixture of benzyl chloride and benzene. — Colorless crystalline mass, con sisting of long prismatic needles ; fusing point, 26-27°; boiling point, 261-262° ; easily soluble in alcohol, ether, and chloroform. Oxidized by means of potassium bichromate and sulphuric acid, it yields benzophenone of fusing point, 26-26.5° (which see). Benzyltoluene, C14H14 = C6H5.C1P.C6H4.CH3. Is formed from benzyl chloride and toluene by the same method as the preceding compound. — Colorless liquid, of a pleasant odor, easily soluble in alcohol, ether, chlo roform, and acetic acid ; boils at 279-280° ; specific gravity, 0.955 at 17.5°. C6H4.CH3 Ditolyl, C14H14 = 64 is obtained, together with an isomeric liquid compound, by the decomposi tion of parabromtoluene with sodium. — Colorless, monoclinate crystals. Fusing point, 121°. C6IP.CH2 Dibenzyl, C14H14 = 2 is produced by the action of sodium on benzyl chloride. — Large, colorless prisms. Easily soluble in hot alcohol, but slightly in cold. Fuses at 52°, and boils at 284°. C6H5 CH Stilbene (Toluylene), C14II12 = 65* is formed by the distillation of benzyl sulphide, benzyl disul- phide, di-r and tribenzylamine ; and by the action of sodium on oil of bitter almonds. — Large, colorless, thin lajninoe, Fusing point, 120°. Easily soluble in hot XYLENES. 283 alcohol, less in cold. Combines directly with bromine, forming a crystalline substance, stilbene bromide, C14H12Br2, which is also produced when bromine is al lowed to act on dibenzyl, no care being taken to keep the substances cool; treated with alcoholic potassa, it yields monobromstilbene, C14HnBr (colorless crystals, fusing point 25°), and tolan. — When treated with hydriodic acid, stilbene is converted into dibenzyl. Tolan, C14H10. Is produced by heating stilbene bromide with alcoholic potassa. — Large, transparent, colorless crystals. Very easily soluble in ether and hot alcohol ; melts at 60°. Combines with bromine, form ing a crystalline substance, tolan dibromide C^H^Br2. — The tetraehloride, C14H10C14, is produced by heating chlorobenzyl with phosphorus pentachloride. Sodium- amalgam reduces it to tolan. 3. Hydrocarbons, C8H10. a. Dimethylbenzenes (Xylenes, Xylols). C6H4(CH3)2. The three modifications, the possibility of the exist ence of which is indicated by the theory, are all known. That portion of light oil that boils between 136-139° consists essentially of a mixture of meta- and paraxylene, which cannot be separated from each other. Metaxylene forms the largest portion of this mixture. 1. Orthoxylene. Is obtained by distilling a mix ture of paraxylylic acid with lime. — Colorless liquid, boiling at 140-141°. Oxidized with nitric acid, it yields orthotoluic acid. Chromic acid burns it up completely. 2. Metaxylene (Isoxylene). Is obtained in a pure state by distilling a mixture of xylylic acid, or mesi- tylic acid with lime. — Liquid boiling at 137°. Dilute 284 XYLENES. nitric acid does not act upon it, chromic acid oxidizes it to isophtalie acid. Monobrommetaxylene, C6H3Br(CH3)2. Liquid boiling at 204-205°. — Dibrommetaxylene, C6HW (CH3)2. Colorless, shining, crystalline laminae ; fusing point, 72°; boiling point, 256°. — Tetrabrommetaxylene, C6Br4(CH3)2. Long, fine needles, difficultly soluble in alcohol. Fusing point, 241°. Nitrometaxylene, C8H9(ISr02). Pale yellow liquid, boiling at 237-239°. Congeals at a low temperature, and melts again at +2°. — Dinitrometaxylene, C8H8(£T02)2, is easily 'produced by heating metaxylene with con centrated nitric acid. Colorless, needly crystals ; easily soluble in hot alcohol; fusing point, 93°. — Trinitro- metaxylene, C8H7(N"02)3, is obtained by pouring meta xylene into a mixture of concentrated sulphuric acid and concentrated nitric acid. Colorless needless, very diificultly soluble in boiling alcohol; fusing point, 176°. Amidometaxylene (Metaxylidin), C8H9(FII2). Colorless liquid, boiling at 216°. Yields salts that crystallize well. — Amidonitrometaxylene, C8H8(]TO2)KH2. Reddish-yellow, monoclinate crystals, diificultly solu ble in hot water, easily soluble in alcohol ; fusing point, 123°. Weak, monatomic base. — Dinitroamidometa- xylene, C8H7(I^02)2KII2. Yellow crystals, very sparingly soluble in water, easily soluble in alcohol. Fusing point, 192°. Hardly possesses basic properties. — Diamidometaxylene, C8H8(l!^H2)2. Fine, colorless needles ; easily soluble in hot water and in alcohol; fusing point, 152°. Changes its color rapidly in contact with the air. Strong, diatomic base. — Nitrodiamidometa- xylene, C8H7(N02)(OTI2). Large, red, shiny prisms; almost insoluble in cold water, more easily soluble in hot water and in alcohol ; fusing point, 213°. "Weak base. ETHYLBENZENE. 285 3. Paraxylene. Prepared, like toluene, by the de composition of a mixture of parabrom toluene or para- dibrombenzene, and methyl iodide with metallic sodium. — Colorless liquid, boiling at 136°. At a low temperature, solid and crystalline. Fusing point, 15°. Dilute nitric acid oxidizes it to paratoluic acid ; chro mic acid to terephtalic acid. Dibromparaxylene, C6H2Br2(CH3)2, ' resembles di- brommetaxylene in all its properties, and melts like this at 12°.— Tollylenebromide, C6H4(CH2Br)2, is formed by the action of bromine on boiling paraxylene. — Color less, lamellar crystals ; fusing point, 145-147°. Dinitroparaxylene, C8H8(N02)2. Is formed by the action of fuming nitric acid on paraxylene. Two iso- meric modifications are produced at the same time, of which the one forms long, thin needles, more difficultly soluble in alcohol, fusing at 123.5°; the other large, monoclinate crystals, more easily soluble in alcohol, fusing at $Z0.— Trinitroparaxylene, C8H7(N02)3. Long, colorless needles. Fusing point, 137°. Moderately easily soluble in hot alcohol, but sparingly in cold. b. Ethylbenzene. C6H5.CH2.CH3. Is obtained by the action of sodium on a mixture of brombenzene and ethyl bromide, which is diluted with ether. — Colorless liquid, boiling at 134° ; specific gravity, 0.866. — Oxidized either with dilute nitric acid or chromic acid, it yields benzoic acid. Bromethylbenzene, C6H4Br.C2H5. Colorless liquid, boiling at 199°.— Benzene-ethyl bromide, C6IRCH2. CH2Br, and chloride, C6IP.CH2.CH2C1, are produced by the action of bromine or chlorine on ethylbenzene with the aid of heat. Liquids that cannot be distilled with out undergoing decomposition. The chloride is con verted into benzene-ethyl cyanide, C6H5.CH2.CH2.GI$r, by boiling with potassium cyanide and alcohol. 286 TRIMETHYLBENZENES. Para- and Orthonitrethylbenzene, C6H4(N02). C2H5, are formed simultaneously when ethylbenzene is treated with fuming nitric acid. Both are liquid; the former boils at 245-246°, the latter at 227-228°. "With tin and hydrochloric acid they yield liquid bases. 4. Hydrocarbons, C9H12. a. Trimethylbenzenes. C6H3(CII3)3. That portion of light coal-oil that boils at 163- 168° contains, together with other unknown hydrocar bons, two isomeric trimethylbenzenes, pseudocumene, and mesitylene. They cannot be separated from the mixture. 1. Mesitylene (1:3: 5). Is produced, together with other bodies, by the distillation of a mixture of acetone and sulphuric acid, and can be separated from the oily distillate by means of partial distillation. — Colorless liquid, boiling at 163°. — Yields mesitylic and uvitic acids, when oxidized by dilute nitric acid. "When heated with phosphonium iodide at 250-300°, it is converted into a hydrocarbon C9H18 (boiling point, 136°), which, under the influence of oxidizing agents, yields the same products as mesitylene. Monochlormesitylene, C6H2C1(CH3)3. Colorless liquid ; does not congeal at — 20° ; boiling point, 204- 206°.— Dichlormesitylene, C6HC12(CH3)3. Prisms; fusing point, 59°; boiling point, 243-244°. — Trichlormesi- tylene, C6C13(CII3)3. Long, fine needles. Fusing point, 204-205°. Monobrommesitylene, C6H2Br(CH3)3. Colorless liquid, boiling at 225°, congeals below 0°. — Dibromme- sitylene, C6HBi^(CH3)3, and tribrommesitylenefi*W(VIl^, are crystalline. The former fuses at 60°, the latter at 224°. PSEUDOCUMENE. 287 Nitromesitylene, C9H11(N"02). Almost colorless prisms; fusing point, 41°; distillable without decom position ; easily soluble in alcohol. — Dinitromesitylene^ C9H10(E"02)2. Fine, colorless needles, of a bright lus tre ; fusing point, 86°— Trinitromesitylene, C9H9(M)2)3. Needles that fuse at 232°, and are very difficultly soluble in alcohol. Amidomesitylene, C9Hn.NH2. Colorless liquid; does not congeal at 0°. — Nitroamidomesitylene, C9H10 (M)2).NH2. Long, yellow needles ; fusing point, 100°. — Dinitroamidomesitylene, C9IP(:N"02).NH2. Short, yellow prisms; fusing point, 193-194°. — Diamidomesitylene, C9H10(N"H2)2. Long, colorless needles ; fusing point, 90°.— Nitrodiamidom,esitylene, C9II9.N02(]STH)2. Large, red, monoclinate crystals ; fusing point, 184°. 2. Pseudocumene (1:3: 4). Is produced by the decomposition of a mixture of brompara- or brom- metaxylene and methyl iodide with sodium. — Color less liquid ; boiling point, 166°. — "When oxidized with nitric acid, it is converted into xylylic and xylidinic acids. Monobrompseudocumene, C9HnBr = C6H2Br (CII3)3. Colorless laminse ; easily soluble in hot alco hol, but slightly soluble in cold alcohol ; fusing point, l^.— Tribrompseudocumene, C6Br3(CH3)3. Fine, color less needles, very difficultly soluble in alcohol ; fusing point, 224°. Nitropseudocumene, C9Hn(N02). Long needles; easily soluble in hot alcohol; fusing point, "71°; boil ing point, 265°.— Trinitropseudocumene, C9H9(ISr02)3. Colorless, quadratic prisms ; fusing point, 185°. Amidopseudocumeiie, C9Hn.KH2. Colorless nee dles, of a silky lustre; sparingly soluble in water, easily soluble in alcohol; fusing point, 62°. — Nitro- 288 PARETHYLMETHYLBENZENE, ETC. amidopseudocumene, C9H10(I^02).OT12. Golden-yellow, shiny needles ; fusing point, 137°. b. Parethylmethylbenzene (Ethyltoluene). CaH4fCIP L \ CH2.CH3. Is obtained, like ethylbenzene, from a mixture of parabromtoluene and ethyl iodide.— Boiling point, 159°. Yields the same products as paraxylene when oxidized. c. Propylbenzene (Cumene). C6H5.C3H7. Is obtained by distilling cuminic acid with lime. — Colorless liquid ; boiling at 151°. Under the influence of oxidizing agents it is converted into benzoic acid. By the decomposition of a mixture of monobrom- benzene and normal propyl bromide with sodium, a hydrocarbon is obtained that is very similar to cumene, but has the boiling point 157°. Cumene is perhaps isopropylbenzene. 5. Hydrocarbons, CIOH14. a. Tetramethylbenzene (Durene). C6IP(CH3)4. Is produced by decomposing a mixture of monobrom- pseudocumene and methyl iodide with sodium.— Color less crystals, easily soluble in alcohol ; fusing point 79-80° ; boiling point, 189-191°. When oxidized with dilute nitric acid, it yields cumylic acid and cumidinic acid. b. Ethyldimethylbenzene (Ethylxylene). >H3 1 C2Ip Is obtained, like the preceding compound, from bromxy lene and ethyl bromide.— Colorless liquid ; boiling point, 183—184°. PARADIETHYLBENZENE, ETC. 289 c. Paradiethylbenzene. C6H4(C2H5)2. Is obtained by the decomposition of a mixture of bromethylbenzene and ethyl bromide with sodium. — Colorless liquid; boiling point, 178-179°. — Subjected to oxidation, it yields efhylbenzoic acid and terephtalic acid. d. Cymene (Parapropylmethylbenzene). C3IF. Is contained in the oil of Roman cumin (the vola tile oil of the seed of Cuminum cyminum), and sev eral other volatile vegetable oils. Is produced to gether with toluene, xylene, mesitylene, and other hydrocarbons by the distillation of camphor over zinc chloride or phosphoric anhydride; terpine (which see), heated with bromine, loses water and hydrogen, and is converted into cymene. Can be most readily ob tained in a pure condition by gently heating camphor with phosphorus pentasulphide. — Liquid, that boils at 178°. — When oxidized, it yields toluic and terephtalic acids. e. Isobutylbenzene. C6H5.C4H9. Is obtained in the same way as ethylbenzene. — Colorless liquid, boiling at 159-161°. Yields benzoic acid by oxidation. 6. Hydrocarbons containing a larger number of Carbon- atoms. Amylbenzene. C11!!16 = C6H5(C5HU) = C6II5.CII2CH2.CII(CH3)2. Is prepared like ethylbenzene. — Liquid, that boils at 193°. — When oxidized, it yields benzoic acid. An isomeric amylbenzene (dicthylized toluene), C6I15. CII(C2II5)2, is produced by the action of zinc ethyl on 290 PHENOL. benzal chloride, (p. 275.) — Liquid, that boils at ITS- ISO0. Amylmethylbenzene, G12H18 = C6H4 SH, and amyl- dimethylbenzene, C13H20 = C6IP i, are prepared like amylbenzene. The former boils at 213°, the latter at 232-233°. B. PHENOLS. The phenols are the hydroxyl-clerivatives of the ben zene-hydrocarbons. They bear the same relation to the latter as the alcohols to the hydrocarbons of the marsh-gas series. They differ from these alcohols in their conduct towards aqueous solutions of the alkalies, the hydrogen of the hydroxyl groups contained in them being readily replaced by metals. From these bodies so formed, however, even carbonic acid sets the phenol free. The entrance of chlorine, bromine, iodine, or hyponitric acid into the composition of the phenols causes their conversion into stronger acids. a. Monatomic Phenols. 1. Phenol (Phenyl alcohol, Carbolic acid). C6H60 = C6H5.OH. Occurrence and formation. Is contained in castoreum; and sometimes in the urine of graminivorous animals; in human urine after taking benzene. Is formed by the dry distillation of coal, bones, wood, and a number of resins ; by heating salicylic acid and the acids iso- meric with it ; by heating potassium sulphobenzolate with caustic potassa ; by boiling diazobenzene nitrate with water. Preparation. Most practicably from the "dead oil." This is shaken with potassa-ley, the insoluble oil re moved, and from the alkaline solution, the phenol, PHENOL. 291 % mixed with cresol and other he-dies, reprecipitated. It is purified by means of partial distillation and by cool ing that portion of the distillate that passes over be tween 180-190° down to —10° ; it is thus deposited in crystals, from which the mother liquor is poured and pressed off. Properties. Large, colorless prisms of a peculiar odor and burning taste. Very difficultly soluble in water, easily in alcohol. Fuses at 37.5°, and boils at 182- 183°. Poisonous. — By the action of phosphorus chlo ride or bromide, it yields substitution-products of ben zene. Phenol-potassium, C6H5.OK, is produced by dis solving potassium in phenol and by mixing phenol with concentrated potassa-ley. — Fine, white needles, easily soluble in water, alcohol, and ether. Phenolether, CW.O.OTP. Is formed when diazo- benzene sulphate (p. 266) is mixed with an excess of phenol. — Long, colorless needles. Fusing point, 28° ; boiling point, 246°. Insoluble in water, easily soluble in alcohol and ether. Phenol-methylether (Anisol), C6II5.O.CII3, is pro duced by heating phenol-potassium with methyl iodide or potassium methylsulphate at 100-120°; and by the distillation of anisic acid or methylsalicylic acid with baryta. — Colorless liquid of a pleasant odor, boiling at 152°. By the action of bromine or hyponitric acid there are produced substitution-products ; heated with hydriodic acid to 130°, it yields phenol and methyl iodide. Phenol-ethylether (Phenetol), C6H5.O.C2H5, and phenol amylether (phenamylol), C6H5.O.C5HU, are pro duced by the action of ethyl or amyl iodide on phenol- potassium. Both compounds are liquid ; the former boils at 172°, the latter at 225°. 292 PHENOL. Phenol-ethylenether, (C6H5.0)2C2H4, is produced in the same way from phenol-potassium and ethylene bromide. — Colorless crystals ; fusing point, 95°. Phenol-acetate, C6H5.O.C2H30. Is obtained by heat ing phenol with acetyl chloride. — Colorless liquid, boiling at 190°. Phenol-succinate, (C6IKO)2C4H402, is obtained by the action of succinyl chloride on phenol. — Laminae of a mother-of-pearl lustre ; fusing point, 118° ; boiling point, 330°. Phenol-carbonate, (C6H5.0)2CO. By heating phenol with carbonyl chloride at 140-150°. — Colorless, shiny needles ; fusing point, 78°. Phenol-cyanate, CO.KC6H5, is obtained by distil ling ethyl phenylcarbamate (p. 263) with phosphoric anhydride. — Colorless liquid ; boiling point, 163° ; yields diphenylurea when brought together with water. Chlorine substitution-products of phenol. Or- thocMorphenol, C6II4C1.0H, is produced by the ac tion of chlorine or sulphuryl chloride (S02C12) on phenol. — Colorless crystals, insoluble in water, easily soluble in alcohol ; fusing point, 41° ; boiling point, 2l8°.—Dichlorphenol, C6II3C12.OII. Colorless, six-sided needles ; fusing point, 42-43° ; boiling point, 209°.— Trichlorphenol, C6H2C13.OH. Long, colorless needles, fusing point, 67-68° ; boiling point, 244°. Moderately strong acid. — Pentachlorphenol, C6C15.OH. Shiny, white needles ; fusing point, 185°. Bromine substitution-products. Orthobromphe- nol, C6H4Br.OH. Colorless liquid ; cannot be distilled without decomposition. — Dibromphenol, C6H3Br2.OII. Colorless crystalline mass ; fusing point, 40°. — Tribrom- phenol, C6II2Br3.OH. Long, fine, colorless needles ; fusing point, 95°. — Tetmbromphenol, C6HBr4.OH, and pentabromphenol, C^i^.OH, are produced by heating tribro in phenol with bromine at 180-220°, Both com- PHENOL. 293 % pounds are crystalline ; the former fuses at 120°, the latter at 225°. Iodine substitution-products, Monoiodophenol, C6H4LOIL When a mixture of iodine, iodic acid, and phenol is dissolved in an excess of dilute caustic po- tassa, there are produced two isomeric compounds, or- thoiodophenol and metaiodophenol, of which only the or- thoiodophenol is known in a pure condition. It is also produced hy hoiling diazoiodobenzene sulphate with water. Flat, shiny needles. — A third isomeric modification, paraiodophenol, separates in the form of fine, colorless, very stable needles when paradiazoiodo- benzene, sulphate is boiled with water. — Diiodophenol, C6H3I2.OIi. Is most easily obtained by adding iodine and mercury oxide to an alcoholic solution of phenol. — Colorless needles, that sublime at 150°. — Triiodo- phenol, C6H2I3.OH. Colorless needles ; fusing point, 156° ; not sublimable. Nitrosubstitution-products. Mononitrophenol, C6H4(N02).OH. When phenol is added to dilute nitric acid two isomeric compounds, nitrophenol and isonitrophenol (orthonitrophenol), are formed ; of these only the former is volatile with water vapor. Nitro phenol forms large prisms of a sulphur-yellow color; sparingly soluble in water, easily soluble in alcohol; fusing point, 45° ; boiling point, 214°. Isonitrophenol crystallizes in long, colorless needles that fuse at 110°. Dinitrophenol, C6H3(N"02)2.OH. Is produced from phenol by treatment with concentrated nitric acid, and also by boiling dinitrochlor- or dinitrobrombenzene with caustic potassa or sodium carbonate. — Almost colorless laminae or plates. Fusing point, 114°. Trinitrophenol (Picric acid), C6II2(N02)3.OIL Is produced by the action of an excess of concentrated nitric acid on phenol and numerous other bodies : indigo, aniliii, salicylic acid, several resins, etc. ; and by heating trinitrochlorbenzene with water, or more 25* 294 PHENOL. quickly, with a solution of sodium carbonate. — Yellow, shiny prisms or laminse, of an exceedingly bitter taste. Fuses at 122.5° ; when carefully heated it is sublimable; detonates when rapidly heated. Difficultly soluble in cold water, more easily in hot water, and still more easily in alcohol. Dyes wool and silk yellow. — Strong acid. With bases it yields yellow salts that crystal lize well. The salts explode violently when heated, and some of them by percussion. Potassium picrate, C6H2(NO'2)3.OK, crystallizes in long needles, very difficultly soluble in warm water. The sodium, ammonium, and barium salts are easily soluble in water. Picrocyamic acid (Isopurpuric acid), C8IKN"506. The free acid cannot be prepared. The potassium salt C8II4N506.K is produced by dropping a hot solution of picric acid (1 part in 9 parts of water) into a warm (60°) solution of potassium cyanate (2 parts of potas sium cyanate in 4 parts of water). Brownish-red scales with a green metallic lustre. Sparingly soluble in cold water, soluble in hot water and in alcohol, form ing a deep-red solution (test for hydrocyanic acid and cyanides). Detonates with a loud report when heated. By the action of nitric acid on chlor-, brom-, and iodophenols there are produced nitrochlorine, nitrobro- mine, and nitroiodine substitution-products, of which a very large number is known. Amido compounds. Amidophenol, C6H4(OTP).OII, and the isomeric compound, isoamidophenol (ortho- amidophenol), are produced by the reduction of the corresponding nitro-compounds, most readily by means of tin and hydrochloric acid. Amidophenol crys tallizes in colorless, rhombic scales; isoamidophenol, which is also produced by heating amidosalicylic acid, forms colorless needles, that turn brown easily. Both compounds are difficultly soluble in cold water, more readily in alcohol; fuse at 170°, and yield with acids salts that crystallize well. — Dinitroamidophcnol (Picra- PHENOL. 295 mic acid) C6H2(N02)2(NH2)OH. The ammonium salt is produced by conducting sulphuretted hydrogen into an alcoholic solution of ammonium picrate ; by decom posing this with acetic acid the free acid is obtained. —Red needles ; fusing point, 165° ; slightly soluble in water, more readily in alcohol and mineral acids. — Diamidonitrophenol C6H2(N02)(N"II2)2.OH. Is obtained, like the preceding compound, when aqueous solutions are employed. — Dark yellow needles or narrow laminae. Yields salts both with bases and acids. Sulphophenolic acid, C6II4 j gQ2 Q^ Phenol dissolves readily in concentrated sulphuric acid, two isomeric acids, parasulphophenolic and metasulphophe- nolic acids, being formed. At the ordinary temperature the meta-acid is formed almost exclusively, but with the aid of heat this is readily converted into the para- acid. The acids can be best separated by the prepara tion and partial crystallization of their potassium salts. Potassium parasulphophenolate crystallizes first in long, hexagonal plates that contain no water. From the mother-liquor, potassium metasulphophenolate is deposited in long, colorless, spicular crystals that con tain two molecules of water of crystallization. The other salts of parasulphophenolic acid are also, as a rule, more difficultly soluble in water than those of metasulphophenolic acid. The para-acid is also ob tained by decomposing diazobenzenesulphuric acid. — The free acids are not known in a free state. Disulphophenolic acid, C6H3 j ,gQ2 Q^^ Is formed by heating phenol or the sulphophenolic acids with an excess of concentrated sulphuric acid ; and by the action of concentrated sulphuric acid on diazoben- zene sulphate (p. 266). — The acid, separated from the barium or lead salt, crystallizes in very deliquescent, concentrically-arranged needles of a silken lustre. The solutions of the free acids, as well as those of its salts, are colored ruby-red on the addition of iron chloride. 296 PHENOL. Barium disulphophenolate, C6H4S207Ba + 4H20. Colorless, shiny, monoclinate prisms. Easily soluble in hot water, less soluble in cold. Phenyl sulphydrate (Benzene sulphydrate), C2H6S = C6H5.SII. Is produced by the action of hydro gen (tin and hydrochloric acid, zinc and dilute sul phuric acid) on benzene sulphochloride (p. 269); by the distillation of phenol over phosphorus pentasulphide ; and by the distillation of sodium sulphobenzolate. — Colorless liquid, of an unpleasant odor; boiling point, 166-168° ; specific gravity, 1.08. Insoluble in water, easily soluble in alcohol and ether. Dissolves sodium easily ; and, when treated with mercury oxide, gives a compound (C6H5S)2Hg, that crystallizes from alcohol in white, shiny needles. Parabromphenyl sulphydrate, C6H4Br.SH. Is formed in the same way from parabrombenzene sul phochloride. — Colorless, lamellar crystals ; fusing point, 93.5°. Phenyl sulphide (Benzene sulphide), (C6H5)2S. Is formed, together with benzene and phenyl sulphy drate, in the destructive distillation of sodium sulpho benzolate ; and in the distillation of phenol over phos phorus sulphide. Is further produced by heating several of the metallic compounds of phenyl sulphy drate. — Colorless liquid, of an unpleasant odor; boiling point, 292° ; specific gravity, 1.12. Insoluble in water, easily soluble in hot alcohol and ether. Phenyl disulphide, (C6H5)2S2. Is produced in small quantity in the preparation of phenyl sulphy drate from benzene sulphochloride ; and can be readily obtained from the sulphydrate by oxidation with di lute nitric acid. Is also formed, when a solution of the sulphydrate, in alcoholic ammonia, is allowed to evaporate spontaneously in the air. It is further formed when iodine is added to an aqueous solution of PHENOL. 297 the sodium compound of the sulphydrate ; by the action of potassium cyanide on an alcoholic solution of benzene sulphochloride ; and, together with other pro ducts, by treating the sulphydrate with phosphorus chloride. — Colorless, shiny needles, that fuse at 60°, and are distillable without decomposition. Insoluble in water, easily soluble in alcohol and ether. Nascent hydrogen reconverts it into phenyl sulphydrate ; when further oxidized it yields sulphobenzolic acid. Phenyl ..oxysulphide (Sulphobenzide), (C6H5)S02. Is formed, together with sulphobenzolic acid, by treat ing benzene with sulphuric anhydride or fuming sul phuric acid ; by the oxidation of phenyl sulphide with chromic acid ; and in small quantity by the distillation of sulphobenzolic acid. — Crystallizes from alcohol in rhombic plates, from water in fine prisms. Fuses at 128°, and distils without decomposition. Very diffi cultly soluble in water, difficultly soluble in cold alco hol, easily soluble in hot alcohol and in ether. — Con centrated sulphuric acid dissolves it ; and converts it, with the aid of heat, into sulphobenzolic acid. Heated with phosphorus chloride it yields benzene sulphochlo ride and monochlorbenzene. The same products are formed by the action of chlorine on heated sulpho- benzide. Oxysulphobenzide, (C6IKOH)2S02. Is produced when a mixture of equal parts of phenol and concen trated sulphuric acid is heated, from five to six hours, at 190°, and the cooled, tenacious mass poured into from two to three times its volume of water. — Stellate, colorless needles ; almost insoluble in cold water, easily in boiling water, and in alcohol and ether. — It gives compounds with bases, in which only one of the two hydrogen-atoms of the hydroxyl groups is replaced; on the other hand it yields others in which both the hydrogen-atoms are replaced by alcohol radicles. Phenyl oxydisulphide, (C6IP)2S202. Is produced together with sulphobenzolic acid by heating benzene- 298 CEESOLS. sulphurous acid (p. 270) with water at 130°. — Long, shiny, four-sided needles. Insoluble in water and alka lies, easily soluble in ether and hot alcohol. Fuses at 36°. 2. Cresols. CH' OH. C7H80=C6H4| a. Orthocresol. Is obtained by melting potassium orthosulphotoluenate with caustic potassa, dissolving the mass in acids, and exhausting with ether. — Limpid liquid ; boiling point, 188-190° ; does not congeal at a low temperature. Heated for a long time with caustic potassa, it is converted into salicylic acid. b. Metacresol. Is produced together with propy- lene gas by heating thymol (p. 300) with phosphoric anhydride. The product, that consists chiefly of cre- sol-phosphate, is decomposed by means of potassium hydroxide, the mass acidified and exhausted with ether. — Colorless liquid of an odor like that of phenol. Boiling point, 195-200°. Does not congeal even in a mixture of solid carbonic anhydride and ether. Fused with caustic potassa it is converted into oxybenzoic acid. Metacresol-ethylether, C7H7.O.C2IP. Is prepared like phenol-ethylether. — Liquid, of boiling point 188- 191°. c. Paracresol. Is prepared from parasulphotoluenic acid like orthocresol. Is also produced by boiling with water the diazotoluene sulphate obtained from parato- luidin (p. 277.) — Colorless prisms of a phenol odor, reminding of decayed urine ; fusing point, 36° ; boiling point, 198° ; very difficultly soluble in water. The aqueous solution gives a blue color with iron chloride. Fusing caustic potassa converts it into paraoxybenzoic acid. DIMETHYL-PHENOLS. 299 Paracresol-methylether, C7H7.O.CIP. Colorless liquid boiling at 174°. Is oxidized to anisic acid by chromic acid. Paracresol-ethylether, C7IF.O.C2H5. Colorless liquid ; boiling point, 188°. Paracresol-acetate, C7H7.O.C2IFO. Liquid; boil ing point, 208-211°. Dinitro-paracresol, C6H2(1TO2)2 ) g*£ Is produced by the action of nitrous acid on paratoluidin. Yellow crystals, that fuse at 84°. The cresol contained in coal-tar and wood-tar to gether with phenol is liquid, and does not congeal. It is either ortho- or meta-cresol, or more probably a mix ture of two or all three of the cresols. 3. Phenols, C8H100. a. Dimethyl-phenols (Xylenols). ( ffflFW OTPJgj? Of the many modifications possible according to the theory, only three are as yet known— 1. Solid Xylenol {(Metaxylene-phenol). Is pro duced together with the following compound, when the mixture of meta- and paraxylene, that is obtained from coal-oil, is converted into sulpho-acids by dissolv ing in sulphuric acid, and the potassium salts of these acids melted with caustic potassa. It is also produced by heating oxymesitylic acid with caustic potassa. — Colorless crystals ; fusing points, 75° ; boiling point, 216°. 2. Liquid Xylenol. Is produced together with the preceding compound. — Colorless liquid, boiling point, 211.5°. 300 3. Fhlorol. Is formed in the destructive distilla tion of barium phloretate ; and is perhaps contained in the creosote of coal-tar and beech-wood tar. — Color less liquid ; boils at 220° ; specific gravity, 1.037. b. Ethyl-phenol. C6H4 i C2IP 1 OH. From potassium sulphethylbenzolate by fusing with caustic potassa. — Large, colorless, prismatic crystals of an odor resembling that of phenol ; fusing point, 47- 48° ; boiling point, 211°. In contact with water it becomes instantaneously liquid. But slightly soluble in water; in alcohol and ether in all proportions. Yields with bromine tetrabromethyl-phenol C6Br4 C2H5 which crystallizes in shiny prisms, that fuse at 105-106°. 4. Phenols, C10H140. Two phenols of this composition are known, both of ( CH» which are methyl-propyl phenols, C6H3 \ C3IF (OH. a. Thymol. Occurs in thyme-oil (from Thymus ser~ pyllum), in the oil of Monarda punctata and of Ptychotis ajowan, together with the hydrocarbons cymene (C10H14) and thymene (C10H16). It is extracted from these oils by means of concentrated soda-ley and the aqueous solution of the sodium compound decomposed with hydrochloric acid. — Large, colorless crystals of a pleas ant odor, like that of thyme ; fusing point, 44° ; boil ing point, 230°. Sparingly soluble in water, easily soluble in alcohol. Is decomposed when heated with phosphoric anhydride, yielding propylene and meta- cresol-phosphate (p. 298.) QUINONE. 301 b. Cy mo phenol. From potassium sulphocymolate with fusing potassa. — Yellowish, thick oil; boiling point, 230°. Benzyl-phenol, C13H120=C6H4 Is formed from benzyl chloride and phenol, like benzylbenzene (p. 282) from benzyl chloride and benzene. — White needles of a silky lustre ; fusing point, 84° ; distils, undergo ing* partial decomposition. b. Quinones. The quinones are derived from the hydrocarbons by the replacement of the hydrogen-atoms of two neigh boring carbon-atoms by means of two united oxygen- atoms. Nascent hydrogen and other reducing agents, even sulphurous anhydride, convert them into phenols belonging to the ortho-series. The latter treated with oxidizing substances are readily reconverted into qui ts nones. 1. Quinone. C6H402 = C6H4Q> Formation and preparation. By oxidation of hydro- quinone, quinic acid, anilin, orthodiamidobenzene, ben- zidine and orthoamidophenol. Is further produced by the distillation of a number of vegetable extracts. Is prepared most readily by heating quinic acid (1 part) with manganese peroxide (4 parts), and sulphuric acid (1 part diluted with J- part of water). Properties. Golden-yellow prisms; fusing point, 116°. Very easily sublimable; volatilizes even at the ordinary temperature ; has a penetrating odor ; and ex cites to tears. Moderately difficultly soluble in water, more readily in alcohol. Chlorine substitution- pro ducts of quinone are formed by the action of chlorine on quinone ; and by the 20 302 QUINHYDRONE. distillation of quinic acid with a chlorine-mixture. Monochlorquinone C6H3C102. Long, yellow needles. — Dichlorquinone C6H2C1202. Is also produced by the ac tion of chlorous anhydride on benzene ; and by treat ing trichlorphenol with nitric acid. Large, yellow prisms ; fusing point, 120°. — Trichlorqirinone C6HC1302. Large, yellow laminae, almost insoluble in water ; fus ing point, 165-166°. — Tetrachlorquinone (chloranile), C6Cf*02, is produced, together with trichlorquinone, also from a number of other organic compounds (phenol, anilin, salicylic acid, isatine, etc.) by treatment with chlorine, or hydrochloric acid and potassium chlorate. Yellow, lamellar crystals, sublimable without decom position, insoluble in water, but slightly soluble in cold alcohol, more readily in hot. — Heated with phos phorus pentachloride, it yields perchlorbenzene, (C6C16) (p. 254). Dissolves in dilute caustic potassa, thus caus ing the formation of potassium chloride and the diffi cultly soluble purplish-red potassium salt of chlorani- lic add, C6C12(OK)202 + H20, from which by means of sulphuric acid the free acid, C6C12(OH)202 + H20, may be obtained in the form of reddish-white, shiny scales, resembling mica. The same acid is also obtained by treating trichlorquinone in the same way. ftuinhydrone (Green hydroquinone), C12H1004, is formed by the action of an insufficient quantity of sul phurous acid on a solution of quinone ; or by mixing solutions of quinone and hydroquinone ; and may hence be considered as a compound of equal molecules of quinone and hydroquinone : C6II4 < QTT'TTQ [ C6H4. In general terms, it is always produced when hydrogen is eliminated from hydroquinone, as, for instance, by means of chlorine water, iron chloride, nitric acid, etc. — Long, thin prisms of a beautiful green metallic lustre, of an odor somewhat resembling that of quinone. It fuses easily, sublimes partially, is slightly soluble in water, easily in alcohol, forming a yellow solution. Further treatment with oxidizing substances converts it readily into quinone ; with reducing agents into hydroquinone. DIOXYBENZENES. 303 2. Toluquinone, C7H602, is not known. Substitution- products of it — trichlortoluquinone and tetrachlortoluqui- none — are produced by the action of hydrochloric acid and potassium chlorate on creosol (p. 309) and the cresol (p. 299) contained in coal-tar. 3. Phlorone, C8H802. Is obtained from the phenols C8H100, contained in coal-tar and beech-wood tar, by distilling them with manganese peroxide and sulphu ric acid.— Yellow, needly crystals. Easily sublimable. Slightly soluble in cold water, more readily in hot water, easily soluble in alcohol and ether. Its vapor attacks the eyes and mucous membranes violently. 4. Thymoquinone, C10H1202. Is obtained by distilling a solution of thymol, diluted with water, with manga nese peroxide. — Yellow, prismatic plates ; fusing point, 45.5° ; boiling point, 200° ; volatile with water vapor. Has a peculiar penetrating odor. Yields, with bro mine, mono- and dibromthymoquinone. The former crys tallizes in long, yellow needles, which, when heated with potassa-ley, are converted into oxythymoquinone, C10IIn(OH)02 ; the latter forms bright-yellow laminse that fuse at 73.5°. c. Diatomic Phenols. 1. Dioxybenzenes. C6H602 = C6H4(OH)2. a. Hydroquinone (Ortho-dioxybenzene). Is pro duced from quinic acid by destructive distillation ; or by the addition of lead superoxide to its aqueous solu tion ; by treating arbutine (see Glucosides) with dilute sulphuric acid; by heating orthoiodophenol (p. 293) with caustic potassa at 180°; and is prepared most readily by treating quinone with sulphurous or hydrio- dic acid. Colorless prisms. Easily soluble in water, alcohol, and ether ; fusing point, 177.5°. When carefully heated it is sublimable. — Combines with sulphuretted hydrogen 304 HYDROQUINONE. and sulphurous anhydride, forming crystalline com pounds that are easily decomposed by water. Oxidizing substances convert it into quiiione. Chlorine substitution-products. These cannot be prepared directly from hydroquinone. They are produced by treating the corresponding substitution- products of qumone with sulphurous acid. — Monochlor- hydroquinone C6H3C1(OH)2 is also produced by evapo rating a solution of quinone in concentrated hydro chloric Mi&.—Dichlorhydroqumone C6H2C12(OH)2. Stel late groups of colorless needles, fusing at 157-158°. — Trichlorhydroquinone C6HC13(OH)2. Colorless prisms, easily soluble in boiling water. Fusing point, 134°.— Tetrachlorhydroquinone C6HC14(OH)2. Laminae, insolu ble in water ; fusing point, above 200°. Dinitrohydroquinone, C6II2(K02)2(OH)2, is pro duced by boiling dinitroarbutine (see Grlucosides) with dilute sulphuric acid. — Golden-yellow, shiny laminrc; but slightly soluble in cold water, easily soluble in boiling water and in alcohol. The aqueous solution turns deep blue on the addition of alkalies or ammonia. Disulphohydroquinonic acid, C6II6S208 = ( (OH)2 C6H2 j /gQ2 Qjj\2 Is produced by treating quinic acid with fuming sulphuric acid. — Non-crystallizing syrup, very easily soluble in water and alcohol. Bibasic acid. Yields salts that crystallize well. Its aqueous solution is colored deep blue by iron chloride. Dichlordisulphohydroquinonic acid, C6°12 1 (SOK)H)2 The Potassium salt of this acid C6C12(OH)2.(S02.OK)2 + 2H20 (shiny, difficultly soluble scales) is produced when chloranile is added to a warm dilute solution of potassium bisulphite. Its solution, as well as that of its salts, is colored indigo-blue by iron chloride. The potassium salt, together with PYROCATECHIlSr. 305 potassa-ley, in contact with the air, is rapidly converted into yellow potassium euthiochronate,C6(Q2) \ (go2 OKY2 ~*~ 2H20. (OH Thiochronic acid, C6^ 0.(S02.OH) The yellow ( (S02.OH)4. potassium salt, C6(OH)0(S02.OK)5 + 4H20, is formed, together with potassium dichlordisulphohydroquino- nate, on adding chloranile to a warm solution of potas sium bisulphite or sulphite. Boiled with hydrochloric acid, and heated with water at 130-140°, it is resolved into potassium bisulphate and potassium p-disulpho- hydroquinonate C6H2(OII)2(S02.OK)2 + 41PO. The free acid, isolated from the latter salt, crystallizes in deliques cent, thick plates. It is isomeric with the disulpho- hydroquinonic acid described above. b. Pyrocatechin (Meta-dioxybenzene, Oxyphenic acid). Is contained in the leaves of Ampelopsis hecle- racea. Is produced by the destructive distillation of morintamric, catechuic, protocatechuic, and oxysali- cylic acids, and a number of vegetable extracts (catechu, kino, etc.). Is furthermore formed from metaiodo- phenol (p.' 293) and metasulphophenolic acid (p. 295) by fusing with caustic potassa; and by heating cellu lose and other hydrocarbons for a long time with water at 200°. — Crystallizes in quadratic prisms, that are easily soluble in water, alcohol, and ether. Fuses at 112° ; sublimes in colorless, shiny laminae ; and boils without decomposition at 240-245°. The aqueous solu tion is colored dark green by iron chloride, and then turns purple on the addition of sodium bicarbonate or tartaric acid, or ammonia. Guaiacol (Pyrocatechin-monomethylether), CrH802= C6H4 TT Is produced by heating equal molecules QTT of pvrocatechin, potassium hydroxide, and potassium 26* 306 RESOKCIN. methylsulphate at 170-180° ; subjecting guaiacum to destructive distillation ; and is contained in beech- wood tar (creosote). — Colorless liquid, boiling at 200°. Slightly soluble in water, easily soluble in acetic acid and alkalies. Forms, like phenol, crystal lizing, easily soluble, and easily decomposable salts with the alkalies and with ammonia. When heated with hydriodic acid (or iodine and phosphorus) it yields methyl iodide and pyrocatechin. The latter substance is also produced when guaiacol is added to fusing potassium hydroxide. Pyrocatechin-dimethylether, C6H4(O.CH3)2. Is obtained by heating guaiacol-potassium with methyl iodide.— Liquid, boiling at 205-206°. Diacetylpyrocatechin, C6II4(O.C2H30)2, is pro duced by the action of acetyl chloride on pyrocate chin. — Needles, easily fusible, insoluble in water, solu ble in alcohol. Tetrabrompyrocatechin, C6Br4(OH)2, is produced when pyrocatechin is mixed with an excess of bro mine. — Reddish-brown, rhombic needles, insoluble in water, soluble in alcohol. c. Resorcin (Para-dioxybenzene). Is formed by adding a number of resins (galbanum, assafoetida, sagapenum, acaroid) to fusing caustic potassa ; is ex tracted from the fused mass by acidifying with sul phuric acid and shaking with ether, and purified by distillation. Is further produced from parachlor- and parabromsulphobenzolic acids, paradisulphobenzolic acid, paraiodophenol, and parasulphophenolic acid by fusing with caustic potassa. — Plates or columns, easily soluble in water, alcohol, and ether. Fuses at 104°, and boils at 271°, evaporates at a lower temperature. The aqueous solution is colored dark-purple by iron chloride. ORCIN. 307 Diacetylresorcin, C6H4(O.C2H30)2, is ^ produced by the action of acetyl chloride on resorcin. — Colorless liquid, insoluble in water. Trinitroresorcin (Oxypicric acid, Styphnic acid), C6H(K"02)3(OII)2. Is produced by the action of nitric acid on morintannic acid, a number of gum-resins, (galbanum, sagapenum, ammonia-gum), and a number of vegetable extracts (of sapon-wood, Brazil-wood, etc.) Is obtained from orcin by the action of nitric acid at a low temperature. — Pale yellow prisms or lamellae; sublimable when carefully heated; difficultly soluble in water; fusing point, 175.5°. — Strong, bibasic acid ; yields salts that crystallize well and explode violently when heated. Thiores orcin, C6H4(SH)2. Is produced when para- disulphobenzolchloride (p. 270) is heated gently with tin and hydrochloric acid. — Crystalline mass, easily volatile with water- vapor; fusing point, 27°; boiling point, 243°. TJmbelliferone, C6H402 (or C9H603). Isomeric with quinone. Is produced in the destructive distillation of a number of resins, chiefly of umbelliferous plants, as galbanum. — Colorless, rhombic prisms, sparingly solu ble in cold water, easily soluble in alcohol, and ether. The aqueous solution exhibits, by reflected light, a splendid blue color. Melts at 240° ; sublimes with out decomposition. Yields resorcin when fused with caustic potassa. 2. Orcin. It appears to be ready formed in a number of lichens. Is formed from orsellic acid and other acids (lecanoric, evernic, erythric acids) that occur in various lichens, and bear a close relation to orsellic acid, either by heating them alone, or by boiling them with strong bases. It is further produced when aloes is melted 308 ORCIN. with caustic potassa. — In order to prepare it in large quantity a lichen, belonging to the species roccella or lecanora, is boiled with milk of lime, filtered, and the filtrate evaporated to about one-fourth. The lime is now precipitated by means of carbonic anhydride, and the solution evaporated nearly to dryness over the water-bath. The residue is boiled several times with benzene, the orcin extracted from its solution in ben zene by shaking with water, and the aqueous solution evaporated. Crystallizes in large, colorless, six-sided prisms with 1 molecule of water of crystallization. It has a repulsive, sweet taste. Easily soluble in water, alcohol, and ether. With its water of crystal lization it fuses at 58°, anhydrous at 86° ; it boils at 290° without undergoing decomposition. In contact with the air it turns red. Its aqueous solution is colored deep violet by iron chloride. Orcin combines with dry ammonia, forming a crys talline compound. Exposed to the simultaneous influ ence of moist air and ammonia, it is converted into a dark brown substance orcein, C7H71^03, which dissolves in alkalies, forming solutions of a beautiful red color; from these solutions acetic acid precipitates the dis solved orcin. Upon this conduct depends the employ ment of a number of lichens in the preparation of the beautiful red dyes, known as archil, cudbear, persio. These dyes are obtained by mixing the finely-ground lichens with decaying urine and lime, or with ammo nia-water, and allowing the mixture to stand for a long time in contact with the air. Litmus is prepared in the same way, particularly from Leconora tartarea. ( 0 C2IF Orcin-monethylether, C7H6 ' and -diethyl- ether, C7H6(O.C2H5)2, are produced by the action of caustic potassa and ethyl iodide on orcin. Both com pounds are syrupy liquids. The diethylether boils without decomposition at 240-250°. Diacetylorcin, C7H6(O.C2H30)2, is formed, even at the ordinary temperature, by pouring acetyl chloride CREOSOL — HYDROPHLORON, ETC. 309 on orciu. — Colorless needles; fusing at 25°; sublimes almost without decomposition. Scarcely soluble in water, easily soluble in alcohol and ether. Trinitro-orcin, C6(N02)3 j Is produced by dissolving orcin in well-cooled nitric acid, and pouring the solution into concentrated sulphuric acid at — 10°; when this mixture is poured into a large quantity of water the mtro-compound separates. — Long, yellow needles. Easily soluble in hot water, but slightly in cold. Fuses at 162°, and at a slightly higher tempera ture it decomposes with a weak explosion. Strong, bibasic acid. Yields salts that crystallize well, and are for the greater part easily soluble. Creosol, C8H1002 = C7II6 is formed, together with its homologue, guaiacol (p. 305), by the distillation of beech-wood and guaiacum; and can be separated from it by partial distillation. — Colorless liquid, very similar to guaiacol ; boiling point, 219°. Treated with hydriodic acid, it yields methyl iodide and a non- crystallizing body, isomeric with orcin (homopyro- catechin). 3. Phenols, C8II1002 = C8H8(OH)2. a. Hydrophloron, Is obtained by the action of sulphurous acid on phlorone (p. 303) that is suspended in water. — Colorless laminae, of a mother-of-pearl lustre. Fusible and sublimable. Easily .soluble in water, alco hol, and ether. Oxidizing substances convert it readily into phlorone. b. Betaorcin is formed from beta-usnic acid and a few other acids, occurring in lichens, in the same manner as orcin. — Quadratic prisms, sublimable, easily soluble in alcohol and ether. Turns red in contact with the air. 310 PYROGALLOL. c. Veratrol is produced by heating veratric acid with an excess of baryta. — Colorless oil, of an aromatic odor; boils at 202-205°, and congeals in crystalline format +15°. 4. Thijmohydroquinone, C10H1402 = C10H12(OH)2. Is obtained from thymoquinone by treating with sul phurous acid. — Clear, four-sided prisms, of a vitreous lustre. Fusing point, 139.5° Sublimes without de composition. Difficultly soluble in cold water, easily in boiling water. Oxidizing substances convert it easily into thymoquinone. d. Triatomic Phenols. Pyrogallol (Pyrogallic Add). •ogauoi (Jryrogauic JLCI CCH603 = C6H3(OH)3. Formation. By heating gallic acid alone, most ad vantageously in an atmosphere of carbonic anhydride, at 210-220°, or with two to three times its weight of water, in a closed vessel, at 200-210°. In smaller quantity by heating gallotannic acid. Properties. Shiny, colorless laminae or needles of a bitter taste. Poisonous. Sublimable without decom position when the air is not allowed to have access. Easily soluble in water. In the presence of alkalies it takes up oxygen rapidly from the air, and decomposes, yielding carbonic anhydride, acetic acid, and brown, amorphous substances. It gives a blackish-blue color with iron sulphate, a red color with iron chloride. It reduces the metals rapidly from gold, silver, and mer cury salts. Triacetylpyrogallol, C6H3(O.C2IPO)3, is produced by dissolving pyrogallol in an excess of acetyl chloride, and remains behind on evaporation in small, sublimable crystals, insoluble in water. Tribrompyrogallol, CGBr3(OH)3, is produced "by mixing pyrogallol with bromine. — Shiny, flat, rhombic PHLOROGLUCIN, ETC. 311 needles, of a bright leather-color. Very difficultly solu ble in cold water, more easily soluble in hot water. The following substance is isomeric with pyrogallol: Phloroglucin, C6H603 = C6H3(OH)3. Is produced by heating phloretin, quercetin (see Glucosides), dragon's blood, gamboge, kino, etc. with caustic potassa. — Rhombic crystals, with two molecules of water of crys tallization, of sweet taste. They effloresce in dry air, give up their water at 100°, fuse at 220°, and sublime almost without decomposition. Easily soluble in water, alcohol, and ether. The aqueous solution turns a deep violet color on the addition of iron chloride. Com bines with the alkalies, forming deliquescent salts. Triacetylphloroglucin, C6H3(O.C2H30)3. Small, colorless prisms, but slightly soluble in water. Phloramine, C6H^02 = C6H3 Is formed by dissolving phloroglucin in heated aqueous ammonia, and by conducting dry ammonia gas over heated phlo roglucin. — Thin, shiny laminae, resembling mica. But slightly soluble in cold water, easily in alcohol. The solution turns rapidly brown in contact with the air. Well characterized base ; combines with acids, forming crystallizing salts. e. Tetr atomic Phenols. These are as yet unknown, though a few substitu tion-products of tetroxybenzene, C6H2(OH)4, have been discovered. Dichlortetroxybenzene (Hydrochloranilic acid), C6C12(OII)4. Is produced by the action of nascent hydrogen (sodium-amalgam and hydrochloric acid, tin and hydrochloric acid) on chloranilic acid (p. 302); can be prepared most readily by heating chloranilic acid with a concentrated solution of sulphurous acid at 100°. — Colorless needles. But slightly soluble in cold 312 ALCOHOLS — BENZYL ALCOHOL. water, easily soluble in alcohol, and ether. In a moist condition it is reconverted into chloranilic acid in con tact with the air. "With acetyl chloride, it yields an ether, C6C12(O.C2IPO)4, that crystallizes well, fuses at 235°, and is very stable. Disulphotetroxybenzolic acid, C6 j /go2 OH)2 The alkaline salts of this acid are produced by boiling the salts of euthiochronic acid (p. 305) with tin and hy drochloric acid. _ The potassium salt, C6(OH)4(S02.OK)2 + 2IPO, crystallizes in colorless columns, which, when dry, are stable in the air, but when moist or in solution are oxidized, and turn red in contact with the air. The free acid is not known. C. ALCOHOLS. The aromatic alcohols are isomeric with the phenols. They differ from the phenols, in that the hydroxyl groups do not replace hydrogen-atoms of the benzene nucleus, but of the substituting methyl, ethyl groups, etc. They conduct themselves in every way analo gously to the alcohols of the marsh-gas series. • 1. Benzyl Alcohol. C7H80 = C6IP.CIP.OH. Occurrence. In the form of benzyl benzoate and cinnamate in Peru- and Tolu-balsams.* Formation and preparation. From oil of bitter al monds by means of nascent hydrogen (sodium-amal gam and water) ; or by mixing with an alcoholic solu tion of potassium hydroxide, it being thus resolved into benzyl alcohol and potassium benzoate, an evolu tion of heat accompanying the action. After distilling * Peru- and Tolu-balsams are tenacious yellow or reddish-brown liquids, which are obtained in Mexico and Peru from the branches and bark of Myroxylon peruiferum and Myroxylon toluiferum by means of soaking or boiling with water, or, less frequently, from incisions, from which they flow spontaneously. BENZYL ALCOHOL. 313 off the alcohol and adding water, the benzyl alcohol is extracted by means of ether. Benzyl chloride (p. 274), when heated with an alcoholic solution of potassium acetate, yields benzyl acetate, which is transformed into potassium acetate and benzyl alcohol, by boiling with an alcoholic solution of potassium hydroxide. Properties. Colorless liquid of a weak, pleasant odor ; specific gravity, 1.06 ; boiling point, 207°. It is liquid at —18°. Oxidizing substances convert it into oil of bitter al monds and benzoic acid ; hydrochloric and hydrobromic acids into benzyl chloride or bromide (pp. 274 and 276). When distilled with a concentrated solution of potassa, it is resolved into benzoic acid and toluene. Sulphuric acid and other dehydrating agents convert in into a resin. Benzylic ether, (C7H7)20, is produced by heating benzyl alcohol with anhydrous boracic acid; and by heating benzyl chloride with water at 190°. — Colorless oil, boiling above 300°. Benzyl acetate, C7II7.O.C2H30, is formed by mixing benzyl alcohol with acetic and sulphuric acids; arid by heating benzyl chloride with potassium acetate. — Colorless liquid of a pleasant odor, boiling at 210°. Heavier than water. Parachlorbenzyl alcohol, C6II4C1.CH2.OH. The liquid ether (boiling point, 240°) of this alcohol is pro duced by heating chlorbenzyl chloride (p. 275) with sil ver acetate. This, heated to 100° with ammonia, yields the alcohol. — Long, colorless, spicular crystals. Insolu ble in cold water, difficultly soluble in boiling water. Fuses at 66°, and boils without undergoing decomposi tion. Paradichlorbenzyl alcohol, C6H3C12.CH2.OH, is prepared from dichlorbenzyl chloride (p. 275) like the preceding compound. — Colorless needles, but slightly soluble in water ; fusing point, 77°. 27 314 BENZYL ALCOHOL. Metanitrobenzyl alcohol, C6H4(N02).CH2.OH, is formed together with potassium nitrobenzoate by heat ing nitrobenzylic aldehyde with alcoholic potassa. — Thick oil, that cannot be distilled without decomposi tion. Paranitrobenzyl alcohol, C6H4(N02).CH2.OH. The acetic ether of this alcohol (long, pale yellow needles, fusing at 78°) is produced by adding benzyl acetate to cold concentrated nitric acid. By heating with aqueous ammonia to 100°, the alcohol is obtained from this. — Colorless, fine needles ; fusing point, 93°. Easily solu ble in hot water andammonia^but slightly in cold water. Dissolved in very concentrated nitric acid, it is con verted into dinitrobenzyl alcohol, C6H3(N02)2.CH2.OII. (Colorless needles, fusing at 71°.) Benzyl sulphydrate (Benzylmercaptan), C6IP. CTP.SH. Is producing by mixing an alcoholic solution of potassium sulphydrate with benzyl chloride, a spon taneous evolution of heat accompanying the action. It is thrown down on the addition of water. — Color less, highly refracting liquid of an unpleasant leeky odor ; boiling point, 194-195°. Yields with mercury oxide a mercaptide, that crystallizes well. Benzyl sulphide, (C6H5.CH2)2S, is formed when an alcoholic solution of potassium sulphide is mixed with benzyl chloride, a strong evolution of heat accompany- the action. — Long, colorless needles or laminae. Insolu ble in water, easily soluble in alcohol and ether. Fuses at 49°. Not volatile without decomposition. — Nitric acid converts it into benzyl sulphoxide, (C6H5.CH2)2SO, a substance that crystallizes in colorless laminae, fusing at 130°. Benzyl disulphide, (C6H5.CH2)2S2, is formed from benzyl sulphide by oxidation in contact with the air, particularly when a solution of the latter containing ammonia is evaporated in the air. — Colorless, shiny laminae. Insoluble in water, difficultly soluble in cold TOLYL ALCOHOL. 315 alcohol, easily in hot. Fuses at 66-67°. Nascent hy drogen converts it into benzyl sulphydrate. When heated it is resolved into toluene, stilbene (p. 282), and other products. The same substances are formed by heating benzyl sulphide. Saligenin (Ortho-oxybenzyl alcohol), C7H802 = C6H4 1 |p Q-JJ Is produced from salicin (see Gluco- sides) by rowans of treating with emulsin or saliva and by the action of nascent hydrogen on salicylous acid (p. 322). — Tables, having a pearly lustre ; easily soluble in hot water, in alcohol, and ether. Fuses at 82°, and sublimes at 100°. Its solution is colored deep blue by iron chloride. Dilute acids convert it into a resin, saliretin, C14H1403. Oxidizing agents convert it into salicylous and salicylic acids. Anise alcohol (Methylparaoxy benzyl alcohol), C8II1002 {O OTT^ CH2 OH ^S PrePare^ from anisic aldehyde (p. 324) in the same manner as benzyl alcohol from the oil of bitter almonds. — Colorless, shiny prisms, that fuse at 20°, and distill without decomposition at 250°. Of a faint odor and burning taste. Oxidizing sub stances convert it into anisic aldehyde and anisic acid ; hydrochloric acid into a liquid chloride, C6II4 •! 2. Toli/l Alcohol (Paramethylbenzyl Alcohol). Is prepared from paratolylic aldehyde like benzyl al cohol. — Colorless needles, but slightly soluble in water, easily soluble in alcohol. Fuses at 59°, and boils at 217°. With hydrochloric acid, it yields liquid tolyl chloride, C6H4 \ njpnj which is converted into tolyl 316 CUMINE, SYCOCERYL ALCOHOLS, ETC. cyanide by boiling with an alcoholic solution of potas sium cyanide. The following substances are isomeric with tolyl al cohol: — Styryl alcohol (primary phciiylethyl alcohol), C8H100 = CCIKCH2.CII2.OH. Is prepared from benzene-ethyl bromide (p. 285) in the same manner as benzyl alcohol from benzyl chloride. — Liquid, boiling at 225°. Secondary phenylethyl alcohol, C6H5.CH(OH).CH3. Is produced by the action of sodium-amalgam on a solu tion of acetophenone in water and alcohol. — Long, colorless spiculse ; fusing point, 120° ; distils almost without decomposition. 3. Cumine alcohol, C10H140 = CCH4 QQg Is pro duced from the cuminic aldehyde (contained in the oil of Roman cumin), by heating with alcoholic potassa. — Colorless liquid of a pleasant odor ; boiling at 243°. Insoluble in water ; mixes with alcohol in all propor tions. 4. Sycoceryl alcohol, C18H300. That portion of the resin of Ficus rubiginosa which is insoluble in cold alcohol consists of sycoceryl acetate, C18H29.O.C2II30. This crys tallizes in flat prisms or scales, fuses at 118-120°, and yields sycoceryl alcohol, when boiled with alcoholic potassa. — Colorless, fine crystals, insoluble in wrater and alkalies, easily soluble in ether and alcohol. Fuses at 90°. Not distillable without partial decomposition. Benzhydrol, C13H120 = C6H5.C(OH).C6H5. Is ob tained by the action of sodium-amalgam on a solution of benzophenone in dilute alcohol. — Needles of a silky lustre. Fusing point, 67.5° ; boils at 297-298°, at the same time being partially decomposed into water and BENZYLIC ALDEHYDE. 317 benzhydrolic ether (C13Hn)2O. But slightly soluble in water, easily soluble in alcohol and ether. Oxidizing substances reconvert it into benzophenone. Benzhydrol acetate, C13Hn.O.C2H30. Colorless liquid, boiling at 301-302° ; does not congeal at —15°. Tollylene alcohol, C*H1002 = CTF j cJS.oi. Is obtained by heating tollylenebromide (p. 285) with water at 170-180°.— Colorless needles. Fusing point, 112-113°. Easily soluble in water. Diatomic alcohol. Oxidizing substances convert it into terephtalic acid. Tollylene acetate, C6H4(CH2.O.C2H30)2. Hard, shiny laminae. Fusing point, 47°. D. ALDEHYDES. 1. Benzylic Aldehyde (Oil of Bitter Almonds). C7II6O = C6H5.CHO. Formation and preparation. Together with hydro cyanic acid and sugar by the action of dilute acids or emulsin (an albuminous substance contained in almonds) on amygclalin (see Glucosides). By the distillation of a mixture of calcium benzoate and formate. By the oxidation of benzyl alcohol with nitric acid ; by heat ing benzal chloride (p. 275) with water at 130-140°, with alcoholic potassa or with mercury oxide ; by dis solving benzal chloride in concentrated sulphuric acid at 50°, and afterward adding water; by boiling benzyl chloride with dilute nitric acid, or, better, with a dilute solution of lead nitrate ; by conducting the vapor of benzoic or phtalic acids over heated powdered zinc. — In order to prepare it, bitter almonds or other vegetable substances, containing amygdalin, freed of fixed oil by pressing, are stirred up with water, allowed to stand a day, aiicl the mass then distilled. The oil Basses over with the water, together with hydrocyanic acid, and 318 BENZYLIC ALDEHYDE. remains partially dissolved in the water (aqua amygda- larum amararum, aqua laurocerasi) ; the greater part collects below the waiter. In order to separate it from hydrocyanic acid, it is shaken with a concentrated so lution of sodium bisulphite, with which it (like the other aldehydes) combines, forming a difficultly soluble, crystalline compound, C7II5.S03^"a + 1JH20. This is purified by pressing, and washing with alcohol, and then decomposed with sodium carbonate. Properties. Colorless, highly refracting, thin oil, of a peculiar pleasant odor. Specific gravity, 1.063. Boil ing point, 180°. Soluble in 30 parts of water. The pure oil, free of hydrocyanic acid, is not poisonous. — It combines, like acetic aldehyde, with acetic anhydride, forming a crystalline compound, C6H5.CH(O.C2IPO)2, fusing at 45-46° ; the same compound is also formed by the action of silver acetate on benzal chloride. It combines with ammonia and amides with elimination of water. — Oxidizing agents convert it into benzoic acid. — When distilled with phosphorus chloride or phosphorus bromide, it yields benzal chloride or benzal bromide (p. 274 and 276). — Nascent hydrogen (from sodium-amalgam and water) converts it into benzyl alcohol, hydrobenzoin and isohydrobenzoi'n (p. 320). — When boiled with an alcoholic solution of potassa, it yields benzyl alcohol and benzoic acid. Orthochlorbenzylic aldehyde, C6H4C1.CHO. Is produced by heating orthochlorbenzal chloride (see Salicylic aldehyde, p. 322) with water at 170°. — Liquid, boiling at 210°. Parachlorbenzylic aldehyde, C6HCIP Is produced by distill- (CHO. ing a dilute solution of one part potassium piperate with two parts potassium hypermanganate. — Long, lus trous, colorless crystals, of a very pleasant odor; fusing point, 37°; boiling point, 263°; difficultly soluble in cold water, more easily in hot water, very easily soluble in alcohol. Combines with alkaline bisulphites. Nas cent hydrogen converts it into piperonyl alcohol, C8H803, and two isomeric compounds, corresponding to hydro- benzoin (p. 320). When heated with three molecules phosphorus chloride it yields a liquid body, dichlorinpe- ronal chloride, C8II4C14O2, which, with cold water, yields dichlorpiperonal, C8H4C1203, and hydrochloric acid, and BEN ZOIC ACID. 325 when boiled with water, is resolved into carbonic anhydride and protocatechuic aldehyde. 2. Paratolylic aldehyde, C8H80 = C6H4 Q Is obtained by distilling a mixture of calcium paratoluate and formate. — Colorless liquid, boiling at 204°. Yields paratoluic acid by oxidation. 3. CuminSc aldehyde (Cuminol), C10H12O = C6H4 1 p-cTQ Occurs, together with cymene, in oil of Roman cumin and in the oil from the seeds of Cicuta virosa. Is obtained from these oils by shaking with alkaline bisulphites, and decomposing the crystalline compounds with sodium carbonate. — Colorless oil, of a pleasant odor, boiling at 237°. When added to fusing potassic hydrate, or boiled with alcoholic potassa, it yields cuminic acid : in the latter case cuminic alcohol is also formed. Yields by oxidation terephtalic acid. E. ACIDS. a. Monobasic, Monatomic Acids. 1. Benzole Acid. OTTO2 = OTP.CO.OII. Occurrence. In a number of resins, particularly in gum-benzoin; occasionally in the urine of herbivorous animals. Formation. From monobrombenzene by the simul taneous action of sodium and carbonic acid ; the ethyl ether, by the decomposition of a mixture of monobrom benzene and ethyl chlorocarbonate with sodium. By the oxidation of all hydrocarbons, alcohols, aldehydes, and acids in which only one hydrogen-atom of the benzene is replaced by a monovalent carbon-group (for instance, toluene, ethyl benzene, benzyl chloride, benzyl alcohol, oil of bitter almonds, alphatoluic acid, hydro- 28 326 BENZOIC ACID. cinnamic acid, cinnamic acid) by means of dilute nitric acid or chromic acid ; by heating a mixture of equal parts, by weight, of potassium sulphobenzolate and sodium formate to fusion ; by heating benzotrichloride (p. 275) with water to 150° ; by heating a mixture of equal molecules of calcium phtalate and calcium hy droxide to 330-350° ; by treating hippuric acid and populin with acids or bases ; by the action of acids on cocain ; by the oxidation of albuminoid substances. Preparation. By fusing gum-benzoin. The best way is to heat the gum in a shallow basin, over which is placed a paper cone, made of blotting paper : the acid condenses in this cone in the form of needly crystals. More readily by boiling the powdered gum with cal cium hydroxide, filtering, and concentrating the result ing solution of calcium benzoate, and decomposing the latter with hydrochloric acid ; the benzoic acid thus separating in crystalline form. It can be purified by recrystallization or sublimation. Most advantageously from hippuric acid. (See Preparation of Glycocol, p. 84.) Properties. Lustrous, white, long, very thin, some what flexible needles and laminse. — Fuses at 120°, and boils at 250°. Difficultly soluble in cold water, easily soluble in hot water and in alcohol. Easily sublimable. Passes over with the vapor of water on heating its aqueous solution. Its vapor and its boiling solution possess a peculiar odor, that excites coughing. Most of its salts are soluble in water. Their solu tions give a reddish precipitate with iron chloride, con sisting of iron benzoate. Calcium benzoate, (OTF02)2Ca -f 3IPO, crystallizes in lustrous, colorless, radiating prisms. Easily soluble in water. Silver benzoate, C7IP02.Ag, is very difficultly so luble in cold water ; crystallizes from hot water. Ethyl benzoate, C7H5O.O.C2H5. Colorless, viscid, fragrant liquid ; specific gravity, 1.054 ; boiling point, 213°. BENZOIC ACID. 327 Benzoyl chloride, C6IF.COC1. Is produced by the action of phosphorus chloride on ben zoic acid ; and of chlorine on oil of bitter almonds. — Colorless oil, boil ing at 199°, of an exceedingly pungent odor. Is de composed by water and by contact with moist air, yielding benzoic and hydrochloric acids. Distilled with bromides, iodides, or cyanides, it yields benzoyl bromide, iodide, and cyanide, all of which are crystal lizing compounds. Heated with an excess of phosphorus pentachloride, it is converted into benzotrichloride, C6H5.CC13 (p. 275). Benzamide, C6IF.CO.NH2. Is formed by continued action of ammonia on ethyl benzoate or benzoic anhy dride ; and by bringing benzoyl chloride together with concentrated aqueous ammonia or dry ammonium carbonate. — Colorless, lustrous crystals ; fuses at 125°; and sublimes without decomposition. But slightly so luble in cold water, easily soluble in hot water and in alcohol. Benzhydroxamic acid, C'IF.CO.NOH.H. Is ob tained by the action of benzoyl chloride on an aqueous solution of hydroxylamine hydrochlorate, which is saturated with sodium carbonate. — Colorless rhombic crystals. Comparatively difficultly soluble in cold water (44J parts at 6°), much more readily in warm water, very easily in alcohol. Has an acid reaction ; fuses at 124-1 25°, and decomposes at a higher tempera ture suddenly and violently. By heating with dilute hydrochloric or sulphuric acid, it is decomposed into benzoic acid and hydroxylamine salt. — Monobasic acid ; yields crystallizing salts. Dibenzhydroxamic acid, (C6H5.CO)2IsTOH. Is formed together with the preceding compound in the described reaction. — Lustrous, rhombic crystals. Al most insoluble in water, difficultly soluble in cold alco hol, more readily in hot, very slightly in ether. Has an acid reaction, fuses at 145-146°, and decomposes 328 BEN ZOIC ACID. with violence at a higher temperature. Monobasic acid ; yields crystallizing salts. Tribenzhydroxylamine, (C6IP.CO)2.N.O(C6H5.CO). Is formed by the action of benzoyl chloride on dry hy- droxylamirie hydrochlorate, which is dissolved in a hydrocarbon boiling at 110° ; also when potassium di- benzhydroxamate is heated with benzoyl chloride. — Lustrous prisms ; fusing point, 141-142° ; decomposes at 190° ; insoluble in water, ether, and benzene ; very difficultly soluble in cold alcohol, much more readily in hot alcohol. Benzole anhydride, (C7IPO)20. Is produced by the action of benzoyl chloride on sodium benzoate ; and by heating 6 parts dry sodium benzoate with 1 part phosphorus oxichloride to 150°. The salts (sodium metaphosphate and sodium chloride), that are formed are extracted with water. — Oblique prisms, insoluble in cold water, soluble in alcohol, forming a neutral so lution. Fuses at 42°, and distils at 310°. When boiled with water, it is gradually converted into benzoic acid ; and when heated in hydrochloric acid gas, is decom posed, yielding benzoic acid and benzoyl chloride. Substitution-products of benzoic acid. Those substitution-products which are formed by the direct action of chlorine, bromine, etc., on benzoic acid, be long to the meta-series ; the isomeric ortho-compounds are obtained from salicylic acid ; the para-corn pounds by oxidation of the para-substitution-products of toluene. By the latter method the meta-compounds can also be obtained, but not the ortho-compounds (cf. p. 274). Orthochlorbenzoic acid (Chlorsalylic acid), C7II5C102 = C6H4C1.CO.OH. The chloride (chlorsalyl chloride), C6H4C1.COC1 (a colorless oil, boiling at 240°), is produced by the action of phosphorus chloride on salicylic acid. This yields the acid when treated with water. — Needles, that fuse at 137° ; more readily solu- BENZOIC ACID. 329 blc in water than the isomeric compounds. Fuses under boiling water. Metachlorbenzoic acid. Is produced from ben- zoic acid by beating with hydrochloric acid and potas sium chlorate or antimony chloride or calcium hypo- chlorite ; by the decomposition of chlorhippuric with hydrochloric acid ; by boiling cinnamic acid with a solu tion of bleaching lime ; and by oxidation of meta-ehlor- toluene.— Colorless needles, that fuse at 152°, and sub lime without decomposition. Very difficultly soluble in cold wafer. Parachlorbenzoic acid (Chlordracylic acid), formed by the oxidation of parachlortoluene.— Sublimes in colorless scales, that fuse at 236-237°. Diehlorbenzoic acid, C61FC12.CO.OH. Is produced from meta- and parachlorbenzoic acids by boiling with a solution of bleaching lime, or by treating with anti mony chloride; by oxidation of dichlortoluene, dichlor- benzyl chloride, and dichlorbenzal chloride (p. 275) with chromic acid; and by heating dichlorbenzotri- chloride (p. 275) with water.— Colorless needles fusing at 201-202°. Trichlorbenzoic acid, C6H2CKCO.OH, and Tetra- chlorbenzoic acid, C6HC14.CO.OH, are obtained by heat ing tri- and tetrachlorbenzotrichloride (p. 275) with water to 260-280°. Both crystallize in colorless nee dles ; the former fuses at 163°, the latter at 187°. Metabrombenzoic acid, CrH5Br02, is formed by heatino- benzoic acid with bromine and water to 130- 160°.— Colorless needles ; fuse at 152^-153° ; but slightly soluble in water. — Parabrombenzoic acid (Bromdracylic acid), C7H5Br02, is obtained by the oxidation ^ of para- bromtoluene.— -Small, colorless needles, almost insoluble in cold water, Fusing point, 251°. Dibrombenzoic acid, C7H4Br202 (fusing point, 223-227°), Tribrombenztic add, C7H3Br303 (fusing 28* 330 BENZOIC ACID. point, 234-235°), and Pentabrombenzoic add, C7HBr602 (fusing point, 234-235 °), are formed by heating benzoic acid with bromine to 200° and over. Paraiodobenzoic acid, C7IPI02. From paraiodo- toluene by oxidation. — Colorless scales ; fusing point, 250°. Fluorbenzoic acid, C7IFF102. Is produced by treating diazoamidobenzoic acid with hydrofluoric acid. — Shombic prisms ; fusing point, 182°. Orthonitrobenzoic acid, C7IF(^02)02. Is obtained by oxidation of nitrociniiamic acid (which see). — Easily soluble in water, fuses at 232°. — Metanitrobenzoic acid is formed by treating benzoic acid with hot very con centrated nitric acid, or with a mixture of sulphuric and nitric acids. — Crystallizes in fine needles or laminae, which fuse at 141-142°. — Paranitrobenzoic add (Nitro- dracylic acid) is produced by the oxidation of para- nitrotoluene. — Slightly yellowish colored laminae, that fuse at 240°. Much less easily soluble in water than the two isomeric compounds. Dinitrobenzoic acid, C7H4(M)2)2q2. By continued heating of metanitrobenzoic acid with a mixture of nitric and sulphuric acids. — Crystallizes from water in large, very thin quadratic plates; from alcohol in prisms. Fusing point, 204-205°. By treating chlor- or brombenzoic acids with nitric acid, there are formed chlornitro- and bromnitrobenzoic adds. From metabrombenzoic acid are formed simul taneously two isomeric modifications a-bromnitrobenzoic add (fusing point, 246-248°, but very slightly soluble in water), and ^bromnitrobenzoic add (fusing point, 140- 141°, more easily soluble in water). Ortho^amidobenzoic acid (Anthranilic acid), C6II4(NH2).CO.OH. Is formed, when indigo (1 part) is boiled with soda-ley (10 parts, of 1.38 specific gravity) for several days, finely powdered black oxide BENZOIC ACID. 331 of manganese being gradually added, and the evapo rated water being replaced, until the color of the mass has become bright yellow. This is then dissolved in water, the solution neutralized with sulphuric acid, filtered, evaporated to dryness, and the sodium anthra- nilate extracted by means of alcohol. The salt that remains behind after the evaporation of the alcohol is then dissolved in water and decomposed by acetic acid. — It is also formed by the action of sodium-amal gam on the bromamidobenzoic acids (obtained by re duction o£ the two bromnitrobenzoic acids). — Thin, colorless prisms or laminse, but slightly soluble in cold water, easily in hot water and in alcohol. Fuses at 144°, and decomposes at a higher temperature, yield ing aiiilin and carbonic anhydride. Meta-amidobenzoic acid is formed by heating an alcoholic solution of metanitrobenzoic acid with ammonium sulphide, and decomposing the ammonium salt thus obtained with acetic acid. — Is obtained more readily by gently heating metanitrobenzoic acid with tin and concentrated hydrochloric acid. After the ac tion is over the solution is precipitated with an excess of sodium carbonate, and the concentrated solution acidified with acetic acid. — Small, colorless prisms, easily soluble in hot water, slightly in cold. Fuses at 164-165°; and is resolved, by heating with caustic potassa, into carbonic anhydride and anilin. Yields crystallizing salts with bases, as well as with acids. Para-amidobenzoic acid (Amidodracylic acid) is obtained from paranitrobenzoic acid in the same way as the meta-acid. — Long, fine, lustrous needles. Fusing point, 186-187° ; moderately easily soluble in water. Diamidobenzoic acid, CGII3(^rH2)2.CO.OH. Is ob tained from dinitrobenzoic acid by reduction with tin and hydrochloric acid. — Almost colorless, long, thin needles ; fusing point, 240° ; not volatile without de composition. Difficultly soluble in cold water ; com bines with bases and acids, forming salts. 332 BENZOIC ACID. Azobenzoic acid, C14II10N204 4- |H20. Is formed by the action of sodium-amalgam on an aqueous solution of sodium metanitrobenzoate, and is precipitated by hydrochloric acid after the completion of the action.— Amorphous, bright yellow powder, very slightly soluble in water, alcohol, and ether; not volatile without de composition. Very stable, bibasic acid ; yields crys tallizing, yellow colored salts, and ethers. — Parazoben- zoic adds (azodracylic acid), C14HION204. Is obtained from paranitrobenzoic in the same way as azobenzoic acid. — Flesh-colored, amorphous powder very similar to azobenzoic acid. Hydrazobenzoie acid, C14H12K2O. Is formed, when a solution of iron sulphate is added to sodium azoben- zoate, dissolved in an excess of soda-ley. The acid is then precipitated from the filtered solution by means of hydrochloric acid. — Yellowish-white, indistinctly crystalline flocks. Insoluble in water, difficultly solu ble in boiling alcohol. Weak acid. In aqueous solu tion, its. salts absorb oxygen from the air and are con verted into azobenzoates. When heated with concen trated hydrochloric acid, it is resolved into azobenzoic and amidobenzoic acids. — Parahydrazobenzoic acid^ (hydrazodracylic acid), C14H12N204. Small, lustrous, crystalline needles. Is prepared like hydrazobenzoic acid, and conducts itself like this. Azoxybenzoic acid, C14H1(rN"205, is produced by boiling an alcoholic solution of metanitrobenzoic acid, to which is added solid caustic potassa. — Microscopical needles or laminae. Insoluble in water ; difficultly so luble in alcohol and ether. Bibasic acid. Diazobenzoic acid, C7H4N202. Is precipitated as a yellow, very unstable mass, when an alkali is added to a solution of nitric-diazobenzoic acid. — Nitric-diazoben- zoic acid, C7H4]^202.H]TO3, is thrown down, when a current of nitrous acid is conducted into meta-amido- benzoic acid dissolved in cold nitric acid. Colorless prisms, very easily soluble in cold water. Is decomposed BENZOIC ACID. 333 by boiling with water, yielding nitrogen, nitric acid, and meta-oxybenzoic acid. Explodes violently when heated. Diazobenzoic-Amidobenzoic acid, C7H4N202 + C7H5(NH2)02. Is produced by mixing aqueous solu tions of nitric-diazobenzoic acid and meta-amidobenzoic acid. Can be prepared most readily by conducting nitrous acid into an alcoholic solution of meta-amido benzoic acid, or by mixing this solution at 30° with ethyl nitrite, the acid in this case being thrown down immediately. — Orange-yellow crystalline granules, or small microscopical prisms. Inodorous and tasteless. Almost insoluble in water, alcohol, and ether. Is de composed at 180°, the decomposition being accom panied by a detonation. Weak, bibasic acid. The salts are easily decomposed in aqueous solution, nitro gen being evolved. Heated with hydrochloric acid the acid is decomposed below 100°, yielding chlorben- zoic acid and meta-amidobenzoic acid hydrochlorate. Hydrobromic and hydriodic acids cause an analogous decomposition. Para-amidobenzoic acid conducts itself like meta- amidobenzoic acid when treated with nitrous acid, and yields diazo-compounds, which are isomeric with those just described, and completely analogous to them. Meta-sulphobenzoic acid, C7II6S05 = C6II4 Is formed> together with a sma11 quantity of the para-acid, by the action of fuming sulphuric acid on benzoic acid, and when the vapor of sulphuric anhydride is conducted upon dry benzoic acid. Separated from the barium salt, it forms a crys talline, colorless, very deliquescent, strongly acid mass. Very stable bibasic acid. The neutral barium salt, C7H4S05Ba, is very easily soluble; the acid salt, (C7H5S05)2Ba + 3H20, crystallizes in difficultly soluble, oblique rhombic prisms. 334 BENZOIC ACID. A mixture of concentrated nitric and sulphuric acids converts it into nitrosulphobenzoic acid, C6H3(^s"02) I SO2' OH — we^ developed crystals, easily soluble in water — which, when treated with ammonium hydro- sulphide, is transformed into amidosulphobenzoic acid, C6H3(^N"H2) j gQ2' QJT — radiating, colorless needles. When distilled with phosphorus chloride, sulphoben- zoic acid yields metachlorbenzoyl chloride. Parasulphobenzoicacid, C7IPS05=C6IP 1 ^ OH Is formed in varying quantities, together with the preceding compound, in the preparation of the latter; and by oxidizing parasulphotoluene with potassium bichromate and sulphuric acid. The free acid is very similar to the meta-acid ; is not, however, deliquescent. The add barium salt, (C7H5S05)2Ba + 3II20, crystallizes in long, flat needles, which are very difficultly soluble in water. Disulphobenzoic acid, C6H3 j ,g(j2 QJ™ Is formed by the action of concentrated sulphuric acid and phos phoric anhydride on benzoic acid in sealed tubes. — • Crystalline, deliquescent mass. The neutral barium salt, (C7H38208)2Ba3 + 7H20, crystallizes in small, well- formed prisms. Thiobenzoic acid, C6IP.CO.SH. Is obtained by the action of benzoyl chloride on an alkaline solution of potassium sulphite and precipitation with hydro chloric acid. — White, radiating, crystalline mass. Fus ing point, 24°. But slightly soluble in warm water. Not distillable alone, but very easily with water va por. In ethereal solution, in contact with the air, it easily becomes oxidized, forming benzoyl disulphide (C6IP.CO)2S2. A thiobenzoic acid, C6IP.CS.OH, isomeric with the foregoing, is formed, together with benzoic acid, by the BENZOPHENONE. 385 oxidation of sulphobenzy lie aldehyde (p. 319) — colorless needles, united in fascicles, which, under the influence of heat, decompose without melting. Dithiobenzoic acid, C6H5.CS.SH. The potassium salt is formed by mixing benzotrichloride (p. 275) with an alcoholic solution of potassium sulphite. The free acid is a heavy, violet, very unstable oil. ACETONES. Benzophenone (Diphenylketone), C13H100 = C6H5. CO.C6IP, is formed, together with benzene, by the destructive distillation of calcium benzoate. Is also formed by heating mercury-phenyl (p. 272) with ben- zoyl chloride. — Colorless, rhombic prisms, insoluble in water, easily soluble in alcohol. Fuses at 48°, and boils at 295.° Hydrogen, in stain nascendi, converts it into benzhydrol (p. 316). — Under certain conditions, the nature of which is not understood, a second modi fication of benzophenone is formed. This fuses at 26- 26.5°, and appears to belong to the monoclinic system. It is very easily converted into the rhombic modi fication. The reverse transformation has not been observed. Methylbenzophenone, C'4II120 = C6IP.CO.C6H4. CH3. Is formed, together with benzoylbenzoic acid, by the oxidation of benzyltoluene with a mixture of potassium bichromate and dilute sulphuric acid. — Colorless oil, of a weak aromatic odor; insoluble in water, easily soluble in alcohol or ether. It boils at 307-312°.— Yields benzoylbenzoic acid (p. 322) by oxidation. Acetophenone (Methylphenylketone), C6IKCO.CH3. Is obtained by distilling a mixture of calcium benzo ate and acetate ; and by the action of benzoyl chlo ride on zincmethyl. — Colorless, large, crystal plates. Fusing point, 14°; boiling point, 198°. Treated with 336 HIPPURIC ACID. clilorine at a slightly elevated temperature, it is con verted into Moracetyl benzene C6IP.CO.CH2C1 (crystal line; fusing point, 41° ; boiling point, 246°). Yields nitrosubstitution-products with nitric acid. Hydrogen, in statu nascendi, converts it into secondary phenyl- ethyl alcohol (p. 316). Oxidizing agents convert it into benzoic and carbonic acids. Ethylphenylketone, C6H5.CO.C2H5. Is prepared by the action of benzoyl chloride on zincethyl. — Boil ing point, 208-212°. Insoluble in water. Yields by oxidation benzoic and acetic acids. mric acid (Benzoylglycocol) C9H9]TO2 = CH2 < pQ QTT Occurs in small quantity in normal human urine, in large quantity in the normal urine of graminivorous animals. — Toluene, benzoic acid, cinna- mic acid, and oil of bitter almonds, taken into the system, are converted into hippuric acid in all animals ; quinic acid, in the case of man and graminivorous animals, likewise undergoes the same change. — Ob tained artificially, by the action of benzoyl chloride on glycocol-zinc or glycocol-silver (p. 85). — To prepare it, fresh urine of horses or cows is evaporated to about one-fourth its volume, and then acidified with hydro chloric acid, the hippuric acid being thus thrown down as a crystalline magma. The yield varies very much, according to the fodder of the animals, and ac cording as they have lived in stalls or in the open air. The crude acid is washed out with cold water, pressed, digested with a large quantity of chlorine water, and finally dissolved in it at boiling temperature. On cooling it separates in colorless needles. Or the crude acid is dissolved in boiling weak soda-ley, sodium hypochlorite gradually added until the color is removed, and then, when the solution has ceased boiling, hydro chloric acid is added until the whole has an acid reaction. It is completely purified by recrystallizing from water. IIIPPURIC ACID. 337 Large, colorless, rhombic prisms, of a weak taste; soluble in 600 parts of cold water, much more readily in boiling water, and in akohol. Fusible ^ without decomposition. Heated above its fusing point, it^ is decomposed, and yields hydrocyanic and benzoic acids and benzonitrile. By boiling with acids or alkalies, it is resolved into benzoic acid and glycocol, the elements of water being assimilated. The same decomposition is eftected by ferments. By heating with manganese superoxide and dilute sulphuric acid, it yields benzoic acid, car bonic anhydride, and ammonia. Nitrous acid converts ( 0 C7IPO it into benzoylglycolic acid, C9H804 = CH2 j QQ.OH, which crystallizes in thin, colorless prisms, difficultly soluble in cold water, easily in hot water, and alcohol. Monobasic acid. Most of the hippurates, even the silver and lead salts, are soluble in water, and crystal- lizable. Ethyl hippurate, C8H8N03.C2H5, is produced by saturating a boiling solution of hippuric acid in alcohol with hydrochloric acid gas. On the addition of water, the ether subsequently separates as an oil, which soon becomes crystalline.— It crystallizes in long, colorless prisms of a silky lustre, but slightly soluble in water, easily in alcohol and ether ; fuses at 44° ; not volatile without decomposition. Chlorhippuric acid, C9H8C1N03, and Dichlorhip- puric acid, C9H7C12X03, are produced, when to hippuric acid, in a vessel containing concentrated hydrochloric acid, potassium chlorate is added and the whole gently heated. The former is oleaginous, viscid, uncrystal- line ; the latter crystallizes gradually, when left in con tact with the air or under water. Boiled with acids or alkalies, chlorhippuric acid yields glycocol $ and meta- chlorbcnzoic acid ; — dichlorhippuric acid yields glyco col and dichlorbenzoic acid. Chlorhippuric acid occurs in the urine after metachlorbenzoic acid is taken into the system. 29 338 TOLUIC ACIDS. Nitrohippuric acid, C9H8(N02)^03,is formed, when hippuric acid is added to a mixture of equal volumes of concentrated sulphuric and nitric acids ; and separates on the addition of water, and partial neutralization of the acid with sodium carbonate. — Fine, w^hite prisms of a silky lustre; fuses between 150° and 160° ; diffi cultly soluble in cold water, easily soluble in hot water and in alcohol. Boiled with hydrochloric acid, it is resolved into glycocol and nitrobenzoic acid ; ammo nium hydrosulphide reduces it to amidohippuric acid, C9H8(OTI2)(ISr03), which crystallizes in small, white laminae, difficultly soluble in water. 2. Acids, C8II802. a. Toluic Acids. CH3 CO.OIL 1. Ortho-toluic acid. Is obtained by oxidation of ortho-xylene with dilute nitric acid, and is purified in the same way as para-toluic acid (see below). Also by distilling potassium ortho-sulphotoluenate with potas sium cyanide, and treating the cyanide thus formed with alcoholic potassa. — Long, very fine needles ; fus ing point, 102° ; difficultly soluble in cold water, easily in hot water. When warmed with chromic acid (potassium bichromate and dilute sulphuric acid), it is burned completely, yielding carbonic anhydride and water. Calcium ortho-toluate, (C8H702)2Ca + 2H20, crys tallizes in easily soluble needles. 2. Meta-toluie acid (Isotoluic acid). Is produced together with para-toluic acid by oxidation of the xylenes (p. 283) contained in coal-tar ; it cannot, how ever, be separated from the para-acid. It is obtained in a pure condition by the action of sodium-amalgam on a solution of brommeta-toluic acid. — Colorless nee- TOLUIC ACIDS. 339 dies ; fusing point, 90-93°. Chromic acid oxidizes it, forming isophtalic acid. Calcium meta-toluate, (C8H702)2Ca + 2H20. Nee dles, easily soluble in water. Brommeta-toluic acid, C6H3Br | QQQH Is formed together with the isomeric compound, brompara-toluic acid, when the mixture of brommeta- and brompara- xylene, obtained by the action of bromine on xylene from coal-t9,r, is boiled for a long time with potassium bichromate and dilute sulphuric acid. By preparing the barium salt, which is comparatively difficultly solu ble in water, it can be readily separated from the para- acid. — Crystalline powder, difficultly soluble even in boiling water. Fusing point, 205-206°. 3. Para-toluic acid. Is produced from parabrom- toluene by the simultaneous action of sodium and car bonic acid ; from para-xylene or cyrnene by boiling for several days with dilute nitric acid (mixture of 1 vol ume nitric acid of specific gravity, 1.4 with 2-3 vol umes water), in a flask connected with a reversed con densing apparatus. The acid, that separates on cool ing, still contains impurities in the form of nitro-sub- stitution-products. In order to free it from these, it is suspended in water and this distilled, the acid passing over with the vapors ; or the crude acid is heated for some time with tin and concentrated hydrochloric acid, and the undissolved portion crystallized from boiling water. — Fine, colorless, needly crystals. But slightly soluble in cold water, comparatively easily in boiling water, but less so than benzoic acid, very readily solu ble in alcohol. Fuses at 176°, and sublimes easily. Chromic acid oxidizes it, forming terephtalic acid. Calcium para-toluate, (C8H702)2Ca -f 3H20, crystal lizes in lustrous, colorless needles, that are easily soluble in water. 340 ALPHATOLUIC ACID, ETC. b. Alphatoluic Acid (Phenylacetie Acid). C6IF.CIF.C0.6H. Is produced by boiling benzyl cyanide (p. 276) with alkalies ; by the action of hydriodic acid on mandelic acid ; together with methyl alcohol and oxalic acid by boiling vulpic acid with barium hydroxide ; by melt ing atropic acid with caustic potassa ; its ethyl ether by heating a mixture of monobrombenzene and ethyl chloracetate with copper to 180-200°. — Crystallizes in broad, lustrous laminae. Very similar to benzoic acid. Fuses at 76.5°, and boils without decomposition at 261-262°. — Oxidized with chromic acid, it is converted into benzoic acid. When bromine and nitric acid are allowed to act upon alphatoluic acid without the aid of heat, substi tution-products result which consist principally of members of the para-series, and by oxidation yield para- brom- or paranitrobenzoic acids. Together with these, in small quantities, are formed isomeric compounds, pro bably belonging to the meta-series. When mandelic acid is heated with concentrated hy drochloric acid to 140-150°, and when bromine acts upon heated alphatoluic acid, another class of substitu tion-products is formed, in which the hydrogen of the acetic acid residue is replaced (for example : phenyl- chloracetic acid C6H5.CHC1.CO.OH). 3. Adds, C9IP°02. 1. Mesitylenic acid, CW (1:3: 5). Is formed by oxidizing mesitylene with dilute nitric acid. The crude acid is purified like para-toluic acid. — Crystal lizes from water in small, colorless needles, from alco hol in large, transparent, monoclinate crystals. Almost insoluble in cold water, very difficultly in hot water, very easily in alcohol. Fuses at 166°, and sublimes with out undergoing decomposition. — By further oxidation, it is converted into uvitic and trimesic acids. Distilled with an excess of lime, it yields meta-xylene. XYLYLIC ACID, ETC 841 Barium mesitylate, (C9IP02)2Ba, crystallizes in large, lustrous prisms, easily soluble in water. 2. Xylylicacid,OTPJ(cC^ (1:2: 4)* is pro- duced by the simultaneous action of sodium and car bonic acid on monobrommeta-xylene ; and together with para-xylylic acid by oxidation of pseudo-cumene. The mixture of acids is purified by distilling off with water vapor, and heating gently with tin and hydrochloric acid ; and the two acids then separated by means ot partial crystallization of the calcium salts. Calcium para-xylylate separates first, and afterward the xylylate. The acids are precipitated from the solutions of their salts by hydrochloric acid.— Crystallizes from alcohol in large, transparent, monoclinate prisms, from water in fine needles. Fuses at 126°. Very similar to mesity- lenic acid. Distilled with lime, it, like mesitylenic acid, yields meta-xylene, but is converted into xylidinic acid by further oxidation. Calcium xylylate, (C9H900'Ca + 2IPO, forms large, hard, transparent, monoclinate prisms. 3. Para-xylylic aoid,C«H» { g^n (1:3: 4).* In regard to the formation and preparation see Xylylic Acid. Separates from boiling water in indistinctly crystalline flocks, from alcohoHn lanceolar prisms, con centrically grouped. Fusing point, 163°. More easily soluble in alcohol than xylylic acid. By further oxida tion it is converted, like xylylic acid, into xylidinic acid, but yields ortho-xylene by distillation with lime. Calcium para-xylylate, (C9IP02)2Ca -f 3JII20,forms soft, untransparent, fascicular crystals. C2IF 4. Ethyl-benzoic acid (Para-), C6H4 j CO.QH, is obtained by the action of sodium and carbonic acid on * The position of the group CO. Oil is designated by 1. 29* 342 ALPHAXYLYLIC ACID, ETC. brometh}Tlbenzene ; and by oxidation of diethylbenzene with dilute nitric acid. — Colorless, lustrous laminae, similar to benzoic acid. But slightly soluble in cold water, more readily in hot water, very easily soluble in alcohol. Fuses at 110°. Further oxidation con verts it into terephtalic acid. 5. Alphaxylylic acid, C6II4 j c*p CQ QH Is pro duced from tolyl cyanide (p. 315) by boiling with alco holic potassa. — Colorless, lustrous, broad laminae. Easily soluble in hot water. Fuses at 42°. 6. Hydrocinnamic acid (Phenylpropiome acid), C6IP.CII2.CII2.CO.OII. Is formed by the action of nascent hydrogen (sodium-amalgam) on cinnamic acid ; and by boiling benzene-ethyl cyanide (p. 285) with al coholic potassa. — Crystallizes from water in long, fine needles. Easily soluble in boiling water and in alco hol, difficultly soluble in cold water, but more readily than benzoic acid. Fuses at 47°, and boils without decomposition at 280°. — Chromic acid oxidizes it, forming benzoic acid. 7. Hydratropic acid, CCIF.CII j QQ QH Is l)ro" duced by the action of nascent hydrogen (sodium-amal gam) on atropic acid. — Colorless liquid, which does not congeal at a low temperature. 4. Acids, C10II1203. 1. Durylic acid (Cumylic acid), C6IF j Is obtained by oxidizing durene with dilute nitric acid. — Crystallizes from alcohol in lustrous, hard prisms ; fus ing point, 149-150°. Almost insoluble in cold water, easily soluble in alcohol and ether. "When further oxidized it is converted into cumidinic acid. OXYBENZOIC ACIDS. 343 2. Cuminic acid, C6II4| nornr Is produced from cuminol (p. 325) by boiling with alcoholic potassa or by adding to fusing caustic potassa ; probably also by boiling cuminol with dilute nitric acid. — Colorless, tabular or prismatic crystals. Almost insoluble in cold water, very difficultly in hot water, easily soluble in alcohol. Fuses at 113°, and sublimes without decom position in long needles. Is converted into terephtalic acid when oxidized with nitric or chromic acids ; and yields cumene when heated with lime. 5. Adds, C11!!1^2. Homocuminic acid, C6II4 j ^p QQ QH Is pro duced from cumyl cyanide (from cumine alcohol, p. 316) by boiling it with alcoholic potassa. — Small crystals, fusing atc52°. b. Monobasic, Diatomic Acids. 1. Oxybenzoic Adds. , OTF03 = C'H<{gJon The three isomeric oxyacids corresponding to the other substitution-products of benzoic acid are well known. 1. Salicylic acid (Ortho-oxybenzoic acid). Is con tained in the blossoms of Spiraea ulmaria ; and in the form of the methyl ether in wintergreen oil (the vola tile oil of Gaultheria procumbens). — The sodium salt is produced by the direct combination of phenol and carbonic anhydride in the presence of sodium ; the ethyl ether, by bringing a mixture of equal parts by weight of phenol and chlorcarbonic ether (p. 222) to gether with sodium. It is produced further by treat ing saligenin and salicylous acid (p. 322) with oxi dizing agents; by melting ortho-cresol (p. 298) and salicin (see Glucosides) with caustic potassa ; by con- 344 SALICYLIC ACID. ducting nitrous acid into a dilute aqueous solution of anthranilic acid (p. 330) ; in small quantity, by the ac tion of fusing caustic potassa on phenol. — Is prepared most advantageously by warming gaultheria-oil with potassa-ley, by which means it is converted into methyl alcohol and potassium salicylate. From the solution of this salt, the acid is precipitated by means of hydro chloric acid ; and by recrystallization from hot water it is purified. Colorless, inodorous prisms, difficultly soluble in cold water ; fusing point, 155-156°. Sublimable, when carefully heated ; heated rapidly either alone or with water, it is resolved at 220-230° into carbonic anhy dride and phenol ; heated with hydriodic acid to 140- 150°, the same decomposition takes place. Treated with chromic acid it .undergoes rapid and complete combustion, yielding carbonic anhydride and water. Its solution turns deep violet when treated with iron chloride. It conducts itself towards bases as a monobasic acid. Under certain circumstances however the second hy drogen-atom can be replaced by metals. The salts, which are formed in this way, however, can, only with difficulty, be prepared in pure condition, and are decom posed even by carbonic acid. Methyl salicylate, C6H4 j cao.CIP. B^ distil~ ling Gaultheriaprocumbensvriihw&teT. — Colorless oil of a pleasant odor ; specific gravity, 1.197 ; boiling point, 224°. But slightly soluble in water, easily soluble in alcohol. Combines with bases in the cold, forming in- stable salts, which are decomposed by heat. Ethyl salicylate, C6H4 j QQ o ^jp is formed by distilling salicylic acid with alcohol and sulphuric acid. — Colorless oil, boiling at 221°. Methylsalicylic acid, C6II4 j CQ QH By heating 2 parts of gaultheria-oil with 1 part of potassium hy- SALICYLIC ACID. 345 droxide (dissolved in alcohol), and 3-4 parts of methyl iodide at 100-120°, there is produced the liquid (boil ing point, 248°) methyl ether of methylsalicylic acid, C6H4 i n(?o^QTj3 which when boiled with soda-ley yields sodium methylsalicylate ; from the solution of this salt hydrochloric acid precipitates the free acid. — • Large, colorless plates, difficultly soluble in cold water, easily soluble in hot water and in alcohol ; fuses at 98.5°, and above 200° is resolved into anisol (p. 291) and carbonic anhydride. Strong monobasic acid. Its salts are just as instable as the salicylates. Ethylsalicylic acid, C6II4 j OOOH. Is obtained in the same way as methylsalicylic acid. — Crystalline mass ; fusing point, 19.5° ; is resolved into carbonic anhydride and phenol-ethylether at 300°. Acetylsalicylic acid, C6H4 j CQ Q^- is produced by the action of acetyl chloride on salicylic acid or salicylates. — Colorless, fine prisms. Salicylamide (Salicylamic acid), C6H4 1 QQ -^jp (isomeric with the amidobenzoic acids) is produced by continued action of ammonia on gaul- theria oil, and by heating ammonium salicylate. — -Pale yellow, crystalline laminae, difficultly soluble in water ; fusing point, 142° ; sublimable. When salicylic acid is distilled with phosphorus chloride, orthochlorbenzoyl chloride (p. 328) is pro duced. — Dry chlorine tranforms it, according as sali cylic acid or chlorine is in excess, into chlorsalicylic acid, C7H5C103, or dichlorsalicylic add, C7H4CP03 ; bromine also forms brom- or dibromsalicylic acid ; iodine in alka line solution or in aqueous solution in the presence of iodic acid converts it into a mixture of iodo-, diiodo- and triiodosalicylic adds, which are difficult of separa tion. All these acids crystallize well, and are but 346 OXYBEXZOIC ACID. slightly soluble in water, more readily in alcohol. When distilled (best when previously mixed with sand and baryta), they are decomposed like salicylic acid, yielding carbonic anhydride and substitution-products of phenols. By the action of vapors of sulphuric anhydride and subsequent treatment with water, it is converted into sulphosalicylic add, C6H3(OH) j QQ "Q^ Nitrosalicylic acid (Anilic acid), C7II5(N02)03, is formed by treating salicylic acid, indigo, or salicin with nitric acid. — Needly crystals, very difficultly soluble in cold water, more easily in hot water and in alcohol. When boiled with nitric acid it is converted into picric acid. Amidosalicylic acid, C7IP(KtI)203 = C6H3(KEI2) | QQQH Is obtained by the reduction of nitrosalicylic acid with tin and hydrochloric acid. — Needles of the lustre of satin. Insoluble in cold water and alcohol, difficultly soluble in hot water. Combines with bases and acids. Easily decomposable. At a high temperature it is resolved into carbonic anhydride and isoamidophenol (p. 294). 2, Oxybenzoic acid (Meta-oxybenzoic acid), {OH CO OPT "^s Pr°duccd by conducting nitrous acid into a dilute aqueous solution of amidobenzoic acid ; by boiling nitric-diazobenzoic acid (p. 332) with water; and by melting metachlor-, metaiodo-, metasul- phobenzoic acids, and meta-cresol with caustic potassa. — Crystalline powder, consisting of small quadratic plates, or large verrucose crystals, without water of crystallization. But slightly soluble in cold water, more readily in hot water. Fuses at 200°, and is de composed only at a very high temperature. PARA-OXYBENZOIC ACID. 347 Ethyl oxybenzoate, C6H4 j 0Q^g Colorless plates; fusing point, 72° ; boiling point, 282°; almost insoluble in cold water, moderately soluble in boiling water. Treated witb cold, concentrated soda-ley, it yields a colorless, crystalline, easily soluble sodium compound C6II4 j QQ Q Q2jj5 Methyloxybenzoic acid, C6H4 j QQ^ The potassium salt is obtained by heating one molecule oxybenzoic acid with two molecules potassium hydrox ide and two molecules methyl iodide to 140°, and de composing the ether thus formed by means of potassa- ley. The sodium salt is formed by the simultaneous action of sodium and carbonic anhydride on the methyl ether of monobromphenol. — The acid, precipi tated from these salts by means of hydrochloric acid, crystallizes in long, colorless needles. But slightly soluble in cold water, easily soluble in hot water and in alcohol. Fuses at 95°, and sublimes without decom position. {O C2H5 CO OH Colorless needles; fusing point, 137°. Acetyloxybenzoic acid, C6H4 j ^Q QJJ Colorless crystals ; fusing point, 127°. 3, Para-oxybenzoic acid, C6H4 j ^Q QJJ Is pro duced by conducting nitrous acid into a boiling, very dilute, aqueous solution of para-amidobenzoic acid ; and by fusing anisic acid, paraiodo-, and parasulphobenzoic acids, para-cresol, phloretic acid, amidohydrocinnamic acid, and a number of resins (gum-benzoin, aloes, dragon's blood, acaro'id) with potassium hydroxide. Is much more easily soluble in cold water than sali- 348 PARA-OXYBENZOIC ACID. cylic acid, more easily in hot water and in alcohol. Fuses at 210°, hut decomposes partially even at this temperature, forming carbonic anhydride and phenol. Its solution gives a yellow, amorphous precipitate with iron chloride, soluble in an excess of the reagent. — Treated with phosphorus chloride it yields parachlor- benzoyl chloride. Methyl para-oxybenzoate, C6II4| QQOCHS is obtained by heating equal molecules of paraoxybenzoic acid, potassium hydrate, and methyl iodide to 120°. — Crystallizes from ether in large tablets; fuses at 17°, and boils at 283°. iOTT CO 0 C2H5 is prepared like the methyl ether. — Colorless, crystalline mass; fuses at 113°, and boils at 297°; but slightly soluble in water, easily soluble in alcohol. "With soda- ley it yields a solid, easily soluble sodium compound. Methylpara-oxybenzoic acid (Anisic acid), C8H803 = C6H4 Is obtained from benzoic acid in the same way as methyloxybenzoic acid from oxybenzoic acid. Is further produced by the oxidation of anisic aldehyde and anethol (cf. p. 324) with nitric acid or a mixture of potassium bichromate and dilute sulphuric acid; and by the oxidation of paracresol-methylether (p. 299) with potassium bi chromate and dilute sulphuric acid. — Large, colorless prisms. Almost insoluble in cold water, easily soluble in alcohol ; fuses at 175° ; sublimes ; its salts are almost all soluble in water, and crystallize well. — Heated with hydriodic or hydrochloric acids it yields paraoxyben zoic acid and methyl iodide or chloride. Fusing potassium hydroxide converts it into paraoxybenzoic acid. Heated with lime or baryta it is resolved into anisol (p. 291) and carbonic anhydride. PARAOXYBENZOIC ACID. 349 Chloranisic acid, C8H7C1O3, is produced by conduct ing chlorine into melted anisic acid. — Small, colorless prisms ; fuse at 180° ; sublimable ; insoluble in water, soluble in alcohol. — Bromanisic add and iodanisic add are very similar to the chlorinated acid. Distilled with baryta, they yield substitution-products of anisol. Nitroanisic acid, C8H7(^"02)03, is formed when anisic acid, or the oils which anisic acid yields by oxidation, are boiled with nitric acid until completely dissolved.— Small, lustrous prisms, that fuse at ITS- ISO0, and are volatile only with partial decomposition. But slightly soluble in water and cold alcohol, easily in hot alcohol. Treated in alcoholic solution with ammonium sulphide, it is converted into Amidoanisic acid, C8H7(KE2)03 = C6H3(N"H2) | c(XJH CrJstalllzes from alcohol in short, four-sided prisms. Difficultly soluble in water, easily in hot alcohol; fuses at 180° ; not volatile with out decomposition. Combines with bases and acids, forming salts. ( O Ethylparaoxybenzoic acid, C6H4 j tained from paraoxybenzoic acid and paracresol-ethyl- ether in the same way as anisic acid. — Colorless nee dles ; very difficultly soluble in boiling water. Fuses at 195°, and sublimes without decomposition. Chlorparaoxybenzoic acid, C7H5C103, lodo-, and Diiodoparaoxybenzoic acids, are crystallizing acids, which are prepared like the substitution-products of salicylic acid. Nitroparaoxybenzoic acid, C7H5(N02)03, is formed by treating paraoxybenzoic acid with very dilute nitric acid. Small, flesh-colored crystals. Treated with tin and hydrochloric acid it is reduced, forming amido- xybenzoicadd,mi\NW)0*=C*Ii\mi2) j QQ OH 30 350 TYROSIN. which crystallizes in easily decomposable needles with one and a half moleclues water of crystallization. Tyrosin, C9Hn]TO3 (perhaps ethylamidoparaoxyben- zoic acid = C6H3(NHC2H5) | CQOH) Is Produced> together with leucine (p. 98) and other products, hy continued boiling of albuminous substances, horn, etc., with hydrochloric acid or dilute sulphuric acid, and by fusing them with potassium hydroxide. It also occurs in the living organism, particularly in a diseased con dition of the organism. It is prepared most advan tageously from horn, which, in the form of shavings, is kept boiling, for about sixteen hours, with double its weight of concentrated sulphuric acid, previously diluted with from four to four and a half times its volume of water. During the boiling the evaporated water is replaced, the original volume being retained. At the end of the time mentioned the liquid is neutral ized with milk of lime. The filtered solution is evapo rated to half its volume, then acidified with sulphuric acid, and, after filtering, mixed with enough white lead to form a thin pasty mass. The solution, which contains the tyrosin, in the form of the lead salt, is treated with sulphuretted hydrogen. On evaporating the filtrate from lead sulphide, the tyrosin crystallizes out, and can be easily obtained in a pure condition by repeated recrystallization. Leucine remains in the mother-liquor. Colorless, long, fragile, usually radiating prisms ; very slightly soluble in alcohol, more easily in hot water, insoluble in ether. — Combines with bases and acids. — When heated alone, it is decomposed and yields phenol and other compounds. When fused with caustic potassa it yields paraoxybenzoic and acetic acids and ammonia. — Dilute nitric acid (4 parts water and 4 parts concentrated nitric acid to 1 part tyrosin) converts it, without the aid of heat, into nitrotyrosin nitrate, a crystallizing substance, from the solution of which nitrotyrosin C9H10(N02)N03 may be precipitated by ammonia. It crystallizes in thin, pale-yellow nee- OXYTOLUIC ACIDS, ETC. 351 dies, which are very slightly soluble in cold water. It also unites with bases and acids.— When a mixture of ty rosin with nitric acid is evaporated at a slightly elevated temperature, dinitrotyrosin, C9H9(E"02)2X03, is formed. This crystallizes in golden-yellow laminse. Simultaneously with these two compounds, a red color ing matter (erythrosin) is produced by the action of nitric acid on tyrosin. — When heated with concen trated sulphuric acid, tyrosin yields several sulpho- acids, the soluble salts of which are colored a beautiful violet by iipn chloride. 2. Acids, C8H803. a. Oxytoluic Acids (Cresotic Acids). (OH C6H3 1 CH3 ( CO.OIL Three acids of this composition are known. They are formed, like salicylic acid, by the simultaneous action of sodium and carbonic anhydride on the three modifi cations of cresol (p. 298). a-Cresotic acid, From para-cresol Long, colorless needles; fusing point, 147-150°. 0-Cresotic acid. From ortho-cresol. Long, color less needles ; fusing point, 114°. r-Cresotic acid. From meta-cresol. Needles; fusing point, 168-173°.. The solutions of all three acids are colored violet by iron chloride. b. Oxymethylphenylformic Acid. CH'.OH CO.OH. When para-toluic acid is treated with bromine with ( f^T-T2~Pri the aid of heat, an acid C6H4 j CQ OH is produced, which as yet has not been prepared in a pure condition. 352 MANDELIC ACID, ETC. "When this acid is boiled with baryta water, it yields barium bromide and the barium salt of oxymethyl- phenylformic acid. Hydrochloric acid throws down the free acid from the solution thus obtained. — Flat needles ; fusing point, 176°. Moderately easily soluble in water, particularly in hot water. c. 1 Mandelic Acid (Phenylgly colic Acid). r,6TT5 OH -I ^ 1 1 CO.OIJ. Is formed when a solution of oil of bitter almonds, containing hydrocyanic and dilute hydrochloric acids, is heated for thirty to thirty-six hours in a flask con nected with an inverted condensing apparatus, and the solution then evaporated. It is also formed by heating amygdalin with concentrated hydrochloric acid. By dissolving it in ether, it may be separated from the sal ammoniac, which is formed at the same time. — Crystallizes in prisms or plates. Easily soluble in water, alcohol, and ether. Heated alone, it yields oil of bitter almonds and a resin. Oxidizing agents convert it into benzoie acid. Hydriodic acid reduces it, forming alphatoluic acid ; with hydrochloric and hydrobromic acids it yields water and chlor- and bromcdphatoluic acids (p. 340). 3. Acids, C9H1003. (OH 1. Oxymesitylenic acid, C6H2 \ (CH3)2 Is pro- ( CO.OH. duced by heating potassium sulphomesitylenate with potassium hydroxide to 240-250°. — Colorless, fine nee dles, of a silky lustre. Fusing point, 176°. Almost insoluble in cold water, difficultly in boiling water, easily soluble in alcohol and ether. The solution of the free acid and its salts is colored deep blue by iron chloride. When heated with potassium hydroxide to a high temperature, it is resolved into carbonic anhy dride and solid xylenol (p. 299). PHLORETIC ACID, ETC. 353 (OH 2. Phloretic acid, C6H2](CH3)2 Is formed, ( CO.OH. together with phloroglucin (p. 311), by evaporating phloretiii with potassa-ley. Potassium phloretate is extracted from the residue by means of alcohol, pre cipitated from this solution by ether, and after dis solving in water, decomposed by hydrochloric acid.— Long, brittle, colorless prisms, difficultly soluble in cold water, easily soluble in hot water and in alcohol. Fuses at 128-130°, and when heated with baryta, is decomposed into carbonic anhydride and phlorol (p. 300). Its solution is colored green by iron chloride. (OH 3 Alorcic acid, C6H2 -I (CH3)2 In small quantity, ( CO.OH. together with orciii and paraoxybenzoic acid, in the preparation of orcin from aloes.— Fine, brittle needles; difficultly soluble in cold water, easily in boiling water, in alcohol and ether. Fusing caustic potassa converts it into orcin and acetic acid. 4. Melilotic acid (Hydrocoumaric acid), °6H4 1 CH2 CH2 CO OH Is contained in common meli- lot (Melilotus officinalis), in the leaves of Faham, some times in combination with coumarin, sometimes free^ and is produced by treating an aqueous solution of coumarin with sodium-amalgam. — Large, colorless, lan- ceolar crystals. Very easily soluble in hot water, alcohol, and ether, moderately easily in cold water (in 20 parts of 18°). Fuses at 82°. Its solution is colored bluish for the moment by iron chloride. Heated alone it is resolved into water and its anhydride, C9H802, a substance that crystallizes in rhombic plates, fuses at 25°, and boils at 272°. Fusing potassium hydroxide decomposes it, yielding acetic and salicylic acids, the action being accompanied by an evolution of hydro gen. — its salts, when carefully heated, yield the anhy dride, when more strongly heated, phenol. 30* 354 HYDROPARACOUMARIC ACID, ETC. 5. Hydroparacoumaric acid, C6I14 j QJT2 rrrp (-IQ QTT Is formed from paracouinaric acid by treating it with sodium-amalgam; and by the action of nitrous acid on amidohydrocinnamic acid. — Small, well-formed, monoclinate crystals; easily solu ble in water, alcohol, and ether; fuses at 125°. 6. Tropic acid (Phenylsarcolactic acid), ( OTT2 OTT C6H5.CH j QQ ATT Is formed by heating atropin (see Alkaloids) for several hours with fuming hydrochloric acid to 120-130°. — Fine, colorless, prismatic crystals. Moderately easily soluble in water (in 49 parts at 14.5°), easily soluble in alcohol and ether; fuses at 117-118°. When heated higher with hydrochloric acid or with barium hydroxide, it is converted into atropic and isatropic acids, at the same time giving up water. 7. Phenyllactic acid, C6IF.CH2.CH j QQOH Is produced by the action of sodium-amalgam in a cold solution of phenylchlor- or phenylbromlactic acid.— Pointed needles, united in hemispherical groups. Ex ceedingly easily soluble in hot water ; fuses at 93-94° ; when heated to 180°, it is resolved into water and. cinnamic acid ; and when its solution is mixed with concentrated hydrochloric, hydrobromic, or hydriodic acid, it is converted into substitution-products of hydro- cinnamic acid (p. 342). Phenylchlorlactic acid, CTPCIO3 = C6H5.C2H2C1 1 °o OH The sodium salt is produced, when chlorine gas is conducted into a solution of equal molecules of cinnamic acid and sodium carbonate, un til a portion of the liquid, when tested, bleaches vege table colors. The solution is acidified with hydro chloric acid, filtered arid evaporated, and the acid then extracted by shaking with ether,— -Crystallizes from water in fine, hexagonal laminae with one molecule of OXYSALICYLIC ACID, ETC. 355 water of crystallization. Soluble in hot water in almost every proportion. Fuses at 70-80° while still contain ing water; in an anhydrous condition at 104°. Phenylbromlactic acid, C9H9Br03. Is obtained from cinnamic acid dibromide, by boiling with water. —Very similar to the chlorinated acid. Fuses in an anhydrous condition at 125°. 4. Acids, CnH1403. roH Thymotic acid, C6H2 *j ^7 Is formed from LCO.OIL thymol (p. 300) by the simultaneous action of sodium and carbonic anhydride. — Long, fine needles ; very difficultly soluble in water ; fuses at 120°, and is sub- limable without decomposition. The solutions of the acid and those of its salts, particularly that of the ammonium salt, turn a beautiful blue when warmed with iron chloride. When the potassium salt is heated with phosphorus chloride, or when the free acid is heated with phosphoric anhydride, a substance called thymotide, CnH1202, is produced. This crystallizes well, and fuses at 187°. c. Monobasic, Triatomic Acids. 1. Dioxybenzoic adds. - COT Three isomeric acids of this composition are posi tively known. 1. Oxy salicylic acid. Is produced when a solu tion of monoiodosalicylic acid is boiled with concen trated potassa-ley until on acidifying no precipitate is formed. It may now be extracted from the acidified solution by agitating with ether. — Lustrous needles; 356 PROTOCATECHUIC ACID, ETC. moderately difficultly soluble in cold water (in 58 parts at 21°), easily soluble in hot water, alcohol, and ether ; contains no water of crystallization ; fuses at 183°, and is decomposed at 210-212° into carbonic anhydride and a mixture of hydroquinone and pyrocatechin. Iron chloride turns its solution deep blue, which be comes blood-red on a subsequent addition of a little ammonia. The salts are very unstable, and are decom posed, when left in aqueous solution in contact with the air. 2. Protocatechuic acid. Is formed by the action of melting caustic potassa on iodoparaoxybenzoic acid, bromanisic acid, para- and ortho-cresol sulphuric acids, piperic acid, catechin and a great many resins (guaia- cum, gum-benzoin, dragonsblood, assafcetida, myrrh, acaroid, etc) ; the production from resins is usually ac companied by the formation of paraoxybenzoic acid. — Crystallizes from water in colorless laminae or needles with one molecule of water of crystallization. Diffi cultly soluble in cold water, more easily in hot water, in alcohol, and ether. Fuses at 199°, and decomposes at a higher temperature into carbonic anhydride and pyrocatechin. Its solution is turned dark green by iron chloride ; this color changes to a beautiful blue on the addition of a small quantity of a dilute solution of sodium carbonate, the addition of more of the latter solution giving rise to a dark red. The solutions of its salts turn violet on the addition of salts of iron sub- oxide. — "When mixed with bromine it is converted into monobromprotocatechuic acid, C7H5BrO, which crystal lizes in fine rhombic needles. Dimethyl-protocatechuic acid, C6IP j Is obtained by heating 1 part of protocatechuic acid, 4 parts of methyl iodide, and 1 part of potassium hydrox ide with methyl alcohol in sealed tubes at 140° about three hours. The mass thus obtained is boiled with caustic soda ; and the acid precipitated by means of sul- DIETHYL-PROTOCATECHUIC ACID,ETC. 357 phuric acid. — Fine lustrous needles ; gives no reaction with iron chloride ; fusing point, 170-171°. ( (0 C2!!5")2 Diethyl-protocatechuic acid, C6H3c6oiI prepared in the same way as the preceding acid, forms lustrous, white needles, which give no reaction with iron chloride, and fuse at 149°. Piperonylic acid (Methylen-protocateehuic ( >CIT2 acid), C6H3 •< Cr Is produced by further oxidation ( CO.OH. of piperonal (p. 324) by means of potassium hyperman- ganate; and boiling piperonal with alcoholic potassa. Is prepared artificially by heating protocatechuic acid, methylene iodide, and potassium hydroxide together in sealed tubes; boiling the product with potassa-ley, and acidifying the solution. — Colorless needles; fusing point, 228° ; sublimable without decomposition ; insoluble in cold water, difficultly soluble in boiling water and cold alcohol, more easily soluble in hot alcohol. Monobasic acid. When heated with dilute hydrochloric acid, it is resolved into carbon and protocatechuic acid. Ethylene-protocatechuic acid, C6H3I O^0'11' ( CO.OII, is prepared by heating protocatechuic acid, ethylene bromide, and potassium hydroxide together, and treat ing the mass thus obtained as in the previous case. This acid resembles the preceding one. A substance called carbohydroquinonic acid, which is obtained by the action of bromine on an aqueous solu tion of quinic acid (p. 361) ; and by fusing quinic acid with caustic potassa, is in all probability identical with protocatechuic acid. 3. Dioxybenzoic acid. Obtained by fusing the potassium salt of disulphobenzoic acid (p. 334) with caustic potassa. — Crystallizes from water with 1 J mole- 358 OllSELLIC ACID. cules water of crystallization ; fusing point above 220° ; gives no reaction with iron chloride. 2. Orsellic Acid. ( (OH)2 C8H804 = C6H2 \ CH3 ( CO.OH. Is formed by boiling erythrin with baryta-water and by heating a neutral solution of lecanoric acid in lime- water. — Colorless prisms, soluble in water, alcohol, and ether; fuses at 176°, undergoing decomposition into carbonic anhydride arid orcin (p. 307). Its solution is turned purple by iron chloride. Erythrin (Erythrite biorsellate), C20H22010 = C4H8(C8H703)204. Is contained in the lichen Eoccdla fuciformis, which is employed in the manufacture of archil (p. 308). It can be extracted from this by means of cold milk of lime. The solution is decom posed rapidly with carbonic acid ; and the erythrin ex tracted from the precipitate with alcohol. — Crystalline, globular mass with 1J molecule water of crystalli zation. Almost insoluble in cold water, difficultly so luble in hot water, easily soluble in alcohol. When boiled for a long time with water or baryta, it is de composed into orsellic acid and picroerythrin (erythrite monorsellate), C12H1607 + H20, which forms colorless, bitter tasting crystals, that are easily soluble in water and alcohol. — By continued boiling of erythrin with baryta there are formed carbonic acid, orcin, and erythrite (p. 180). Lecanoric acid (Diorsellic acid), C16H1407 + IPO. Occurs in several lichens, belonging to the genera Roc- cella, Lecanora, and Variolaria. It can be extracted from these by means of ether or milk of lime, and is then precipitated by hydrochloric acid. — Crystallizes from alcohol and ether in colorless prisms ; almost in soluble in water. Dissolved in lime or baryta water and boiled, it is at first converted into orsellic acid; by VERATRIC ACID, ETC. 359 continued boiling, into carbonic acid and orcin. When its alcoholic solution is boiled ethyl orsellate, a crys talline body, is produced. 3. Acids, C9H100 = C8H7 1. Veratric acid, C9H1004. Is contained in sabadilla- seeds (from Veratrum sabadilla)^ To prepare it, ^ the powdered seeds are exhausted with alcohol and a little sulphuric acid, the extract mixed with lime, filtered and the alcoW distilled off from the filtrate. Veratrin (see Alkaloids) separates, and from the filtered solution, which contains calcium veratrate, the free acid is ob tained by precipitating with hydrochloric acid. By recrystallization from alcohol it is purified. Colorless prisms ; difficultly soluble in cold water, more readily in hot water, and in alcohol ; fusible, and when carefully heated, sublimable. — Gently warmed with an excess of baryta it is resolved into carbonic acid and veratrol (p. 310). 2. Everninic acid, C9H10O. In the lichen Evernia prunastri there occurs an acid, evernic acid, C17H1607, that crystallizes in small, colorless prisms and is very similar to lecanoric acid. This can be extracted from the lichen by milk of lime and precipitated from the filtered solution by hydrochloric acid. This acid is resolved into orsellic acid (p. 358, or its decomposition- products, orcin and carbonic acid) and everninic acid when boiled with alkalies or baryta-water. — Fine, colorless crystals, resembling those of benzoic acid, al most insoluble in cold water, easily soluble in hot water, in alcohol, and ether; fuses at 157°. Its aqueous solu tion is colored violet by iron chloride. 3. Umbellic acid, C9H1004. Is produced by heat ing an alkaline solution of umbelliferone (p. 307) with sodium-amalgam. — Colorless, granular crystals ; diffi cultly soluble in cold water, easily soluble in alcohol and ether ; fuses below 125°, but suffers partial decom- 360 GALLIC ACID. position even at this temperature ; its solution reduces an alkaline solution of copper and an ammoniacal solu tion of silver ; and gives a green reaction with iron chloride. It is decomposed in alkaline solution in con tact with the air. 4. Hydrocaffeie acid, C9H10O. Is produced by the action of sodium-amalgam on a hot solution of caf- feic acid. — Colorless, rhombic crystals ; easily soluble in water; the aqueous solution is colored an intense green by iron chloride, this turning to a cherry-color on the subsequent addition of sodium carbonate. Its salts are amorphous, decompose readily in a moist con dition in contact with the air, and reduce solutions of copper and silver. d. Monobasic, Tetr atomic Acids. Gallic Acid. Occurrence. In gallnuts, in mango kernels, in divi- divi (fruit of Ccesalpina coriaria], in tea, in the bark of the root of the pomegranate tree, and in several other plants. Formation and preparation. From gallotannic acid by boiling with dilute acids or alkalies, and by keep ing the solution in contact with the air ; by heating diiodosalicylic acid with an excess of an alkaline car bonate at 140-150° ; and also probably by evaporating a solution of bromprotocatechuic acid (p. 356) in an excess of potassa-ley. Properties. Crystallizes from water in fine prisms of a silky lustre with one molecule of water of crystalli zation ; soluble in 100 parts cold, in 3 parts of boiling water, easily in alcohol ; fuses by about 200°, and is resolved into carbonic anhydride and pyrogallol (p. 310) at 210-220°. The aqueous solution reduces solutions of gold and silver, throwing down the metals, and yields a blue-black precipitate with iron chloride. Its salts QUINIC ACID. 361 do not undergo change, when in a dry condition or when in acid solution in contact with the air, but, when contained in alkaline solution, they absorb oxy gen rapidly and decompose. Heated with phosphorus oxichloride to 120°, it is converted into an amorphous body, digallic acid, C14ir°09, which is reconverted into gallic acid when boiled with concentrated hydrochloric acid. Mono- and Dibromgallic acids, C7IFBr05 and C7H4Br*05, $re formed by the action of bromine on gal lic acid at the ordinary temperature. Both compounds consist of colorless crystals, which are but slightly so luble in cold water, and are not sublimable. Rufigallic acid, C7HX)4 + H20, is formed by the slow heating of gallic acid (1 part) with concentrated sulphuric acid (4 parts) to 140° ; and separates^ in red dish-brown, granular crystals, when the mass is subse quently diluted with water. — Small, lustrous crystals ; loses its water of crystallization at 120°, and sublimes at a higher temperature in the form of cinnabar-red prisms.- — Soluble in alkalies, forming a red solution, which is decomposed if air is allowed to have access to it ; when treated with baryta-water, it becomes indigo-blue without dissolving. Materials mordanted with alumina salts are colored a beautiful red by it.— Fused with potassium hydroxide it yields carbonic acid and a substance called oxyquinone, C6H403, which crystallizes in straw-colored needles. The following acid bears a close relation to the pre ceding acids : — ftuinic acid, C7H1206. Occurs principally in cin chona barks (also in the false Cinchona nova) ; further, in the bilberry plant, in coffee-beans, in G-alium mol- lugo, and probably in small quantity in a great many other plants. — Is obtained as a secondary product in the preparation of quinine. The extract, obtained 31 362 PHTALIC ACID. from the broken-up bark, with water or dilute sul phuric acid, is treated with milk of lime in order to precipitate the alkaloids. The filtered solution, on being evaporated, leaves calcium quinate behind, and this may be purified by recrystallization, and then decomposed by oxalic acid. Transparent, colorless, oblique rhombic prisms. Easily soluble in water, but very slightly in. absolute alcohol ; fuses at 162°, and, when heated above its fusing point, yields hydroquinone, pyrocatechin, benzoic acid, phe nol, and other products. Oxidizing agents (manganese peroxide and sulphuric acid) resolve it into quinone (p. 301), carbonic anhydride, and formic acid. Heated with concentrated hydriodic acid, it is reduced to benzoic acid. "When quinic acid is taken into the system of man or graminivorous animals, it is con verted into hippuric acid. Monobasic acid. All its salts are soluble in water. Calcium quinate, (C7Hn06)2Ca + 10H20, forms large, easily soluble rhombic crystals, that effloresce in contact with the air. Is contained in cinchona barks. e. Bibasic Acids. • 1. Benzenedicarbonic Acids. O8H6O4 — P6TT4 j CO. OH L | CO.OH. 1. Phtalic acid (Ortho-phtalic acid) is produced by the oxidation of naphthalene and several of its deriva tives ; also of alizarin and purpurin with nitric acid or black oxide of manganese and sulphuric acid. Is also formed by treating benzene or benzoic acid with black oxide of manganese and sulphuric acid. — Colorless laminae, or short, thick prisms; difficultly soluble in cold water, easily soluble in hot water, in alcohol and ether; fuses at 182°, and when heated to a higher temperature it is resolved into water and phtalic anhy dride, C8H403, a substance that crystallizes in long lustrous needles; fusing point, 127-128°. — Heated PHTALIC ACID. 363 with an excess of potassa or lime, it breaks up into benzene and carbonic acid ; when 1 molecule of its calcium salt is heated with 1 molecule calcium hydroxide at 330-350°, calcium benzoate is the result. "When heated with hydriodic acid, it undergoes the same change. With phosphorus chloride it yields phtalyl chloride C6H4(CO.C1)2, a light-yellow liquid, boil ing at 270°. Barium phtalate, C8H404Ba, forms small laminae, which are yery difficultly soluble in water. Methyl and ethyl phtalate are colorless liquids. Dichlorphtalic acid, C6H2C12(CO.OH)2, is prepared by boiling dichlornaphthalene tetrachloride (which see) with ordinary nitric acid. — Slightly yellowish colored, thick, intertangled prisms ; fusing point, 183-185° ; easily soluble in ether, alcohol, and hot water. Tetrachlorphtalic acid, C6C14(CO.OH)2, is obtained by heating pentachlornaphthalene with dilute nitric acid to 180-200°. — Colorless laminae, or hard, thick plates ; fuses at 250°, at the same time breaking up into water and anhydride. Monobromphtalic acid, C6H3Br(CO.OH)2. By heating phtalic acid, for a long time, with an excess of bromine and water at 180-200°. — White, crystalline powder ; fusing point, 136-138° ; easily soluble in water, alcohol, and ether. Nitrophtalic acid, C6H3(K02)(CO.OH)2. By digest, ing phtalic acid with nitric-sulphuric acid. — Pale yel low prisms ; fusing point, 208-210° ; easily soluble in water, alcohol, and ether. When heated with tin and hydrochloric acid it is converted into meta-amidoben- zoic acid, carbonic anhydride being given off. Hydrophtalic acid, C8H804. Is produced by con tinued action of sodium-amalgam on a cold solution ot 364 ISOPHTALIC ACID. 1 part phtalic acid and 1 part crystallized sodium car bonate. — Hard, tabular crystals ; difficultly soluble in cold water and ether, more easily in hot water and in alcohol; fuses above 200°, water being given off and phtalic anhydride formed. Is decomposed when heated with soda-lime, yielding benzene, hydrogen, and car bonic acid ; when fused with potassa, it yields benzoic acid, hydrogen, and carbonic acid ; when it is gently warmed with phosphorus chloride, it yields benzoyl chloride, carbonic oxide, hydrochloric acid, and phos phorus oxichloride; when dissolved in concentrated sulphuric acid, when bromine is allowed to act on its aqueous solution, and when oxidized with dilute nitric acid, it is converted into benzoic acid ; when its alco holic solution is saturated with hydrochloric acid gas, ethyl benzoate is formed. Tetrahydrophtalic acid, C8H1004. The anhydride of this acid (C8H803, colorless laminae, fusing at 68°) is formed in the dry distillation of hydropyromellitic acid. "When this anhydride is heated with water, the acid is generated. — Easily soluble laminse; fuses at 96°, being resolved at this temperature into water and the anhydride. Bibasic acid. Bromine, when added to its aqueous solution, converts it into brommalophtalic acid, C8H10Br(OH)04, which crystallizes in hard crusts, and, when heated with baryta-water, is converted into tartrophtalic add, C8H10(OH)204 (large, easily soluble prisms). Hexahydrophtalic acid, C8H1204. Is obtained by heating tetrahydrophtalic acid with concentrated hydriodic acid to 230° ; or, better, by heating hydro- phtalic acid with concentrated hydriodic acid to 240- 250°. — Indistinct, small, hard crystals; fusing point, 203-205°; somewhat difficultly soluble in water; bi- basic. 2. Isophtalic acid (Meta-phtalic acid), C8II604. Is obtained by oxidizing meta-xylene (p. 283) and meta- TEEEPHTALIC ACID. 365 toluic acid (p. 338) with potassium bichromate and dilute sulphuric acid. — Is also formed by melting an intimate mixture of potassium metabrom- or meta- sulphobenzoate with sodium formate ; and by heating hydropyromellitic and hydroprehnitic acids.— Long colorless, very fine crystals; almost insoluble in cold water, difficultly soluble in boiling water, more easily soluble in alcohol ; fuses above 300°, and can be sub limed without undergoing decomposition. Barium isophtalate, C8H404Ba + 3H20. Crystal lizes in colorless, lustrous prisms ; easily soluble in water. Methyl isophtalate, C6H4(CO.O.CH3)2. Colorless needles, fusing at 64-65°. The ethyl ether is a colorless liquid, boiling at 285°, and congealing at 0°. Nitroisophtalic acid, CGH3(^02)(CO.OII)2. By heating isophtalic acid with fuming nitric acid. — Large, colorless, lustrous, thin laminse ; fusing point, 248-249° ; easily soluble in water and alcohol ; is con verted into amido-isophtalic acid, C6H3(NH2)(CO.OH)2, by tin and hydrochloric acid. 3. Terephtalic acid (Para-phtalic acid). Is pro duced from bodies belonging to the para-series : para- xylene, ethylmethylbenzene, cymene, amylmethylben- zene, cuminol, para-toluic acid, cuminic acid, ethyl- benzoic acid, oil of turpentine, etc., by oxidizing them with a mixture of potassium bichromate (2 parts) and sulphuric acid (3 parts concentrated acid diluted with three times its volume of water) ; by boiling paradi- cyanbenzene (p. 256) with potassa-ley; and by melt ing a mixture of sodium parasulphobenzoate with sodium formate. — White powder; when allowed to separate slowly it is crystalline; almost insoluble in water, alcohol, and ether; freshly precipitated from a solution of one of its salts, it is moderately easily soluble in hot alcohol, and separates from this solution 81* 366 UVITIC ACID* in crystalline form on cooling; sublimes undecomposed without previously melting. Calcium terephtalate, C8H404Ca + 3IPO, and Barium terephtalate, C8H404Ba + 4IPO, are crys talline compounds, very difficultly soluble in water. Methyl terephtalate, C6H4(CO.O.CH3)2. Long prisms, fusing at 140°, and subliming without decom position ; but slightly soluble in cold alcohol, easily soluble in hot alcohol. — The ethyl ether crystallizes in prisms that fuse at 44°. Nitroterephtalic acid, C6II3(^q2)(CO.OH)2. Is formed by boiling terephtalic acid with very concen trated nitric acid. — Cauliflower-like masses ; fusing point, 259° ; moderately easily soluble in water. Sulphoterephtalic acid, C6H3(S02.OH)(CO.OH)2, is formed by heating terephtalic acid with fuming sul phuric acid in sealed tubes for six hours. — The barium salt can be purified by recrystallization. Hydroterephtalic acid, C8H804, is formed by the action of nascent hydrogen (sodium-amalgam) on terephtalic acid in a strongly alkaline solution. — "White powder, very similar to terephtalic acid. 2. Acids, C9H80 = C«H? 1. TJvitic acid (1:3: 5). Is produced, together with mesitylenic acid (p. 340) by continued boiling of mesitylene with dilute nitric acid ; and by boiling pyro- racemic acid (p. 175) with barium hydroxide. — Color less, fine needles; fusing point, 287° ; almost insoluble in cold water, difficultly soluble in hot water, easily soluble in ether and alcohol ; not volatile with water vapor; when oxidized with chromic acid, it is con verted into trimesic acid, and, when heated with an TBIMESIC ACID. 367 excess of lime, it is resolved into carbonic acid and toluene. 2. Xylidinic acid (1:3: 4).* Is formed from pseudocumene, xylylic, and paraxylylic acids by boil ing them for a long time with dilute nitric acid. — Indistinct, colorless crystals ; fusing point, 280-283° ; almost insoluble in cold water, very slightly in boiling water, more easily in alcohol. 3. Isuvitic acid. Is formed, together with phloro- glucin, pyrotartaric, and acetic acids, by fusing gam boge with caustic potassa. — Short, thick, rhombic, columnar crystals ; but slightly soluble in cold water, more easily in hot water ; fuses at about 160°. 3. Acids, CWH'°0 = C6H2 Cumidinic acid. Is produced from durene and durylic acid by continued boiling with dilute nitric acid. — Long, transparent prisms; almost insoluble in water, even at the boiling temperature ; easily soluble in hot alcohol ; sublimes at a high temperature in plates, without previously fusing. /. Tribasic Acids. Benzenetricarbonic Acids. C9IF06 = C6H3(CO.OH)3. 1. Trimesic acid (1 : 3 : 5). Is obtained by oxidizing mesitylenic and uvitic acids with potassium bichro mate and dilute sulphuric acid; is also produced, together with carbonic anhydride and benzenetetra- carbonic acids, by heating hydro- and isohydromellitic acids with concentrated sulphuric acid. — Short, color less prisms ; rather difficultly soluble in cold water, easily soluble in hot water, in alcohol and ether; fuses * 1 and 4 indicate the position of the CO.OH groups; 3 that of the group CH3. 368 PYROMELLITIC ACID. above 300°, arid sublimes without decomposition ; heated with an excess of lime, it is resolved into car bonic acid and benzene. Barium trimesate. The neutral salt, (C9H306)2Ba3 + 3H20, is a crystalline precipitate, almost insoluble in water. The add salt, (C9IP06)2Ba + 4H20, is thrown down when barium chloride is added to a solution of the free acid ; fine, colorless needles, but slightly soluble in hot water. Ethyl trimesate, C6H3(CO.O.C2H5)3. Long prisms, of a silky lustre, fusing at 129°. 2. Hemimellitic acid (1:2: 3). Is produced, together with phtalic anhydride, by heating hydro- *mellophanic acid (p. 370) with concentrated sulphuric acid. — Colorless needles ; rather difficultly soluble in water; from its concentrated aqueous solution it is precipitated by hydrochloric acid ; fuses at 185°, and, when heated to a higher temperature, yields phtalic anhydride and benzoic acid. 3. Trimellitic acid (1:2: 4). Is formed, together with isophtalic acid and pyromellitic anhydride, by heating hydropyromellitic acid with concentrated sul phuric acid. — Indistinct, verrucous crystals ; fusing point, 216° ; moderately easily soluble in water and ether. Barium trimellitate, (C9IP06)2Ba3 + 3H20, forms diificultly soluble, verrucous crystals. g. Tetrabasic Acids. Benzenetetracarbonic Acids. Ci°H608 = C6H2(CO.OH)4. 1. Pyromellitic acid. Is formed by careful dis tillation of mellitic acid ; and is obtained most readily by heating sodium mellitate with sulphuric acid. — PREHNITIC ACID. 369 Crystallizes from water with two molecules of water of crystallization, in colorless prisms; but slightly soluble in cold water, easily in hot water and in alco hol ; fuses at 264°, and when distilled is converted into the anhydride, C10H206, which forms large crystals and fuses at 286°. Barium pyromellitate, C10H208Ba2, and Calcium pyromellitate, C10H208Ca2, are white precipitates, insoluble in water. Ethyl pyromellitate, C6H2(CO.O.C2H5)4. Short, flat needles, insoluble in water; fusing point, 53°. Hydropyromellitic acid, C10H1008. Is slowly formed by the action of sodium-amalgam on an aqueous solution of ammonium pyromellitate. — Colorless syrup, gradually congealing in crystalline form ; very easily soluble in water ; when heated alone, it is converted into the anhydride of tetrahydrophtalic acid (p. 364) ; when heated with concentrated sulphuric acid, it yields carbonic anhydride, pyromellitic anhydride, tri- mellitic and isophtalic acids. 2. Prehnitic acid. Is formed, together with car bonic anhydride, trimesic and mellophanic acids, by heating hydro- and isohydromellitic acids (p. 371) with concentrated sulphuric acid. — Large prisms united in groups ; contain two molecules of water of crystalliza tion ; easily soluble in water ; fuses at 237-250°, the anhydride being formed at the same time. Hydroprehnitic acid, C10H1008. Is obtained like hydropyromellitic acid. — Syrupy. "When heated with sulphuric acid, it yields prehnitic and isophtalic acids and carbonic anhydride. 3. Mellophanic acid. Is formed together with the preceding acid. — Small, indistinct crystals, united in crusts, without water of crystallization ; fuses at 215-238°, giving rise to the formation of the anhy- 370 MELLITIC ACID. dride; with sodium-amalgam it yields hydromello- phanic acid. h. Hexabasic Acids. Mellitic Add. Ci2H60i2 = C6(CO.OH)6. Occurrence and formation. In the mineral king dom ; in honeystone or mellite (found in lignite), which consists of aluminium mellitate crystallized in yellow, quadratic octahedrons. The ammonium salt, which crystallizes well, is prepared from this by boiling with ammonium carbonate ; and from the ammonium salt the insoluble barium or silver salt is prepared by precipitation ; the salt thus obtained is decomposed by dilute sulphuric or hydrochloric acid. — It can be pre pared artificially by oxidizing pure carbon by means of potassium hypermanganate in an alkaline solution. Properties. Fine needles of a silky lustre; easily soluble in water and alcohol. "When heated it melts ; when distilled alone it is resolved into carbonic anhy dride, water, and pyromellitic anhydride ; when heated with an excess of lime it yields carbonic acid and ben zene. Very stable acid ; is not decomposed by con centrated sulphuric, nitric, and hydriodic acids, nor bromine even at an elevated temperature. Ammonium mellitate, C12012(NH4)6 + 9EPO. Crys tallizes in large, colorless rhombic prisms. — Barium mellitate, Cl2012J3a3 -f 3II20, and Calcium mellitate are precipitates, insoluble in water, rapidly becoming crystalline. Methyl mellitate, C6(CO.O.CH3)6, crystallizes in colorless laminee, that fuse at 140°. The Ethyl ether, C"(CO.O.C2H5)6, forms lozenge-shaped crystals, that fuse at 69°. MELLITIC ACID. 371 Paramide (Mellimide), C12H3K306 = Ammonium mellitate, when heated to 160°, is re solved into water, ammonia, paramide, and ammo nium euchronate. Paramide, which is insoluble in water, can be freed of the euchronate by water. — "White, amorphous mass, insoluble in water and alco hol ; is converted into acid ammonium mellitate when heated with water to 200°. Euchronic acid, C12H4JST208 = C6(cO I NH}2(CO.OH)2. Is separated from its ammo nium salt (see above, Paramide) by means of hydro chloric acid. — Colorless, short prisms ; but slightly soluble in cold water; heated with water to 200°, it is converted into acid ammonium mellitate. Its solution, when brought in contact with zinc or nascent hydro gen from any source, throws down a deep-blue, insolu ble body, euchron, which, when gently heated in the air, is reconverted into colorless euchronic acid, and dissolves in alkalies, forming beautiful, purple-red solutions, which rapidly become colorless in contact with air. Hydromellitic acid, C12H12012. Is formed slowly by the action of sodium amalgam on ammonium melli tate. — Colorless, indistinct crystals ; easily soluble in water ; hexabasic. "When kept it is slowly converted into isohydromellitic acid^ C12H12012; the same change takes place rapidly when it is heated with concentrated hydrochloric acid to 180°. Isohydromellitic acid crys tallizes in thick, four-sided prisms, is easily soluble in water, and is precipitated from the aqueous solution by hydrochloric acid. By heating hydromellitic acid with concentrated sulphuric acid, there is formed, under certain conditions, a third isomeric acid, meso- hydromellitic acid, which forms voluminous needles, very difficultly soluble in cold water. 372 CINNAMENE. SECOND GROUP. Cinnamene (Styrol). C8H8 = C6H6.Cil:CH2. Is contained in liquid storax, the expressed viscid juice of the bark of Liquidambar orientate; and is ob tained from this by distilling with water and sodium carbonate.. Is formed by heating benzene-ethyl bro mide (p. 285) with water or baryta, and by heating acetylene gas (cf. Benzene). Is probably also con tained in coal-tar. — Colorless, mobile liquid, of an aromatic odor ; refracts light strongly. Boiling point, 146° ; specific gravity, 0.924. When kept it is slowly converted into metacinnamene, a body polymeric with it ; the same change takes place rapidly by heating it to 200°. Metacinnamene is a solid, amorphous, trans parent mass, which, when distilled, is reconverted into cinnamene. Cinnamene 37ields benzoic acid when sub jected to the influence of oxidizing agents. Cinnamene chloride, C8H8C12 = C6H5.CHC1.CH2C1, and Cinnamene bromide, C8H8Br2, are produced by the direct combination of cinnamene with chlorine or bromine. The chloride is liquid ; the bromide crys tallizes in colorless laminae or needles, that fuse at 67°. Heated alone, or, better, with caustic lime or alcoholic potassa, these compounds are converted respectively into 0,-chlor cinnamene, C6H5.CH:CHC1, or a-bromcinna- mene. Both of these latter compounds are heavy liquids, not distillable without decomposition, the vapor of which excites to tears. The isomeric substi tution-products, $-chlor cinnamene, C6H5.CC1:CH2 (liquid, boiling, without decomposition, at 199°, of a pleasant odor like that of hyacinthes), and p-bromcinnamene, C6H5.CBr:CH2 (boiling point, 228°), are formed by heating phenylchlor- and phenylbromlactic acids (pp. 354 and 355) with water at 200°. Cinnamene iodide, C8H8I2, separates in crystals when a solution of iodine in potassium iodide is added STYKYL ALCOHOL. 373 to cinnamene. When kept it is rapidly converted into metacinnamene, iodine being thrown down. Nitro cinnamene, C8H7(N02), crystallizes in large prisms. Styryl Alcohol. C9H10O = C6H5.CH:CH.CH2.OH. Is obtained by distilling styryl cinnamate (Styracin, p. 375) with concentrated potassa-ley. Is also produced in small quantity by heating styrylic aldehyde with alcoholic potassa. — Colorless, lustrous needles, of a pleasant odor; fuses at 33°, and boils at 250°. "When oxidized slowly it is converted into cinnamic acid; when oxidized rapidly, oil of bitter almonds and ben- zoic acid are formed ; when treated with hydrochloric acid gas or phosphorus iodide, liquid chlorstyryl C9H9C1 or iodostyryl C9H9I are formed. Cinnamic Aldehyde (Styrylic Aldehyde). C9H80 = C6H5.CII:CH.CHO. Is contained in oil of cinnamon or oil of cassia (the vola tile oils of the bark of Persea cinnamomum and Persea cassia)', and can be extracted from them by agitating with alkaline bisulphites, and decomposing the sepa rated crystalline compound with dilute sulphuric acid. Is formed by the distillation of a mixture of calcium cinnamate and formate; and when a mixture of acetic aldehyde and oil of bitter almonds is saturated with hydrochloric acid gas. Colorless oil, heavier than water, does not mix with it. Not distillable alone, but very readily with water vapor. In contact with air it changes to cinnamic acid. Oxidizing agents convert it into oil of bitter almonds and benzoic acid. Combines with dry am monia, forming water and a crystalline substance, hydrocinnamide (C9H8)3K2. 32 374 CINNAMIC ACID. Cinnamic Acid. C9H802 = C6H5.CH:CH.CO.OH. Occurrence and formation. In storax, in Tolu- and Peru-balsams (p. 312), and in a few varieties of gum- benzoin. Is formed from cinnamic aldehyde by oxida tion ; by boiling styracin with potassa ; by the simul taneous action of sodium and carbonic anhydride on a-bromcinnamene ; and by heating oil of bitter almonds with acetyl chloride. Preparation. Most advantageously from storax. This is boiled for a long time with a solution of sodium carbonate or with potassa-ley, the clear solution of so dium or potassium cinnamate filtered off from the un- dissolved resin, and the cinnamic acid precipitated by hydrochloric acid. By recrystallizing from hot water or by subliming, it is purified. Properties. Crystallized from hot water, it forms fine needly crystals; from alcohol, large, clear, easily cleavable prisms ; inodorous ; of a weak taste ; fuses at 133°, and is distillable almost completely without decomposition. Monobasic acid. Very similar to benzoic acid ; its salts also resemble the benzoates very strongly, but give a yellow precipitate with iron chloride; fusing potassium hydroxide converts it into benzoic and acetic acids. Subjected to the influence of oxidizing agents (dilute nitric acid, potassium hypermanganate, potassium bichromate, and sulphuric acid), it yields oil of bitter almonds and benzoic acid. Nascent hydrogen converts it into hydrocinnamic acid (p. 342). Heated with water to 180-200°, and with lime, it is resolved into carbonic acid and cinnamene. Ethyl cinnamate, C9H702.C2H5, is produced by conducting hydrochloric acid gas into a solution of cinnamic acid in absolute alcohol. Benzyl cinnamate, C9H702.C7H7, is contained in Tolu- and Peru-balsams ; and is produced by heating sodium cinnamate with benzyl chloride. — Lustrous CINNAMIC ACID. 375 prisms; fusing point, 39°; distillable without decom position only in a vacuum. Styryl cinnamate (Styracin), C9H702.C9H9, is con tained in the brown resin, the residue from the prepa ration of cinnamic acid from storax. Can be most readily prepared by digesting storax with dilute soda- ley, at a temperature not higher than 30°, until the residual styracin has become colorless. After it is washed out and dried, it is recrystallized from alcohol, which contains ether. — Fine, colorless needles, united in nodules, insoluble in water; fuses at 50°. Nitrocinnamic acid, C9H7(£T02)02. When nitric acid is allowed to act upon cinnamic acid, two nitro- acids are formed, which can be separated by means of crystallization. — One fuses at 265°, is difficultly solu ble in water, and yields paranitrobenzoic acid when oxidized. The second is easily soluble in water, and yields orthonitrobenzoic acid when oxidized. Cinnamic acid dibromide (Dibromhydrocinnamic acid), C9H8Br202 = C6H5.CHBr.CHBr.CO.OH. Is formed by direct union, when bromine in the form of vapor is allowed to act on cinnamic acid, either at the ordinary temperature or at 100°. — Colorless, rhombic laminae; insoluble in cold water, easily soluble in alcohol and ether; not fusible without decomposition; when boiled with water it .is decomposed, yielding j3-bromcinnamene and phenylbromlactic acid (p. 355). Nascent hydrogen converts it into hydrocinnamic acid. Monobromcinnamic acid, C9H7Br02. Two iso- meric modifications of this acid are formed by the addition of alcoholic potassa to a boiling-hot alcoholic solution of cinnamic acid dibromide. They can be separated by means of partial crystallization. The salt of a-bromcinnamic acid is difficultly soluble in water, that of 6-bromcinnamic acid is very easily soluble and even deliquescent in the air. — o.-Bromcinnamic add 376 ATROPIC ACID. crystallizes in long, lustrous, four-sided needles, which are but slightly soluble in cold water, more easily in boiling water, in alcohol in all proportions ; fusing point, 130-131°; distil almost entirely without de composition. — $-Bromcinnamic add crystallizes from boiling water in large, hexagonal, flat crystals, which are easily soluble in boiling water and in alcohol; fuse at 120°; and are converted in a-bromcinnamic acid when subjected to distillation. The following acids are isomeric with cinnamic acid : — Atropic and Isatropic acids, C9H802. Both acids are produced from tropic acid (p. 354) when this is heated with baryta or concentrated hydrochloric acid ; and are hence formed, together with tropic acid, in the decomposition of atropin. Atropic acid is particularly formed when baryta is employed ; isatropic acid, on the other hand, when hydrochloric acid is the decom posing agent. Atropic acid crystallizes in monoclinic plates, dissolves in 700-800 parts water of the ordinary temperature, easily in boiling water ; fuses at 106.5° ; yields benzoic acid when oxidized with chromic acid ; alphatoluic acid (p. 340) when melted with potassium hydroxide; and hydratropie acid (p. 342) when treated with nascent hydrogen. — Isatropic acid forms thin, rhombic laminae; is almost insoluble in cold water, but very slightly in boiling water; and also in alcohol it is less soluble than atropic acid. It melts at 200°, is not acted upon by chromic acid, and does not combine with hydrogen. Phenylangelic acid, CnH1202 = C6H5.C4H6.CO.OH. Is formed, like cinnamic acid, by heating oil of bitter almonds with butyryl chloride at 120-130°. — Long, fine, colorless needles ; fusing point, 81° ; difficultly COUMARIN. 377 soluble in water, easily in alcohol. Chromic acid oxi dizes it, forming benzoic acid. Coumarin, C9H602. Occurs in Tonka beans (the fruit of Dipterix odorata), partially in the form of crystals ; in Melilotus officinalis, Asperula odorata, and Anthoxanthum odoratum; and can be extracted by means of alcohol. After distilling off the greater part of the alcohpl, the residue is mixed with boiling water and filtered, when the greater part of the coumarin separates. It is also formed by the action of acetic anhydride on the sodium compound of salicylic alde hyde (p. 323). — Colorless, lustrous prisms, of a pleasant aromatic odor; but slightly soluble in cold water, more readily in hot water; fuses at 67°, and boils without decomposition at 291°. "When its aqueous solution is treated with sodium-amalgam, it is ^ con verted into coumaric and melilotic acids (p. 353); if on the other hand, sodium-amalgam is allowed to act on its alcoholic solution, the principal product formed is the sodium salt of hydrocoumaric acid, C18H1806, which crys tallizes in fine needles, difficultly soluble in cold water. This acid, when heated, is resolved into water and its anhydride, hydrocoumarin, C18H1404 (needles; fusing point, 222°). Coumarin dichloride, C9H6C1202 (syrupy mass), and Coumarin dibromide, C9H6Br202 (colorless prisms), are formed by the action of chlorine or bromine on solutions of coumarin in chloroform or carbon bisul phide. When treated with alcoholic potassa, they yield substitution-products of coumarin. The latter are also formed by the action of phosphorus chloride or of bro mine on coumarin at a slightly elevated temperature., When the sodium compound of chlor- or bromsalicylic aldehyde is treated with acetic anhydride, substitution- products of coumarin are obtained that are isomeric with those formed by direct action of the reagents. Coumarin is probably the anhydride of coumaric 32' M7H (JOI! M A II II! A i1 1 I*, MTO , HIM! rnilMlihlli'd li''< 'oidiiK/ In MM* I'm null i i O ."hmMMrl(\y, . ( lolorh'MM, hiFil.roim hriwtiiN; «;h'il\ Molllblo ill linl. \vii.l«T (Hi'l III »il«-nlml. |l|M(1|4 nl. HI/T'; llOt VohttlUl wilboiil dooOIUpONitlofli tTuMCMJ vvilb i»nliiMM,ii, il. jii'ldM (inliiMMiinn WttildyltttO mid tM'olnii*. TllO I'nlul inni'. nf llfi nil iilitic fiilli1. JI,M l'imu oinmmr sind, ( 'II " ,fll|4) nil i i i i 1 i cihOll.on.nn. l t'roduoc iHjiM'OUM Noltif/iotl "I' idnoM, lo whii'li Inm been nddcd M 1 1 ,|iiii'ie neid ; nnd, iil'ler lillei'in^;, it (!iui |M« exlriidcd 1 1 '>ni I be «. lull-. n I . •/ nieiiliM nl el b«*r, ( /oloi'h'NN| Inn 1 1 • .M In 1 1 1 1« in « 'II' I '.n I c.| iju- b 1 1 y rill 1 1 Me in eit Id w n Id I', onMily Holublo in but will or HIM! in ulcobol; riiM««nl, I7i) IHO". KuHud wil.h iiolimMiuin b(ydi'oxid(«, It IN (!onv(iri«id inln iiHi'uoxylMMi/oii1 iM'id. M coinliiiiew vvilb niiwutil, liydrd^cn, l'n i' lump; li(ydi'M|iiii'(i,einiiiiiii'ie ncid (j». JUrl). \\'l"n b»i|ei| wild lui. MI.- nil I'ie neid, il, ^'ieMK l/K'I'ic in id. urid, ("'110'- C"ll" ,, IM InniM-d, wilb wu^nr, bty boiling cull- ffttlhlc m-id (or n|' rnll'iM-) Wllll | •< >l IIWMII ll^y J (Mid N<«pfimh*M IV A CKTIHN V UHUN/, UN H!, H II,. ..lull. .11 nn id- nl. .•,.!• i.l litldil inn n| ul|. I IM'id, Y<f^«i«nvllHHK» l"'iMl<', colocl^rtw, mid I I<'n; riming poinl,, i)7(/ ; Jnwolul/U' in v/.ii'i I.I' in .. l- ',!,•, i .uid • » I,- i 380 PHEN^LPROPIOLIC ACID. Phenylpropiolic Acid. C6H5.C:C.CO.OH. Is formed by the simultaneous action of sodium and carbonic anhydride on /3-bromcinnamene ; by bringing the sodium compound of acetenylbenzene together with carbonic anhydride ; and by heating a-bromcinnarnie acid with alcoholic potassa. — Long, colorless needles ; fusing point, 136-137° ; easily sublimable ; but slightly soluble in cold water, easily soluble in boiling water, in alcohol and ether. It combines directly with four atoms of bromine, forming an acid that crystallizes only with great difficulty. Nascent hydrogen (sodium- amalgam) converts it into hydroehmamic acid. Chro mic acid oxidizes it, forming benzoic acid. Heated with water to 120°, it is resolved into carbonic anhy dride and acetenylbenzene. In connection with this group a few aromatic com pounds will be here described, that have not been so well investigated. They also, for the greater part, differ from the compounds of the first group by con taining a smaller number of hydrogen-atoms, the car bon-atoms being combined more closely instead. Anethol, Cl°II12o(= C6H4| ^pp ?). Is con tained in oils of anise, fenchel and tarragon, and sepa rates on cooling these oils. — Colorless, lustrous laminse ; fusing point, 21° ; boiling point, 232°. When heated with hydriodic acid, it yields methyl iodide and a resin; heated with potassium hydroxide for a long time at 200-230°, it yields paraoxybenzoic acid and a substance, having the character of phenols, anol, C9H100 (= C6H4 1 ^p ? j , which forms white, lustrous laminse; fusing point, 92.5°; not distillable without de composition. When anethol is oxidized with nitric or chromic acids, it is converted into anisic aldehyde EUGENOL. 381 (p. 324) and anisic acid. Under the influence of con centrated phosphoric acid, concentrated sulphuric acid, antimony chloride, iodine in potassium iodide, etc., it is transformed into isomeric or polymeric compounds. An isomeric liquid compound also appears to be con tained in the oils mentioned, together with the solid variety. Eugenol (Eugenic acid), C10H1202( = ( OH \ C6H3 1 O.CH3 ? 1 Is contained in oil of cloves (from ( C3H5 J . the bud blossoms of Caryophyllus aromaticus), in oil of pimenta (from the fruit of Myrtus pimenta), in the volatile oils of Per sea caryophyllata, and in the bark of Canella alba. Can be obtained therefrom by dissolving in caustic potassa, removing the undissolved portions of the oils by filtering and heating, and reprecipitating with carbonic anhydride. — Colorless liquid, boiling at 253° ; of an aromatic odor and sharp taste ; insoluble in water ; becomes brown when kept. Conducts itself chemically like a phenol. When distilled with hydri- odic acid, it yields methyl iodide and a red resin, C9H1002; fused with potassium hydroxide, proto- catechuic acid (p. 356) and acetic acid, ( O.CH3 -\ Eugetic acid, C11!!1^ = C9IF \ OH ? I Is (CO.OII J. formed by the simultaneous action of sodium and car bonic anhydride on eugenol. — Thin, colorless prisms ; difficultly soluble in cold water, easily in alcohol and ether ; its aqueous solution is turned deep blue by iron chloride ; fuses at 124°, and is resolved by stronger heat into carbonic anhydride and eugenol. Sinapic acid, CnH1205. Is formed by boiling the salts of sinapin (see Alkaloids) with barium hydroxide. — Small, colorless prisms, not volatile without decom position. But slightly soluble in cold water and cold f^ Of IBM 382 FERULIC ACID. alcohol, more easily soluble in the hot liquids. Bibasic acid. Ferulic acid, C10II1004. Is contained in assafcetida. The alcoholic solution of the latter is precipitated with an alcoholic solution of lead acetate and the pre cipitate, after being repeatedly pressed and washed with alcohol, decomposed with dilute sulphuric acid. — Colorless, long, four-sided needles ; almost insoluble in cold water, easily soluble in hot water and in alcohol ; fusing point, 153-154°; not sublimable. The aqueous solution gives a yellowish-brown precipitate with iron chloride ; monobasic, diatomic acid ; yields protocate- chuic and acetic acids when fused with potassa. Hemipinic acid, C10H1006 ((HP j [°o OH)* ?). Is produced, together with cotarnin, meconin, and opianic acid, by the oxidation of narcotin (see Alkaloids) with dilute nitric acid or black oxide of manganese and sul phuric acid. — Large, four-sided prisms with varying quantities of water of crystallization ; difficultly solu ble in cold water, more easily in alcohol ; fuses at 180°, and sublimes without decomposition. When heated with hydriodk or hydrochloric acids, it yields methyl iodide or chloride, carbonic anhydride, and two isomeric acids, opinic acid and isopinic acid, C|4H1008 -f 3H20. Opianic acid, C10H1005. Is formed from narcotin together with the preceding compound. — Colorless, fine prisms, but slightly soluble in cold water; fuses at 140° ; conducts itself in most reactions like an alde hyde ; yields meconin and hemipinic acid when heated with potassa-ley ; and when oxidized is completely converted into hemipinic acid. Meconin, C10H1004. Is contained in opium ; is formed together with cotarnin (see Alkaloids) from narcotin by heating with water at 100°; and from opianic acid by the action of nascent hydrogen or by treatment with potassa-ley. — Lustrous, colorless crys- INDIGO-BLUE. tals, difficultly soluble in cold water, more easily solu ble in hot water ; fuses at 110° ; combines with acids by heating, water being eliminated and bodies, like ethers, being formed. Piperic acid, C12H1004. The potassium salt is formed together with piperidin by boiling piperin (see Alkaloids) with alcoholic potassa. Hydrochloric acid throws down the free acid from the solution of the salt. — Crystallizes from alcohol in long, capillary needles ; almost insoluble in water, but slightly soluble in cold alcohol, more easily in hot alcohol ; fuses at 216-217° and sublimes, at the same time undergoing partial decomposition. Monobasic acid ; yields proto- catechuic (p. 356), acetic, and oxalic acids when fused with potassium hydroxide. Potassium bichromate and dilute sulphuric acid destroy it completely with the aid of gentle heat, forming carbonic anhydride and water. Potassium hypermanganate converts it into piperonal (p. 324). Hydropiperic acid, C12H1204. Is formed from piperic acid by direct combination with nascent hydro gen. — Long, colorless, fine needles, fusing at 70-71°. FOURTH GROUP (INDIGO-GROUP). Indigo-blue, C8H6KO or C16H10£T202. Indigo is ob tained from the various species of Indigo/era of East India and South America, from Isatis tinctoria, Nerium tinctorium, Polygonum tinctorium, and other plants. The blossoming plants are cut off and allowed to 'stand under water from twelve to fifteen hours. The liquid is then drawn off, and, by means of beating with wooden shovels, etc., brought in contact with the air as much as possible. The indigo, which separates dur ing this process, is separated from the brown liquid, boiled with water, and dried. — Indigo is not contained, ready formed, in the plants. From what compound 384 INDIGO-BLUE. and by what decomposition it is formed during the process of preparation, is not positively known. A substance yielding indigo (probably indol, de scribed below), is sometimes contained in human urine and blood. The conversion of this substance into in digo-blue is the cause of the lilac or blue color fre quently noticed in urine on the rapid addition of sul phuric acid. In order to prepare indigo-blue in a pure condition from commercial indigo, which often contains foreign substances mixed with it in large quantities, the latter is finely powdered; mixed with calcium hydroxide and iron vitriol ; the mixture put in a flask, that can be closed ; this filled completely with boiling hot water and hermetically closed.* In this operation the real indigo-blue, by the action of ferrous hydroxide which becomes ferric hydroxide, takes up hydrogen and is con verted into indigo-white, which dissolves in combina tion with lime (indigo vat of dyers). After the trans formation is completed and this" solution has turned a clear, deep yellow, it is allowed to pour through a siphon into a vessel containing very dilute hydro chloric acid, the indigo-blue, in consequence of the access of air, being regenerated and separating in the form of 3, deep-blue powder, after violent shaking with air. This powder is then filtered off, washed out and dried. Or indigo is mixed with an equal weight of grape- sugar ; hot alcohol and 1 J part of the most concen trated soda-ley poured upon it in a large flask ; the flask then completely filled with hot alcohol, and allowed to stand for some time. The clear liquid, being thereupon poured off, gradually deposits indigo-blue in crystal line form when allowed to remain in contact with air. Indigo is obtained artificially in very small quantity when liquid nitro-acetophenone (p. 386) is converted into a solid resinous mass by being heated alone, * Three parts indigo, the hydrate of 6 parts lime, 4 parts iron vitriol, and about 450 parts water. INDIGO-WHITE. 385 and this mass then heated with zinc-dust and soda- lime. Properties. Deep blue, approaching purple; pressure gives it a copper color and a half metallic lustre. Tasteless, inodorous; completely insoluble in water, alcohol, ether, dilute sulphuric acid, hydrochloric acid, and alkalies ; soluble in anilin. At about 300°, it is transformed into a purple vapor, which condenses in the form of lustrous, deep copper-colored prisms ; this property can also be made use of for the purpose of preparing pure indigo, though it involves loss in consequence of decomposition and carbonization. Dis tilled with potassium hydroxide, it is resolved into anilin and carbonic acid. — When boiled for a long time with potassa-ley and finely-divided black oxide of manganese, it is converted into anthranilic acid (p. 330). Indigo-white, C16H12K202. Is produced from in digo-blue when this conies in contact with nascent hydrogen or with any other reducing agents in the presence of a base. It is contained in the solutions described above, which are not colored blue, and can be obtained from them in an isolated condition when they are allowed to flow directly into boiled, dilute hydrochloric acid by means of a siphon, care being taken that they do not come in contact with air. The indigo-white is thus separated in the form of white, glittering flocks. After being filtered off and washed with water, that has been boiled for a long time, it must be dried either in a vacuum or in a current of hydrogen. — • White, fine, crystalline powder ; inodorous and taste less ; insoluble in water. In contact with air, particu larly when in a moist condition or in water containing air, it is soon reconverted into indigo-blue. It is a weak acid, and is readily dissolved by alkalies, forming yellow solutions. These solutions, as well as its salts formed by double decomposition, are exceedingly un- 33 386 SULPHINDIGOTIC ACID. stable, take up oxygen rapidly from the air, and deposit indigo-blue. Sulphindigotic acid (Sulphocoerulic acid), C8HWO. S02.OH, is formed when 1 part indigo is digested for three days, at 30-40°, with 15 parts concentrated sul phuric acid. Pure wool is then placed in the diluted solution. Upon this the acid formed is deposited, there remaining in the liquid only the excess of free sul phuric acid. The wool, which is dyed blue, is now well washed with water; and the acid extracted by means of ammonium carbonate; the solution evapo rated at as low a temperature as possible; and the residue washed with alcohol for the purpose of re moving another acid, hyposidphindigotic acid, which is formed, together with sulphindigotic acid, particu larly when indigo is dissolved in fuming sulphuric acid; thereupon the substance is dissolveid in water; precipitated with lead acetate; and the lead salt, suspended in water, decomposed by sulphuretted hydrogen. On evaporating the filtered solution at a but slightly elevated temperature, the acid remains behind in the form of a blue, amorphous mass, easily soluble in water and alcohol. Its salts are amorphous. The potassium salt, C8IKNX). S03K, and the sodium salt occur in commerce under the name of indigo-carmine, and are prepared on the large scale by adding potassium acetate, or Glaubers salt, to a diluted solution of indigo-blue in sulphuric acid ; wash ing out the blue precipitate with solutions of the salts employed; and pressing. They form copper-colored masses, which appear blue in a finely-divided condition, and dissolve with blue color in pure water. If, in the preparation of sulphindigotic acid, less (only 8 parts) sulphuric acid is employed, on subse quently diluting with water, a blue precipitate is thrown down, consisting of Sulphophoenicic acid (Sulphopurpuric acid), C16H9N202.S02.OH, which dissolves in pure water, free of acids, and forms purplish-red salts with bases ; these ISATIN. 387 salts are soluble in water, the solutions having a blue color. Isatin, C8H5M)2, is formed by the oxidation ^ of indigo-blue. Finely powdered indigo is heated with water to boiling, and to the liquid concentrated nitric acid is added, until the blue color has completely dis appeared. By repeatedly boiling the mass with^ water, the isatin formed is dissolved, and, on cooling, it gradually crystallizes out. It may now be purified by dissolving* in potassa, precipitating with hydrochloric acid and recrystallizing. Yellowish-red prisms, of a strong lustre; soluble in alcohol, forming a brown-red solution; in cold potassa- ley forming a violet solution; fusible; partially sub- limable without decomposition. Combines with the alkaline bisulphites, forming crystallizing compounds. When distilled with concentrated- potassa-ley, anilin passes over, hydrogen being at the same time set free. Suspended in water, and treated .with nitrous acid, it is converted into nitrosalicylic acid (p. 346)> a gas being evolved at the same time ; treated with ammonia in an alcoholic solution, it yields a large number ^ of crystallizing compounds, the composition of which shows that they have resulted from isatin by the addi tion of ammonia and the elimination of water. Chlorisatin, C8H4C1K02. Is produced by the action of chlorine gas on a boiling-hot solution of isatin in water, it being thrown down under these circumstances as a yellow, nocky precipitate ; further, together with secondary products, by conducting chlorine into pure indigo mixed with water. From the crude product thus obtained, the chlorisatin is extracted by means of boiling water, and separated by means of crystalli zation from dichlorisatin, C8II3Cl2iSr02, which is formed at the same time, and is more easily soluble in water. — Orange-yellow, transparent, four-sided prisms, of bitter taste ; inodorous ; scarcely soluble in cold water, soluble in alcohol; partially sublimable. — Towards bromine it conducts itself in the same way. The sub- 388 ISATOSULPHURIC ACID. stitution-products of isatin are decomposed by fusing caustic potassa like isatiri, substitution-products of ani- lin being formed. Isatosulphuric acid, C8H4N02.S02.OH, is formed by the action of potassium bichromate and sulphuric acid on sulphindigotates (indigo-carmine). — Difficultly crystallizable, very easily soluble acid ; monobasic. Its barium salt, (C8H4NS05)2Ba + 4H20, forms brass-red, strongly lustrous, crystalline scales, but slightly soluble in cofd water. Trioxindol (Isatic acid), C8H7N03. The violet solu tion of isatin in potassa-ley becomes yellow when boiled, and then contains potassium isatate. The free acid is exceedingly unstable ; when the attempt is made to set it free by means of another acid, it breaks up into isatin and water. The substitution-products of isatin conduct them selves towards caustic potassa in like manner. They yield chlorinated or brominated isatic acids, which are likewise exceedingly unstable in a free condition. Dioxindol (Hydrindic acid), C8H7N02, is formed by the action of sodium-amalgam on isatin, to which is added water, by reduction of the isatic acid, which is at first formed. — Transparent, rhombic prisms ; easily soluble in water and alcohol ; fuses at 180°, and decom poses at 195°, anilin being formed. The aqueous solu tion in contact with air turns red, oxygen being taken up and isatin formed. Combines with acids and bases, forming salts. Treated with chlorine or bromine it yields crystallizing substitution-products. Treated with nitrous acid in an alcoholic solution, it is at first con verted into a crystalline substance, nitrosodioxindol, C8H6(NO)M)2, insoluble in water; fusing at 300-310° ; further action converts it into ethyl benzoate and other products. It yields oil of bitter almonds when gently warmed with nitric acid or silver oxide. OXINDOL. 389 Oxindol, C8H7l!s"0. Is formed by further reduction of dioxindol with tin and hydrochloric acid or with sodium-amalgam in a dilute solution, kept constantly acid.— Long, colorless needles or feathery groups. Difficultly soluble in cold water, easily soluble in hot water and in alcohol; fuses at 120° ; and in small quan tities, it can be distilled without undergoing decom position. When its aqueous solution is evaporated in contact with air, it becomes partially oxidized again, forming dioxindol. Like dioxindol, it yields crystal lizing salts- with acids, as well as bases. Nitrous acid transforms it in very dilute aqueous solutions into nitrosb-oxindol, C8II6(]TO)NO, a substance that crystal lizes in long, golden needles, difficultly soluble in water. Indol, C8IKN". Is formed when the vapors of oxin- dol are conducted over heated zinc-dust ; or when in digo-blue is boiled with zinc and hydrochloric acid until it is converted into a brownish-yellow powder, and this then distilled with an excess of zinc-dust. It is also formed in small quantity when nitroeinnamic acid is fused with potassium hydroxide with an addi tion of iron filings. — Large, colorless laminse similar to benzole acid ; fusing point, 52° ; not distillable alone, but very well with water vapor. Very weak base. "With hydrochloric acid, it forms a difficultly soluble salt, which, when boiled with water, yields free indol. Isatyde, C16H12N204, is formed by heating isatin with dilute sulphuric acid ; or when its warm saturated alcoholic solution is mixed with ammonium sulphy- drate in a closed flask, and allowed to stand for some time, it being deposited gradually in the form of crys talline scales. It bears the same relation to isatin, as indigo-white bears to indigo-blue. — Colorless, fine crys talline inodorous and tasteless substance, insoluble in water, but slightly in alcohol. Sulphisatyde, C16H12N202S2. When sulphuretted hydrogen is conducted into an alcoholic solution of ° 33* 390 INDIN. isatin, a mixture of sulphur and isatyde is thrown down, and the solution contains sulphisatyde, which is precipitated when the solution is allowed to drop in water. — Grayish-yellow, pulverous substance ; becomes soft in hot water, soluble in alcohol, not crystallizable. Indin, C16H10N202, isorneric with indigo-blue; is formed when sulphisatyde is well mixed with alcohol, and a solution of potassa gradually added ; and the mass, when it has become red, washed out with water. — Beautiful rose-colored, crystalline powder ; insoluble in water, but slightly soluble in alcohol. It dissolves, when warmed with alcoholic potassa, and, on cooling, indm-potassium, C16H9N202K, is deposited in small black crystals. III. NAPHTHALENE-DERIVATIVES. THE bodies of this group are derived from naphtha lene C10H8, in the same way as the aromatic compounds are derived from benzene. Naphthalene is constituted very similarly to benzene ; it consists of two benzene- groups, which are so united that they have two carbon atoms in common : — CH:CH.C.CH:CH CH:CILC.CH:CH A. HYDROCARBONS, CnlI2n-12- 1. Naphthalene. C10H8. Formation. By the dry distillation of a great many organic substances at a high temperature, particularly when the distillation-products are conducted through a red-hot tube. It is hence contained in coal-tar and wood-tar. It is also formed from alcohol, acetic acid, and a number of other substances, when their vapors are passed through red-hot tubes. Preparation. Most advantageously from coal-tar oil by partial distillation and strong cooling of the distil late between 180 and 220°. The crude naphthalene thus separated is purified by recrystallization from hot alco hol, or, better, by means of sublimation. Properties. Large, lustrous, colorless crystalline la- minse of peculiar odor and burning taste. Fuses at 80° ; boils at 218°, and sublimes at a lower tempera ture ; insoluble in water, but slightly in cold alcohol, 392 NAPHTHALENE. easily in hot alcohol and in ether. Distils over readily with water. Burns with a luminous sooty flame. Combines with picric acid, forming a compound, CIOJP + C6H3(1TO2)30, which crystallizes in stellate, yellow needles. When oxidized with nitric acid, it yields phtalic acid (p. 362). When heated with phos- phonium iodide to 170-190°, it yields a liquid hydro carbon, C10H12 ; boiling point, 201°. With chlorine it forms products of addition and sub stitution. Naphthalene dichloride, C10IP.C12, pale yellow oil, heavier than water, and insoluble in it. Naphthalene tetrachloride, C10H8.C14, transparent rhombohedral crystals ; fusing point, 182° ; difficultly soluble in alcohol and ether. Chlornaphthalene tetrachloride, C10H7C1.C14, klinorhombic prisms ; fusing point, 128-130°. Dichlornaphthalene tetrachloride, C10II6C12.C14, klinorhombic prisms ; fusing point, 172°. When these chlorine compounds are boiled with alcoholic potassa, hydrochloric acid is given off and chlorine-substitution-products of naphthalene are formed. These, when further subjected to the action of chlorine, again form addition-products and substi tution-products, containing more chlorine. Monochlornaphthalene, C10II7C1. Colorless liquid; boiling point, 250-252°. a-Dichlornapthalene, C10IPC12. Crystalline mass ; fusing point, 35-36° ; boiling point, 282°. /3-Dichlornaphthalene, C'°II6C12. Colorless prisms ; fusing point, 68° ; boiling point, 281-283°. Trichlornaphthalene, C10H5C13. Brittle prisms; fusing point, 81°. NAPHTHALENE. 893 Tetrachlornaphthalene, CIOH4C14. Colorless nee dles ; fusing point, 130°. Enneachlordinaphthalene, C20H7C19. The end- product of the action of chlorine on heated chlorinated naphthalene. — "White, delicate needles; fusing point, 156-158°. Pentachlornaphthalene, C10H3C15. Is formed by the action of phosphorus chloride on dichlornaphtho- quinone and chloroxynaphthalenic acid. — Colorless nee dles ; fusing point, 168.5°. Perchlornaphthalene, C10C18. Prisms ; fusing point, 135°. Naphthalene yields substitution-products with bro mine, but does not combine directly with it. — Mono- bromnaphthalene, C10II7Br. Colorless liquid ; boiling point, 211°.—a-Dibromnaphthalene, C^IFBr2. Long needles of a silky lustre ; fusing point, 81°. — p-Dibrom- naphthalene, C10H6Br2, is formed together with the a-compound when bromine acts upon a-sulphonaphtha- lic acid. Needles; fusing point, 126-127°. — Tribrom- naphthalene, C10H5Br3. Colorless needles ; fusing point, 750. — Tetrabromnaphthalene, C10H4Br4. Colorless prisms, but slightly soluble in alcohol. — Pentabromnaphthalene, C10H3Br5. Colorless granular crystals, insoluble in alcohol. a-Cyannaphthalene, C10H7.CN, is formed by the distillation of a mixture of potassium a-sulpho- naphthalate with potassium cyanide. Is also formed when naphthylamine oxalate is distilled, and the distil late, which contains a great deal of naphthylformamide, heated with concentrated hydrochloric acid. — Color less, broad needles; insoluble in water, easily soluble in alcohol*. Fuses at 37.5° ; has a strong tendency to remain liquid, and boils without undergoing decompo sition at 297-298°.— p-Cyannaphthalene, C10H7.CK Is obtained in the same way from potassium j3-sulpho- 394 NAPHTHALENE. naphthalate. — Colorless laminae ; fusing point, 66.5° ; boiling point, 304-305°. Nitronaphthalene, C10H7(N02), is formed by the action of concentrated nitric acid on naphthalene ; slowly at the ordinary temperature, rapidly by boiling. — Crystallizes from alcohol in sulphur-colored prisms ; fusing point, 58.5°, and sublimes when carefully heated; insoluble in water, easily soluble in alcohol and ether. a-Dinitronaphthalene and p-Dinitronaphthalene, Clori6(lTO2)2, are produced simultaneously when the preceding compound, or naphthalene, is boiled with nitric acid until no oily body (melted nitronaphtha- lene) can be detected on the surface of the liquid. The two compounds may be separated by boiling with alcohol, in which the a-compound is more easily solu ble; and crystallizing from chloroform. a-Dinitro- riaphthalene crystallizes in four- or six-sided rhombic plates, that detonate when heated; fusing point, 170° ; j3-dinitronaphthalene crystallizes in colorless, sublima- ble prisms, that fuse at 214°. — If the boiling with nitric acid is continued for several days trinitronaphtha- lene, C10H5(X02)3, is formed; small, monoclinate prisms, fusing at 214°. When this is heated for a long time with fuming nitric acid in sealed tubes at 100°, it is converted into tetmnitronaphthalenc, C10II4(N02)4, which crystallizes in fine needles, resembling asbestos; fusing point, 200°. Naphthylamine (N"aphthalidine), C10H7.^H2, is produced from nitronaphthalene in the same way that anilin is produced from nitrobenzene (cf. p. 258). — Fine, colorless prisms, of an unpleasant odor; almost insolu ble in water, easily soluble in alcohol ; fuses at 50° ; sublimes easily, and boils at 300°. Turns t gradually red in contact with the air. Combines with acids, forming crystallizing and, for the greater part, easily soluble salts. Oxidizing agents, iron chloride, silver nitrate, chromic acid, tin chloride produce a blue pro- NAPHTHALENE. 395 cipitate in the solutions of these salts, which is rapidly converted into a purple-red, amorphous powder, oxy- naphthylamine, C10H9XO. When nitrous acid is allowed to act on naphthy- lamine, diazocompounds are formed as in the case of anilin. Sulphonaphthalic acids, C10H7.S02.OH. When naphthalene is carefully heated with sulphuric acid, two isomeric sulphonaphthalic acids are formed, which may be separated hy partial crystallization of the lead or barium salts. Both salts of a-sulphonaphthalic acid are much more easily soluble in water and alcohol than those of the j3-acid. The a-acid, when heated, is converted into the j3-acid, and hence, when naphtha lene is treated with sulphuric acid at an elevated tem perature (160°), the product consists almost entirely of j3-sulphonaphthalic acid. Barium a-sulphonaphthalate, (C10H7.S03)2Ba-h H20. Colorless laminae ; soluble in 87 parts water and 350 parts alcohol (of 85 per cent.) at 10°. The lead salt, (C10H7S03)2Pb + 3H20, forms lustrous, colorless laminae; soluble in 27 parts water and 11 parts alcohol at 10°. Barium £-sulphonaphthalate,(C10H7.S03)2Ba + IPO. Colorless laminae; soluble in 290 parts water and 1950 parts alcohol at 10°. — The lead salt crystallizes in small, hard scales, with varying amounts of water of crys tallization ; soluble in 115 parts water and 305 parts alcohol at 10°. Naphthalene sulpho chlorides, C10H7.S02C1, are obtained by gently heating potassium a- and )3-sulpho- naphthalate with phosphorus chloride. The ^.-chloride forms lustrous laminae; easily soluble in ether; fusing at 66° ; the ^-chloride is more difficultly soluble in ether, and fuses at 76°. Disulphonaphthalic acid, C10H6(S02.OH)2,is formed by continued heating of naphthalene with an excess 396 NAPHTHALENE. of sulphuric acid. — Bibasic acid. The barium salt, C10H6S206Ba, is much less easily soluble in water, and particularly in alcohol, than the sulphonaphthalates. Mercurynaphthyl, (CIOH7)2Hg. Is formed by con tinued boiling of a solution of monobromnaphthalene in benzene with sodium-amalgam. — Small, colorless, rhombic, columnar crystals. Insoluble in water, diffi cultly soluble in boiling alcohol, easily in carbon bisul phide and in chloroform. Fuses at 243° ; not volatile without decomposition ; combines directly with iodine ; and, when heated with hydriodic, hydrobromic, or hydrochloric acids, it yields naphthalene and mercury iodide, bromide, or chloride. Conducts itself exactly like mercuryphenyl (p. 272). Dinaphthyl, C20H14 = (C10H7)2, is formed by the decomposition of monobromnaphthalene with sodium ; and by heating naphthalene with black oxide of man ganese and sulphuric acid. — Colorless laminse, of a mother-of-pearl lustre. But slightly soluble in cold alcohol, easily soluble in ether ; fuses at 154° ; and is sublimable without decomposition. "When further oxidized with black oxide of manganese and sulphuric acid, it is converted into phtalic acid (p. 362). 2. Methylnaphthalene. CUH10 = C10H7.CIP. Is obtained by the action of sodium on a mixture of monobromnaphthalene and methyl iodide, diluted with ether. — Colorless, clear, somewhat viscid liquid; specific gravity, 1.0287; boiling point, 231-232°; does not congeal at — 18°. 3. Mhylnaphihalene, C12H12 = C10H7.CH2.CH3. Is formed like methylnaphthalene. — Colorless, clear li quid; specific gravity, 1.0184; boiling point, 251-252°; still liquid at —14°. NAPHTHOL. 397 B. PHENOLS. 1. Naphthol (a-Naphthol). C10H80 = C10H7.OH. Is formed by heating potassium a-sulphonaphthalate with potassium hydroxide. — Colorless, monocliiiate prisms ; fusing point, 94° ; boiling point, 270-280° ; almost insoluble in cold water, somewhat soluble in hot water, easily in alcohol and ether. Towards alka lies it conducts itself like phenol (p. 290). Naphthol-ethylether, C10H7.O.C2H5. By heating naphthol-potassium with ethyl iodide. — Colorless liquid ; boiling point, 272° ; does not congeal at — 5°. Naphthol-acetate, C10H7.O.C2H30. By the action of acetyl chloride on naphthol. — Yellowish liquid, in soluble in water. Nitronaphthol, C10H6(N02).OH. Is formed, when 1 part nitronaphthalene is heated in a current of air for a long time at 140°, intimately mixed with 1 part potassium hydroxide and 2 parts calcium hydroxide, and the aqueous extract from the mass decomposed with hydrochloric acid. — Bright-yellow, light mass; crystallizing from acetic acid or acetone in golden-yel low prisms ; fusing point, 151-152°. Dinitronaphthol, C10H5(1TO2)2.OH. Cannot be pre pared directly from naphthol. Is, however, readily obtained by pouring nitric acid (specific gravity, 1.35) upon naphthylamine ; and by gently heating a solution of sulphonaphthalic acid, to which is added nitric acid. Is also formed by boiling diazonaphthalene hydrochlor- ate (from naphthylamine hydrochlorate with nitrous acid) with nitric acid. — Lustrous sulphur-colored crys tals ; fusing point, 138° ; almost insoluble in boiling water, difficultly soluble in alcohol and ether, more easily in chloroform. With bases it yields salts ; and liberates 34 398 NAPHTHOL. carbonic acid from its salts. The sodium and calcium salts are excellent' yellow dyes (naphthalene yellow). Diamidonaphthol, C10H6(KH2)2.OH. Cannot be isolated and obtained in a free condition. Its double salt with stannous chloride, C10IP(NH2)2.OH + 2HC1 + SnCl2 + 2H20, is obtained by heating dinitronaphthol with tin and hydrochloric acid. It crystallizes in large, lustrous, monoclinate prisms. "When its solution is precipitated with sulphuretted hydrogen, a solution of diamidonaphthol hydrochlorate is obtained, which, in contact with air, and rapidly on the addition of iron chloride, yields diimidonaphthol hydrochlorate C10H5(OH) | ^> + HC1. This salt crystallizes in large columnar or tabular crystals of a metallic lustre, which in transmitted light are dark red ; in reflected light, green. With ammonia it yields diimidonaphthol, C10H5(OH)(HN)2, a yellow crystalline body, almost in soluble in water. Naphtholsulphuric acid, C10H6 j ®^ OH By heating naphthol with double its weight of concentra ted sulphuric acid. The free acid, separated from the lead salt, forms long, colorless, deliquescent needles ; fusing point, 101° ; its solution is colored deep blue on the addition of iron chloride ; if heated it becomes green. Naphthyl sulphydrate, C10H7.SH. Is formed by the action of zinc and dilute sulphuric acid ona-naphthyl sulphochloride. — Colorless liquid, insoluble in water; boiling point, 285° ; volatile with water vapor ; yields salts with bases. Naphthyl disulphide, (C10H7)2S2. Is formed by the spontaneous evaporation of an ammoniacal alcoholic solution of the sulphydrate in contact with air. — Yellowish, transparent crystals ; fusing point, 85°. ISDN API! TIIOL. 399 2. Isonaphthol (s-Naphthol). CioH80 ^ C10H7.OH. Is obtained, like naphthol, from potassium /3-sulpho- naphthalate.— Small, colorless, rhombic plates ; fusing point, 122° ; boiling point, 285-290° ; easily sublim- able. Difficultly soluble in boiling water ; easily in alcohol and ether. The derivatives of isonaphthol are prepared like those of n^phthol. Isonaphthol-ethylether, C10H7.O.C2H5. Colorless, crystalline mass ; fusing point, 33°. Isonaphthpl-acetate, C10II7.O.C2II30. Small, color less needles ; fusing point, 60°. Dinitro-isonaphthol, C10H5(N02)2.OH. Is obtained by warming an alcoholic solution of isonaphthol with dilute nitric acid. — Lustrous, bright-yellow needles ; fusing point, 195°. iOTT S02.OII. Small, colorless laminated crystals ; fusing point, 125° ; not deliquescent, but easily soluble in water and alco hol. The aqueous solution turns slightly green on the addition of iron chloride, and, when heated with it, it deposits brown nocks. Isonaphthyl sulphydrate, C10H7.SH. Small, lus trous scales ; fusing point, 136° ; not volatile with water vapor ; insoluble in water ; easily soluble in ether and alcohol. 3. Dioxynaphthalene. C10H802 = CIOH6(OH)2. Is obtained by melting potassium disulphonaphtha- late with potassium hydroxide. — Colorless needles, which become violet in the air; difficultly soluble in water, easily in alcohol and ether ; s.ublimable ; in an alkaline solution it absorbs oxygen rapidly from the air, and turns black. 400 QUINONES. 4. Trioxynaphthalene. CioH803 = CIOIF(OII)3. Is formed by the action of tin and hydrochloric acid on oxynaphthoquinone, and after the solution has been freed from tin by sulphuretted hydrogen, it can be extracted by means of ether. — Yellow needles ; so luble in water, alcohol, and ether ; the solutions, which are at first colorless, turn yellow and brown in the air. Is a strong reducing agent, especially in alkaline solution, C. QUINONES. Naphthoquinone, C10H6| Q>, is as yet not known. Only substitution-products and other derivatives of it have been discovered. Dichlornaphthoquinone (Chloroxynaphthalene chloride), C10H4C12 j Q>. Is produced by the action of nitric acid on chlornaphthalene chloride. Can be most easily prepared by treating naphthol or commercial naphthalene yellow (see Dinitronaphthol p. 397) with hydrochloric acid and potassium chlorate, or by the addition of chromium oxichloride to a solution of naphthalene in concentrated acetic acid. — Golden-yel low needles ; fusing point, 189° ; insoluble in water, but slightly in cold alcohol and in ether, more readily in hot alcohol ; easily sublimable. Hot concentrated nitric acid converts it into phtalic acid. Sulphurous acid and hydriodic acid convert it into dichlordioxy- naphthalene, C10H4C12(OH)2, which crystallizes in reddish- colored needles, that fuse at 135-140°, and are recon verted into dichlornaphthoquinone by iron chloride. — Heated with two molecules phosphorus chloride at 180- 200°, dichlornaphthoquinone is transformed into penta- chlornaphthalene (p. 393). A Oxynaphthoquinone (Naphthalic acid), C10IP(OH) j Q>. Is most readily obtained by heating DIOXYNAPHTHOQUINONE. 401 diimidonaphthol hydrochlorate (p. 398) with dilute hydrochloric or sulphuric acid at 120°.— Bright yellow, electric powder, or yellow needles ; sublimes partially when carefully heated, condensing in reddish-yellow needles. Almost insoluble in cold water, somewhat soluble in boiling water, easily in alcohol and ether. It combines with nascent hydrogen, forming trioxy- naphthalene. — It conducts itself as a moderately strong monobasic acid towards bases, and liberates carbonic acid from its salts. The alkaline salts are blood-red and easily soluble in water. Chloroxynaphthoquinone (Chloroxynaphthalic acid), C10H5C103 = G10H4C1(OH) j Q>. The potassium salt, C10H4C1(OK)02, is obtained, when dichlornaphtho- quinone is placed under alcohol, and concentrated po- tassa-ley then added. It forms cherry-colored needles, which are but slightly soluble in cold water, easily so luble in hot water ; hydrochloric acid throws down the free acid from this solution.— Straw-colored, crystalline powder ; fuses somewhat above 200°, and sublimes in needles ; but slightly soluble in cold water, moderately in boiling, more easily in alcohol and ether. Strong monobasic acid ; its salts, when heated, give a sublim ate of phtalic anhydride. Heated with phosphorus chloride, pentachlornaphthalene is formed. Dioxynaphthoquinone (Naphthazarin), C'°H604 = C10II4(OH)2 | S>. Is obtained by simultaneously add ing /3-dinitronaphthalene and zinc in small quantities to concentrated sulphuric acid heated to 200°. Subse quently the mass is diluted with water, boiled, filtered boiling hot and the gelatinous mass, that separates on cooling, purified, when dried, by means of sublimation. Long needles with a beautiful green metallic lustre. But slightly soluble in boiling water, more easily in alcohol, the solution having a red color. It dissolves in ammonia forming a sky-blue solution, which turns reddish-violet on standing. Its solution gives beauti- 34* 402 NAPHTHOIC ACID. ful violet precipitates with baryta and lime-water. Excellent dye, very similar to alizarin. " D. ACIDS. 1. Naphihoic Acid (Menaphthoxylic Acid). Q.1JJ8Q2 ^ C10H7.CO.OH. Formation. From a-cyannaphthalene (p. 393), by boiling with alcoholic potassa, and decomposing the po tassium salt thus formed with hydrochloric acid. Its ether is also formed by the action of sodium-amalgam on a mixture of monobromnaphthalene and ethyl chlor- carbonate ; its potassium salt, by fusing a mixture of potassium a-sulphonaphthalate with sodium formate. Properties. Colorless crystalline needles ; fusing point, 160° ; difficultly soluble in boiling water, easily soluble in boiling alcohol. Heated with baryta, it is resolved into naphthalene and carbonic acid. Barium naphthoate, (CnII702)2Ba + 4H20, and Calcium naphthoate (CnII702)2Ca + 2H20, are diffi cultly soluble in water (the calcium salt in 93 parts at 15°) ; and crystallize in colorless needles. Ethyl naphthoate, C10H7.CO.O.C2H5. Liquid of an aromatic odor ; boiling point, 309°. Naphthoyl chloride, C10H7.COC1. By the action of phosphorus chloride on naphthoic acid. — Liquid ; boils at 297.5° ; congeals at a low temperature. Naphthoylamide, C10H7.CO.]$rH2. Is obtained by the action of ammonia on the chloride ; and by dissolv- ving a-cyannaphthalene in alcoholic soda-ley and pre cipitating with water. — Colorless needles ; fusing point, 204° ; insoluble in water, difficultly soluble in alcohol ; sublimable. 2. Isonaphthoic Acid (jB-Naphthoic Acid). CnH802= C10H7.r^ Is obtained from P-cyannaphthalene like naphthoic OXYNAPHTHOIC ACID. 403 acid.— Long, colorless needles ; fusing point, 182°; boils above 300° without undergoing decomposition. But slightly soluble in boiling water, easily soluble in alcohol and ether. Heated with barium hydroxide, it is resolved like naphthoic acid into carbonic acid and naphthalene. Barium isonaphthoate (CnH702)2Ba + 4H20, and Calcium isonaphthoate (C^IFO^Ca + 3H20, crys tallize in needles and are insoluble in cold water (in 1400-1800 ^arts at 15°). 3. Oxynaphthoic Acid (Carbonaphtholic Acid). The sodium salt is produced by the simultaneous ac tion of sodium and carbonic anhydride on a-naphthol. Hydrochloric acid precipitates the acid from the solu tion of this salt. — Small, stellate, colorless needles ; fusing point, 185-186°; but slightly soluble in water even at boiling temperature, easily soluble in alcohol and ether. Its salts are, for the greater part, difficultly soluble in water. These solutions are turned deep blue by iron chloride. $-Naphthol (p. 399), when treated in the same way, yields with difficulty an isomeric oxyacid of similar properties. IV. ANTHRACENE-DERIVATIVES. ANTHRACENE, the substance from which the bodies of this group are derived, has a chemical constitution similar to that of benzene and naphthalene. It bears the same relation to naphthalene that the latter bears to benzene. It may be considered as a combination of three benzene-rings, of which each one has two carbon atoms in common with one or both the others : — CH:CH.C.CH:C.CH:CH CH:CH.C.CH:C.CH:CH Anthracene. C14H10. Formation. By dry distillation of anthracite coal ; hence contained in coal-tar. By heating benzyl chlo ride (p. 274) with water at 190°, together with liquid ditolyl (p. 282) and benzylic ether (p. 313). Preparation. From those portions of coal-tar, that boil at high temperatures, by means of repeated dis tillations, pressing, and recrystallizing from benzene. To obtain it perfectly pure and colorless, it must be sublimed at as low a temperature as possible, best by heating it until it begins to boil, and then blowing a strong current of air over it by means of a pair of bel lows. Or the solution in hot benzene is bleached in direct sunlight. Properties. Colorless, monoclinate plates ; when per fectly pure exhibiting a beautiful blue fluorescence ; fusing point, 213°; boiling point, somewhat above ANTHKACENE. 405 360°. Insoluble in water, difficultly soluble in alcohol and ether, easily in boiling benzene, less soluble in cold benzene. Heated with picric acid and benzene, it yields a compound, C14H10 + 2C6H3(]TO2)30, that crys tallizes in red needles. Paranthracene, C14H10. When a cold saturated solution of anthracene in benzene is exposed to direct sunlight, tabular crystals of this compound, which is isomeric or polymeric with anthracene, are deposited. It is almost insoluble in benzene, and is much more stable than anthracene ; it is attacked neither by bro mine nor hot concentrated nitric acid. It fuses at 244°, and is at this temperature reconverted into anthracene. Anthracene dihydride, C14H12. Is formed by heat ing anthracene with hydriodic acid and a little phos phorus at 160-170° ; and by gently heating it for a long time with alcohol and sodium-amalgam. — Small, color less, monoclinate plates; fusing point, 106°; boiling point, 305° ; sublimes readily in the form of needles. Easily soluble in alcohol and ether. When conducted in the form of vapor through a tube heated to low red- heat, it is resolved into anthracene and hydrogen. Heated with concentrated sulphuric acid, it yields sul phurous anhydride and anthracene ; with bromine and oxidizing agents, the same products as anthracene. Anthracene hexahydride, C14H16. Is obtained by heating the preceding compound for a long time with hydriodic acid and a little phosphorus at 200-220°. — Colorless laminse; fusing point, 63°; boiling point, 290°. Very easily soluble in alcohol, ether, and ben zene. At red-heat it is broken up, like the dihydride, into anthracene and hydrogen. Anthracene forms addition- and substitution-pro ducts with chlorine and bromine. Anthracene dichloride, C14H10C12. Long, radiating needles ; easily soluble in alcohol, but slightly soluble in ether. 406 ANTIIRAQUINONE. Monpchloranthracene, C14II9C1. Is obtained di rectly from anthracene in a current of chlorine gas; and by decomposing the dichloride with alcoholic potassa. — Small, hard, scaly crystals. — Dichloranthra- cene, C14H8C12. Yellow laminae or needles ; fusing point, 205°; sublimable.— Tetmchlomnthracene,CuII6Cl*. Stel late, gold-colored needles ; fusing point, 220°. Dibromanthracene, C14H8Br2, is formed alone when bromine is added to a solution of anthracene in carbon bisulphide. — Gold-colored needles ; fusing point, 221°. Heated with alcoholic ammonia at 160-170°, it is reconverted into anthracene. — Dibromanthracene tetrabromide, C14H8Br2.Br4, is formed when bromine vapor is allowed to act on finely divided anthracene or dibromanthracene. — Hard, thick, colorless plates ; fuses at 170-180°, undergoing decomposition. — Tri- bromanthracene, C14H7Br3, by heating the preceding compound to 200.° — Yellow needles ; fusing point, 169° ; sublimable. — Tetrabromanthracene, C14H6Br4. From dibromanthracene tetrabromide with alcoholic potassa. — Yellow crystals ; fusing point, 254°. Nitroanthracene, C14H9(N"02). Is obtained by heat ing an alcoholic solution of anthracene with nitric acid. — Stellate, red needles. Insoluble in cold alcohol and benzene, difficultly soluble in the hot liquids. Sublimable. Anthraquinone ( Oxanthracene). .Formation and preparation. By the oxidation of anthracene, dichlor-, or dibromanthracene with nitric or chromic acid. Can be most readily prepared by adding a solution of chromic acid in glacial acetic acid, or finely powdered potassium bichromate, to a hot solution of anthracene in glacial acetic acid. Properties. Purified by sublimation, it forms lus trous, yellow needles; fusing point, 273° ; insoluble in ANTHRAQUINONE. 407 water, but slightly soluble in alcohol, ether, and cold benzene, more easily in hot benzene. Very stable; alcoholic potassa-ley produces no effect upon it. Heated with hydriodic acid at 150°, or with zinc-dust, it is converted into anthracene. Fused with caustic potassa it yields benzoic acid. Dichloranthraquinone, C14H6C1202. Is obtained by oxidizing tetrachloranthracene like anthraquinone. — Yellow needles. Monobromanthraquinone, C14II7Br02. By oxida tion of tribromanthracene. — Bright-yellow needles; fusing point, 187° ; sublimable. — Dibromanthraquinone, C14H6Br202. By heating anthraquinone with two molecules bromine at 100° ; more readily by oxidizing tetrabromanthracene. — Bright-yellow needles ; sub limable. Dinitroanthraquinone, C14H6(lSr02)202. Is formed together with anthraquinone, by heating anthracene with dilute nitric acid. From the solution of the pro duct in a great deal of hot alcohol, it separates first on cooling. It is more readily obtained by the action of nitric-sulphuric acid on anthraquinone. — Small, bright- yellow, monoclinate crystals; difficultly soluble in alcohol, ether, and benzene ; sublimes in the form of yellow needles, at the same time undergoing partial decomposition. Combines with hydrocarbons, the same as picric acid, forming very characteristic com pounds. Diamidoanthraquinone, C14H6(^H2)202. Is ob tained from dinitroanthroquinone by warming with tin and hydrochloric acid, or with a solution of sodium sulphydrate. — Small, cinnabar-colored needles ; fusing point, 236°. Scarcely soluble in water, soluble in alco hol, ether, and concentrated acids. Sublimes in garnet- colored, flat needles. Very weak base. From its solutions in acids it is thrown down in a free condition on the addition of water. 408 ALIZARIN. Anthraquinonedisulphuric acid, C14H602(S02.OH)2. Dichlor- and dibromanthracene dis solve readily in fuming sulphuric acid with the aid of gentle heat, forming dichlor-or dibromanthracenedisul- phuric acids, C141PC12(S02.OH)2, which when treated with oxidizing agents, and also when heated with concentrated sulphuric acid, are easily converted into anthraquinonedisulphuric acid. The barium salt, C14H602.(S03)2Ba, is difficultly soluble in water. Oxyanthrajuinone, C14H803 = C14H7(OH)02. Is formed by fusing potassium anthraquinonedisulphate with potassium hydroxide, when the action is moder ated by the addition of indifferent bodies (sodium chloride, chalk). — Yellow laminae or needles, sublim- able. Soluble in alkalies and baryta-water forming reddish-brown solutions. Alizarin (Dioxyanthraquinone), C14H804 = C14H6(OH)202. Is contained in old madder, and is ob tained from rubianic acid (see Glucosides, p. 418), which is contained in fresh madder, by boiling with acids or alkalies. It can be artificially prepared by heating dichloranthraquinone, mono- or dibromanthraquinone, oxyanthraquinone and potassium anthraquinonedisul phate with potassium hydroxide at 250-270°. The mass is then dissolved in water, precipitated with hy drochloric acid, and the precipitate purified by recrys- tallization from alcohol, or, better, by sublimation. — Long, orange-red needles. Carefully heated, sublim- able without decomposition. Almost insoluble in cold water, more easily in boiling water, in alcohol and ether. Towards bases it conducts itself like a weak bibasic acid ; soluble in alkalies, forming purple solutions. The alcoholic solution g;ives blue precipitates, C14H6(02Ba)02 + IPO and C14H6(02Ca)O2 + H20, with baryta- or lime-water ; the solution in alkalies gives a beautiful red precipitate (madder lake) with a solution of alum. CHKYSOPHANIC ACID. 409 When heated with zinc-dust, alizarin is converted into anthracene ; when oxidized with nitric acid, phta- lic acid is the product. Excellent dye. Chrysophanic acid (Parietic acid, Eheic acid), OWH^OHJW or C14H8(OH)202 (isomeric with alizarin or an analogous derivative of anthracene dihydride). Is contained in the lichen Parmelia parietina ; in rhubarb (the root of various species of Rheum) ; and in senna leaves (from*Cassia lanceolata and Cassia obovata). Can be readily obtained from these plants by extracting with caustic potassa, precipitating with hydrochloric acid and recrystallizing from chloroform. — Yellow, lustrous prisms ; fusing point, 162° ; partially sublimable ; al most insoluble in water, but slightly in alcohol, easily soluble in ether. Soluble in alkalies, the solutions being red. Heated with zinc-dust it is converted into anthracene. Chrysammic acid (Tetranitro- Dioxyanthraqui- none), C14H2(2s"02)4(OH)202. Is formed by warming crysophanic acid and aloes (see Aloin) with concentrat ed nitric acid. — Golden yellow, lustrous laniinse, very similar to lead iodide. But slightly soluble in water. Strong bibasic acid. Reducing substances (hydriodic acid, zinc and dilute sulphuric acid, potassium sul phide) convert it into hydrochrysamide, C14IP(OTI2)3 (N02)(OH)202, a body that forms indigo-colored nee dles; sublimable, when carefully heated ; insoluble in water. Purpurin (Trioxyanthraquinone), C14H805 = C14H6(OH)302. Is contained in old madder, and is also sometimes formed as a by-product in the artificial pre paration of alizarin. — Reddish-yellow prisms. Easily fusible and sublimable. Somewhat more easily solu ble in water than alizarin, easily soluble in alcohol, ether, and alkalies, the solutions having a red color. It gives purplish-red precipitates with lime- and baryta-water. When heated with zinc-dust it is con verted into anthracene. 35 410 PYRENE. Anthracenecarbonic Acid. c,5Hio02 = C14H9.CO.OH. Preparation. By heating anthracene with phosgene in sealed tubes for twelve hours at 200°, dissolving the product in a solution of sodium carbonate, and precipi tating with hydrochloric acid. Properties. Long bright-yellow needles of a silky lustre. Fuses at 206°, with decomposition. Almost insoluble in cold water, difficultly in boiling water, easily soluble in alcohol. Heated alone or with soda- lime, it is resolved into anthracene and carbonic acid. When its solution in glacial acetic acid containing chromic acid is gently warmed it is converted into anthraquinone. Most of its salts are soluble in water and alcohol. In connection with this group, a few hydrocarbons that are not so well known, will here be described. Pyrene, C16H10 (isomeric with diacetenylphenyl, p. 379). Is contained in those portions of coal-tar that boil at a high temperature. Those hydrocarbons that boil higher than anthracene are extracted by means of carbon bisulphide. Crude chrysene (p. 411) is thus left behind, while pyrene and other hydrocarbons are dis solved. In order to purify the pyrene, the carbon bisulphide is distilled off, the residue dissolved in alco hol, and mixed with an alcoholic solution of picric acid. Red crystals of a compound of pyrene with picric acid are deposited, which, after repeated recrys- tallizations from alcohol, are decomposed with ammo nia. — Colorless lamine ; fusing point, 142° ; but slightly soluble in cold alcohol, more readily in hot alcohol, very easily soluble in benzene, ether, and carbon bisul phide. Nitric acid readily converts it into substitution-pro ducts ; bromine yields substitution- and addition-pro ducts. Heated with potassium bichromate and dilute sulphuric acid, it is converted into pyrenequinone. CHRYSENE. 411 C16H802, a brick-red powder, which, when heated sub limes partially in red needles and decomposes partially. Chrysene, C18H12. That portion of the high-boil ing hydrocarbons of coal-tar (see Pyrene), which is in soluble in carbon bisulphide, is repeatedly recrystallized from benzene. — Small, yellow laminae ; fusing point, 245-248°; difficultly soluble in alcohol, ether, and car bon bisulphide; more easily in hot benzene. Treated with picric acid in boiling benzene, it yields a compound, C18H12 4- C663(M)2)30, that crystallizes in brown needles. — Nitric acid and bromine yield substitution-products. Heated with glacial acetic acid and chromic acid, it is converted into chrysoquinone, C18H1002, which crystal lizes in beautiful red needles, dissolves in cold concen trated sulphuric acid forming a deep indigo-blue solu tion, and is reprecipitated from this solution, un changed, by the addition of water. Ketene, C18H18. Is contained in the tar from very resinous pine- and fir-wood; and is formed together with benzene, cinnamene and other hydrocarbons by heating acetylene. — White laminae of a mother-of-pearl lustre ; fusing point, 98-99° ; difficultly soluble in al cohol, easily in ether and benzene. Combines with picric acid forming a compound, C18H18 -h C6IP(E"02)30, that crystallizes in orange-yellow needles. It dissolves in concentrated sulphuric acid, a crystalline disulpho- acid, C18H16(S02.OH)2, being formed, the barium salt of which crystallizes in colorless needles. When treated with potassium bichromate and dilute sulphuric acid, it yields carbonic anhydride, acetic and phtalic acids, and a brick-red powder, dioxyretistene, C16H1402, which crystallizes in long, flat, orange-colored needles ; fuses at 194-195°; and, when heated with zinc dust, yields a solid hydrocarbon retistene, C16II14. Fichtelite in old pine trunks, idrialin in the mer cury-ore of Idria, scheererite in beds of bituminous coal, are similar hydrocarbons, the chemical character of which is but little understood. V. GLUCOSIDES. A NUMBER of natural substances possess the common property of breaking up into sugar and other bodies by the action of certain agents (ferments, acids, alkalies). Neither the sugar nor the other bodies exist ready formed in them, but are formed during the process of decomposition, water being assimilated. With very few exceptions, the variety of sugar that results from the glucosides is grape-sugar; the other bodies, how ever, which make their appearance, are of very various character. The glucosides are to be considered as complicated ether-like compounds of grape-sugar. They still contain a number of hydroxyl-groups, the hydrogen of which is readily displaced by acid radicles. 1. Amygdalin. Occurrence. In bitter almonds; in the leaves and berries of Prunus laurocerasus ; in the blossoms, bark, and fruit kernels of Primus padus ; in the bark and young shoots and leaves of Sorbus aucuparia ; in the fruit kernels of cherries, apricots, peaches, and in a great many other plants of the orders Amygdalece and Pomacece. Preparation. The fatty oil is pressed from the paste of bitter almonds, and the mass then boiled repeatedly with fresh quantities of alcohol, the liquid being filtered each time boiling hot; and then about three- fourths of the alcohol distilled off from the mixed solutions. The amygdalin separates from the residue after being allowed to stand for several days in a cool SOLANIN. 413 place, in the form of a stellate, crystalline mass. By maceration with ether and subsequent reerystallization from alcohol it is freed of fatty oil. Properties. Crystallized from alcohol, it forms color less, fine crystalline scales, of a pearly lustre, with out odor, of a slightly bitter taste. Easily soluble in water, from which it crystallizes in large, trans parent prisms with three molecules of water. Not volatile. "When heated with acetic anhydride, it is con verted into heptacetyl-amygdalin, C20H20N04(O.C2H30)7, which crystallizes in long needles, of a silky lustre, insoluble in water, soluble in alcohol and ether. Decompositions. It is resolved by treatment with dilute acids, or when in contact with emulsin (an albuminous body contained in almonds) into sugar, hydrocyanic acid, and oil of bitter almonds (p. 317), two molecules of water being taken up. Boiled with potassium or barium hydroxide, it is decomposed, forming ammonia and a white, crystalline, deliquescent acid, amygdalic acid, C20H28013. 2. Solanin. Occurrence. In the various species of Solanum, par ticularly in the young sprouts of old potatoes. Preparation. Potato sprouts are macerated with water containing a little sulphuric acid, the quickly filtered solution mixed warm with ammonia, the pre cipitate filtered off after prolonged standing, thoroughly dried, and repeatedly boiled with alcohol. On the cooling of the boiling-hot filtered solution, the greater part of the solanin separates, and, by recrystallization from alcohol, is now thoroughly purified. Properties. Fine prisms, of a silky lustre, almost insoluble in water, but slightly soluble in cold alcohol, more easily in hot ; fuses at 235°. Acts poisonously. It is a weak base, possesses a weak alkaline reaction, dis solves readily in acids, and yields with them gummy, uncrystalline salts, which can be precipitated from their solutions in alcohol by ether. 35* 414 SALICIN. .Decompositions. By boiling with dilute hydrochloric or sulphuric acid, it is resolved into sugar and solanidin, with assimilation of three molecules of water. On cool ing, the solanidin is deposited in the form of a sulphate or hydrochlorate, from the solutions of which in alcohol, solanidin is precipitated by means of ammonia, Solanidin, C25H41M)(?). Fine needles, of silky lustre ; but slightly soluble in water, in alcohol more easily soluble. It fuses above 200°, and sublimes by rapid heating almost without decomposition. A stronger base than solanin; gives with acids easily crystallizing salts ; difficultly soluble in water. Solanidin hydrochlorate, C25H41M).HC1, forms rhombic columns ; can be sublimed undecomposed. Solanin, in contact with concentrated cold acids, yields sugar, but no solanidin, but two other, still but slightly known, bases, which are also formed from solanidin when it is heated with concentrated acids. 3. Salicin. C13H1807. Occurrence. In the bark and leaves of most willows (Salix species) and of some poplar species. Preparation. The bark is cut up and boiled with water, the liquid concentrated and boiled with litharge until decolorized, by which means gums, tannic acid, etc., are thrown down. The dissolved lead combined with salicin is at first precipitated with sulphuric acid, afterwards completely with sulphuretted hydrogen or barium sulphide ; the solution of salicin, filtered from the precipitate, is evaporated to the point of crystalli zation. Properties. Small, colorless, lustrous prisms or laminae, of a bitter taste ; fusible at 198° ; easily solu ble in hot water, difficultly soluble in cold water, solu ble in alcohol. — In contact with emulsin or saliva, it as similates one molecule of water, and is resolved into 415 sugar and saligenin (p. 315). When heated with dilute hydrochloric or sulphuric acid, it yields sugar and saliretin (p. 315). Tetracetyl-salicin, C13H14(C2H30)407. Is obtained by heating salicin with acetyl chloride or acetic anhy dride. — Colorless, lustrous needles ; but slightly soluble in water, ether, and cold alcohol, easily soluble in hot alcohol. Benzoyl-salicin (Populin), C20H2208 + 2H20 = C13H17(C7H50)07 + 2H20. Is contained in the bark and leaves of Populus tremula, from which it may be pre pared in the same manner as salicin. It is formed to gether with di- and tribenzoyl-salicin by the action of benzoyl chloride on salicin ; and by fusing salicin and benzoic anhydride together. — Small, colorless prisms of a sweetish taste, difficultly soluble in cold water, more easily soluble in hot water and in alcohol. — When boiled with baryta-water or milk of lime, it yields ben- zoic acid and salicin. Dilute acids (but not emulsin), resolve it into sugar, saliretin, and benzoic acid. Dibenzoyl-salicin, C13H16(C7H50)207, and tribenzoyl- salicin, C13H15(C7H50)307, are formed from salicin to gether with populin. They are white powders, insolu ble in water, scarcely crystalline. Helicin, C13II1607. Is formed together with nitro- salicylic acid by the action of nitric acid (containing hyponitric acid) on salicin. — Small, white needles, diffi cultly soluble in water, more easily in alcohol ; fusing point, 175°. Ferments, dilute acids, and alkalies re solve it into sugar and salicylic aldehyde (p. 322). 4. JEsculin. Occurrence. In the bark of JEsculus hippocastanum, and several other trees. Preparation. The bark of horsechestnut-trees is 416 PHLORIZIN. cut up into small pieces, boiled with water, foreign substances precipitated by means of lead acetate, the excess of lead removed from the filtered solution by means of sulphuretted hydrogen, and the filtrate eva porated to a syrup from which the sesculin gradually crystallizes. Properties. Colorless, fine prisms, of a slightly bit ter taste, but little soluble in water. Even an exceed ingly dilute solution is very fluorescent, the reflected light being of a bright-blue color. The fluorescence disappears in the presence of acids, reappears on the addition of alkalies. Difficultly soluble in alcohol. Dilute acids resolve it into sugar and aesculetin. Hexacetyl-sesculin, C15H10(C2IPO)609 + H20. Is formed by the action of acetyl chloride or acetic anhy dride on aesculin. — Small, colorless needles, that give up water at 130°. Brought in contact with anilin at the boiling temperature sesculin yields tnanil-cesculin, C15H1609 + 3C6EraT — 3H20. C9H6O + H20. Exists ready formed in the bark of the horsechestnut. If sesculin is di gested with dilute sulphuric acid, it dissolves, the solu tion having a yellow color, and sesculetin is deposited in its place in crystals. — Fine, colorless needles and laminae, very sparingly soluble in water, but slightly in alcohol, very easily soluble in alkalies, the solutions being yellow. Is decomposed by heating with caustic potassa into formic acid, oxalic acid, and protocatechuic acid (p. 356), or an acid isomeric with the latter, cesci- oxalic acid. 5. Phlorizin. C21H24010 + 2II20. Occurrence. In the bark, especially the root-bark, of the apple, cherry, pear, and plum-tree, from which it can be extracted by means of boiling water or warm dilute alcohol. It is purified by recrystallizing from hot water. QUERCITRIN. 417 Properties. Fine, silky prisms of a bitter taste; easily soluble in boiling water and alcohol, difficultly soluble in cold water. It loses its water of crystalliza tion at 100°; fuses at 106-109°; solidifies again at 130° ; and appears to be converted into another modifi cation at this temperature, which does not fuse again below 160°, is less soluble in water, and is deposited in an amorphous condition from this solution, gradually passing into the crystalline modification. Treated with acetic anhydride, it yields acety 1-compounds (with 1, 3, and 5 times the group C2H30), similar to those of salicin. Decompositions. Under a bell-jar filled with ammo nia vapors and moist air, phlorizin deliquesces, forming a thick, dark syrup, from which, by means of careful evaporation and washing with alcohol, is obtained phlorizein, C21H30]N"2O13, a red, amorphous body, easily soluble in hot water, very sparingly soluble in alcohol. Boiled for a long time with dilute hydrochloric or sulphuric acid, two molecules of water are assimilated and phlorizin is resolved into grape-sugar and Phloretin, C15H1405, which separates from the solu tion on cooling. — Small, colorless laminse, very slightly soluble in water, easily soluble in alcohol, dissolves also easily in alkalies, but on evaporating this solution, it is decomposed into phloretic acid (p. 353), and phloro- glucin (p. 311). 6. Quercitrin. C33H3007 (?). Occurrence. In the bark of Quercus tinctoria (which occurs in commerce under the name of quercitron, and is used as a yellow dye) ; and the blossoms of ^Esculus hippocastanum ; and is prepared from these sources in the manner described in connection with phlorizin. Properties. Yellow, crystalline powder, difficultly soluble in water even at boiling temperature. Treated with acids, it is resolved into a crystallizing, unfer- mentable, saccharine body, isodulcite, and into 418 EUBIANIC ACID. ftuercitin, C27H18012, which also occurs ready formed in Calluna vulgaris, in tea, in the root-bark and trunk- bark of the apple-tree and other plants. — Yellow, crys talline powder, sublimes in large yellow needles with partial decomposition. But slightly soluble in water, easily soluble in alcohol. Fusing potassa decomposes it, like phloretin, into phlorogludn and quercetic acid, C15H1007, which crystallizes in fine, silky prisms ; sparing^ soluble in cold water. By further treatment with fusing potassa, it yields protoeatechuic acid (p. 356), quercimeric add, C8H605 4- H20 and paradatiscetin, C15H1006. Rutin is a glucoside, very similar to quercitrin, but not identical with it, contained in Huta graveolens — the loppers (blossom-buds) of Capparis spinosa. Yields, when treated with acids, quercitin and an unferment- able sugar, which appears to be different from isodul- cite. 7. Frangulin. C20H20010. In the bark of Rhamnus frangula. — Yellow, crys talline mass ; fusing point, 226°. Almost insoluble in cold water, difficultly soluble in cold alcohol and ether, easily in hot alcohol. Soluble in alkalies, forming red solutions. Acids resolve it into sugar and frangulic acid, C14H1005 + H20, which forms an orange-yellow, loose crystalline mass, but slightly soluble in water, easily soluble in alcohol ; fusing point, 246-248°. 8. Rubianic Acid. C20H22On (?). In madder (the root of Rubia tinctorum). In order to prepare it, fresh madder-root is boiled with water, foreign substances removed from the solution by means of neutral lead acetate, the liquid filtered, the rubianic acid precipitated from it by means of basic lead acetate, AEBUTIN. 419 and the red precipitate then decomposed. The acid is thrown down with the lead sulphide, and separated from this by extracting with alcohol. — Yellow prisms, sparingly soluble in cold water, easily in hot water, ^al cohol, and ether. — By boiling with acids and alkalies, as well as by contact with a ferment contained in mad der, it is resolved into sugar and alizarin. In old madder, as it is used in dying, this decomposition has already partially taken place ; it is accelerated by treating the madder with sulphuric acid (G-arancin, a commercial product, is madder which has been treated in this way). Morindin, a body contained in the root-bark of Mo- rinda citrifolia, is probably identical with rubianic acid ; and the dye morindon^ prepared from it by means of sublimation, appears to be alizarin. 9. Arbutin. C12H1607. In the leaves of the bearberry (Arbutus uva ursi), and of winter-green (Pyrola umbellata). — Long, color less, bitter tasting needles, which fuse at 170°, the so lution of which is colored deep blue by iron chloride. In contact with emulsin, and by boiling with dilute sulphuric acid, it is resolved into sugar and hydroquinone (p. 303), which is also formed by the dry distillation of arbutin. Concentrated nitric acid converts it into bright-yellow needles of dinitroarbutin, C12H14(N02)207 + 2H20. "When chlorine is conducted into a watery solution of arbutin, substitution-products of quinone (p. 301) are formed. 10. Fraxin. C32H36020. In the bark of Fmxinus excelsior and JEsculus hippo- castanum. — Fine, fascicular needles ; slightly soluble in 420 CONVOLVULIN. cold water, easily soluble in alcohol; fuses at 190°. "With dilute acids it yields sugar &nd.fraxetin, C10H805. 11. Phillyrin. C27H34On Contained in the bark of Phyllyrea latifolia. — Color less crystals ; difficultly soluble in cold water ; fusing at 160°. Dilute acids resolve it into sugar and philly- genin, C21H2406. 12. DapJinin. C31H34019 + 4IPO. In the bark of Daphne alpina and Daphne meze- reum. — Colorless, transparent prisms ; fusing at 200° ; insoluble in cold water and in ether, easily soluble in hot water and alcohol. Emulsin or dilute acids resolve it into sugar and daphnetin, C19H1409. 13. Myronic Acid. C10H19NS2010. In the seed of black-mustard in the form of the potas sium salt. This can be extracted from the residue by means of water after the powdered seed has been boiled with alcohol. — Small, silky needles ; easily sol uble in water. In contact with myrosin, a ferment contained in mustard seed, and heated with baryta- water, it is decomposed into allyl mustard-oil (p. 215) and potassium bisulphate. Its solution gives a white precipitate with silver nitrate, C4IKN"S04Ag2, which, when treated with sulphuretted hydrogen, yields silver sulphide, sulphur, free sulphuric acid, and allvl cyanide (p. 120). 14. Convolvulin (Rhodeorethi). C31IF°016. In jalap root (of Convolvulus schiedeanus). The root is first thoroughly exhausted with boiling water, then treated with alcohol ; the alcoholic solution decolor- SAPONIN. 421 ized with animal charcoal; evaporated ; the crude con- volvulin dissolved in alcohol, and reprecipitated with ether. — Colorless, resinous mass; inodorous and taste less ; fuses at 150° ; but slightly soluble in water, easily in alcohol. It exerts a purgative action. Dis solves in alkalies, and is converted by them into an easily soluble, amorphous substance, c'onvolvulic acid (rhodeoretic acid), C31H52O17(?), water being assimilated in the reaction. Convolvulin, as well as convolvulic acid, in contact with emulsin, or when treated with dilute acids, is decomposed into sugar and convolvu- linol, C13H2403 -f JH20, which dissolves in alkalies, forming convolvulinolic acid, C13H2604. 15. Jalapin. C34H56016. Homologous with convolvulin. In jalap-root (of Convolvulus orizabensis) and scammony-resin (the hard ened sap of Convolvulus scammonia). — Very similar to convolvulin. Is decomposed by emulsin or acids into sugar and jalapinol, C16H3003 4- 1 JH20 ; and conducts itself towards alkalies like convolvulin. Turpethin, a resinous glucoside, isomeric with jalap- in, is contained in turpeth-resin (from the root of Ipomoea turpethum). It yields, when treated with baryta-water, amorphous turpethic acid, C34H60018, and is decomposed by mineral acids into sugar and white, amorphous turpetholic acid, C16H3204. 16. Saponin. C32II54018. In the root of a number of plants (Saponaria officina- lis, Gypsophila struthium, Poly gala senega, Agraslemma githago). — White, amorphous powder, which causes sneezing; poisonous; easily soluble in hot water. This solution foams like soap-water, even when very dilute. Treated with hydrochloric acid gas or fuming hydrochloric acid, it yields an uncrystalline, saccharine 86 422 CARMINIC ACID. body, and sapogenin, C14H2204, white crystals, sparingly soluble in water and alcohol. 17. Ca'incin (Ca'incic Acid). C40H64018. In the root of Chiocca racemosa. — Fine, colorless prisms ; sparingly soluble in cold water, easily soluble in alcohol. Is resolved by hydrochloric acid gas into an uncrystalline sugar, and crystalline caincetin, C22H3403, which, treated with fusing potassa, is decomposed into butyric acid and ca'incigenin, C14H2402. 18. Quinovin. C30H4808. In cinchona-bark, particularly in a false bark, China nova. — White, amorphous substance; insoluble in water. "When hydrochloric acid gas is conducted into its alcoholic solution, and when it is treated with sodium-amalgam, it is decomposed into a sugar, very similar to mannitan (p. 189), perhaps identical with it, and quinovic acid, C24H3804, which separates as a white, crystalline powder. 19. Pinipicrin. C22H36On. In the bark and needles of Pinus sylvestris ; in the green portions of Thvja occidentalis. — Yellow, amor phous, bitter powder, soluble in water and alcohol. Is decomposed by heating with sulphuric acid into sugar and ericinol, C10H160. 20. Carminic Acid. C17H18010. In the blossoms of Monarda didyma, and probably also in other plants. Most particularly, however, in cochineal (the female of the insect Coccus cacti), from which it is obtained by boiling with water, precipitating with lead acetate, and decomposing the lead precipitate GLYCYREHIZIN. 423 with sulphuretted hydrogen.— Purple, amorphous mass. Easily soluble in water and alcohol. Combines with bases, forming colored salts. When boiled with dilute sulphuric acid, it is decomposed, yielding a peculiar uncrystalline, unfermentable sugar, which is optically inactive ; and carmine red, CnH12Or, dark-purple, shiny mass ; soluble in water and alcohol, the solution formed being of a red color. Weak acid. Fused with potassium hydroxide, carminic acid yields oxalk, succinic, and acetic acids, and a yellow, crystalline substance, coccinin, C14H1205; heated with concentrated nitric acid : oxalic acid and nitrococcusic add, C8H5(N02)303 -h H20. 21. Helleborein. C26H44015. In the root of Helleborus niger, and in smaller quan tity in that of Helleborus viridis.— Colorless nodules, consisting of microscopical needles. Easily soluble in water, but slightly in alcohol. Has a narcotic action. Is resolved, by boiling with dilute acids, into sugar and amorphous helleboretin, C14H2003, which is deposited as a dark-violet precipitate, that, however, becomes grayish-green by drying. 22. Helleborin. Q36JJ42Q6. In the root of Helleborus viridis, and in traces in that of Helleborus niger.— Shiny, colorless needles, arranged concentrically. Insoluble in cold water, easily soluble in boiling alcohol. Is colored an intense red by con centrated sulphuric acid. Has a stronger narcotic ac tion than helleborem. "When heated with dilute acids, it is resolved into sugar and an amorphous, resinous substance, helleboresin, C30H3804. 23. Qlycyrrhizin. C24H3609(?). In liquorice root (from Glycyrrhiza glabra), and^ in the extract prepared from it. — Amorphous, yellowish- 424 TANNIC ACIDS. white powder, easity soluble in hot water and in alco hol. By boiling with dilute acids, it yields sugar and a yellowish resin glycyrrhetin, C18H2604 (?). 24. Digitalin. In Digitalis purpurea. — Small colorless crystals ; spar ingly soluble in water, easily soluble in alcohol, of an intensely bitter taste. Exceedingly poisonous. Very difficult to obtain in a pure state, and hence but little known as yet. Is resolved by sulphuric acid into sugar and amorphous digitalretin. 25. Tannic Adds. By the name tannic acids is understood a class of weak acids, which are widely distributed in the vege table kingdom, and which bear a close relation to each other, as regards their properties, as well as their com position ; the composition is, however, not yet deter mined with certainty for all of them. Most of the tannic acids have been shown to be glucosides. In general they are characterized by a sharp astringent taste ; by the property of giving bluish-black or green compounds with iron salts; of precipitating solutions of gelatin ; and by the ability to tan animal hides ; i. e. to convert them into leather. Their important uses in dyeing, in the preparation of ink, and dressing of leather, depend upon these properties. They also con stitute the active principles of a number of plants em ployed in medicine. Gallotannic acid (Tannin), C27H22017. Occurs particu larly in gall-nuts, the excrescences found on the young branches of Quercus infectoria, caused by the punctures of the gall-wasp ; these contain about half their weight of tannic acid ; in still larger quantity in Chinese gall- iiuts, formed in a similar manner ; also in the various species of sumach (the branches of Rhus coriaria) ; and probably in still other plants. Eight parts powdered gall-nuts (most profitably TA.NNIC ACIDS. 425 from Chinese gall-nuts) are macerated with 12 parts ether and 3 parts alcohol for two days, the mixture being frequently shaken ; the solution is then poured off, and the residue again treated in the same way with the same quantity of ether and alcohol. To the united extracts 12 parts of water are added; the alcohol and ether distilled off over a water bath ; the solution fil tered ; and the filtrate evaporated to dry ness. Colorless amorphous mass, of a purely astringent taste; inodorous; easily soluble in water; reddens lit mus. It forms bluish-black precipitates with solutions of ferric salts. It is thrown down from its solution by mineral acids and a number of alkaline salts (sodium and potassium chlorides, not by saltpetre and sodium sulphate); most thoroughly by a solution of gelatin and by animal membranes. Further, it precipitates most organic bases, starch, albumen. — Tribasic acid. Its salts are amorphous and difficult to obtain of constant composition. The solutions of the alkaline salts be come colored red or brown rapidly in the air, oxygen being taken up and the acid decomposed. The free acid in an aqueous solution is also decomposed in the air. If a concentrated extract of gall-nuts is allowed to stand in contact with the air, gallic acid is deposited from it, mixed with another crystalline acid, ellagic add, C14I1608 + 2H20. This is very difficultly soluble in water ; it is also formed by heating two molecules gallic acid with one molecule arsenic acid in aqueous solution, and is the principal ingredient of a known in testinal concretion, bezoar, found in a species of goat of Persia. By boiling with dilute acids, it is resolved into sugar and gallic acid (p. 360) ; also by boiling with alkalies (only in the latter case the sugar undergoes further de composition) ; and also by the action of yeast, emulsin, or a ferment contained in gall-nuts. Heated alone it yields pyrogallic acid (p. 310). Catechutannic acid. In catechu, a dark or light brown extract prepared from Acacia catechu, Areca catechu, and Nauclea gambir. — Very similar to gallo- 86* 426 TANXIC ACIDS. tannic acid. With iron salts, however, it does not give a bluish-black, but a dirty green precipitate ; it can also not be converted into gallic acid. Compo sition unknown. Catechin (Catechuic acid), C19H1808(?). Occurs to gether with tannic acid in catechu, more especially in the cubical variety from Nauclea gambir. Powdered catechu is macerated with cold water ; the brown tannic acid solution filtered from the undis- solved catechin; this pressed and dissolved in boiling water, from which it is deposited slowly on cooling, generally not yet quite white. It is purified by recrys- tallization. Colorless mass consisting of interwoven fine crystal line scales ; almost tasteless ; fusible at 217° ; diffi cultly soluble in cold water, easily in boiling water and in alcohol. Turns a reddish color in the air, finally brown. Ferric salts are colored green by it ; solutions of salts of the noble metals are reduced. Very weak acid, does not expel carbonic acid from it salts. — When heated, it yields pyrocatechin (p. 305); when fused \vith potassa, protocatechuic acid (p. 356) and phloroglucin (p. 311). Kinotannic acid. Forms the principal ingredient of kino, a brittle reddish-brown extract, which is pre pared in West India from Coccoloba uvifera, in Africa, from Pterocarpus erinaccus. The tannic acid contained in it has been but little investigated; it is not yet known in a pure condition. It colors ferric salts blackish-green. Fused with potassa, it yields phloro glucin. Morintannic acid (Maclurin), C13H1006 + H20. In old fustic (of Morns tinctoria), from which it is ob tained by boiling with water. On evaporation of the solution, morin is at first deposited and then morin- tannic acid. — Bright-yellow, crystalline powder, easily soluble in hot water and alcohol. Its solution gives with ferrous sulphate a blackish-green precipitate. Heated alone, it yields pyrocatechin; fused with po- TANNIC ACIDS. 427 tassa, phloroe;lucm and protocatechuic acid. Treated with zinc and sulphuric acid, it is resolved into phloro- glucin and a white, crystalline substance, machromin, G"H1005, which is converted into an indigo-blue body by the action of light, heat, or oxidizing agents. Morin (Moric acid), C12H805. Is contained in old fustic, together with morintannic acid, and, being much less soluble in water than the latter, it can be easily separated from it.— Crystallizes from alcohol m almost colorless, shiny needles; almost insoluble in cold water, but sparingly soluble in boiling water. Treated with sodium-amalgam in an alkaline solution, and fused with potassa, it is converted into phloro- glucin. ftuino-tannic acid. In the bark of the various species of cinchona, partially combined with bases also contained in the bark.— Very similar to gallotanmc acid; precipitates ferrous salts, however, green or gray- ish-o-reen. By boiling with acids it is resolved into sugar and quino-red, C28H22014, a reddish-brown, amor phous substance, with weak acid properties, which is itself contained ready formed in cinchona-bark, and can be extracted from it by means of ammonia. With fusing potassa it yields protocatechuic and acetic acids. Oak-bark-tannic acid. In oak bark, together with a small quantity of gallotannic acid. ^The bark ex tract is subjected to partial precipitation with lead acetate; the dirty-brown precipitate, which is first formed, and that formed later, of a lighter color, are decomposed with sulphuretted hydrogen. On evapo rating the filtrate, the tannic acid remains behind as an easily soluble, yellowish-brown, amorphous mass. Its solution is colored a deep blue by iron chloride. By boiling with dilute sulphuric acid, it is resolved into sugar and oak-red, a body very similar to quino- red, which, it appears, is also contained in oak bark. It yields, when fused with potassa, phloroglucin and protocatechuic acid. 428 TANNIC ACIDS. Rattinhia-tannic acid, in ratanhia-root, filix-tannic acid, in fern-root, and tormentill-tannic acid, in tormen- till-rpot, conduct themselves very similarly to quino- tannic acid and oak-bark-tannic acid. When boiled with dilute acids they are all resolved into sugar and reddish-brown bodies, which possess the greatest simi larity with oak-red and quino-red; and when fused with potassa they yield phloroglucin and protocate- chuic acid. Caffetannic acid, C15H1808(?). In coffee. Coffee is boiled with alcohol ; the acid precipitated by means of lead acetate; and the precipitate decomposed by sulphuretted hydrogen. — Gummy mass; easily soluble in water; colors ferric salts green. — With ammonia it becomes rapidly green in the air. — Subjected to dry distillation, it yields pyrocatechin (p. 305) ; when fused with potassa, protocatechuic acid. Heated with potassa-ley, it is decomposed, forming an uncrystalline sugar and caffeic acid (p. 378). VI. VEGETABLE SUBSTANCES BUT LITTLE MOWN. THERE is a large number of compounds occurring in nature, whose chemical constitution and the relation they bear to other better known bodies have not yet been ascertained. Only the more important and better investigated of these will be here described. A. ACIDS. 1. Usnic acid, C18II1807. In a great many lichens, particularly in the various species of Usnea, from which it is extracted by means of ether. — Sulphur- yellow, transparent prisms; insoluble in water, but sparingly soluble in alcohol ; fusible at 202°. (A modi fication of usnic acid, from Cladonia rangiferina, called beta-usnic acid, fuses at 175°). Its solution, in an excess of alkali, becomes first red and then black in the air. Subjected to dry distillation, it yields betaordn (p. 309). 2. Cetraric acid, C18II1508. In Iceland moss (Cetraria islandica). It can be obtained pure only with diffi culty. — Very fine, white needles, of an intensely bitter taste ; neither fusible nor volatile ; scarcely soluble in water, easily soluble in alcohol. Dissolves in alkalies with yellow color, which is, however, rapidly converted into brown in the air, the acid undergoing decomposi tion. It suffers a similar rapid decomposition when boiled in alcohol or water, with access of air. 430 ME CONIC ACID. 3. Lichenstearic acid, C14II2403. Together with cetraric acid in Iceland moss. — Fine, shiny crystalline laminae; insoluble in water, easily soluble in alcohol and ether. 4. Vulpic add, C19II1405. In the lichens, Cetraria vul- pina, and a variety of Parmelia parietina, from which it can be extracted by lukewarm water and milk of lime ; and then reprecipitated by hydrochloric acid. — Yellow crystals, very similar to usnic acid ; insoluble in water, but slightly soluble in alcohol, more readily in ether. By boiling with barium hydroxide, it is decomposed into methyl alcohol, oxalic acid, and alpha- toluic acid (p. 340); by boiling with dilute caustic potassa, into methyl alcohol, carbonic acid, and oxa- tolylic add, C16H1603. The latter crystallizes in color less, four-sided columns, fusing at 154° ; insoluble in water ; in alcohol and ether more easily soluble ; and is resolved, by continued boiling with concentrated potassa-ley, into oxalic acid and toluene. 5. Meconic add, C7H407( = C4 j 9^ QH)8®) In the milky juice of the poppy (Papaver somniferum) and the opium prepared from this. — The crude calcium meco- nate, obtained in the preparation of morphine, is re peatedly treated with dilute, hot hydrochloric acid ; the acid, which crystallizes out in a still impure con dition on cooling, is dissolved in dilute, warm am monia; the salt recrystallized several times from hot water, and finally the acid precipitated from the hot solution of the salt by means of hydrochloric acid. Crystallizes from water in colorless, shiny laminae or prisms, with three molecules of water of crystalliza tion. Of a weak, sour taste ; difficultly soluble in cold water, more easily in hot water and alcohol. Colors solutions of ferric salts a deep red. Tribasic acid. — When treated with sodium-amalgam, it yields an amorphous, deliquescent acid, difficultly soluble in alcohol, hydromeconic add, C7H1007.— Heated to 220°, or boiled for a long time with water, particularly with dilute hydrochloric acid, meconic acid is resolved into CHELIDONIC ACID. 431 carbonic anhydride and comenic add, C6H405, which consists of very hard and difficultly soluble granules. Comenic acid, in its turn, yields by distillation another, easily fusible, monobasic acid, subliming in shiny laminae, pyrocomenic acid, C5H403. 6. Chelidonic acid, C7H406. In Chelidonium majus, particularly at the blossoming period of the plant. — The expressed, boiled, and filtered juice is acidified with nitric acid ; and lead chelidonate precipitated with lead nitrate. This, when decomposed with sulphuretted hydrogen, yields impure chelidonic acid, which is purified by preparation of salts, and recrystallization. — Long, shiny needles. Difficultly soluble in cold water and alcohol, more easily Ui hot water ; not volatile without decomposition. Strong acid ; dissolves iron and zinc with evolution of hydrogen. Tribasic. Treated with bromine and water it is decomposed, forming bromoform, pentabromacetone (C3HBr50), and oxalic acid. B. BASES (ALKALOIDS). In a large number of plants occur peculiar nitrogen- ized bases, combined with acids. Although present in but very small quantity, they form, as a rule, the active principle of these plants, which are mostly distin guished for poisonous or healing properties. The majority of these bases are crystallizable and not volatile ; only a few are liquid and distillable. Nearly all of them are sparingly soluble in water, easily soluble in alcohol, turn litmus-paper blue, and have a bitter taste. Their preparation takes place usually in the follow ing manner : the proper portions of the plants are ex hausted with water or dilute hydrochloric acid, and the bases (if volatile) separated by distilling with an alkali, or (if not volatile) precipitated by means of a stronger, inorganic base. As in the latter case, how ever, a number of other substances are precipitated at 432 CONINE. the same time, it is necessary that the product be still subjected to various other purifying processes (prepa ration of salts, recrystallization and subsequent decom position, etc.). Frequently the extract is mixed with neutral or basic lead acetate for the purpose of pre cipitating foreign substances ; the nitrate is then freed of dissolved lead by sulphuretted hydrogen ; and the alkaloid now precipitated by means of a stronger base. All alkaloids are precipitated from their solutions by tannic acid, by phosphormolybdenic acid,* by potas- sio-mercuric iodide, potassio-cadmic iodide and potas- sio-bismuthic iodide, and can be set free from these precipitates by means of alkalies or barium hydroxide, and extracted by solvents (ether, benzene, amyl alco hol, chloroform, etc.). 1. Conine. C8H15ISr - C8H14.KEL Occurrence. In all parts of the hemlock (Conium maculatum), most abundantly in the ripe seeds. formation. When butyric aldehyde is treated with alcoholic ammonia a base, butyraldin, C8HirN"0, not known in a pure state, is produced together with other substances. When this is subjected to dry distillation, it yields conine. Preparation. The plant or the crushed seeds are dis tilled with dilute caustic potassa, in which process conine passes over dissolved in water. The distillate is satu rated accurately with sulphuric acid, evaporated to a syrupy consistence, and distilled with concentrated caustic potassa, the conine now passing over as an oil, floating on a saturated solution in water. It is freed of ammonia in a vacuum. Properties. Colorless, clear, oily liquid, specific grav ity, 0.89 ; of a suffocating, unpleasant odor (somewhat resembling hemlock) ; and a very repulsive penetrating * Prepared by precipitating ammonium molybdenate with sodium phosphate, dissolving the well-washed precipitate in hot sodium carbo nate, evaporating, and then igniting the mass. The salt which remains behind is heated with ten parts of water; nitric acid added until the solution shows a strong acid reaction ; and then filtered. CONINE. 433 taste. Boils at 163.5°. Dissolves water, which is sepa rated by the aid of heat ; hence the property of conine, of becoming turbid even from the warmth of the hand. Soluble in 100 parts of water ; miscible with alcohol and water. Strongly alkaline, and very poisonous. Monatomic. Decomposition. On exposure to the air, conine, as well as the solutions of its salts, soon becomes brown, and is finally entirely destroyed, ammonia being evolved. "Warmed with oxidizing substances, it yields butyric acid. By treatment with dry nitrous acid and subsequent addition of water, there is formed azocony- drine, C8H16^"20, a bright-yellow liquid, insoluble in water, which, heated with phosphoric anhydride, is re solved into nitrogen, water, and a hydrocarbon, conylene, C8HU (homologous with acetylene, p. 131). Colorless, mobile liquid, boiling at 126°; combines directly with bromine, forming a liquid product, C8H14Br2. Methylconine, C8H14.KCIP, and Ethylconine, C8H14.N\C2H5, are colorless liquids, which are formed when conine is heated with methyl or ethyl iodide, and afterwards distilled with caustic potassa. The former is frequently contained in commercial conine. They both combine directly with another molecule of ethyl iodide, forming crystallizing iodides, which, when decomposed with silver oxide, yield bases, analogous to tetrethylammonium hydroxide ; not vola tile ; very easily soluble in water. Conhydrine, C8H17NO, occurs together with conine, particularly in the fresh blossoms, but also in the ripe seed of hemlock. Can be separated from conine by distillation in a current of hydrogen, the tempera ture being raised very slowly. At iirst conine passes over, and, at a higher temperature, crystals of conhy- drine are deposited in the neck of the retort. — Color less, iridescent, crystalline laminaB ; sublimes at 100° ; fuses at 120.6°; and boils at 224°. Moderately soluble in water, more readily in alcohol and ether. Heated with phosphoric anhydride, it is decomposed into 37 434: NICOTINE. conine and water. Treated with sodium, it is also converted into conine. 2. Nicotine. C10II14JST2. Occurrence. In the leaves and seed of the tobacco species in varying quantity ; in poor qualities of tobacco as much as 7 and 8 per cent., in Havana tobacco only 2 per cent. Preparation. Tobacco leaves are digested repeatedly with water containing sulphuric acid, pressed, and the liquid evaporated half down. It is then distilled with caustic potassa, and the nicotine exhausted from the distillate by ether. The ether is removed from the ethereal solution by evaporating, finally elevating the temperature to 140°. The nicotine, which is still im pure, of a brown color, is distilled at 180° in a cur rent of dry hydrogen over quicklime. Properties. Colorless liquid of a weak odor; when heated, of a suffocating tobacco-odor ; specific gravity, 1.048 ; soluble in water, alcohol, and ether. Boils at 250° with partial decomposition ; can, however, be slowly distilled over, even at 146°. Has an alkaline reaction ; turns brown, and is decomposed in contact with the air. Exceedingly poisonous. Diatomic base. The salts are easily soluble, and crystallize with diffi culty. The free base as well as its salts give crystal lizing compounds with iodine, bromine, and metallic salts. Nicotine hydrochloro-chloromer curate, C10H14^"2.HC1 + 4HgCl2, is obtained by adding an ex cess of a solution of corrosive sublimate to a solution of nicotine, neutralized with hydrochloric acid. Crys tallizes from water in colorless, radiating groups of needles. — Nicotine chloromercurate, C10H14N2 + SHgCl2, crystallizes in large prisms, when sufficient of a solu tion of corrosive sublimate is added to a dilute solu tion of nicotine hydrochlorate to just cause it to re main turbid. SPAKTEINE. 435 Bromonicotine, C10H12Br2N"2. When an ethereal solution of nicotine is poured into an ethereal solution of bromine, shiny, bright-red prisms, C10H12BrsmBra. HBr, are deposited, which lose hydrobromic acid in contact with the air, and when boiled with water or alcohol, or when their solution is allowed to stand for a long time, are converted into bromonicotine hydrobrom- ate, C10H12Br2N2.HBr, bromine being given up. Potassa or ammonia separates free bromonicotine from the cold solutions of these salts. — Crystallizes from ^water^ in long colorless needles, permanent in the air. Diffi cultly soluble in cold water, easily soluble in hot water and in alcohol. A weaker base than nicotine. By boiling with caustic potassa it is reconverted into nico tine. Nicotine combines with the iodides of alcohol radi cles, forming crystalline iodine-compounds, from which silver oxide separates strongly alkaline ammonium bases, which are not volatile. 3. Sarteine. Occurrence. In Spartium scoparium. Preparation. The plant is exhausted ^with^ water, which is slightly acidified with sulphuric acid; the extract evaporated down to a small volume, and dis tilled with caustic soda. The distillate is evaporated to dry ness with hydrochloric acid ; and the residue dis tilled with solid potassium hydroxide. Properties. Colorless, thick oil, of a bitter taste; sparingly soluble in water; boils at 288°. Strongly alkaline. Has a narcotic action. Diatomic base. Conducts itself towards alcoholic iodides in the same manner as nicotine. 4. Opium Bases. - In opium, the dried juice of the capsules of the poppy (Papaver sowra/entw), are contained, in addition 436 OPIUM BASES. to meconic acid (p. 430) and meconin (p. 382), six well- investigated alkaloids: — Morphine, C17H19N03, Codeine, C18H21^03, Thebaine, C19H21]ST03, Papaverine, C21H21^sT04, Narcotine, C22II23^07, Narceiiie, C23H29IsT09. In all varieties of opium, morphine and narcotine are contained in the largest quantity. Preparation. Opium is broken up and exhausted with a small quantity of water of 65° ; the extract mixed with calcium chloride ; filtered from precipitated calcium meconate ; the filtrate concentrated by evapo ration, and allowed to stand undisturbed for a long time. Morphine and codeine hydrochlorate crystallize out, and are separated from the black, treacly mother- liquor by pressing. To separate the two from each other, ammonia is added to their solution, which pre cipitates only the morphine, the codeine remaining in the liquid. This is concentrated by evaporation, when more morphine is deposited, and the codeine now precipitated by an excess of concentrated caustic potassa, in which any morphine, which may still be present, remains dissolved. The mother-liquor, from morphine hydrochlorate and codeine, is diluted with water ; strained through a cloth ; and thoroughly precipitated with ammonia. The precipitate, collected on a cloth filter, and purified by repeated pressing and moistening with water, con sists essentially of narcotine with a little papaverine and thebaine, and a great deal of resin. It is stirred with concentrated potassa-ley, forming a paste ; after a time water is added, and the deposited narcotine, after being washed with water repeatedly, crystallized from boiling alcohol. Papaverine and thebaine remain in the mother-liquor. After distilling off the alcohol, the residue is exhausted with hot dilute acetic acid, and from the solution, narcotine, papaverine, and the OPIUM BASES. 437 resin precipitated with basic lead acetate. Thebaine remains in solution, and after removing the lead with sulphuric acid, it is precipitated with ammonia. For the purpose of separating the papaverine from narco- tine and the resin, the precipitate is boiled with alco hol, the solution evaporated, and the residue extracted with hydrochloric acid. After evaporating again, and allowing to stand for several days, papaverine hydro- chlorate, wjiich is difficultly soluble, separates, while narcotine remains dissolved. The arnmoniacal liquid, filtered off from narcotine, papaverine, and thebaine, which contains the narceine, is mixed with lead acetate ; filtered ; the lead removed from the filtrate by sulphuric acid; then supersatu rated with ammonia; and evaporated at a gentle heat, until a thin crust shows itself upon the surface. In a few days narceine separates in a crystalline form, and is purified by recrystallizing from water and alcohol. Preparation of morphine and narcotine. The separa tion of all the bases can only be accomplished when large quantities of opium are employed. If the object is only to obtain morphine and narcotine, the opium is exhausted by digesting with dilute alcohol, and the fil trate then allowed to stand for a long time mixed with an excess of ammonia. The separated bases are treated with caustic potassa. The morphi ne is dissolved by this, while the narcotine remains undissolved. The latter is purified by recrystallization from alcohol. From the alkaline solution the morphine is reprecipitated by ammonium carbonate ; and by dissolving in hydro chloric acid, recrystallizing the hydrochlorate, and decomposing it with ammonia, and recrystallizing the precipitate from alcohol, it is purified. 1. Morphine, C17H19N03 + H20. Crystallized from alcohol it forms small, colorless shiny prisms ; precipi tated by ammonia, a white powdery mass. Has a slightly bitter taste ; an alkaline reaction. Soluble in 500 parts of boiling water, but very slightly in cold water, much more easily soluble in alcohol, insoluble in ether, chloroform, and benzene; easily soluble in 37* 438 OPIUM BASES. caustic potassa, but very slightly in ammonia. Fusible, with loss of water of crystallization, congealing in a crystalline form. Narcotic poison; in small quantity causes sleep. Monatomic base. Morphine hydrochlorate, C17H19N03. HC1 + 3II20, forms line prisms, of a silky lustre ; easily soluble in alcohol and hot water, less soluble in cold water (in 16-20 parts). Morphine sulphate, 2(C17H19]sr03)II2S04 + 5IPO, is similar to the hydro- chlorate. A solution of pure neutral morphine salts and also the free base are colored a beautiful dark blue by iron chloride. Heated with concentrated sulphuric acid, morphine is dissolved ; the solution has a dirty, grayish- red color; and is turned a beautiful, bright blood-red by the addition of a drop of nitric acid. Heated with potassa to 200°, morphine evolves methylamine. Oxymorphine (Pseudomorphine), CI7II19]NT04. Is occasionally contained in opium. Is produced by heating a solution of one molecule of morphine hydro- chlorate with one molecule of silver nitrate to 60°. By treating the precipitate with hydrochloric acid, oxymorphine hydrochlorate is obtained. It is sparingly soluble in cold water, more easily in hot water. When treated with ammonia the free base is thrown down from its solution. — Shiny powder, consisting of fine needles. Insoluble in water, alcohol, ether, and chloro form even at the boiling temperature. Fuses at 245°, at the same time undergoing decomposition ; soluble in caustic potassa and soda, and in a large excess of am monia. Gives the same reaction with iron chloride as morphine. — Monatomic base. The salts are nearly all difficultly soluble in water. Apomorphine, C17H17ITO2. The salts of this base are produced by heating morphine or codeine with con centrated hydrochloric acid at 140-150° ; by treating morphine with concentrated sulphuric acid, and by heating morphine hydrochlorate with a concentrated solution of zinc chloride to 120°. Sodium bicarbonate OPIUM BASES. 439 precipitates the free base from it.— White amorphous powder; somewhat soluble in water, soluble in alcohol, ether, and chloroform. Turns green rapidly in the air, and then forms an emerald-green solution in water. Apomorphine hydrochlorate, C17H17N02.HC1. Forms colorless crystals, which, when heated or when exposed to the air in a moist condition, also become green. 2, Narcotine, C22H23^07. Colorless, shiny prisms, without taste; fuses at 176°, and is decomposed when heated a few degrees higher. Insoluble in cold water and caustic potassa, soluble in boiling water and in alcohol and ether. Less poisonous than morphine. Monatomic base. The salts crystallize either badly or not at all. From their solutions alkalies precipitate narcotine in an amorphous condition. Narcotine dissolves in concentrated hydrochloric acid, the solution having a yellow color; and this solu tion becomes blood-red when gently heated, and dark- violet when the heat is increased. Narcotine, when heated with water to 250°, yields trimethylamine, together with other products; heated with concentrated hydrochloric or hydriodic acid, three methyl groups are successively eliminated, and in this way there are formed three new bases: C21H21N07, C20H19N07, and C19II17N07, which as yet have not been further investigated. Heated with dilute sulphuric acid and manganese peroxide, narcotine yields opianic acid (p. 382) ^ and cotarnine; boiled for a long time with water it is resolved into meconin (p. 382) and cotarnine ; warmed with dilute nitric acid, there are formed opianic acid, cotarnine, meconin, hemipinic acid (p. 382), and other bodies. Cotarnine, C12H13N03 -f H20 , is most readily ob tained by heating narcotine with diluted (with ten times its weight of water) nitric acid at 49° until solution results. From the solution, filtered after 440 OPIUM BASES. being allowed to cool, it is precipitated by means of potassa. — Colorless, stellate prisms; soluble in boiling water, in alcohol and ammonia, but not in potassa ; fuses at 100°. Monatomic base. When boiled with very dilute nitric acid, it is converted into cotarnic acid, CUII1205, and a substance forming good crystals, apophyllic add, C8H7NO. At the same time methyl- amine nitrate is formed. 3. Codeine, C18II21N03. Crystallizes, anhydrous in octahedrons, or, with one molecule of water of crystal lization, in rhombic crystals. Fuses at 150°. Easily soluble in hot water, alcohol, and ether; less soluble in cold water (80 parts), insoluble in potassa, soluble in ammonia. When heated from twelve to fifteen hours with concentrated hydrochloric acid, under a layer of paraffin over a water bath, it yields chlorocodide hydro- chlorate, C18H20C1N02.HC1, from which, by means of sodium bicarbonate, the chlorinated base may be pre cipitated in the form of a white powder; easily soluble in alcohol and ether. When the hydrochlorate is heated with water at 130-140°, it is resolved into codeine hydrochlorate. If, on the other hand, codeine or chlorocodide hydrochlorate be heated with concen trated hydrochloric acid at 140-150°, they are both broken up, yielding methyl chloride and apomorphine hydrochlorate (p. 439). 4. Thebaine, C19H21JsT03. Quadratic plates, of a silvery lustre; insoluble in water, potassa, and am monia. Easily soluble in alcohol and ether. Soluble in concentrated sulphuric acid, the solution being deep-red. Its salts can only with difficulty be obtained in a crystalline form from water, as they decompose, when their solutions are evaporated. Exceedingly poisonous. When boiled with hydrochloric acid, it is converted into an isomeric base, thebenine, which is amorphous, absorbs oxygen from the air, especially in the presence of alkalies, and yields salts that crystal lize well. BASES OF CINCH ON A -BARK. 441 5. Papaverine, C21H21]Sr04. Colorless prisms ; fusing point, 147° ; insoluble in water, difficultly soluble in cold alcohol and ether, more easily in the hot liquids. 6. Narceine, C23H29N09. White, fine needles, of a silky lustre ; fusing point, 145°. But slightly soluble in cold water and cold alcohol, more easily in the hot liquids, insoluble in ether. Is colored blue by iodine, like starch, if care be taken to avoid an excess of iodine. Taken in small quantity it causes a very sound and quiet sleep. In addition to these, in some varieties of opium, there occur, in exceedingly small quantity, other alka loids : mecomdine, C21H23N04; laudanine, C20H251TO3; codamine, C19H23N03 ; cryptopine, C21H23^T05 ; protopine, C10H19^"05; laudanosine, C21H27lSr04 ; hydrocotarnine, C12H15M)3; lanthopine, C^IP^O4; opianine, metamor- phine, and rhoeadine, C21H21N06. The latter base is also contained in Papaver rhoeas. 5. Bases of Cinchona-bark. In true cinchona-barks there occur principally two alkaloids : — Quinine, C20H24^202, and Cinchonine, C20H24K20, in varying quantities. Calisaya bark (China regia) contains the most quinine (between 2 and 3 per cent, quinine, and 0.2-0.3 cinchonine); Huanaco bark con tains the most cinchonine* (2.24 per cent, cinchonine, and 0.85 per cent, quinine). A few other alkaloids, as, for instance, aricine, C23H26N204, paytine, C21H24N20 + H20, occur in only a few cinchona-barks ; other bases, isomeric with quinine and cinchonine, as quinidine, cinchonine, do not appear to occur in the plants origin ally, but to be formed from quinine and cinchonine by a process of transformation. * The base, kuanocine, which has been prepared from this bark, is probably identical with cinchonine. 442 BASES OF CINCHONA-BARK. Preparation. Coarse cinchona powder is repeatedly macerated with water containing hydrochloric acid ; the filtered solution mixed with sodium carbonate; the precipitate washed, pressed, and dried. It contains quinine and cinchonine, calcium tannate, and other substances. Both bases are extracted with boiling alcohol ; the filtered, strongly colored solution neutral ized with dilute sulphuric acid ; and the alcohol dis tilled off. On cooling, quinine sulphate crystallizes out, which is obtained colorless by treatment with animal charcoal, and recrystallization. From the col ored mother-liquor cinchonine sulphate is obtained. To isolate the bases their salts are dissolved in water, and precipitated with ammonia. 1. Quinine, C20H2W02 + IPO. Precipitated by ammonia, it forms a white, earthy mass ; and it is diffi cult to obtain it in a crystalline form even from alco hol. It is fusible, writh loss of water, forming a resin ous mass; tastes very bitter; reacts alkaline; soluble in 1667 parts water of 20°, in 900 parts boiling water, moderately soluble in ether, very easily soluble in alcohol. Combines with one and with two molecules of a monobasic acid, forming salts. Most of these are crys- tallizable, have a very bitter taste, and are precipitated by oxalic acid ; also by alkalies, platinum chloride, and tannic acid. Quinine hydrochlorate. The salt, with one mole cule of hydrochloric acid, C20H24]ST202HC1 + 1JIPO, forms long prisms, of a silky lustre ; the salt, with two molecules of the acid, is converted into the first salt by the action of water. Platinum chloride gives a bright-yellow precipitate in the hydrochloric acid solution, which, after a time, becomes crystalline and orange-red (C20H24N2O2.2HCl.PtCl4 + H20); mercury chloride gives a white precipitate. Quinine sulphate, 2p°H24N202)H2S04 + 7JIPO (the principal form in which quinine is employed as a BASES OF CINCHONA-BARK. 443 medicament), crystallizes out of a hot saturated solu tion of quinine, in dilute sulphuric acid, in long, shiny prisms; as prepared in manufacturing establishments, it usually forms a white, porous, light mass, consisting of very fine and short needles, which have partially lost their water of crystallization. It tastes exceed ingly bitter ; is very difficultly soluble in water (in 780 parts at the ordinary temperature), more easily soluble in alcohol, easily soluble in water containing sulphuric acid, forming a blue, fluorescent liquid. Fuses like wax, and, when more strongly heated, turns a beautiful red, and is then carbonized. — If an alcoholic solution of iodine is added to a solution of this salt in acetic acid, after a time large, thin plates, consisting of a compound of quinine sulphate with iodine (herapa- thite) separate. These crystals are almost colorless in transmitted light ; in reflected light they have a beau tiful, green color and a metallic lustre, and polarize light like tourmaline plates. 'The biarid salt, C20H24F202.H2S(> -f 7H20, crystallizes in transparent, four-sided prisms ; is more easily soluble ; and has an acid reaction. If chlorine water is added to a salt of quinine, and then ammonia, it turns an intensely emerald-green color. If, after the addition of chlorine water, a little potassium ferrocyanide and then ammonia are added, a deep red color makes its appearance. 2. Cinchonine, C20H2W20. Precipitated with am monia, it forms a white, earthy mass. Crystallizes easily from alcohol in shiny prisms. Insoluble in water and ether, soluble in hot alcohol, less easily than qui nine. The salts resemble the salts of quinine, but are more easily soluble. They give no green color with chlorine water and ammonia, but a yellowish-white precipitate. When heated with bromine or chlorine, substitution- products of cinchonine are formed. Dibromicinchowne, C20H22Br2N20, is formed by heating cinchonine hydro- chlorate with an excess of bromine, and, on dissolving 444 BASES OF CINCHONA-BARK. the product in hot water, and adding alcohol and am monia, separates on cooling in colorless crystalline lami nae. These are decomposed by boiling with alcoholic po- tassa, forming potassium hromide and a crystallizing base, oxy cinchonine, which is isomeric with quinine, but essentially different from it ; insoluble in water and ether. The chinoidine of commerce, which in the manufac ture of quinine is obtained from the last mother- liquors, contains principally two bases, isomeric with quinine and cinchonine, viz. : quinidine arid cinchonidine. 3. ftuinidine (Conquinine), C20H24]$r202 + 2II20. Is contained in all cinchona-barks, but more especially in the Pitaya bark ; is obtained from chinoidine by ex tracting with a little ether, adding alcohol to the fil tered solution, and evaporating it slowly. — Crystallizes from alcohol in large prisms, which are sparingly solu ble in water, and effloresce readily. Fusing point, 168°. Gives the quinine reaction with chlorine water and ammonia. 4. Cinchonidine and P-Cinchonine are the names which have been given to two bases very similar to, but not identical with, cinchonine. A base isomeric with cinchonine is contained in quinoidine and in commercial quinidine ; another, of the composition C18H22N20, has been found in a few varieties of cinchona. "When the sulphates of these four cinchona bases are moistened with water and sulphuric acid, and carefully kept fusing at 130° for a few hours, they are converted into the sulphates of two new resinous bases, quinicine and cinchonicine. These are isomeric with quinine and cinchonine, but entirely different from them in all their properties. Quinicine is formed from quinine and quinidine, cinchonicine from cinchonine and cin chonidine (that prepared from quinoidine). Heated with caustic potassa, the cinchona bases yield volatile bases, chinoline, and homologous sub stances (see end of this section). BASES OF THE STRYCHNOS SPECIES. 445 6. Bases of the Strychnos Species. In various species of Strychnos, particularly in nux- vomica (the seed of Strychnos nux vomica), and in the bean of St. Ignatius (seed of Strychnos Ignatii\ are con tained two alkaloids : — Strychnine C2lH22]Sr202, and Brucine, C23H26^sT204, which are distinguished by their extraordinary, poison ous properties, and the power of causing tetanus when taken even in very small quantities. Preparation. The nuts boiled with alcohol, and then dried and powdered, are exhausted by boiling with di lute alcohol. The extracts are freed of alcohol by distil lation, and foreign substances precipitated by means of lead acetate ; the filtrate, after the removal of lead by sul phuretted hydrogen, evaporated ; and the bases precipi tated by magnesia. In a week the precipitate is filtered off, dried and boiled with alcohol. On evaporating, strychnine crystallizes at first: in the mother-liquor remains brucine together with strychnine. By neutral izing with very dilute nitric acid, and allowing the strychnine nitrate to crystallize out, the two are sepa rated, as the brucine salt remains in the mother-liquor, and crystallizes out afterwards. The salts decolorized by means of animal charcoal are now dissolved in water, and the bases precipitated by means of ammo nia. 1. Strychnine, C21H22N202. Small colorless prisms of an exceedingly bitter taste ; reacts alkaline. Scarcely soluble in water, insoluble in ether and anhy drous alcohol, most easily soluble in dilute alcohol, in benzene, and in chloroform. Most salts of strychnine are crystallizable, possess an exceedingly bitter taste, and act like strychnine itself as deadly poisons. — Its solution is precipitated in a crys talline form by potassium sulphocyanide. Strychnine nitrate, C21H22N202.msT03. Colorless 38 4:46 BASES OF THE VEKATRUM SPECIES. fascicular needles. But slightly soluble in cold water and alcohol, more easily soluble in hot water. Strychnine dissolves in concentrated sulphuric acid, forming a colorless liquid, which becomes a beautiful violet, when a few small pieces of potassium bichrom ate are added. 2. Brucine, C23H26K204 + 4H20. Crystalline laminae or large colorless prisms, which effloresce in the air. Very similar to strychnine, but more easily soluble in water, and particularly in alcohol; and less poisonous. Concentrated nitric acid colors it red ; on heating, yel low : and if tin chloride or ammonium sulphide is added, the yellow color is converted into a very in tense violet. Concentrated sulphuric acid dissolves it, the solution having a pale red color, which soon passes into yellowish-green. 7. Bases of the Veratrum Species. In the different species of Veratrum are contained two alkaloids : — Yeratrine, C32H52]^"208, and Jervine, C30H46K203. Yeratrine occurs chiefly in sabadilla seeds (of Vera trum sabadilla\ together with veratric acid (p. 359) ; and in the root of Veratrum album; jervine occurs only in the latter. Preparation. In a manner similar to that described in connection with the preceding bases. They can be easily separated from each other by treatment with dilute sulphuric acid, which readily dissolves the vera- trine, but converts the jervine into a very difficultly soluble sulphate. 1. Veratrine, C32H52^"208. "White powder or color less prisms, becoming untransparent in the air; fuses at 115°, and solidifies, forming a resin-like mass. Scarcely soluble in water, easily soluble in alcohol and ether. Yery poisonous ; it causes violent sneezing, when in- BASES OF BERBERIS VULGARIS. 447 troduced into the nose in the form of powder or in solution in small quantity. It dissolves in concen trated sulphuric acid, forming a yellow liquid, which soon becomes reddish-yellow, and finally intense blood- red. It is dissolved by concentrated hydrochloric acid, forming a colorless liquid, which, boiled for a long time, becomes colored an intense violet. 2. Jervine, C30H46N203 4- 2H20. Colorless prisms, insoluble in water, soluble in alcohol ; fuses when heated. Its salts are for the greater part very diffi cultly soluble in water. 8. Bases of Berberis Vulgar is. In the root of these plants are contained two alka loids : — Berberine, C20H17NO, and Oxyacanthine, C32H36^20U (?). Berberine occurs besides in a great many other plants; in colombo-root (of Cocculus palmatus), in several Menispermacece and Ranwiculacece (in large quantity, for example, in the wood of Cosdnium fenes- tratum, and in the root of Hydrastis Ganadensis, which is officinal in North America.) The preparation of berberine takes place in the same manner as that of the other bases. For the purpose of purification, the difficult solubility of the nitrate in nitric acid is made use of. 1. Berberine, C20H17ISr04. Fine yellow prisms, of a strong bitter taste, easily soluble in hot water and alco hol, insoluble in ether; loses five molecules of water of crystallization at 100°, becoming brown; fuses at 120°. Its salts are yellow and crystallizable, most of them insoluble in an excess of acid. If a dilute solution of iodine in potassium iodide be added, not in excess, to a hot alcoholic solution of a salt of berberine, green crystalline laminse, of a metallic lustre very similar to herapathite (p. 443), separate from the solution on cool ing. Nascent hydrogen (zinc and dilute sulphuric acid or acetic acid) convert it into another base, hydroberberine. 448 THEOBBROMINE. C20H21ND4, which crystallizes from alcohol in small, colorless, granular crystals of a diamond lustre, or long, flat needles, and is reconverted into berberine by nitric acid. 2. Oxyacanthine. White amorphous powder; be comes yellow in direct sunlight. Crystallizes from alcohol and ether in fine colorless prisms. Insoluble in water, soluble in alcohol and ether, particularly in the boiling liquid. 9. T/ieobromine. Occurrence. In the cacao-bean. Preparation. The watery extract of the broken-up beans is precipitated by lead acetate ; filtered ; the lead removed from the filtrate by sulphuretted hydrogen ; then evaporated; and the base extracted from the resi due with absolute alcohol. Properties. White crystalline powder of a weak, bit ter taste; but slightly soluble in water, alcohol, and ether, more easily in ammonia; sublimable. Weak base. The hydrochlorate, C7HM402.HC1, crystallizes from a solution in hydrochloric acid. The solution of the free base in ammonia gives a granular crystalline precipitate of theobromine-silver, 7H7AgK402, when boiled for a length of time with silver nitrate. 10. Caffeine, The'ine (Methyl- Theobromine). C8H102W + H20. Occurrence. Contained in coffee, tea, Paraguay tea (of Ilex Paraguayensis), in cola-beans and in guarana (a mass prepared from the fruit of Paullinia sorbilis) ; and is obtained from them by the same method as that described for theobromine. Formation. By heating theobromine-silver with methyl-iodide in sealed tubes for twenty-four hours. Properties. Colorless, long and very thin prisms of a silky lustre ; of a weakly bitter taste ; difficultly solu ble in cold water and alcohol, more easily in hot water. PIPERINE. 449 Loses its water of crystallization completely at 100° ; fuses at 234-235°, and sublimes undecomposed. Weak base. If a trace of caffeine is dissolved in chlorine-water and the colorless liquid evaporated, there remains be hind a brownish-red spot, which dissolves in ammonia, forming a beautiful violet solution. By t!he action of chlorine or nitric acid on caffeine suspended in water, it is converted into amalic acid, C12H12N407 (tetramethylalloxahtine, C8(CII3)4N407, see Uric acid, p. 237), methylamine and cyanogen chloride being formed at the same time. It forms colorless, difficultly soluble crystals, which become purple in contact with alkalies, and color the skin red. Further action of chlorine causes the formation of cholestrophan, C5H6SP03( = dimethyl-parabaiiic acid, C3(CH3)2N203, p. 235). Boiled with alcoholic potassa or with barium hy droxide, caffeine assimilates water and gives^ up car bonic acid, and is converted into an uncrystalline base, cajfeidine, C7II12N40, easily soluble in water and alco hol. This is a stronger base than caffeine. Its sul phate crystallizes in colorless long needles. When boiled continuously with barium hydroxide, there are formed ammonia, methylamine, carbonic acid, formic acid, and sarcosine (p. 85). 11. Piper inc. Occurrence. In the various kinds of pepper. Preparation. Powdered white pepper is exhausted with alcohol ; the solution distilled off until it forms an extract ; this is then washed with water, mixed with potassa, and again dissolved in alcohol. On evapo rating, piperine separates, which is purified by repeat edly dissolving in alcohol, and crystallizing. Properties. Colorless, four-sided prisms, without taste or odor, fusing at 100°, not volatile. Scarcely soluble in water, easily soluble in alcohol. The solu tion tastes sharp, like pepper, and is neutral. Soluble 58* 450 SINAPINE. in cold concentrated sulphuric acid, giving a dark red colored solution. Very weak base. Decompositions. Heated with soda-lime, it yields piperidine ; by boiling with an alcoholic solution of po- tassa, it is resolved into piperidine and piperic acid (p. 383), one molecule of water being taken up. Piperidine, C5HnK = C5II10.KH. Colorless fluid ; mixes with water and alcohol ; boils at 106° ; strongly alkaline ; gives well crystallizing salts with acids. It conducts itself towards the iodides of the alco holic radicles exactly like conine. Methylpiperidine, C5H10.KCH3,and Ethylpiperi- dine, C5H10.KC2H5, are colorless fluids, boiling at 118° and 128°, respectively. Piperine is decomposed by ben- zoyl chloride, forming piperidine hydrochlorate and crystalline benzoylpiperidine, C5II10.KC7H50. Other acid chlorides conduct themselves in an analogous manner. Piperine is a compound of this kind. 12. Sinapine. C16H23M)5. Occurrence. In the seeds of Sinapis alba as sinapine sulphocyanate. Preparation. Yellow mustard is freed of most of its fatty oil by pressure ; first exhausted with cold alcohol, and then with hot 85 per cent, alcohol ; most of the alcohol distilled off; and the lighter layer of liquid, which separates on cooling, removed. Sinapine sul phocyanate crystallizes from the residue, which is purified by pressing and recrystallizing from alcohol. The free base cannot be prepared on account of the ease with which it undergoes decomposition. Sinapine sulphocyanate, C16H23K05.HCNS. Colorless very voluminous crystalline mass, consisting of fine needles, difficultly soluble in cold water and alcohol, easily in hot ; fuses at 130°. Sinapine sulphate, C16H23K05.H2S04 + 2H20, crystal lizes from a hot alcoholic solution of the sulphocyanate HARMALINE. 451 on the addition of sulphuric acid. From this salt the hasc can be set free hy means of baryta, but it remains dissolved, imparting to the solution a deep yellow color ; and on evaporating, it is decomposed. On boil ing its salts with potassium or barium hy droxide, sinapine is decomposed, yielding choline (p. 140) and sinapic acid (p. 381). 13. Harmaline. Occurrence. In the seeds of Peganwn harmala (a plant growing on the steppes of Russia). Preparation. The powdered seeds are exhausted with water containing a little sulphuric or acetic acid. The alkaloid is precipitated from the extract with a concentrated solution of sodium chloride, in the form of the hydrochlorate ; and this, after being purified by recrystallization, decomposed with ammo nia. Properties. Colorless, rhombic octahedrons; spar ingly soluble in water and cold alcohol, more easily in hot alcohol ; fuses when heated. Combines with acids, forming yellow salts, which are for the greater part easily soluble. Monatomic base. Harmine, C13H12K20, occurs together with harma- line in the seeds of Peganum harmala, and can be sepa rated from this by subjecting a warm hydrochloric acid solution to partial precipitation with ammonia. It is formed from harmaline by oxidation, when ^its nitrate is warmed with alcohol and hydrochloric acid ; or from its bichromate, when heated to 120°.— Colorless sbiny prisms, but slightly soluble in water, more easily soluble in alcohol. 14. Cocaine. C17H21N04. Occurrence. In coca leaves (from Erythroxylon coca). Preparation. The leaves are repeatedly extracted with water of 60-80° ; the extract precipitated with 452 ATROPINE. lead acetate; the lead removed from the filtrate by means of sodium sulphate ; after concentrating by eva poration, and adding sodium carbonate until the liquid shows a weak alkaline reaction, the cocaine is ex tracted by shaking with ether. Properties. Colorless and tasteless, four- or six-sided monoclinic prisms. Fuses at 98°. But slightly solu ble in cold water, more easily in alcohol, very easily in ether ; reacts alkaline, and has a weak, bitter taste. On. heating with hydrochloric acid it is decomposed with assimilation of water, yielding benzoic acid, methyl alcohol, and ecgonine, C9II15iTO3 + H20, a base, easily soluble in water ; less soluble in absolute alco hol, in ether insoluble ; crystallizing in colorless prisms, of a vitreous lustre, which melt at 198°. There is also contained in coca leaves, together with cocaine, a liquid, volatile alkaloid, hygrine. 15. Atr opine. C17H23]TO3. Occurrence. In all parts of Atropa belladonna and Datura stramonium. Preparation. Fresh belladonna leaves, gathered at the commencement of the period of flowering, are pressed; the juice heated to 80-90° ; filtered ; and after the addition of potassa, the atropine extracted by shak ing with chloroform. It is extracted from the roots of the belladonna and from the seeds of the thorn- apple in a manner similar to that described in connec tion with the other alkaloids. Properties. Crystallizes in fine, white prisms ; fusible at 90° ; tastes very disagreeably bitter and sharp. Soluble in thirty parts of boiling water, less in cold water, easily soluble in alcohol. Easily decomposable in solution, even when combined with acids, forming ammonia. Atropine sulphate and hydrochlorate crystallize in fine needles, are permanent in the air, easily soluble in water. It is very poisonous, and the smallest quantity causes dilatation of the pupils. When heated with barium hydroxide or hydro- ACONITINE. 453 chloric acid, it is resolved into tropic acid (p. 354) and the acids resulting from this, atropic and isatropic acids (p. 376); and into tropine, C8H15NO, a base easily soluble in water and alcohol, which crystallizes from ether in colorless plates, fusing at 61°. Water is as similated in this decomposition. 16. Thysostigmine (Eserine), C15II21^NT302. In the Cala bar bean (the seed of Physostigma venenosum, a plant growing in Upper Guinea). — Yellow, amorphous mass, fusing at 45° ; sparingly soluble in water, easily sol uble in alcohol, ether, benzene, and chloroform. Strongly alkaline; tasteless; exceedingly poisonous; causes a decided contraction of the pupil. The free base as well as its salts are decomposed in aqueous solu tions in the air. 17. Hyoscyamine, C15H23N03. In the leaves and seeds of Hyoscyamus niger and albus. — Fine prisms, of a silky lustre ; inodorous when pure, when moist or im pure of a very repulsive, suffocating odor, and sharp, disagreeable taste ; easily fusible. Moderately solu ble in water ; alkaline ; very decomposable in contact with alkalies. Very poisonous; causes, like atropine, dilatation of the pupil. When heated with barium hydroxide, it is resolved into hyoscinic acid, C9H1003 (identical or isomeric with tropic acid), and a crystal line base hyoscine, C5H13N\ \ 18. Emetine. In ipecacuanha (the root of Cephaelis ipecacuanha). — White powder ; fusing point, 70° ; sparingly soluble in cold water, very easily soluble in alcohol ; of a weak, bitter taste. — Even in very small doses it causes violent vomiting. 19. Aconitine, C27H39^"010 (?). In the leaves and seeds of Aconitwn napellus, in company with aconitic acid (p. 179). — Colorless, rhombic plates ; almost inso luble in water even at the boiling temperature ; a drop of acid causes instantaneous solution ; soluble in alcohol, 454 CHINOLINE BASES. ether, benzene, and chloroform. Has a weak alkaline reaction. Very poisonous. 20. Cokhicine, C17H193T05. In all parts of Colchicum dvtymnale. — Colorless, amorphous mass, without odor; of a, Very bitter and sharp taste. Moderately soluble in water ; in alcohol very easily soluble ; insoluble in ether. Fuses at 140°. Very poisonous; in small quantity causes vomiting and diarrhoea. Hardly possesses basic properties, and when heated with dilute acids is con verted into a substance of the same composition, colchiceine, which crystallizes in needles and possesses weak acid properties. In addition to those already described, numerous other vegetable alkaloids have been prepared, but for the greater part but slightly investigated. ^ In the distillation of several natural alkaloids (qui nine, cinchonine, strychnine), with potassa, there re sults a number of fluid bases (chinoline bases), very similar to each other, which are distillable without de composition. These do not occur ready formed in nature, but bases of the same composition, and perhaps identical with them, are produced in the distillation of several other bodies, and are contained in coal tar. They form an homologous series, the better known members of which are chinoline, C9H7N (boiling point, 238°), lepidine, C10H9]^ (boiling point, 266-271°), and cryptidine, CnHnK They are colorless liquids, spar ingly soluble in water, easily soluble in alcohol and ether, and yield with acids easily soluble, crystallizing salts. They contain no hydrogen capable of replace ment by alcoholic radicles, but, on the contrary, unite directly with the alcoholic iodides, forming well crys tallizing iodides, from which, by treatment with silver oxide, are obtained bases analogous to tetrethylammo- nium hydroxide. Chinoline, heated with amyl iodide, yields amyl- ALOIN. 455 chinoline iodide, C14H18OT = C»HT.C8HnNI, which, when heated with potassa, yields a beautiful, but not very permanent blue dye, cyanide iodide (the cyanine of commerce), C28H35^"2I. This crystallizes in beautiful green plates, of a metallic lustre ; is insoluble in water and ether, easily soluble in warm alcohol; fuses at 100°. It combines directly, and without separation of iodine, with two molecules of hydrochloric acid, form ing a colorless salt; when heated with silver oxide, however, it gives up its iodine, and yields a bronze- colored, amorphous base. Lepidine conducts itself like chinoline, and yields a very similar dye, C30II39K2I. The cyanine of commerce is either the derivative of chinoline or of lepidine, or of a mixture of both. C. COLORING MATTERS, BITTER PRINCIPLES, ETC. These names are applied to a large number of pecu liar neutral or weakly acid substances, of which only a few have been moderately well investigated. Least known are the uiicrystalline, although these often possess interest from the fact that they are frequently constituents of the so-called vegetable extracts. The following, which are mostly crystalline, are among the more remarkable substances of this kind, arranged in alphabetical order. Aloin, C1TII1807. Is the purging, active principle of aloes, the juice, dried in the sun, obtained from various species of aloe, either by cutting the leaves, and allowing it to exude spontaneously, or by pressing the separated leaves. The best sort of aloes consists of brown or dark greenish-brown transparent masses, of a lustrous fracture, of a disagreeable odor and a disagree able, bitter taste. — Aloin forms small, colorless crystals, of a sweetish-bitter taste ; difficultly soluble in cold water and alcohol; becoming brown and resinous when melted, and readily becoming amorphous under all circumstances. — "When aloes is heated with nitric acid, an orange-yellow powder, aloetic acid, C7H2(K02)20, 456 CANTHARIDIN. is at first produced, and afterwards, by further action, chrysammic add (p. 409). When fused with caustic potassa, it yields orcine (p. 307), paraoxybenzoic (p. 347), alorcic (p. 353), and oxalic acids. Athamantin, C24H300T. In the root and half-ripe seeds of Athamanta oreoselinum. — Lustrous, crystalline mass, consisting of fine needles or large, four-sided prisms. Insoluble in water, easily soluble in alcohol and ether. Combines with dry hydrochloric acid and sulphurous anhydride, forming crystalline compounds. The hydrochloric acid compound is decomposed when heated alone or when its alcoholic solution is evaporated, yielding valeric and hydrochloric acids and oreoselone, C14H1003, which crystallizes in colorless needles ; insolu ble in water, difficultly soluble in alcohol jind ether ; is converted into a crystalline substance, oreoselin,CuIl120\ when boiled with water containing hydrochloric acid. Antiarin, C14H2005, a neutral substance, crystallizing in colorless laminae; difficultly soluble in alcohol; forms compounds with acids, bases, and metallic salts ; is the exceedingly poisonous ingredient of a variety of upas, an extract prepared in Java, from the sap of Antiaris toxicaria. Brasilin, C22H2007(?), the coloring matter of Brazil and Pernambuco wood. Small, reddish-yellow prisms, soluble in water and alcohol, forming a red solution. Acids turn it yellow, citric acid causes this change especially beautifully ; when now neutralized with an excess of alkali it turns violet or blue, with ammonia deep carmine-red. It is decolorized by sulphuretted hydrogen and sulphurous anhydride. Cantharidin, C5H602. Is contained in beetles of the genera Lytta, Meloe, and Myldbris, especially in Spanish flies (Lytta vesicatoria), arid can be extracted from them with ether. — Colorless, four-sided prisms, or laminae. Insoluble in water, sparingly in alcohol, easily soluble in ether; melts at 250°, and sublimes at a lower temperature without decomposition. Raises CHLOROPHYL. 457 blisters on the skin. Dissolves when heated for a length of time with aqueous alkalies, assimilating water and forming salts of cantharidic acid, C5H803. These crystallize well, but on the addition of acids to the solutions, cantharidin separates, but no cantharidic acid. Carotin, C18H240, together with hydrocarotin, C18H300, in ^carrots (Daucus carota), deposited in the cells in microscopical crystals, the cause of the color of the carrots. — Small, reddish-brown, cubical crystals; fusible at 168° ; insoluble in water, difficultly soluble in alcohol. Carthamin, C14II1607, the red coloring principle of safflower, the dried flowers of Carthamus tinctorius. After exhausting the yellow coloring principle from pure safflower by means of cold water, the carthamin is extracted by treating with a dilute solution of sodium carbonate. The red liquid is then neutralized with acetic acid, and pure cotton immersed in it, on which all the carthamin is deposited. After washing with water the carthamin is again extracted with a dilute solu tion of sodium carbonate, precipitated with citric acid, and the beautifully crimson-colored precipitate washed by decantation. — Amorphous, deep-red powder, with greenish iridescence; in thin layers it has a beautiful green metallic lustre. Sparingly soluble in water, more soluble in alcohol. Soluble in alkalies, yielding a deep yellowish-red solution. Very unstable in these solu tions. Melted with potassa it yields paraoxybenzoic acid and oxalic acid. Chlorophyl. The green color of plants is occa sioned by the presence of microscopical, green globules, which float in the cells. These so-called chlorophyl- globules consist of several substances, which inclose a green coloring principle. The composition, as well as the nature of this coloring principle, is as yet unknown ; it appears to contain no nitrogen, but iron, as an essential ingredient. It dissolves in hydrochloric 39 458 H^EMATOXYLIN. acid, forming a green liquid, from which it can be thrown down with boiling water. It is also soluble in alcohol and ether. Columbin, C21H2207, in columbo-root (of Cocculus palmatus), together with berberine and a pale-yellow, almost insoluble substance, columbic acid. — Colorless prisms, having a bitter taste. Curcumin, C10H1003. The coloring matter of tur meric root. Can be most readily extracted by means of boiling benzene, in which but little of the remain ing constituents of the root is soluble. — Orange-yel low prisms, of a weak, vanilla-like odor ; fusing point, 165° ; almost insoluble in water, difficultly soluble in carbon bisulphide and benzene at the boiling tempera ture, easily soluble in ether and alcohol ; soluble in alkalies and alkaline carbonates, the solutions having a brownish-red color. Acids precipitate the curcumin from the solutions in the form of yellow powder. Paper colored with curcumin turns a brownish-red when brought in contact with liquids that have an alkaline reaction; on drying, this color changes to violet ; acids restore the original yellow color ; when moistened with a solution of borax, and then- dried, it turns orange-yellow, and this color is not changed by dilute acids, but is converted into blue by alkalies. Gentianin (Gentianic acid), C14II1005, in the root of Gentiana lutea, which owes its bitter taste, however, not to this, but to another, uninvestigated substance. — Fine, bright-yellow prisms, without taste; scarcely soluble in water, soluble in alcohol; partially subli'm- able ; soluble in alkalies, forming bright-yellow solu tions. Yields, with alkalies, salts which crystallize well, and are decomposed even by carbonic acid. Haematoxylin, C16H1406, in logwood (Hcematoxylin campechianum), from which it can be extracted with water or, better, ether. — Yellow, transparent prisms, which, when heated, give up water of crystallization. It possesses a sweetish taste, and is sparingly soluble in PICROTOXIN. 459 cold water, easily soluble in boiling water, in alcohol and ether, the solution being of a yellow color. ^ Solu ble in very large quantity in a saturated solution of borax. Ammonia dissolves it, forming a purple solu tion, which, in contact with the air, becomes ^ dark-red, and, when evaporated, leaves behind dark-violet crys tals of hcematetn-ammmia, C16H9(NH4)05 + 2H20(?). From a solution of the latter body, acetic acid throws down a brownish-red, voluminous precipitate of hcema- tein, C16H1005(?). Helenin, C21H2803, in the root of Inula Helenium, from which it can be extracted by means of alcohol. — Colorless, four-sided prisms ; insoluble in water, easily soluble in alcohol and ether ; fuses at 72°. Is decom posed, by heating with phosphoric anhydride, into water, carbonic oxide, and a liquid hydrocarbon, hele- nene, C19H26. Laserpitin, C24H3607, in the root of Laserpitium latifolium. — Colorless, rhombic prisms ; insoluble in water, easily soluble in alcohol and ether. Fuses at 114°. Sublimes undecomposed. Is resolved into angelic acid (p. 124) and an amorphous substance, laser ol, C14H2204, when heated with caustic potassa. Peucedanin (Imperatorin), C12H1203, in the root of Peucedanum officinale and Imperatoria obstruthium. — Colorless prisms, of bright lustre. Insoluble in water, soluble in alcohol and ether ; fuses at 75° ; not sub- limable. Is decomposed by boiling with an alcoholic solution of potassa into angelic acid and oreosilin (com pare Athamantin, p. 456). Picrotoxin, C12H1405, in the seeds of Cocculus indicus (Menispermum cocculus). The powdered seeds are extracted with boiling alcohol, the alcohol distilled off from the extract, and the residue boiled with a large quantity of water. Foreign bodies are precipi tated from the aqueous solution by means of lead acetate; the nitrate evaporated after treatment with sulphuretted hydrogen; and the picrotoxin, which 460 SA'NTALIC ACID. now separates, purified by repeated crystallization from water. — Stellate groups of colorless needles, of an in tensely bitter taste. Difficultly soluble in cold water, more easily soluble in hot water and in alcohol. Very poisonous. Combines with alkalies, baryta, and lime, forming gummy compounds, which are obtained pure only with great difficulty. "When boiled with weak acids, it is converted into non-crystallizing, weak acids. By boiling it with nitric acid, oxalic acid is produced. Porrisic acid (Euxanthic acid), C19H16010, in purree, a yellowish coloring matter, imported from^ the East Indies, probably the juice of a plant evaporated with magnesia. Purree consists essentially of magnesium euxanthate. — The acid forms yellow, shiny "prisms, sparingly soluble in cold water, easily soluble in alco hol and ether. Its salts, with the alkaline metals, are yellow, crystallizable. The magnesium salt crystal lizes particularly beautifully. With chlorine and bro mine, it forms yellow-colored crystallizing acids, con taining chlorine and bromine (C19H14C12010 and C19H14 Br2010). "When heated to 180°, it is decomposed into carbonic- anhydride, water, and euxanthon, C13HS04, which is also formed when the acid is dissolved in con centrated nitric acid; this substance crystallizes in- yellow prisms ; when melted with potassium hydrox ide it yields, first euxanihonie acid, C13H1005, at a higher temperature hydroquinone (p. 303). ftuassin, C10II1203, the bitter ingredient in the wood of Quassia amara and excelsa from South America. — Fine, colorless, crystalline laminae, of an exceedingly bitter taste ; but slightly soluble in water, easily soluble in alcohol ; fusible, solidifying in a resinous state. Santalic acid (Santalin), C15H1405, in sandal wood (from Iterocarpus santalinus), from which it is ex tracted with alcohol. It is precipitated from the solu tion with lead acetate, and the precipitate decomposed with dilute sulphuric acid and alcohol. — Microscopical crystals, of a beautiful red ; insoluble in water, soluble SMILACIN. 461 in alcohol and ether. Soluble in alkalies, with a violet color. Santonin (Santonic acid), C15H1803, in the seeds of Artemisia santonica, of which it forms the active prin ciple. The seeds are mixed with about half their weight of caustic lime, and extracted with dilute alco hol. The extract, after being distilled, is filtered and boiled with acetic acid. The santonin, which crystal lizes out on" cooling, is purified by recrystallizing from alcohol, and treating with animal charcoal. — Very shiny, colorless prisms, of a slightly bitter taste; scarcely soluble in water, easily soluble in hot alcohol; fusible" at 170°, solidifying in a crystalline form, but when cooled suddenly becoming amorphous ; only par tially sublimable. Weak acid. The colorless crystals become a bright yellow in direct sunlight, frequently cracking ; their composition, however, does not appear to be changed. Exposed to direct sunlight for a long time in an alcoholic solution, it is converted into pho- tosantonin, C23H3406(?), formic acid and other products being formed at the same time. Photosantonin crys tallizes in colorless laminae, fusing at 64-65°. Scoparin, C21II22010,in Spartium scoparium, together with sparteine (p. 435). — When its alcoholic solution is allowed to evaporate spontaneously, it is obtained in small, stellate crystals. Slightly soluble in cold water and cold alcohol, easily soluble in the hot liquids. It is dissolved by the alkalies with a yellowish-green color, and from these solutions it is thrown down by acids as a white, amorphous precipitate. Fused with potassa it yields phloroglucin and protocatechuic acid. Smilacin, C18II3006 (?), in sarsaparilla (the root of various species of Smilax), from which it can be ob tained by boiling with alcohol. — Fine, colorless prisms. Insoluble in cold water, slightly soluble in hot water, forming a disagreeably tasting and strongly foaming liquid. Easily soluble in ether and hot alcohol. 39: 462 TURPENTINE OIL. D. ETHEREAL OILS. The name ethereal or volatile oils has been applied to all those compounds, which pass over with the vapor on heating certain plants or parts of plants with water, and form the odorous constituent of these plants. Most of them are mixtures of compounds containing oxygen and hydrocarbons. The oxygenized bodies are of very various character, and belong to entirely dif ferent chemical groups. They are in some cases acids (valeric acid in oil of valerian, pelargomc acid in the oil of Pelargonium roseum) ; in some, aldehydes (cumi- nol in oil of cumin, cinnamic aldehyde in oil of cinna mon) ; in others, ethers (methyl salicylate in gaultheria oil) ; in others still, phenols (thymol in oils of thy- mian and monarda), etc. They have already been described, as far as they are well known, in connection with these compounds, to which they bear a close chemical relation. The hydrocarbons called terpenes, contained in the various ethereal oils, have nearly all the same composition in percentages. Their formula is a multiple of the simple formula, C5H8. By far the greater number boils without decomposi tion at 160-170°, and these have the molecular for mula, C10H16. A smaller number boils at 250-260°, and has the molecular formula, C15H24; and a still smaller number, which boils above 300°, has the for mula, C20H32. The hydrocarbons of the formula C10H16 show the greatest similarity in their chemical and physical pro perties, and with many the observed difference between them is confined to the smell and the action upon polarized light. Most of them are imperfectly investi gated, and a more careful investigation will probably show a thorough chemical identity of many of them. The best known is Turpentine-oil. C10H16. Occurrence. In all parts "of all coniferous trees. When fir, pine, larch trees, etc., are accidentally TURPENTINE OIL. 463 bruised or intentionally incised, there flows from them a clear, thick, viscid liquid, turpentine. This is a so lution of a resin in oil of turpentine. As it occurs in commerce, it is yellow, sometimes clear, sometimes turbid, of a bitter taste and slight odor. Distilled with water, oil of turpentine passes over and the resin remains behind. Properties. Colorless, thin oil of a peculiar, unpleas ant odor ; specific gravity, 0.89 ; boiling point, 160°. Vapor density, 4.698. Almost insoluble in water, miscible with alcohol and ether in all proportions. It dissolves sulphur, phosphorus, and a great many other substances that are insoluble in water. It absorbs oxygen from the air, and converts it partially into ozone. Towards polarized light it conducts itself dif ferently, according to its origin: that obtained from the turpentine of Pinus maritima (French oil of turpen tine), of Pinus Mughus, Abies pectinata (templin oil), and Laryx europcea, rotates the plane of polarization towards the left ; that from the turpentine of Pinus australis (English oil of turpentine), however, towards the right. Under the influence of heat, acids, etc., it is con verted into other varieties with other properties, but without a change in the percentage composition. The oil, which is originally produced in the trees, too, ap pears to be different from that prepared from turpen tine. Pine branches distilled with water give an en tirely different, almost agreeably smelling oil, which, when distilled over potassa, becomes ordinary oil of turpentine. Transformations. Oil of turpentine, left for months in contact with acidified water,* is partially converted into a colorless and inodorous body, terpine (hydrate of oil of turpentine), C^IP'O2 -f H20, which crystallizes very regularly ; fuses at 100°, losing its water of crys tallization ; sublimes at a higher temperature undecom- posed ; is sparingly soluble in cold water, easily soluble in hot water and in alcohol and ether. When its so- * A well-shaken mixture of eight parts of oil of turpentine, two parts of weak nitric acid, and one part of alcohol, is the best. 464 TUKPENTINE OIL. lution is heated with a trace of some acid, it is con verted into a volatile oil, terpinol C20H340, of an odor like hyacinthes; specific- gravity, 0.852; boiling point, 168°. Both compounds, terpine and terpiiiole, form, with hydrochloric acid gas, bihydrochlorate of oil o/ turpentine, C10H16.2HC1, a crystallizing substance.— Oil of turpentine also absorbs this gas in large quan tity, and forms with it a liquid and a solid compound. Both have the. composition C10H17C1 = C10H16.HC1. The solid one crystallizes from alcohol, or when care fully sublimed, forming clear shiny prisms; has an odor like camphor, and fuses at 115°. The fluid com pound is a neutral, colorless oil, that floats on water. Both, when heated with caustic lime, yield oils of thf composition C5H8, but differing from oil of turpentine in odor and other physical properties (camphilene, ter- pilene, terebilene). The action of fuming hydrochloric acid on oil of turpentine, continued for months, causes the formation of C10H16.2HC1, which is identical with the compound resulting from terpine and terpinole. Chlorine converts oil of turpentine into two isomeric chlorine compounds, C10H12C14, one of which is crystal line and fuses at 110-115°, the other a colorless, viscid liquid. When heated with phosphonium iodide, oil of tur pentine is converted into a hydrocarbon, C10II20, boil ing at 160°. Boiled continuously with dilute nitric acid, oil of tur pentine yields acetic, propionic, butyric, oxalic, toluic, terephtalic, camphresinic acids (see Camphor p. 468), and Terebic acid, C7IF°04, a body that crystallizes in colorless prisms, which fuse at 168°. Difficultly solu ble in cold water, easily soluble in hot water. Is re solved into carbonic anhydride and pyroterebic acid, C61P02 (p. 125), when subjected to distillation. Terebentilic acid, C8II1002, results when terpine in the form of vapor is conducted over heated (to 400°) soda-lime, and the product decomposed with hydro chloric acid.— Small, white needles ; fuses at 90°, and ETHEKEAL OILS. 465 boils at 250° ; almost insoluble in cold water, more easily soluble in hot water. Tbe following oils consist entirely of hydrocarbons, which are isomeric with oil of turpentine, and very similar to it : — Oils of lemon, orange, apricot, and bergamot, in the shells of the various species of Citrus ; oils of lavender and spike, in the blossoms and leaves of Lavandula angustifolia and Lavandula latifolia ; oils of juniper and sabine, in the berries of Juniperus communis and Juniperus sabina ; oil of camphor trees, the oil in elemi, in balsam oj copaiva, in black pepper, in cubebs, etc. The following are mixtures of several compounds, which are partially but little known : — Anise oil, from the seed of Pimpinella Anisum (p. 380).* Apricot-blossom oil, from the blossoms of Citrus Au- rantium. Cajeput oil, from the leaves of species of Melaleuca. Calamus oil, from the root of Acorus Calamus. Caraway oil, from the seeds of Carum carvi. Cascarilla oil, from the bark of Croton Eluteria. Chamomile oil, from the flowers of Matricaria Chamo- milla. Deep blue. Cinnamon oil, from the barks of Persea Cinnamomum and Persea cassia (p. 373). Clove oil, from cloves (blossom-buds of Caryophyllus aromaticus) (p. 381). Coriander oil, from the leaves of Coriandrum sativum. Curled-mint oil, from the green portions of Mentha crispa. Fennel oil, from the seeds of Fwnicidum officinale.* Lozenge oil, from Ruta graveolens (p. 112). * The oils marked with a star solidify even above 0°, depositing oxygenized compounds (stearoptenes). 466 CAMPHOR. ^ Peppermint oil, from the green portions of Mentha piperita.* Roman-caraway oil, from the seeds of Cuminum Cymi- num (pp. 289 and 385)J Roman-chamomile oil, from Anthemis nobilis (p. 124). Eose oil, from the petals of Rosa centifolia* Rosemary oil, from the green portions of Rosmarinus officinalis. Sage oil, from the green portions of Salvia officinalis. Sassafras oil, from the roots of Laurus Sassafras. Tansy oil, from all parts of Tanacetum vulga.re. Taragon oil, from the leaves of Artemisia Dracuncu- lus (p. 380). Thyme oil, from the green portions of Thymus vul gar is. Wormseed oil, from the seeds of Artemisia santonica. Wormwood oil, from the green portions of Artemisia Absinthium. E. CAMPHOR. 1. Japan Camphor (Ordinary Camphor}. C10IF60. Is obtained in Japan and China by distilling all portions of Laurus camphora with water. Is prepared artificially by heating the oil of sage or valerian with nitric acid. — Colorless, translucent, tough mass of pecu liar odor and taste. Crystallizes readily, either from its solution in alcohol or by sublimation, in shiny crys tals, which refract light very strongly. Floats on water, rotating when in small pieces ; fuses at 175° ; boils at 204°. In an alcoholic solution, it turns the plane of polarization to the right. Volatilizes, even at the ordinary temperature, and sublimes in crystals. Easily inflammable. Sparingly soluble in water, easily in alcohol, ether, and oils. "When heated with an alcoholic solution of potassa, camphor is resolved into camphic acid, C10H1602, an acid insoluble in water, but little known, and borneol, C10II180. Oxidizing substances convert it into cam- CAMPHOLIC ACID. 467 phoric and camphoronic acids. Distilled with phosphorus pentasulphide, it is resolved into water and cymene (p. 289) ; the same decomposition takes place when it is distilled over phosphoric anhydride or zinc chloride, but in the two latter cases, toluene, xylene, pseudocu- mene, and other hydrocarbons are produced in con siderable quantity at the same time. When heated with phosphorus chloride, two crystalline chlorine compounds, £10H15C1 and C10H16C12, are produced, which lose hydrochloric acid easily, and are then converted into cymene. When heated with hydriodic acid, it yields a mixture of hydrocarbons. Monochlorcamphor, C10H15C1O, is produced by adding camphor to an aqueous solution of hypochlor- ous acid. — Colorless, crystalline mass ; but slightly soluble in water, easily soluble in alcohol and ether. Fuses at 95°, and decomposes at 200°, hydrochloric acid being given off. Heated with alcoholic potassa, it yields oxycamphor, C10H1602, together 'with other substances as yet unknown. Colorless needles ; fuse at 137° ; sublime without decomposition ; insoluble in water, easily soluble in alcohol. Monobromcamphor, C10H15BrO, and JDibromcam- phor, C10H14Br20, are produced by the action of bromine on camphor at 100-120°. — Both compounds crystallize in colorless prisms. Monobromcamphor melts at 76°, and boils without decomposition at 274° ; dibromcam- phor melts at 114.5°, and boils at 285°, undergoing material decomposition. — "When bromine is added to a saturated solution of camphor in chloroform, crys- talline camphor bromide, C10H16OBr2, is deposited, which, when kept, especially in sunlight, is converted into monobromcamphor. Campholic acid, C10H1802, is produced when cam phor, in the form of vapor, is passed through a heated mixture of calcium hydroxide and potassium hydrox ide ; and by the action of potassium on a solution of camphor in petroleum. — Crystallizes from alcohol in 468 CAMPHOCARBONIC ACID. colorless prisms ; insoluble in water ; fuses at 80° ; sublimes. Camphoric acid, C10H16O = C8H14(CO.OH)2, is pro duced by digesting, for a long time, and repeatedly distilling camphor with 10 parts concentrated nitric acid. — Crystallizes from water in thin, colorless laminae, of a weak acid taste, without odor. Fuses at ITS- ITS0, and emits a pungent odor. Difficultly soluble in cold water, more easily 'soluble in hot water and in alcohol. When heated it is decomposed into water and camphoric anhydride, C10II1403, which sublimes in long, shiny prisms, and fuses at 21T°. Bibasic acid. The calcium salt, C10H140'Ca + 8H20, forms easily soluble crystals ; when heated is resolved into carbonic anhydride, water, and phoroii (p. 109). Camphoronic acid, C9H1205. Is formed, together with the preceding compound, when camphor is heated with nitric acid. Also by direct oxidation of cam phoric acid. — Brilliant, white, microscopic needles; very easily soluble in water, alcohol, and ether. When fused with potassium hydroxide, it yields butyric acid. The substance, formerly described as camphresinic acid, C10H1407, is a mixture of camphoric and cam- phoronic acids. Oxy camphoronic acid, C9H1206 + H20, is obtained by heating camphoronic acid with two atoms of bro mine in sealed tubes. — Crystallizes in the monoclinate system from water ; easily soluble in alcohol, ether, and water. Loses its water of crystallization at 100° ; begins to melt at 210° ; distillable. Appears to be triatomic, bibasic. — Is decomposed by potassium hy droxide like camphoric acid. Camphocarbonic acid, CnH1603. Sodium acts very violently, but without an evolution of hydrogen, on a solution of camphor in toluene, and a yellowish, amorphous mass is deposited, consisting of sodium- CAMPHOR OF BORNEO. 469 camphor and sodiimi-borneol. If carbonic anhydride is now conducted into the solution, and, after satu rating with this, water is added, and the aqueous solu tion separated from the toluene, borneol is deposited from the solution in a short time. This is filtered off, and to the filtrate hydrochloric acid added, when cam- phocarbonic acid is precipitated. — Small, colorless crys tals. Difficultly soluble in water, easily soluble in ether. Begins to melt at 118-119°, but at this tem perature it is resolved into camphor and carbonic anhydride. Monobasic acid. A camphor, very similar to the ordinary variety just described, separates from the oil of Matricaria par- thenium, when that portion of the oil, which boils between 200-220°, is cooled down to —5°. It differs from ordinary camphor only in the fact of its turning the plane of polarization to the left. When oxidized it also yields camphoric acid, but while ordinary cam phoric acid is dextro-rotatory, the acid obtained from Matricaria-camphor rotates the plane of polarization just as far to the left, and by mixing equal weights of both acids, an optically inactive camphor is produced. Here exists hence exactly the same relation as between dextro- and Irevo-tartaric acids, and racemic acid (p. 184). 2. Gamj)hor of Borneo (Borneol, Camphol). Ci6Hi30 = C10H'7.OH. Obtained in Borneo and Sumatra from Dryobalanops camphora. It occurs partially in a solid, crystalline state, in cavities in the trunks of old trees, in company with a volatile oil, which is contained in larger quan tity in the younger trees, and flows out of "incisions made in them. It is produced from camphor when this is heated with alcoholic potassa, or heated succes sively with sodium and water (see Camphocarbonic acid, p. 468). — Very similar to ordinary camphor, but more friable, having an odor like that of camphor and 40 470 EESINS. of pepper ; fusing point, 198° ; boiling point, 212°. Heated with phosphoric anhydride, it is resolved into water and borneene, C10H16, which appears to be identi cal with the oil of camphor (from Laurus camphora), occurring in nature, as well as with the non-oxygen ized portion of oil of valerian. "When the latter is allowed to stand in contact with caustic potassa, and then subjected to distillation, it is converted into borneol. Borneol is an alcohol. Heated to 200° with acids, it yields ethers, water being eliminated. Stearic ether , C10H17.O.C18H350, is a colorless, thick, volatile oil, solidi fying after a time. — When borneol is heated with con centrated hydrochloric acid, a crystallizing chloride, C10H17C1, is produced, which is isomeric with hydro- chlorate of oil of turpentine, and very similar to the solid variety of the latter. Bodies isomeric with borneol are contained in oil of hops, cajeput oil, coriander oil, in the oil from Osmitopsis asterisco'ides, and in oil of Indian geranium. Patchouli-camphor, C15H280, in oil of patchouli, is homologous with borneol. — Crystalline mass. Fusing point, 54-55° ; boiling point, 296°. 3. Meniha-Camplwr (Menthol}. C10H200 = C10H» OIL Is obtained by distilling Mentha piperita with water, and separates from the oil (oil of peppermint) that passes over when subjected to a very low temperature. —Colorless, transparent prisms, of a strong odor and taste of peppermint; fuses at 36°, and boils at 210°. Combines with acids, forming ethers, like borneol; when heated with hydrochloric acid or phosphorus chloride, yields a liquid chloride, C10H19C1 ; and with phosphoric anhydride a liquid hydrocarbon, menthene, C10H18; boiling at 163°. F. EBSINS. This name is applied to a group of bodies but little known, which occur, very widely distributed, in the RESINS PROPER. 471 most various portions of plants, mostly in company with, volatile oils, dissolved in which they frequently flow from trees from accidental or intentional cuts. The crude resins are never crystallized ; they have the form of drops, like gum ; are colored mostly yellow or brown; translucent, brittle, with a shiny, conchoidal fracture ; often possessing a weak smell and taste. In a pure state they are colorless, inodorous, and tasteless; several are^ then crystallizable. They are fusible, in flammable, not volatile, non-conductors of electricity; insoluble in water, soluble in alcohol, in ether and volatile oils. Most resins, occurring in nature, consist of several simple compounds, which, however, as a rule, are exceedingly difficult to separate and prepare in a pure condition. Most resins are weak acids or anhydrides of acids. The number of resins is very large. Only a few of them, which are of importance on account of technical or pharmaceutical employment, are investigated. The conduct of a great many resins, when heated with fusing potassa (to 1 part of resin 3 parts potassa), is of interest. They then yield, as a rule, together with fatty acids: protocatechuic acid (p. 356), paraoxy- benzoic acid (p. 347), phloroglucin (p. 311), and resorcin (p. 306.) 1. Resins Proper. 1. Colophony (Pine-resin). The turpentine, which flows from the pines, firs, larches, and other species of Pinus, solidifies gradually on the trees, forming a resin, partially by evaporation, partially by oxidation of the oil. Distilled with water, oil of turpentine passes over, the resin remains behind ; it is known under the name of colophony. Colophony is brownish-yellow, translucent, brittle, fusible ; easily soluble in alcohol, ether, fatty and vola tile oils. When it is digested for several days with ordinary alcohol (at the strongest 70 per cent.), filtered hot, and water added to the filtrate until a slight 472 COPAIBA-RESIN. turbid ness remains, crystals separate in a few hours, consisting of Sylvic acid (Abiotic acid), C20H3002. Crystallizes from alcohol in pointed, oval lamina. Insoluble in water, soluble in alcohol, ether, benzene, and chloro form ; fuses at 120° ; monobasic acid. The alkaline salts are yellowish, brittle masses; easily soluble in water and alcohol. The magnesium, calcium, and barium salts are white, flocculent precipitates; diffi cultly soluble in water, more easily in alcohol. An acid, isomeric with sylvic acid, Pimaric acid, C20H3002, forms the principal ingre dient of the resin from Pinus maritima (Galipot). ° It is deposited from its alcoholic solution in hard crusts. Fusing point, 149°; perfectly insoluble in water, diffi cultly soluble in cold alcohol and ether, easily in the hot liquids. Monobasic acid. Yields crystallizable salts. Boils above 320°, and, when distilled, is converted into sylvic acid. f 2. Copaiba-resin. From species of Copaifera, in digenous in Brazil, is obtained, by means of incisions, balsam of copaiba, a bright-yellow, clear, thick liquid, resembling oil of turpentine, which consists of resin and a turpene. The resin, freed of oil by distillation with water, is an acid, copaivic acid, C20H3002(?), isomeric with sylvic and pimaric acids; it can be obtained in exceedingly regular, clear, colorless crystals by dissolving the resin in alcohol and allowing it to evaporate spontaneously; or by shaking the balsam for a long time with a con centrated solution of ammonium carbonate, and then acidifying the lower aqueous solution of the ammo nium salt with acetic acid. — On the other hand, the different varieties of balsam appear to contain some what different or altered resins, and hence the resin cannot always be obtained in a crystalline form. In Maricaibo balsam there is contained an acid, meta- copaivic acid, C22H3404, very similar to copaivic acid; it crystallizes in laminae, and fuses at 205-206.° MASTIC. 473 3. Elemi, from several species of Amyris in East and' West Indies.— Yellow, translucent, soft, smelling somewhat of volatile oil. It contains a non-crystal- lizable resin, easily soluble in cold alcohol, and a crys- tallizable resin, soluble only in boiling alcohol. The latter can be obtained only in fine needles, and does not combine with bases ; takes up water from the air and from alcohol, and becomes amorphous. It is also contained in anime-resin and in euphorbium. 4. Betulin, in birch-bark. Appears as a fleecy vege tation in the bark when gradually heated. ^ Obtained most readily by boiling the outer bark with water, drying and boiling with alcohol, from which it crys tallizes in nodules. Colorless ; fuses at 200°, emitting an odor like that of the bark ; is sublimable in a cur rent of air. 5. Lactucone, in the juice of Lactuca virosa.—Fine, colorless prisms, solidifying after fusion in an amor phous form; very similar to betulin. 6. Copal, from Africa, East Indies, etc., of various origin. Large (externally opaque, on a fractured sur face clear), slightly yellowish or yellow pieces, fre quently inclosing insects; hard, brittle, heavier than water. Fusible, but undergoing a change at the same time. Insoluble in alcohol ; soluble in ether ; soluble in caustic potassa, There are different varieties of copal; they consist of several difficultly separable resins. 7. Dammara resin, from Pinus Dammar a, in the Moluccas.— Very similar to copal; fusible, however, without decomposition, and soluble in hot alcohol. 8. Mastic, from Pistada Lentiscus in Greece.— Small, yellowish, translucent, round grains, of a slight aromatic odor and taste, Consists of several amor phous compounds, of different solubility in aqueous alcohol. 40* 474 GUAIACUM. 9. Olibanum (Incense), from a species of Boswdlia, a tree in Abyssinia.— Subglobular, pale-yellow, trans lucent grains; for the greater part soluble in alcohol; fusible with decomposition, and emitting a balsamic odor. 10. Sandarac, from Thuja articulata, in Barbary.— - Small, pale-yellow, translucent, brittle grains ; easily fusible ; soluble in alcohol. 11. Gum-lac is produced in consequence of the sting of an insect (Coccus laced) in the branches of certain trees in the East Indies. When still on the branches it is called in commerce stick-lac, separated from them seed-lac, and in a purified, melted condition shell-lac, in which state it forms thin, brittle, brown, translucent pieces. Gum-lac contains several other products, originated by the insects, especially a color ing principle and fats. 12. Benzoin-gum, from Styrax benzoin, a tree growing in Sumatra.— Large, brittle lumps, which, on the fractured surface, appear to be conglomerated of smaller white and brownish pieces. It has a pleasant vanilla-like odor, evolves vapors of benzole acid when heated, which forms about 18 per cent, of the gum. Some ^ varieties contain cinnamic acid in addition to benzole. 13. Guaiacum, from Guajacum officinale, a tree growing in the West Indies.— Large, translucent, brittle lumps, externally bluish-green, on the fractured surface brown. Its powder becomes green in contact with the^air^or under the influence of chlorine- water. Its solution in alcohol becomes deep blue when acted upon by ozone, nitrous acid, chromic acid, iron sesqui- chloride, etc. ^ The principal ingredient of guaiacum is a weak bibasic acid, crystallizing from acetic acid in concen trically arranged needles, guaiaretic acid, C20H26O, which fuses at 75-80°, and by slow distillation is re solved into pyroguaiacin, CI9IP203, a crystalline sub- CAOUTCHOUC. 475 stance, and into guaiacol, C7H802 (p. 305), a liquid. When the resin is subjected to destructive distillation, there are formed besides these, creosol, C8H1002 (p. 309), and several other bodies. 14. Acaroid resin, from Xanthorhoea hastiUs, a tree growing in New Holland. — Yellow colored; yields picric acid abundantly when heated with nitric acid, and phenol when subjected to distillation. 15. Dragon's blood, from a number of trees in the West Indies. — Small, dark-brown, opaque lumps; in the form of powder blood-red ; soluble in alcohol with red color. Contains a little benzoic acid. Yields toluene when distilled. 16. Amber, a resinous product of extinct coniferse, occurring in lignite beds. — Colorless, yellow or brown ish yellow, transparent or translucent, hard, often in closing insects. Fusible, undergoing decomposition, however, the succinic acid contained in it being volati lized. In addition to this acid it contains a volatile oil and two resins, soluble in alcohol and ether. Its principal mass consists of an amorphous substance, in soluble in alcohol, fatty and volatile oils, as well as in alkalies. 2. Caoutchouc. Flows from incisions in various trees growing in South America and the East Indies (especially several varieties of Siphonia and Ficus dasticd), as a juice of creamy consistence which dries up, forming caoutchouc. The juice contains albumen in solution, in which the caoutchouc is suspended in the form of globules. "When heated, the albumen coagulates, and the caout chouc globules adhere together with it in coagulated masses. Pure caoutchouc, as it does not occur in com mence, is colorless and transparent. Its characteristic property is elasticity. It loses this property when kneaded for a long time between warm rollers, and is converted into an homogeneous, black, 476 BALSAMS. conglomerated mass, which, as long as it is warm, can be moulded at desire. In this condition other sab- stances, especially sulphur, can he intimately mixed with it (vulcanization of caoutchouc), hy which means its valuable properties are materially increased. It is not fusible without decomposition. It is insoluble in alcohol, soluble in ether, carbon bisulphide, and a few volatile oils. Insoluble in caustic potassa. It contains no oxygen, arid when subjected to dry distillation is resolved almost entirely into a mixture of liquid hy drocarbons. — Gutta-percha is a very similar substance, from various species of Isonandra in Madras. It is solid at ordinary temperatures, scarcely elastic, becomes soft and elastic, however, when warmed. 3. Gum-resins. Important on account of their employment in medi cine ; are usually mixtures of peculiar resins, fre quently also caoutchouc with protein compounds, guru and volatile oils. They exude from the plants as milky juices or emulsions, which contain the gum or protein compounds in solution, the oils and resins in suspension, and besides these, frequently other sub stances. ^ Of these latter may be mentioned, assafoetida, euphorbium, galbanum, gamboge, myrrh, opium, etc. Their consideration belongs to the field of pharma cology. 4. Balsams. Under this head are understood exuded or expressed thick, ropy, odorous liquids from certain trees or shrubs. They are either solutions of resins in ethereal oils, or mixtures of substances which bear a close rela tion to the latter. The following substances are bal sams : — Turpentine (p. 462). Canada balsam, from Abies balsamea. Balsam of copaiba (p. 472). Storax balsam (p. 372). Peru and Tolu balsams (p. 312). VII. BILIARY COMPOUNDS.* 1. Glycocholic acid, C26H43^06. Fresh ox-bile is evaporated to dry ness over a water-bath, the residue exhausted with absolute alcohol, the alcohol separated from the filtered solution by evaporation or distillation, and the residue, which, if necessary, is diluted with water, mixed with milk of lime, and gently warmed, the greater part of the pigment present being by this means thrown down in combination with lime. The mixture is filtered and to the cold filtrate dilute sul phuric acid is added until turbidness remains (an ex cess to be avoided). In a few hours the whole liquid has become a pulpy mass, consisting of crystals of gly- cocholic acid, which is purified by pressing, dissolving in a great deal of lime-water, and reprecipitating with sulphuric acid. — Or the bile, evaporated to dryness, is extracted when cold with absolute alcohol, the solu tion decolorized by digesting with animal charcoal, filtered and treated with a little ether; hereupon, after standing for several hours, a plastery, colored mass is deposited ; from this the liquid is poured off, and again treated with fresh ether. After a long time a mixture of sodium glycocholate and taurocholate (crys tallized bile) is deposited in fine, colorless needles, which, after the liquid is poured off, is washed with a little ether, and then dissolved in water. This solu tion is mixed with dilute sulphuric acid until it is decidedly milky, and then allowed to stand. In twenty-four hours the liquid has become filled with * On the occurrence of these substances in the bile, see the section Animal Chemistry, Bile, 478 CHOLIC ACID. crystals of glyeocholic acid, which are purified by re- crystallizing from boiling water. The taurocholic acid remains in solution. The amorphous mass at first de posited also usually becomes crystalline after a lon«- time.— Or fresh ox-bile, decolorized with animal char coal, is precipitated with a solution of sugar of lead, the precipitate exhausted with boiling 85 per cent! alcohol, and this solution treated with sulphuretted hydrogen, _ while still hot. From the filtrate from lead sulphide, glycocholic acid is deposited in crystals, when water is added until turbidness remains. Glyeoholie acid forms very fine, white needles, which pressed together in a mass represent a leaf of a silky lustre. It has a sweetish-bitter taste; is but slightly soluble in water, easily soluble in alcohol. On evapo rating its alcoholic solution, it remains behind as a resinous mass. Fusible, but not volatile. Its alkaline salts are easily soluble, and have a very sweet taste. ITeated with sulphuric acid, and a solution of sugar, it gives a violet color. When boiled with alkalies, glycocholic acid, takes up one molecule of water, and is converted into fflyco- col (p. 84), and Cholic acid, C24IP°05. This is obtained most readily by boiling crystallized bile for several days with baryta- water or potassa.— Colorless, shiny octahe drons, almost insoluble in water, soluble in alcohol and ether. A solution of its alkali salts has a strong, bit ter taste at first, afterward sweetish. It is precipi tated from these solutions by acids, as a soft amor phous mass, which however soon becomes crystalline, especially on the addition of ether. "With sulphuric acid and a solution of sugar, it shows the same reac tion as glycocholic acid. When boiled with acids, glycocholic acid is also re solved into glycocol arid cholic acid, but in this case the^ latter immediately undergoes a further change, giving up water, and being converted into dyslisin, 024H880?, a grayish-white, amorphous body, not acid, TAUROCHOLIC ACID. 479 which, when boiled with an alcoholic solution of potassa, is again converted into cholic acid. 2. Taurocholic acid, C26H45£TS07. When fresh ox- bile is mixed with neutral lead acetate, a white, plas ter-like precipitate is produced, which contains, besides mucus and coloring matter, particularly lead glycocho- late. When the filtered liquid is mixed with basic lead acetate, a similar precipitate is formed, which consists of basic lead glycocholate and lead taurocholate and the lead salts of the fatty acids contained in bile. From this precipitate taurocholic acid can be separated with difficulty. — It is more readily obtained from dog-bile, in which no glycocholic acid is contained, or at the most but traces. The alcoholic extract _of the dried bile, decolorized with animal charcoal, is eva porated to dry-ness, the residue dissolved in a small qauntity of alcohol, and the sodium taurocholate pre cipitated with ether. To an aqueous solution of this salt lead acetate is added together with some ammo nia, the precipitate filtered off, dissolved in boiling absolute alcohol, and decomposed by means of sulphu retted hydrogen. The filtrate from lead sulphide is evaporated down to a small volume at a moderate tem perature, and then a large excess of ether added to it, which causes the separation of free taurocholic acid as a syrupy mass. This is after a time converted for the greater part into acicular crystals of a silky lustre. It is easily soluble in water and alcohol. When dry it can be heated above 100° without decomposi tion. When heated with water to 100°, it is resolved into cholic acid and taurin (p. 141). It suffers the same decomposition, when its salts, or the bile, are boiled with alkalies or acids, or by the putrefaction of bile. Two acids very similar to the two described are hyoglycocholic acid, C27H43^05, and hyotaurocholic acid, C27H45NS06, which are contained in the bile of the pig. When boiled with alkalies they are resolved into glycocol, taurin, and an acid very similar to cholic acid, hyocholic acid, C251I4004. In goose-bile is also 480 CHOLESTERIN. contained a distinct acid, chenotaurocholic acid, C29II49]S"S06, very similar to taurochloric acid, which, when boiled with baryta-water, yields taurin and chcno- colic acid, C27H4404. 3. Lithofellic acid, C20II3604. Is the principal in gredient of a variety of oriental bezoars, and is pro bably a product of a metamorphosis of the ingredients of the bile, taking place in the living body of a species of goat or antelope. It can be extracted from the bezoars with boiling alcohol. — Crystallizes from alco hol in colorless, short prisms. Insoluble in water, soluble in alcohol. Fuses at 204°. "With sulphuric acid and a solution of sugar, it gives the same reaction as glycocholic acid. 4. Cholesterin, C26H440 + H20 = C26H43.OH. It is extracted from evaporated bile by means of ether. It is further an ingredient of the brain, the nerves, the yolk of eggs, the yellow bodies in the ovary of the cow, blood, meconium, of feces, and a number of hy dropic fluids. It has also been lately found in the vegetable kingdom, and apparently it is here likewise very wid'ely distributed ; especially is it contained in vegetable seeds, for example in rye, in barley, in peas, in maize, and in all the young parts of plants. It is collected in largest quantity in biliary calculi, which often consist entirely of it. These concretions are dis solved in boiling alcohol, and then filtered ; on cooling the cholesterin crystallizes out. It crystallizes from alcohol in colorless laminre, of a pearly lustre, from a mixture of alcohol and ether in regular, tabular prisms. Inodorous and tasteless; fuses at 145°, and solidifies in crystalline form; heated without access of air, it sublimes for the greater part undecomposed. Insoluble in water, but slightly solu ble in cold alcohol. Caustic potassa, even by boiling, produces no change in it. In dry chlorine gas, it be comes heated to fusing, hydrochloric acid gas being evolved. When gradually and completely saturated with chlorine gas, it forms a white, amorphous mass, COLORING MATTERS OF BILE. 481 C26H37C170, insoluble in water, fusing at 60°.— It unites directly with one molecule of bromine, when the latter is added to its solution in carbonbisulphide, as long as the color of the bromine disappears. The resulting compound, cholesterindibroniide, C26II44Br20, crystallizes in small needles, insoluble in water, difficultly soluble in alcohol, easily soluble in ether; fusing point, 147° ; reconverted into cholesterin by nascent hydrogen. Cholesterin is a monatomic alcohol. When treated with hydrochloric acid or phosphorus chloride, it yields cholesterol chloride, C26H43C1, which, when in a pure state, forms colorless, acicular crystals, soluble in alcohol. — Cholesterin combines with acids, forming ethers. The stearic ether, C2GH43.O.C18H350, is produced by heating cholesterin with stearic acid to 200° in sealed tubes. — Small, white, needles; fusing at 65°. The benzoic ether, C26H43.O.C7H50, prepared in the same manner, forms small, crystalline plates, which melt be tween 125° and 130°. Dehydrating substances, concentrated sulphuric or phosphoric acid, convert cholesterin into various crys tallizing, isomeric, or polymeric hydrocarbons, C26H42. 5. Coloring matters of bile. Biliary calculi from the human being, which contain a great deal of pigment, are pulverized, freed of cholesterin and fat by treatment with ether, and then freed of other bodies by successive extraction with hot water and chloroform. The residue, which contains earthy phos phates and carbonates and compounds of the coloring matters with lime and magnesia, is treated with hydro chloric acid, and the coloring matters, which remain after drying, extracted with chloroform. This solu tion, on being evaporated to dry ness, leaves a dark, crystalline residue behind, from which absolute alco hol extracts bilifuscin, while bilirubin remains behind, which can be purified by repeatedly dissolving in chloroform and precipitating with alcohol. The por tion that remains uridissolved by chloroform in the first place, still contains a great deal of bilirubin, 41 482 B1LIFUSCIN. together with biliprasin and a brown, humus-like body, bilihumin. It is first treated with alcohol, in which only biliprasin dissolves with a beautiful green color, and the bilirubin is then extracted by means of boiling chloroform. Bilirubin, C16H18N203 (or C9H9ST02). Dark-red crys tals, of the color of chromic acid. In an amorphous state, as obtained by precipitating it from its solution in chloroform by means of alcohol, an orange-red powder. Fuses when heated and is decomposed, swell ing up at the same time. Insoluble in water, very slightly in alcohol and ether, more easily in chloro form, benzene, and carbon bisulphide. It dissolves in alkalies very easily, forming a deep orange-red liquid, which, on the addition of a great deal of water, be comes a pure yellow, and, even in very dilute condition, colors the skin yellow. Hydrochloric acid precipitates the bilirubin from this solution. "When calcium or barium chloride or lead acetate or other metallic salts are added to a weakly ammoniacal solution of bilirubin, dark-brown colored, flocculent precipitates separate, which are the metallic compounds (salts) of bilirubin. "When an alkaline solution of bilirubin is mixed with commercial nitric acid (containing hyponitric acid), the yellow solution becomes first green, then blue, violet, ruby-red, and, finally, a dirty-yellow; especially do these changes of color take place when alcohol is previously added. Biliverdin, C16H20E"206 (or C8H9N02). Is produced when the solution of bilirubin in caustic soda, is shaken with air or boiled. It then becomes green, and, on the addition of hydrochloric acid, biliverdin is de posited.— Lively green precipitate; insoluble in water, ether, and chloroform, easily soluble in alcohol. With nitric acid it gives the same reaction as bilirubin. Bilifuscin, C16H20IsT204. Is contained in biliary cal culi only in very small quantity. In order to obtain it in a pure condition, its alcoholic solution (see above) B I L I II U M 1 N . 483 is evaporated, the residue first freed of fatty acids by treatment with ether, and then of bilirubin, by means of chloroform (bilifuscin purified with ether is insolu ble in chloroform ; its solubility in chloroform is caused by the presence of fatty acids), then dissolved in alcohol, and this solution evaporated. — Almost black, lustrous, brittle mass. Insoluble in water, ether, and chloroform, easily soluble in alcohol, form ing a solution of a deep-brown color; also in alkalies. "With nitric acid it gives the same reaction as bilirubin. O Biliprasin, C46H22N206. Is obtained in a pure con dition when its alcoholic solution (see above) is evapo rated, foreign substances removed from the residue with ether and chloroform, the residue redissolved in a little alcohol, and this solution evaporated. — Lus trous, almost black, in pulverized condition greenish- black mass. Fuses when heated, and decomposes, at the same time increasing in volume. Insoluble in water, ether, chloroform ; easily soluble in alcohol, forming a clear green solution. If ammonia be added to this solution, it turns brown (difference between it and biliverdin) ; hydrochloric acid turns it green again. Bilihumin. Is contained in considerable quantities in biliary calculi, and is produced from all the other biliary coloring-matters when their solutions in soda- ley are exposed to the air for a long time. — Blackish- brown, powdery substance. In addition to the coloring-matters described, others occasionally occur in bile. These are, however, uiiiu- vestigated up to the present. VIII. PROTEIN COMPOUNDS. THE name, protein compounds, is applied to certain nitrogenized substances, very similar to each other, which are widely distributed in the animal and vege table kingdom. Formation. Only in plants. The animal organism receives these most important ingredients ready formed in the food, and it has only power to assimilate them, and to cause multitudinous metamorphoses in them. Composition. This is for all protein compounds so similar that one might be led to suspect that it is the same, and that the variations found are merely caused by the presence of other substances, which they con tain to a certain extent in organized intertexture, and from which they have not as yet been separated.— They all contain carbon, hydrogen, nitrogen, oxygen, and sulphur, but the latter in such small quantity that it is impossible to express its presence by means of a probable formula. The following composition of albu men gives a representation of the composition of these bodies:- ' Carbon ..... 53.5 per cent.' Hydrogen .... 7.0 « Nitrogen .... 15.5' " Oxen ..... 22.4 " Nitrogen .... 15.5' " ygen ..... 22.4 " Sulhur ..... 1.6 Properties. Most protein compounds can apparently exist in two conditions: a soluble condition, in which they usually occur in nature, and an insoluble or coagulated condition, into which they are converted PROTEIN COMPOUNDS. 485 either spontaneously or by the action of heat or acids. In the soluble form they are contained in plants and animal fluids, and can, for the greater part, be obtained by evaporating at a temperature below 50°. It is, however, exceedingly difficult and scarcely possible to thoroughly purify them of all foreign substances. In this condition they form translucent masses, similar to gum Arabic; inodorous and tasteless; soluble in water, in soluble in alcohol and ether. — In the insoluble, coagu lated condition they are white, amorphous, principally flocculent or clotted masses ; insoluble in ordinary solvents. A few of them are soluble in dilute mineral acids. Concentrated acetic acid dissolves them all with the aid of heat, some rapidly, others slowly. Dilute potassa also dissolves them all after a time, when kept at a temperature of 60°, forming potassium sulphydrate and other decomposition-products. In a weak solution in acetic acid, potassium ferrocyanide or ferricyanide, and potassium platinocyanide give white amorphous precipitates. When gently heated with a solution of mercury nitrate (containing nitrous acid),* they turn beautiful red with a slight tinge of violet. Hydrochloric acid dissolves them all with the aid of heat, and this solution, when boiled for a long time, becomes a beautiful and very deep violet. "When a solution of sugar and concentrated sulphuric acid is carefully poured upon them, they turn first red, then dark violet, the colors being the more beautiful, the more freely the air has access. Decompositions. At a high temperature they are decomposed, yielding ammonium carbonate and nume rous other products. When kept in a moist condition they easily undergo putrefaction and yield ammonia, ammonium sulphide, acids of the acetic acid series, leucine (p. 98), tyrosin (p. 350), and other bodies, with which we are only very imperfectly acquainted. Leu- cine and tyrosin are also produced from them when * Milton's reagent. Prepared by dissolving 1 part mercury in 1 part concentrated nitric acid, and diluting the solution with double the volume of water. 41* 486 ALBUMEN. they are heated for a long time with dilute sulphuric acid, and when they are carefully fused with potassium hydroxide. In the first case aspartic acid (p. 160) and glutamic acid (p. 163) are formed at the same time from many protein compounds. "When oxidized with dilute sulphuric acid and manganese peroxide, or potassium bichromate, they yield numerous products : formic, acetic, and other acids of the same series, ben- zoic acid, oil of bitter almonds, and aldehydes of the fatty acids, prussic acid, acetonitrile, and homologous nitriles, etc. The most important varieties of protein compounds are : — 1. Albumen. Three modifications of albumen, differing slightly from each other in their properties, have been distinguished: Vegetable albumen, albumen of serum, and albumen of eggs. Vegetable albumen is contained in nearly all vegetable juices ; albumen of serum in blood-serum of vertebrate animals, in lymph, chyle, in the transudates and pathological cystic fluids, in urine in diseases of the kidneys, abundantly in colostrum, and in small quantity in milk. Albumen of eggs -is contained only in birds' eggs. — Vegetable albumen cannot be obtained in a pure, uncoagulated condition from vegetable juices. — &erum-albumen is obtained most readily from blood-serum or hydrocelic fluid by diluting with twenty volumes of water, and precipitating the protein compounds, which accompany the albumen, by the careful addition of acetic acid or continued passage of carbonic anhydride into the solu tion. The liquid, filtered off after twenty-four hours, is evaporated at 40°, and separated by dialysis from the salts ; or precipitated with lead acetate, and the precipitate decomposed with carbonic anhydride. — Pure serum-albumen forms a clear, not very tenacious liquid, from which it can be precipitated with alcohol. Directly after being thrown down this precipitate is soluble in water, but, in a few minutes, it is converted into the coagulated condition. It is not precipitated by carbonic anhydride, dilute mineral acids, and tar- CASEIN. 487 taric acid, but is gradually changed by them, and the change takes place the more rapidly, the higher the temperature and the stronger the acid is. Concen trated hydrochloric acid gives a precipitate in the solution, soluble in an excess. Perfectly neutral solu tions of serum-albumen coagulate at 72-73°. Acids or salts elevate, alkalies lower the temperature required for coagulation. It is not coagulated by shaking with ether. — For the preparation of egg-albumen, white of egg is passed through linen, filtered without access of air, and then further purified in the same manner as serum-albumen. In most of its properties it shows a perfect resemblance to serum-albumen; it, however, rotates the plane of polarization somewhat less strongly to the left. With hydrochloric acid it gives a pre cipitate, which is very difficultly soluble in water and in an excess of hydrochloric acid ; is thoroughly and instantaneously coagulated by alcohol and also when shaken with ether. — Concentrated potassa-ley, added to a concentrated solution of either modification of albumen, causes the formation of a transparent, solid jelly of potassium albuminate. 2. Casein. In milk and the yolk of eggs. In order to prepare it, skimmed milk is mixed with dilute sulphuric acid, the white precipitate, after being filtered off and washed, while still wet, is digested with lead carbonate ; the filtered solution, containing the casein, then evaporated, after the removal of the lead with carbonic anhydride or sulphuretted hydro gen. — Or the milk is diluted and precipitated with acetic acid ; the precipitate washed with water, alco hol, and ether ; dissolved in very dilute caustic soda ; again precipitated with acetic acid ; and again washed as before. — The nature of casein is not yet sufficiently well known. Its solubility in water appears to be de pendent upon the presence of alkalies. Casein, which is free of alkali, is insoluble in water, and in a solu tion of common salt, but easily soluble in water con taining a very little hydrochloric acid or alkali. From this solution it is precipitated (in the absence of alka- 488 LEGUMIN. line phosphates), when exactly neutralized, in the form of a flocculent, fibrous, non-gelatinous mass. In an alkaline solution and in the milk, it is not coagulated by boiling ; the solution only forms a skin of coagu lated casein on the surface, which, when removed, is re formed. When a slightly alkaline solution of casein is poured into an excess of an acid, a flocculent pre cipitate is formed, which is soluble in pure water. This is a compound of casein with the acid employed. — The real coagulation of casein is brought about in a peculiar manner, as yet not satisfactorily explained : i. e., by contact with the internal mucous membrane of the stomach of the calf. Skimmed milk, warmed with a small piece of such a stomach (rennet) at 50-60°, coagulates so thoroughly, that only very small quantities of casein remain in a state of solution in the whey. The coagulum formed in this way, mixed with fat, forms cheese, when dried. In a coagulated condition casein resembles coagu lated albumen in nearly all its properties. 3. Legumin. In leguminous and many other seeds, a protein compound, very similar to casein, is con tained. In order to prepare it, beans or lentils are softened with warm water and triturated to a paste. This paste is then diluted with water and the skins sieved off. Legumin, in a state of solution, is con tained in the liquid that passes through the sieve ; starch, in a state of suspension, is also contained in it, but the latter is deposited if the liquid is allowed to stand quietly. By adding a very little acetic acid, the legumin is thrown down as a gelatinous mass ; to purify it, it is washed out with water, alcohol, and ether. The crude solution soon becomes acid, if left alone, on account of the formation of lactic acid ; and thus coagulates spontaneously. It does not coagulate when boiled, but, as in the case of milk, a skin is formed on the surface, which is always reformed when removed. The dissolved condition of legumin ap pears, as in the case of casein, to be caused by the presence of alkalies. When oily seeds (e. g., shelled FIBRIN. 489 and broken-up sweet almonds), are freed of most of their oil by pressure, and then boiled for a short time with water, most of the legumin, in addition to sugar and gum, is dissolved and can be reprecipitated by acetic acid ; the albumen, however, remains behind coagulated. Or, if the last particles of fatty oil are extracted from the pressed sweet almonds by means of ether, and they are then treated with cold water, legu min and ajbumen are dissolved. If the solution is now heated to boiling, the albumen is thrown down in a coagulated condition, and the legumin can afterward or also previously be precipitated with acetic acid. In addition to this, another protein compound, emulsin, is contained in sweet almonds. This compound appears to be different from those described, and is character ized by its peculiar action on amygdalin and salicin (pp. 412 and 414). 4. Fibrin. Only known in the insoluble condition. Separates spontaneously from the blood, a short time after the latter has left the living organism, and forms the principal part of the blood-clot. It is not con tained in circulating blood, but is formed after this has left the body, by the union of two albuminoid substances contained in blood and other animal fluids, viz: fibrinogenous and fibrino-plastic substance. The fibrino-plastic substance (paraglobulin) is obtained from blood-serum, by carefully adding acetic acid to serum diluted to twenty times its volume, or better by conducting carbonic anhydride into the diluted solution, and then washing the precipitate with water. The fibrinogenous substance can be prepared in the same manner from the pericardium-fluid of the cow, or the fluid of hydrocele. Both of these protein compounds are insoluble in water, and in a saturated solution of common salt ; soluble in a dilute solution of common salt, and in very dilute hydrochloric acid. When one of these substances is dissolved in a dilute solution of sodi um chloride and an equal amount of the other substance is added in a moist condition, the whole mass coagu lates after a time, forming fibrin. — Fibrin is a grayish- 490 VEGETABLE FIBRIN. white mass, which, in a moist condition, is tough and elastic, in a dry condition, hard and brittle. It is in soluble in water, dilute hydrochloric acid, and in a so lution of sodium chloride, and swells up in the latter, as well as in a solution of saltpetre. If the blood is allowed to flow from the vein directly into a concentrated solution of sodium sulphate, the precipitation of the fibrin is prevented ; if, however, the solution is now poured or filtered off from the blood-globules, and saturated with sodium chloride, there is produced a flocculent precipitate, the aqueous solution of which coagulates in a short time, as fibrin. A body, very similar to the fibrinogenous and fibrino- plastic substances, is globulin, in the crystalline lens. It resembles these substances in nearly all its proper ties, but with neither of them does it form fibrin. A neutral solution of globulin begins to grow turbid at 73°, but is not coagulated below 93°, when it also ex hibits an acid reaction. 5. Vegetable fibrin. A protein compound is con tained in the different varieties of grain in a coagulated condition ; it very strongly resembles animal fibrin. It is obtained from flour, in largest quantity from wheat flour, by mixing it with wafer, so as to form a stiff dough, tying this up in a cloth, and then kneading it for a long time in cold water, thus thoroughly wash ing out the soluble ingredients, starch and albumen. It remains behind as a grayish-yellow, tough, pasty mass, capable of being drawn out in thin layers (glutin). Boiling alcohol extracts from it a sticky substance (vegetable gelatin, glutin), likewise contain ing nitrogen, which, when dried, is brown and viscid ; ether extracts a fatty oil. — When seeds sprout, this protein compound is converted into a soluble sub stance, diastase, which has as yet not been prepared in a pure condition. It is remarkable on account of its property of converting large quantities of starch into glucose, when dissolved in water, and heated to 50-70° (compare p. 194). SANTONIN". 491 6. Myosin. Forms the principal mass of the mus cle-clot, coagulated after death during the stiffening of the body. Can be obtained most readily by washing out cut-up muscular substance with water, treating the pressed residue with a mixture of one volume of a saturated solution of sodium chloride and two volumes of water, and precipitating the slimy liquid thus ob tained with water, or by the addition of sodium chlo ride. — A mass, insoluble in water, also insoluble in a concentrated solution of sodium chloride, but soluble in a solution which does not contain more than 10 per cent, of sodium chloride. It dissolves easily in very dilute hydrochloric acid (4 cc. fuming acid to 1 litre of water), and can be precipitated unchanged from this solution immediately afterward by means of sodium carbonate, but undergoes changes when left in contact with hydrochloric acid. It dissolves in dilute alkalies, forming alkaline compounds, the solutions of which coagulate at a higher or lower temperature according as they are more or less alkaline. In the yolk of egg, in the crystalline lens, and a few cystic liquids, there occur protein compounds, which are very similar to myosin. 7. Syntonin (Parapeptone). Is formed from myosin by dissolving it in very dilute hydrochloric acid, and from all other protein compounds by dissolving them in concentrated hydrochloric acid. Water precipitates a compound of syntonin with hydrochloric acid from these solutions. It also occurs in the gastric juice, being probably the first product of transformation of the protein compounds. — Is obtained most readily by dissolving coagulated white of egg or pure fibrin in fuming* hydrochloric acid, precipitating the filtered solution by the addition of water, redissolving the precipitate in pure water, and carefully precipitating with sodium carbonate. Or chopped meat is washed with water until it is colorless ; and then treated with very dilute hydrochloric acid (0.1 per cent.), which converts the myosin into syntonin, and dissolves it. It is precipitated from the filtered liquid by neutral iza- 492 SYNTONIN. tion. — When thrown down it forms a gelatinous flocculent precipitate; insoluble in water and in a solution of sodium chloride, easily soluble in dilute hydrochloric acid and very dilute alkaline carbonates. The solutions are not coagulated by boiling; the syntonin, however, separates, when they are mixed cold with sodium chloride, ammonium chloride, and various other salts. ANIMAL CHEMISTRY. 1. The Blood. As long as it flows in the veins, the blood consists of a clear liquid and numberless so-called blood-corpuscles, which are suspended in the liquid. The blood-cor puscles are only recognizable with the aid of the micro scope; they are disciform, circular, or elliptical in shape, and of a yellowish-red color in all vertebrate animals. The clear fluid of the blood contains, as its principal ingredients, three dissolved protein com pounds: albumen (serum-albumen), fibririogenous, and fibrino -plastic substances. (In regard to these see pp. 486 and 489.) When drawn from the veins blood coagulates very soon, the fibrinogenous and fibri no-plastic substances uniting with each other to form insoluble fibrin (p. 489), which incloses the blood-corpuscles, and forms with them an adherent, gelatinous mass, the coagulum, placenta sanguinis. From this, on further shrinking, the remaining solution of albumen separates as a yel- lowish, almost clear, alkaline fluid, the serum, serum sanguinis. Only in the case of cold-blooded animals does the blood coagulate so slowly, and are the blood- corpuscles so large that they can be separated from the dissolved fibrin by means of filtration before the coagulation. The reason why the blood remains fluid in the living organism, but coagulates when no longer under the influence of life, is as yet not known with certainty. We only know that it is the walls of the bloodvessels which prevent the coagulation in the organism ; and that, outside of the animal body, the 42 494 THE BLOOD. coagulation may be accelerated by elevated tempera ture, violent motion, and by access of oxygen ; retarded by saturation with carbonic anhydride, by the addition of a small quantity of free potassa or ammonia, by a number of alkaline salts, and by slight acidification with acetic acid; and, finally, entirely prevented by the neutralization of the previously acidified blood with ammonia; or, better, by allowing the blood to fiow directly from the vein into a concentrated solu tion of sodium sulphate. — When blood is beaten while flowing from the vein, the fibrin separates in stringy masses, without inclosing a large amount of corpus cles, which, for the greater part, remain unchanged, suspended in the serum. On account of the slimy character of the latter, however, they cannot be sepa rated from it. If ten times its volume of a mixture of one volume concentrated solution of sodium chlo ride and from nine to ten volumes water is added, and the whole allowed to stand, the separation becomes possible. TJiey then sink, the supernatant liquid can be poured off, and the blood-corpuscles washed with a solution of sodium chloride of the same strength as that employed in the mixture. The red blood-corpusles of man and most mammalia consist almost exclusively of a peculiar body, hcemato- globulin or hcemoglobin, while in the blood-corpuscles of birds and several mammalia, considerable quantities of albuminous substances occur together with this. When free of albuminous substances, or when these are pre viously removed, the corpuscles crystallize, on the ad dition of water at a low temperature, in rhombic crys tals, only a very small quantity remaining dissolved in the water. They can be purified by recrystalliza- tion from water at a low temperature, if a little alco hol is added. After being dried over sulphuric acid at a temperature below 0°, they form a brick-red pow der, still containing 3-4 per cent, of water. When this is dissolved in alcohol, and cooled, crystals are again deposited. It decomposes very readily in the presence of water. If an aqueous solution of pure haemoglobin is allowed to stand for some time at the THE BLOOD. 495 ordinary temperature ; and if haemoglobin is dried at a temperature above 100°, it becomes dirty-brown, and decomposes, yielding a brown coloring-matter, two protein compounds similar to fibrin and albumen, and several acids (formic, butyric). Light that has passed through an aqueous solution of haemoglobin, or through blood, yields a spectrum which shows two very characteristic absorption bands, lying in yejlow and green (between Frauenhofer's lines D and E). If the blood is saturated with carbonic acid, or heated to 40-50° after the addition of a drop of ammonia, or if mixed with a drop of ammonium bisulphide, both of these bands disappear, and, instead of them, there appears a single band (between the lines C and D, nearer C.). The original bands reappear, however, immediately if the blood, thus treated, is shaken with atmospheric air. The most remarkable property of haemoglobin is its capability of uniting with oxygen and other gases, to form peculiar unstable compounds, which also crys tallize, and give up these gases very readily, even^in a vacuum, without losing the capability of reuniting with the gases. Haemoglobin containing oxygen is bright red, that which contains no oxygen is darker. This is the cause of the different color of arterial (with haemoglobin containing a great deal of oxygen) and venous blood (with haemoglobin contain ing little or no oxygen) ; the optical phenomena above mentioned also find their explanation in this fact. Only the haemoglobin containing oxygen (oxyhaemo- globin) gives the characteristic absorption-bands. Haemoglobin decomposes hydrogen peroxide, and sets oxygen free. In contact with alkalies and acids, oxyhaemoglobin is resolved into protein compounds, small quantites of fatty acids, and a coloring-matter, hcematin, which, when dried, has a grayish-brown color, and contains 9 per cent, of iron. Its composition can perhaps be ex pressed by the formula, C34H34FeX405. Haemoglobin containing no oxygen gives another very unstable coloring matter, haemochromogene, which takes up oxygen with great avidity, and is converted into 496 THE BLOOD. hnematin. — If pure haemoglobin, or the blood-corpuscles, or even the blood itself, be heated with an excess of concentrated acetic acid, with an addition of sodium chloride or other chlorine compounds, hceinin is formed. This crystallizes in microscopical, well-developed, rhombic plates, insoluble in water, alcohol, and ether, of a yellowish-red color ; it yields haematin and metal lic chlorides when heated with alkali, s, and is hence, probably, a compound of hsematin with hydrochloric acid. — The formation of these crystals of hsemin is principally made use of for the detection of blood. A coloring matter differing from those described is hczmato'idin, which occurs as a decomposition product of a constituent of blood, probably haemoglobin, par ticularly blood which has been in a stagnated condi tion for some time outside of the vessels, in extravasa tions of blood from ruptured Graafian vesicles, in ex travasations in the brain, in suppurating cavities, etc. It can be prepared most readily from the yellow bodies of the ovaries of the cow. These are triturated with glass-powder ; allowed to stand in contact with chloro form for several days ; the filtered, yellow solution evaporated at the ordinary temperature ; and the resi due treated with a little ether for the purpose of re moving fat. It crystallizes in small, transparent prisms of the color of chromic acid, is insoluble in water and alcohol, difficultly soluble in ether, easily soluble in chloroform, forming a yellow solution, and easily soluble in carbon bisulphide, forming a red solu tion. In many respects, it resembles bilirubin (p. 482), and has frequently been mistaken for this ; it differs from it, however, very materially in its insolubility in alkalies. The yellow coloring matter of the yolk of eggs is probably identical with hsematoidin. As, during the circulation of the blood in the body, in its passage through the capillary vessels and the organs of secretion and excretion, transformations of its principal ingredients are incessantly taking place ; THE BLOOD. 497 and as the material for the formation of its principal ingredients, prepared or formed by digestion from the footP, is constantly added in the form of chyle and lymph, which are emptied into it ; it must contain many other substances besides the principal ingredi ents. The discovery and recognition of these have, however, been but very imperfectly successful. When blood is subjected to microscopical investiga tion, two pther kinds of spherical bodies are seen besides the blood-corpuscles. These are colorless, pre sent in less abundance, and some of them smaller than the corpuscles. The smaller ones are drops of fat, the larger (so-called colorless blood-corpuscles) are the lymph- or chyle-corpuscles. In the chemical analysis of blood, as difficult and imperfect as it is as yet, several other substances besides the principal ingre dients are found. Different kinds of fat are found in it, but in small quantity, partially suspended as minute drops, par tially in solution in saponaceous combination ; and also cholesterin (p. 480). The liquid, which remains over after the coagulation of the blood by heating, leaves behind a yellow, ex tract-like mass when evaporated, consisting of a mix ture of organic substances and salts. Urea and succinic acid belong to the first, the latter are principally sodium chloride and salts of potassium and sodium with fatty acids, phosphoric acid, and sulphuric acid. In carnivorous animals sodium phosphate is principally found ; in graminivorous, sodium carbonate at the same time. Analyzed as a whole, blood has nearly the same elementary composition as the organic muscular sub stance, as a whole, of the same animal, and contains also the same amount of inorganic ingredients. 1000 parts by weight of blood-corpuscles contain 688 parts of water and 312 of solid ingredients. Of the latter 8-9 parts are inorganic salts, not reckoning the iron of haemoglobin. 1000 parts by weight of serum contain 903 of water and 97 of solid ingredients; of the latter 8.5 parts are inorganic salts. . 498 THE BLOOD. The Cntsta inflammatoria or buffy coat, a yellowish- white, semi-solid, membranous mass, which is some times formed 011 blood let from the vein, is produced by the sinking of the blood-corpuscles to a certain ex tent before the coagulation of the iibrin, the upper layer of the solution thus coagulating without inclosing blood-corpuscles. It is produced under the most varied conditions, particularly when the specific gravity of the serum of the blood is lowered, so that the cor puscles can sink more rapidly, as, for example, after frequent letting of blood. It is almost always formed in the blood of certain animals, as, for instance, the horse, in which the corpuscles possess the property of sinking readily. It was formerly incorrectly considered as a sign of inflammation. Many variations in the composition of the blood have been observed in diseased conditions of the body. In diabetes for instance, it contains sugar, which more over is said to be contained in normal blood, though in exceedingly small quantity. Respiration. The dark venous blood, mixed with the chyle of the thoracic duct, is poured into the right auricle of the hearlf, through the two grand trunks of the venous system, the venae cavse; from the auricle if, passes into the corresponding ventricle, and from this is projected into the lungs'. It is returned from the latter to the left auricle as bright-red arterial blood ; passes into the left ventricle from which it is thrown into the whole body by means of the principal artery, the aorta. The lungs consist of the fine, terminal, vesicular branches of the bronchial tubes, on the walls of which exceedingly fine networks of capillary blood vessels are spread out. The inspired air is brought in contact with the venous blood, through the fine walls of these air cells, which are impregnated with water; 4-5 per cent, of the volume of the air being absorbed as oxygen, and a volume of carbonic acid, together with some nitrogen, almost equal to that of the ab sorbed air, being given off, and in the expiration removed from the body, together with a large amount of water vapor. This carbonic acid is formed in the CHYLE. 490 blood during its circulation in the body, probably in the finest capillary networks and in the tissues of the organs themselves ; the oxygen collected in the lungs being at the same time absorbed in its place. Car bonic acid, together with small quantities of oyygen and nitrogen, is found in blood from all parts of the body, more oxygen being present in arterial blood, however, than in venous blood (cf. p. 495). Venous blood, on .the other hand, contains relatively more car bonic acid than arterial blood, the carbonic acid amount ing to about one-fifth the volume of the blood. The quantity of gases given oft' at each normal ex piration is in the case of man about 500 cc. The amount of water given off from the lungs in twenty-four hours is about 320 grm. or about 236 pounds per year. The amount of carbonic -acid expired in twenty-four hours is on an average 867 grm., containing 236.5 grm. of carbon. Hence in a year over 172 pounds of carbon are given off from the body, through the lungs, in the form of carbonic acid. The amount of oxygen consumed in twenty-four hours by the act of respiration is 746 grm., or over 544 pounds per year. 2. Chyle. The chyle contained in the lacteals and in the thoracic duct during digestion in the small intestines, is gener ally a turbid, milky, yellowish-white liquid, in which, with the aid of the microscope, various kinds of minute bodies may be detected, chyle-corpuscles. When re moved from the vessels it coagulates in a short time. The clot becomes red in the air, and contains fibrin as the coagulated ingredient. The serum separated from the clot shows a weak alkaline reaction, and contains, in addition to the usual undetermined animal sub stances and the salts, principally albumen and fat; the latter collects on the surface, and undoubtedly forms one variety of the corpuscles, which are apparently surrounded by a protein compound. 500 SALIVA. 3. Lymph. The lymph in the lymphatics is a clear, pale yellow liquid, in which drops of fat and colorless globules of about the size of the blood-corpuscles may be detected by means of the microscope. It contains for the greater part fibrino-plastic protein compounds, but in very varying quantities, and sometimes they are en tirely wanting. "When they are present, the lymph coagulates rapidly when removed from the vessels, forming a clear gelatinous mass, which incloses the lymph-corpuscles. The liquid which separates from the fibrin contains albumen and the salts of the blood. During fasting, only lymph is contained in the chyle-vessels of the intestinal canal ; during digestion, however, albumin ates, fats, etc., from the food enter this lymph, and it becomes w^hat is called chyle, which is then carried into the blood through the thoracic duct. 4. Saliva. The saliva is secreted by six salivary glands, and emptied into the cavity of the mouth through the ex cretory ducts during chewing or in consequence of irritation. Mixed with the mucus of the mouth, it shows very small, clear corpuscles under the micro scope ; it is generally slightly alkaline. When dried, it leaves behind about 1 per cent, of solid ingredients. These consist of mucus, several salts, traces of albu men and organic substance (ptyaline), that has not been separated nor analyzed. It is difficultly soluble in water, insoluble in alcohol ; the solution does not become turbid by boiling, and the ptyaline is not pre cipitated by acids nor metallic salts. At 70° it con verts starch into dextrin and sugar. — The most re markable ingredient of the solid residue is a small quantity of potassium sulphocyanide, which can be extracted by means of alcohol. The so-called tartar of the teeth, which is deposited from the saliva, consists of bone-earth, held together BILE. 501 by the organic ingredients of the saliva. The saliva stones of the horse and ass consist principally of cal cium carbonate with a little phosphate. 5. Gastric Juice. The gastric juice, secreted by the small glands of the mucous membrane of the stomach during diges tion, is a strongly acid, watery liquid, acid from the presence of free lactic acid, and sometimes hydro chloric, butyric, and acetic acids. At the most it con tains 1.5 per cent, of solid ingredients. It contains a great deal of common salt, small quantities of other salts, and an organic matter (pepsin) of unknown nature, which, iii the presence of an acid, appears to be the cause of the solvent action which the gastric juice exercises upon articles of food otherwise insolu ble, as, for example, coagulated fibrin and albumen. "Water slightly acidified with hydrochloric acid, and digested with a small piece of the mucous membrane of the stomach, attains the property of dissolving (digesting) coagulated fibrin and albumen, meat, etc., transforming them into amorphous, white bodies (peptone, parapeptone (p. 491), metapeptone), some of which are soluble in water, and others in acids and alkalies. Boiling temperature destroys this action. The mucous, alkaline, intestinal fluid has also the property of causing the solution of protein compounds, as well as converting starch into sugar, and sugar into lactic and butyric acids. 6. Bile. Bile is separated from the venous blood of the portal vein in the liver. The liver consists of small cells, which are arranged in net-like, adherent rows. In the interstices between these cells are distributed the finest beginnings of the biliary ducts, which conduct away the secreted bile; the finest branches of the portal vein, from the blood of which the bile is secreted ; the finest terminals of the hepatic artery, which convey 502 BILE. the blood for the support of the liver; and, finally, the delicate veins, which conduct the blood, already employed in the preparation of the bile, into the hepa tic veins, from which it is conveyed back to the lungs through the vena cava, and right auricle of the heart. The finest biliary ducts convey the secreted bile into branches, which grow larger and larger, and finally unite, forming a single canal, the hepatic duct. This conducts the bile during digestion into the duodenum, or at other times through a particular duct into the gall-bladder, in which it remains collected until diges tion commences. When freshly chopped liver is extracted with water, there is obtained a solution of albumen, which coagu lates by heating. This solution further contains glycogen (p. 206), urea, and the other ordinary constitu ents of animal fluids. During life the liver contains no sugar. This is, however, rapidly formed after death from the glycogen. Bile is a mucous, yellowish-green, bitter tasting and disagreeably smelling liquid, differing however in color and odor in different classes of animals. It gen erally reacts slightly alkaline, never acid. It contains between 10 and 14 per cent, solid ingredients, dissolved in water. Bile contains, as characteristic, principal ingredients, the potassium or sodium salts of glycocholic and tauro- cholic acids (p. 479). In ox-bile both acids are con tained in nearly equal quantity ; in human bile, princi pally taurocholic and but little glycocholic acid ; in the bile of the dog and several other animals, almost exclusively taurocholic acid. In the bile of mammalia these acids are contained as the sodium salts ; in the bile of fishes, especially sea fish, however, the potassium salts also occur. Bile contains besides, in smaller quantity, cholesterin (p. 480), mucus, and coloring matters (p. 481). These probably result from the coloring matter of the blood, haemoglobin ; are formed in larger quantity in certain diseases, particularly in icterus ; and then occur widely THE SKIN AND ITS SECKETIONS. 503 distributed in other portions of the organism. Further, bile contains fatty acids ; anorganic base cholin; and undetermined extract-like organic substances. Thoroughly dried bile leaves behind after combus tion, about 12 per cent, of ashes, consisting of the sodium, potassium, calcium, and iron salts of sulphu ric, phosphoric, and carbonic acids, and of chlorine. 7. The Skin and its Secretions. Horny Tissue. The general covering of the body consists of the scarf-skin (cutis, epidermis) and the corium (cutis vera). The epidermis is a horny layer without bloodvessels. It consists of microscopical flat cells, closely joined together. Under this on the corium lies a softer layer of spherical cells (rete MalpighO), without doubt un- hardened epidermis substance. The corium is a solid, elastic skin supplied with bloodvessels, composed of strong, interlacing, fibrous bands. Under it lies the subcutaneous areolar tissue, in which are contained the two kinds of small cutane ous glands, which secrete the fluid perspiration, and the sebaceous matter of the skin. The excretory ducts of the first kind open into the pores of the epidermis, those of the other into the hair-follicles. In addition to these excretions a quantity of water, \vith some car bonic acid, is given off through the skin in gaseous form according to purely physical laws. "When boiled for a long time with water, the corium is converted into gelatin, and is dissolved (see p. 508, Gelatinous Tissues). On cooling, this solution congeals, forming a jelly. This transformation is also brought about more rapidly by acids. — Immersed in a solution of basic iron sulphate or of mercury chloride, the skin combines with these salts, and then does not decay. It possesses the greatest affinity for tannic acid, which it takes up from vegetable infusions containing the acid, and with which it forms a compound (apparently merely mechanical) insoluble in water, and not under- 504 THE SKIN AND ITS SECRETIONS. going decay. Upon this depends the process of tanning, or the conversion of skins into leather (cf. p. 424). The horny tissues, viz., the epidermis, the nails, daws, talons, hoofs, horns, whalebone, wool, feathers, tortoise-shell, and similar continuations and coverings of the skin, are formations composed of various substances, the' principal mass of which, however, appears to consist of one and the same body (keratin), a substance con- taining sulphur and nitrogen, and closely allied to the protein compounds. All three formations are soluble in caustic potassa with the aid of heat, evolving at the same time a great deal of ammonia, and forming potas- sium^sulphide. Acids precipitate from the solution a gelatinous, nitrogenous substance. Nitric acid turns them yellow and destroys them ; when boiled with dilute sulphuric acid, they form leucine (p. 98), and ty rosin (p. 350); subjected to dry distillation, they yield a large quantity of nitrogenous products. The epidermis contains 0.74 per cent., the nails 2.8 per cent., the horse's hoof 4.2 per cent., whalebone 3.6 per cent, of sulphur. They also contain small quanti ties of calcium phosphate, iron, and silicic acid, which latter is contained as a constant ingredient in larger quantity In the vane of bird-feathers.* Human hair contains as principal ingredient a pro tein-like body, that contains over 5 per cent, of sul phur. The presence of this large amount of sulphur is the cause of the turning black of light hair by means of metallic salts. In addition to some calcium phosphate, and small quantities of other salts, hair also contains iron oxide and silicic acid. The cause of the different colors of hair is unknown ; it appears, however, that according as the color of the hair differs, the composition also varies. The sebaceous matter of the human skin contains a * Cliitin, a substance, that forms the real skeleton, the testa and coverings^' the wings of all insects, is entirely different in composition and chemical properties from these formations. Its composition is pro bably C9Hi5N06. It is not dissolved even by the most concentrated potassa, and carbonizes without fusing, when heated. When boiled with sulphuric acid, it yields grape-sugar and ammonia. MUSCLES. 505 liquid and a solid fat (olein and palrnitin). It is acid from the presence -of lactic acid (?),and contains, further, salts from the aqueous secretion. In sheep it consists of several kinds of fat and a saponaceous compound of potassium and calcium with a fatty acid. The perspiration is acid, and contains free acetic, butyric, formic, and carbonic acids. It contains only J to 2 per cent, of solid ingredients, consisting of urea, undetermined animal matters, potassium and sodium chlorides, and small quantities of sulphates and phos phates. Strongly smelling perspiration appears to con tain also caproic acid, and a volatile organic sulphur compound. In certain diseases, as in cholera and kid ney complaints, a large increase of the normal, small quantity of urea, contained in perspiration, takes place. In other diseases sugar and uric acid, and under certain conditions also succinic acid, have been detected in perspiration. 8. Muscles. The finest recognizable parts of voluntary muscles are microscopical, reddish, transversely striated fibres, which are united in bundles. The finest bundles are inclosed in sheaths of cellular tissue, and are united by cellular tissue, forming larger bundles. A large num ber of such larger bundles, bound together by a sheath of cellular tissue, forms a single muscle. In the sheaths is distributed a network of fine bloodvessels and nerves. The principal ingredient of muscular tissue, con gealed after death, is a protein compound, myosin (p. 491). It is not yet decided whether this substance is, as such, contained in a state of solution in the liv ing muscle or, similar to blood-fibrin, is formed after the cessation of life. The peculiar phenomenon of rigor mortis is, however, undoubtedly caused by the coagulation of the myosin, and this occurs quite inde pendently of the acid, which makes its appearance in muscular tissue after death, and generally after the rigidity. 43 506 BONES. After thorough drying, flesh leaves behind only about 23 per cent, of solid substance, the remaining 77 per cent, are water. Of the solid residue about 6 per cent, are soluble in water; chopped meat, after being extracted with water, leaving behind only 17 per cent, of solid substance. The reddish fluid expressed from fresh meat has an acid reaction from the presence of free lactic acid and acid phosphates of the alkalies ; it coagulates when heated. The clot is albumen, colored by a brownish- red coloring matter, very similar to, and probably identical with, hemoglobin (p. 494). Acetic acid and rennet also show the presence of casein. It contains, further, creatine (p. 248), sarcine (p. 246), xanthine (p. 246), inosite (p. 197), dextrin (p. 207), sugar (flesh-sugar, probably identical with grape-sugar), an acid, inosic add, as yet but little known; and salts, particularly potassium paralactate and phosphate, the potassium salts of volatile acids (butyric, acetic, for mic^?)), potassium chloride, and magnesium phosphate. Sodium chloride and calcium phosphate are only pre sent in small quantity, and sulphates not at all. Greatine, xanthine, sarcine are intermediary products of the process of waste in muscular tissue. 9. Bones. Bones excel all other organs in the large amount of inorganic matter (earthy matter) contained in them. Thin lamellae of compact bony tissue appear under the microscope as an homogeneous, structureless, trans parent mass, which is traversed by small canals (the Haversian canals), containing fat and vessels ; and, in the interstices between these, by minute, regularly arranged cavities, with numerous fine tubes issuing from all parts of their circumference. If a bone is placed in very dilute hydrochloric acid, the earthy matter is extracted, and the organic por tion, cartilage, interwoven with all the fine vessels and membranes, contained in the bone, remains behind as a flexible, soft, translucent mass, having the form of a BONES. 507 bone. "When dried it shrinks together somewhat, be comes hard and brittle, but remains translucent, By boiling with water it is dissolved, forming glutin. Water, heated above 100°, i. e. under high pressure, extracts all the cartilage from bone, dissolved as gela tin, leaving the pure earthy matter behind. When bones are burned with access of air, the organic ingredients are destroyed, and the earthy matter remains behind as a white substance, having the form of the bone. It consists of neutral calcium phosphate mixed with calcium carbonate, in varying quantities in different animals; and small quantities of magnesium phosphate and calcium fluoride. Calcium carbonate is contained, as such, in the living bone. Whether bony substance is a chemical compound of cartilage with calcium phosphate, or is ^ merely a mix ture, is undetermined. The facility with which the two constituents can be separated, however, without necessitating a change in the form of the bone, speaks for the latter view. The amount of organic and earthy matter contained in bones, estimated by calcining the bones, is found to vary somewhat in bones of different parts of the body, of different age, and in the bones of different classes of animals. In the parietal bone of man, for example, 68.3 per cent., in the sternum 64.7 per cent., in the tibia 65.5 per cent, of earthy matter have been found. — Human bones, thoroughly dried, contain over 8 per cent, of calcium carbonate. The average amount of calcium phosphate is 57 per cent., that of earthy matter 33 per cent. The bones of all mammalia are very similar in their composition to those of man ; those of birds, however, are much richer in inorganic ingredients. In the femur of the pigeon, for example, 89 per cent, of earthy matter was found, of which 82 per cent, consisted of calcium phosphate. In the bones of amphibious animals and fish, on the contrary, the amount of organic matter is decidedly greater. Fish scales have a composition similar to that of bones, only containing more organic matter. This does not, however, differ in its chemical composition 508 TISSUES YIELDING GELATIN. from cartilage ; and by boiling with water is likewise converted into gelatin. The teeth also contain the same ingredients as bones, but less organic matter. The tooth-bone, dentine, in man, contains over 64 per cent, of calcium phosphate, over 6 per cent, of calcium and magnesium carbonates, and 28 per cent, of organic matter, affording gelatin. The enamel of the teeth, on the other hand, which con sists of perpendicular, closely arranged, microscopical fibres or rods, contains no organic matter similar to that of bone; it contains 84-90 per cent, of calcium phos phate (with magnesium phosphate and some calcium fluoride), 4-9 per cent, of calcium carbonate, and 3-6 per cent, of organic substance. The antlers of the deer-family have the same com position as bones. 10. Tissues yielding Gelatin. These belong to the principal ingredients of the animal body, and do not occur in plants. In an organ ized form they constitute the cartilages, the tendons, the ligaments, cellular tissue, serous membranes, the corium, etc. All of these substances, entirely insoluble them selves in water, possess the property of becoming con verted, by continued boiling with water, into an appa rently isomeric substance, and of being dissolved for the greater part as gelatin, the solution of which, on cooling, forms a jelly-like mass. The elastic tissue, which forms the yellow bands of the vertebral column, the ligamentum nuchse, the ex terior covering of the arteries, etc., does not suffer this change in the slightest degree. The gelatin, which results from all these tissues, differing in composition as well as structure, is of two kinds, ordinary gelatin (glutin) and chondrin; and based upon this, the fundamental substance of the tissues has been divided into collagen and chondrigen. Glutin is produced from bone-cartilage, deer-horns, fish-bones and fish-scales, the skin (corium), tendons, serous membranes, isinglass. The solution, obtained TISSUES YIELDING GELATIN. 509 from these subsfances by boiling them with water, coagulates on cooling, forming a thick jelly, which, when dried, constitutes ordinary carpenter's glue. Pure gelatin is obtained most readily by boiling rasped deer-horns, isinglass, or pure bone-cartilage freed of earthy matter by means of hydrochloric acid, with water, and filtering the solution at about 50°. — Glutin is colorless, transparent, hard, tasteless, and inodorous ; softens when heated, and is then destroyed. In cold water it swells up, and when heated dissolves. The solution forms, on cooling, a clear jelly, even when it contains but one per cent, of gelatin ; this however varies in the gelatin from different tissues. It is inso luble in alcohol and ether, and is precipitated by alco hol from its aqueous solution as a floeculent mass. When subjected to combustion it always leaves behind some earthy matter. A solution of this gelatin is not precipitated by alum, neutral iron sulphate, neutral and basic lead acetate. Tannic acid precipitates it completely from its solu tion. The precipitate, which is at first white and flocculent, generally contracts, forming a thick, tough, sticky mass. Tissues, which have the power to yield gelatin, and are not yet converted into it, take up tannic acid completely from its aqueous solution ; upon this property is founded the process of tanning (converting hides into leather).— Acetic acid readily dissolves gela tin ; the solution possesses the properties of glue but does not gelatinize. Grlutin contains about 18 per cent, of nitrogen and a very small quantity (J per cent.) of sulphur. Its composition cannot be expressed by a probable formula. When boiled for a long time and particularly at a temperature above 100°, its solution loses the property of gelatinizing. On evaporation it then dries up, forming a yellowish, gummy mass, which is easily soluble in cold water/ The change that thus takes place is not understood. — Subjected to dry distillation, it yields a large number of products, among which the most remarkable are ammonium carbonate and the 43* 510 TISSUES YIELDING GELATIN. volatile bases : methylamine, di- and trimethylamine, pyridin, etc.* — When distilled with manganese per oxide, or potassium bichromate and sulphuric acid, gelatin yields the same numerous products as the pro tein compounds under similar treatment (p. 486). When a solution of gelatin is boiled with sulphuric acid or potassa, there are produced, besides ammonia and some not well known products, glycocol (p. 85), and leucine (p. 98). Chondrin is produced from permanent (non-oss:fy- ing) cartilages, as from the cartilages of the ribs, the joints, bronchi, nose, from the cornea, from bone- cartilage before ossification, by boiling with water. — • Its solution congeals on cooling, like that of ordinary gelatin ; in a dried condition it looks like the latter, but its solution is not only precipitated by tannic acid^but by acetic and hydrochloric acids, dilute sul phuric acid, alum, lead acetate, and iron sulphate ; all of which do not precipitate glutin. The precipitate with alum forms large, compact, white flocks, soluble in an excess of alum and several other salt solutions. The precipitates with hydrochloric and sulphuric acids, but not that with acetic acid, are easily redis- solved in an excess of the precipitating substance. — On combustion, chondrin likewise leaves behind earthy matter. — It contains between 14 and 15 per cent, of nitrogen and a small quantity of sulphur. Its decomposition-products are the same as those of glutin ; by boiling with sulphuric acid, however, only leucine, but no glycocol, is formed. When boiled with hydrochloric acid, it yields a fermentable sugar. The gelatin from the bones of placoidians differs from the two other varieties of gelatin in the fact that its solution does not gelatinize ; otherwise it conducts itself like chondrin. In silk is contained a peculiar body, fibroin, C15II23N506, which constitutes about 66 per cent, of * These volatile bases are contained in the substance called Oleum animale Dippdii. It is obtained by rectification of fetid animal oil, which is a by-product in the preparation of bone-black on the large scale, from bones free of fat (see Pyridin bases, p 130). MUCUS. 511 raw silk. It can be obtained pure most readily by re peatedly digesting silk with water at 30°, and treating the bright-yellow, lustrous residue with alcohol^ and ether. By boiling with dilute sulphuric acid, it yields tyrosin, leucine, and some glycocol. In addition to fibroin, silk contains a species of gela tin, in many respects similar to glutin, silk-gelatin (seracin), C15H25N508, which can be extracted by boiling water. It is formed apparently from fibroin by the assimilation of oxygen and water. In a dried condi tion, it forms a colorless and inodorous powder, which swells up largely with water, and dissolves in it more readily than glutin. A solution which contains less than 1 per cent, still congeals on cooling, forming a consistent jelly. By long boiling with dilute sulphu ric acid, it yields a little "leucine, about 5 per cent, of tyrosin, and about 10 per cent, of serine (p. 175). 11. Fat. Fat occurs in a great many forms in the animal organism, partially as minute drops or globules, sus pended in fluids, as in the milk, in blood, partially de posited in a free state in the tissues or inclosed in par ticular fat cells ; in the latter manner for instance in the upper portion of the subcutaneous cellular tissue. In connection with glycerin it has already been men tioned, that the fats which are most widely distri buted in the animal kingdom are identical with the vegetable fats of most general occurrence. In the same connection, the details in regard to the occurrence of the various animal fats, their properties and com position, were given. 12. Mucus. In the mucus secreted by mucous membranes are detected microscopical clear granules, and separated cells or particles of the external coat (epithelium) of the mucous membranes. The characterizing ingredient of mucus is a peculiar 512 THE EYE. nitrogenized body (mucin). It does not appear to be dissolved in the water of the mucus, but to be swollen up into a colloid state. The liquid contains, besides this, potassium and sodium chlorides, and small quan tities of other salts. Mucus is not coagulated by heat ing, but precipitated by alcohol and dilute acetic acid. 13. Transudates of Serous Membranes. The fluid, which collects in dropsical affections, con tains albumen in varying, frequently in very large quantity ; and, in addition to this, the ordinary salts and undetermined substances. It is usually alkaline. Occasionally it contains urea and cholesterin sus pended in fine laminse. The amniotic fluid and the fluid in hydatids contain the same ingredients. When boiled or treated with nitric acid, these fluids become more or less turbid or coagulated. Pus is a creamy, thick, in transparent liquid, which consists of a clear, colorless, or slightly yellow serum (pus-serum), and, suspended in this, the pus-corpuscles and fat-globules. Pus-serum contains albumen, which coagulates by heat, and further,- leucine, sodium chlo ride, and other inorganic salts. Pus-corpuscles possess the greatest resemblance to the colorless blood-cor puscles. 14. The Eye. The sclerotic, formed of very compactly interwoven cartilaginous fibres, can, like the corium, be dissolved as gelatin, by long-continued boiling with water. The cornea is formed of a peculiar tissue, and con ducts itself chemically like chondrigenous cartilage, but swells up in acetic acid. The black pigment (melanin), which is deposited in the form of microscopical, brown granules in separate, closed cells in the choroid, is insoluble in wrater, alco hol, and dilute acids ; soluble in potassa, forming a dark-yellow liquid ; is reprecipitated by acids. It con tains 13-14 per cent of nitrogen. When subjected to THE NERVOUS SYSTEM. 518 combustion it leaves behind an ash containing iron. It is probably a metamorphosis-product of the coloring matter of the blood. "Whether the pigment in the rete mucosum of the negro, and many pigments deposited in diseases, are identical with it, is not decided. The vitreous humor and aqueous humor consist of water with not quite 2 per cent, of solid substances dissolved in it. In the vitreous humor these are albumen^ sodium chloride, undetermined organic sub stances, and urea ; the aqueous humor, on the other hand, contains no albumen. The crystalline lens consists of concentric layers or laminae, which are composed of compactly arranged, clear fibres (probably tubes), and contain a very con centrated liquid. This latter contains about 60 per cent, of fat, cholesterin, and inorganic salts, and 35 per cent, of a protein compound, globulin (p. 490), very similar to fibrinogenous substance. 15. The Nervous System. "Without entering here into a detailed consideration of the fine structure of the brain, it may be remarked in general, that the hemispheres of the cerebrum and cerebellum consist of two masses differing essentially from each other in construction and, without doubt, also in composition. These are an outer gray layer, the substantia cinerea, and a white fibrous mass, covered by the former, the substantia medullaris. The gray matter is very abundantly supplied with bloodvessels and poorly with brain fibres ; its principal mass consists of peculiar microscopical globules. The marrow is less abundantly supplied with blood vessels and water, and is very fibrous. Examined under the microscope it is found to consist of very delicate, transparent cylinders, formed of a thin mem brane. They contain a semi-fluid, oily, clear mass, the nerve-marrow. The white matter contains more fat than the gray. In certain portions of the human brain there have also been discovered microscopical bodies, 514 THE NERVOUS SYSTEM. which conduct themselves towards iodine like cellu lose, but are essentially cholesterin (p. 480). The spinal marrow and the nerves, that have their origin in it and in the brain, have a similar structure. 100 parts of fresh human brain, dried at 100°, leave behind 21.5 parts of solid residue. The characteristic ingredient of the brain substance is lecithin (protagon). To separate it, brain substance, freed as thoroughly as possible from blood and cover ings, is reduced to a pulp, and shaken with water and ether. The mixture is allowed to stand at 0°, until the ethereal solution appears at the top ; this is then removed, and this process repeated several times, the greater portion of the cholesterin being removed in this way by the ether, while the ingredients, which are easily soluble in water, remain dissolved in this sol vent. The ether and water are then filtered off as thoroughly as possible, and the residue digested with 85 per cent, alcohol at 45° over a water bath, and filtered while still warm. This solution, when cooled down to 0°, throws down an abundant precipitate, which is collected and washed with ether until choles terin can no longer be detected in the filtrate. The residue is dried in a vacuum over sulphuric acid, then moistened with a little water and dissolved in alcohol at 45°. By gradual cooling of the filtered solution, protagon is deposited in crystals, which may be puri fied by recrystallization. It forms fine, radiate needles ; after drying over sul phuric acid, a light, flocculent powder. Difficultly soluble in cold alcohol and cold ether, more easily in the warm liquids. When heated with absolute alcohol to a temperature higher than 55°, it is dissolved, under going at the same time partial decomposition. "When treated with water it swells up, forming an opaque, pasty mass, which, with more water, yield's a clear but opalescent solution, from which protagon is precipi tated as a flocculent mass by boiling with concentrated solutions of calcium and sodium chlorides and other Baits. It dissolves in glacial acetic acid, and crystal lizes from this solution unchanged, on cooling. THE EGG. 515 Protagon contains carbon, hydrogen, nitrogen, oxy gen and phosphorus. — It decomposes below 100°, ^the more readily the more anhydrous it is. — When boiled for a longtime with baryta-water it yields barium glycerinphosphate, solid fatty acids, and neurine (p. 140). Protagon is also contained in blood, in yolk of eggs, and in the vegetable kingdom (e. g. in maize). In addition to the substances mentioned, there are contained in the brain protein compounds (particularly casein), cholesterin, lactic acid, inosite, and very small quantities of creatiue, xanthine, sarcine, uric acid, and inorganic salts. Other bodies prepared from the brain, and but little known, as cerebrin, cerebric acid, etc., appear to be mix tures. 16. The Egg. A hen's egg when laid consists of the shell, the white, and the yolk. The egg-shell, provided with small pores penetrable by air, is covered on the inside with a solid mem brane, consisting of two layers, which separate at the larger end of the egg, and leave a space between, which is filled with air. The shell consists of 97 per cent, of calcium carbonate ; 1 per cent, of calcium phosphate with magnesium phosphate ; and 2 per cent, of organic substance, which remains undissolved, when the shell is treated with hydrochloric acid. The white of the egg surrounds the yolk in three layers, of which the outermost is the most liquid. It is inclosed in thin, transparent, membranous cells. At 75° it coagulates, forming a solid, white, elastic mass. It contains 12-14 per cent, of albumen, mostly dis solved in water, as sodium albuminate, besides a very small quantity of fat and grape-sugar, and about 0.7 per cent, of inorganic ingredients. These consist of soda, potassium and sodium chlorides, and earthy phos phates. The yolk, inclosed in a thin membrane, appears un der the microscope as a pulpy mass closely filled with very fine granules, in which yellowish globules and 516 SEMEN. fat-drops are floating. The globules are bubbles or cells, which contain a yellowish oil. The analysis of the yolk of egg shows on an aver age 45 per cent, of water, 30 per cent, of fat, 15 per cent, of protein compounds, and 1 per cent, of inorganic salts. The fat, which can be obtained from the yolk by shaking with ether or, after the yolk is boiled hard, partially by means of pressure, is reddish-yellow, colored by a coloring principle as yet comparatively unknown, perhaps identical with hsematoidin (p. 496). It consists of palmitin and olein. The protein compound (formerly called vitellin) is a mixture of casein and other protein compounds. Besides these, there are contained in the yolk lecithin (p. 514), cholesterin, and apparently also glycogen. The inorganic ingredients are soda, potassium and sodium chlorides, potassium, calcium and magnesium phosphates, and iron oxide. The potassium salts are more abundantly present than the sodium salts, and earthy phosphates are present in much larger quantity than in the white. It is very probable, that the eggs of all classes of animals contain the same ingredients. In the yolk of fishes and several amphibious animals are observed under the microscope transparent crystalline plates, which, however, in different species of animals, possess different forms and properties. They appear to be protein compounds, or at least to be very similar to these. 17. Semen. Animal semen, in a pure condition as formed in the testicles, is a whitish, ropy, inodorous liquid of high specific gravity, and neutral or alkaline reaction ; when ejaculated, it is more translucent, more strongly alkaline, and of a peculiar odor, on account of the presence of the secretions of the prostate and Cowper's glands. It consists of a wratery liquid, which con tains, in a state of suspension, as peculiar, morphologi- MILK. 517 cal elements, the spermatic filaments (spermatozoa), microscopic, fibrous bodies, distinguished by the power of motion; and the seminal cells (seminal granules), cells very similar to the colorless blood-corpuscles. Semen contains 10-12 per cent, of solid ingredients, which consist of fat, inorganic salts, particularly cal cium phosphate, and a peculiar but slightly known body, spermatin, very similar to mucin (p. 512). The latter is the cause of the gelatinous consistence of semen. Il is not precipitated from its solution by boiling ; by evaporation, however, it is converted into a modification, which is completely insoluble in water. 18. Milk. The characterizing ingredients of milk are fat, casein, (p. 487), and sugar of milk (p. 200). The two latter are present in a state of solution ; the fat is suspended in the form of globules. Besides these, milk contains the ordinary undetermined substances and the salts of the animal fluids (particularly alkaline and earthy phosphates), and also some iron oxide. Milk appears under the microscope as a clear liquid, filled with numberless clear globules of different sizes, mostly however smaller than the blood-corpuscles. They are surrounded by an envelope, which incloses the fat. Hence ether, shaken with milk, takes up hardly any fat. This takes place only when the milk has been treated with alkali or acetic acid, and the envelopes broken up by this means. The quantity of solid ingredients in milk is vary ing in different animals, and different individuals. "Woman's milk contains 11-13; cow's and goat's milk, 13-14 ; mare's milk, 16 ; bitch's milk, 25 per cent. The amount of single ingredients contained in it is just as varying. Fat 3-5, casein 2-8, sugar of milk 2-9, salts 0.25-1.5 per cent. Milk is, as a rule, slightly alkaline. It does not coagulate by heating, but easily by acids, by voluntary acidification, and in the presence of the mucous mem- 44 518 brane of the calves' stomach (rennet). When evaporated, a crust of coagulated casein is formed on its surface. The colostrum (the secretion of the glands of the breast for the first two or three days after parturition), contains a larger supply of solid ingredients than ordinary milk. In addition to the much smaller milk- globules, larger spherical masses, the so-called granular bodies, which are apparently conglomerations of casein and fat-vesicles, are observed in it. Cream, which separates from milk on standing un disturbed, is formed of the milk-globules, which, being specifically lighter, rise to the surface. Churning breaks up the envelopes of the globules, and their con tents then adhere together, forming butter. The yellow color of butter is accidental, and arises from certain constituents of the food. In rancid butter, traces of fatty acids have become free. Butter fuses at about 32°. Judging from the products that have been obtained by the saponification of cow's milk, the latter is a mixture of several varieties of fat (compare Glycerin p. 168), which, however, have not as yet allowed of separation. The fatty acids obtained from them are palmitic, stearic, and oleic acids, which form the prin cipal quantity ; further myristic, butyric, caproic, ca- prylic, and capric acids. — Whether the same varieties of fat are contained in the milk of all animals is unin- vestigated. 19. Urine. The urine is secreted by the kidneys from arterial blood. The kidneys consist of microscopical canals (tubuli uriniferi), which are distributed in the cortical substance and towards their open ends unite forming pyramidal tufts, of which each one is grasped at the apex by a short cylindrical sheath, the calyx. The calyces empty into a common larger sac, the pelvis of the kidney. This is continued by the ureter, which in its turn conducts the urine into the bladder. The tubes of the cortical substance commence partially as URINE. 519 small culs-de-sac, in each of which lies a plexus of capillary vessels. Chopped kidney substance, when ground in a mor tar, becomes almost liquid. If this is strained, a com paratively very small quantity of solid substance re mains behind, consisting of the membranes of the fine bloodvessels and the tubuli uriniferi. The strained, milky and mucous liquid coagulates when heated, forming a, gelatinous mass, which consists principally of albumen. The watery extract of kidneys contains, further, in small quantity xanthine, sarcine, inosite, taurine, and leucine. Normal human urine is acid, principally owing to the presence of acid sodium phosphate ; it has an un pleasant saltish and bitter taste ; has a mean specific gravity of 1.020 ; always deposits a cloudy layer of mucus ; and after a time becomes more strongly acid, microscopic crystals of uric acid and sometimes calcium oxalate being thrown down. Later it again becomes neutral, finally alkaline, commencing to undergo de composition and emitting a foul odor, the formation of ammonium carbonate and crystals of magnesium ammonio-phosphate taking place. In its ordinary condition urine contains between 7-8 per cent, of solid ingredients ; the rest is water. This relative proportion is, however, exceedingly vary ing, according to the quantity of liquid taken into the body as drink, according to the evaporation from the skin and the condition of health. The characterizing ingredients of human urine are urea (p. 227), and uric add (p. 232). When urine is evaporated down to the consistence of honey, and allowed to stand for a long time covered up, crystals of urea or of a compound of it with so dium chloride are formed. If in this concentrated condition it is mixed with an excess of nitric acid, it forms a pulp of crystalline scales, which are urea ni trate. Normal human urine contains between 2.5 and 520 URINE. 3.2 per cent, of urea ; a healthy man secretes 22-36 grrns. of urea in twenty-four hours. When fresh urine is mixed with an acid, the uric acid falls after a time, sometimes immediately, as a brownish or reddish powder. Its amount is about 0.1 per cent. Human urine contains, further, creatine (about 0.1 per cent.), frequently succinic acid, traces of hippuric acid and of ammonium oxalurate, occasionally xan- thine and several other organic substances of undeter mined nature, which are obtained as an extractive mass in the analysis. It contains about 2 per cent, of inorganic salts, potassium and sodium chlorides, potassium and sodium sulphates, acid sodium phosphate, calcium and mag nesium phosphates, further, a small quantity of silicic acid and iron. The salts of the alkaline earths can be precipitated from it by means of ammonia. Urine may, further, contain various foreign sub stances, which are brought into the body in a soluble condition, and extracted from the- blood by the kid neys. A number of salts, for example, saltpetre, potas sium ferrocyanide, etc., pass unchanged from the stomach into the urine ; also organic acids, tartaric, oxalic acids, etc. Their salts with the alkaline metals, however, are decomposed during digestion, and they are found in the urine in the form of alkaline carbonates, imparting an alkaline reaction to the urine. Further, several organic coloring principles, volatile oils, resins, etc., pass unchanged into the urine, imparting to it color and odor. Benzoic acid, oil of bitter almonds, cinnamic acid and quinic acid, are found in the urine, transformed into hippuric acid. In diseases the character of the urine is changed in various ways. Occasionally it becomes neutral or even alkaline, and is then turbid from the separation of cal cium phosphate, and microscopical crystals of mag nesium ammonio-phosphate, and calcium oxalate. Or it becomes too concentrated, and on cooling deposits ray or reddish sediments, consisting of alkaline urates. n fevers this sediment is of a brick-color or rosy-red, URINE. 521 and consists principally of sodium urate, colored by a very small quantity of a red substance, as yet unin- vestigated. In diseases, substances are frequently found in the urine, which it does not contain in a healthy condition. In many varieties of dropsy, and a few other diseases, it contains albumen ; it then becomes turbid on the addition of nitric acid and by heating. In jaundice it contains ingredients of bile; in diabetes, grape-sugar, frequently in very large quantity, and is then secreted to an enormous extent. It is in this con dition fermentable, and afterwards, 011 being subjected to distillation, it yields alcohol. When the origin of the pneurnogastric nerve in the brain is injured, sugar occurs in the urine. Further, lactic acid,lactates, indigo, or, rather, a substance capable of producing indigo (cf. p. 384), leucine, ty rosin, taurine, etc., are occa sionally contained in urine. In certain diseased conditions of the body, difficultly soluble ingredients of the urine are deposited even in the urinary canals, and form concretions (gravel and urinary calculi), frequently of great size and hardness, and of very varying composition. Most of them con sist of uric acid with ammonium urate ; others are mixtures of calcium phosphate with magnesium ammo- nio-phosphate ; others consist of calcium-oxalate ; many are formed of alternating layers of all of these sub stances. Calculi consisting of cystine (p. 175) and xan- • thine (p. 246) are the most rare. Urine is of very varying character according to the class of animals from which it is obtained. That of the higher classes always contains urea in predominant quantities; in that of the lower classes, on the other hand, uric acid is more abundant. The urine of the lion and tiger is so abundantly supplied with urea, that frequently, without previous evaporation, the addition of nitric acid causes the nitric acid compound to crystallize out in laminae. In the urine of dogs there is frequently obtained a peculiar crystallizing acid, kynurenic acid, as yet but little known. — The urine of birds and amphibious animals is a white, pulpy mass (after drying, earthy), which consists almost 44* 522 EXCREMENTS. exclusively of acid ammonium urate. — The urine of herbivorous mammalia, as, for example, that of horses and cattle, is usually alkaline; contains urea, but little uric acid ; on the other hand, a large quantity of hippuric acid (p. 336), and frequently phenol (p. 290) ; further, potassium bicarbonate and lactate, but no alkaline phosphate ; it deposits a sediment of cal cium and magnesium carbonates. The urine of suck ing calves contains allantoine (p. 243) and no hip puric acid. The urine of insects contains uric acid and guanine (p. 247). 20. Excrements. Normal human excrements contain about 25 per cent, of solid ingredients, and of these, on an average, 6.5 per cent, are inorganic salts ; the rest is water. Their nature varies according to the food. The ash of human excrements contains 25-30 per cent, of solu ble salts, and about 30 per cent, of phosphoric acid in the form of sodium, potassium, calcium, and magnesium salts. The excrements of herbivorous animals contain all the phosphoric acid which is separated from the organism, as this acid is entirely wanting in the urine. — Human excrements, the organic ingredients of which soon begin to undergo decay, contain mucus, undi gested remnants of food, altered ingredients of the bile (taurin, cholesterin), a peculiar, crystallizing com pound, excretin, containing sulphur, and but little known and undetermined matters. — The excrements of cattle contain a large quantity of undigested cellulose, colored green by chlorophyl. INDEX. ABIETIC ACID, see Syl- vic Acid. Acarold Resin, 475 Aceconitic Acid, 180 Acetal, 104 Acetainide, 88 Acetanilide, 262 Acetenylbenzene, 379 Acetic Acid, 78 Acetic Aldehyde, 102 Acetin, 173 Acetone, 109 Acetone bromide, 110 Acetone chloride, 110 Acetones, 108. Acetonic Acid, see Oxyiso- Imtyric Acid. Acetonitrile, 38 Acetophenone, 335 Acetyl Compounds, 87 ff. Acetylene, 131 Acetyl-Urea, 231 Acoiiic Acid, 163 Aconitic. Acid, 179 Aconitine, 454 Acrolein, 128 Acrylic Acid, 122 Adipic Acid, 164 Adipomalic Acid, 178 ^Escioxalic Acid, 416 vEsculetin, 416 ^5scnlin, 415 Alanin, 91 Albumen, 486 Aldehyde-Ammonia, 104 Aldehyde - hydrocyanate, 104 Aldehydes, 101 Aldehydine, see Collidine. Allizarin, 408 Alkaloids, 431 Allanic Acid, 244 Allantolc Acid, 244 Allantoine, 243 Allanturic Acid, 245 Allituric Acid, 238 Allophanic Acid, 221 Alloxan, 234 Alloxanic Acid, 235 Alloxantine, 237 Allyl Alcohol, 119 Allyl-Compounds, 119 ff. Allylcne, 132 Aloes, 455 Aloetic Acid, 456 Aloin, 455 Alorcic Acid, 353 Alphatoluic Acid, 340 Alphaxylylic Acid, 342 Aluminiumethyl, 63 Amalic Acid, 449 Amarin, 319 Amber, 475 Amido-Compounds, see the original compounds, e.g., for Amidobenzoic Acid see Benzole Acid, etc. Ammeline, 218 Amygdalic Acid, 413 Amygdalin, 412 Amyl Alcohol, 69 Amylbenzene, -toluene, -xylene, 289-290 Amyl-Compounds, 69-70 Amylene, 118 Amylene Alcohol, 143 Amylenehydrate, 71 Amyl Hydride, 29 Amylum, see Starch. Anethol, 380 Angelic Acid, 124 Anilic Acid, 346 Anilides, 262 Anilin, 258 Anilin-Dyes, 278 Anisic Acid, 348 Anisic Aldehyde, 324 Anise Alcohol, 315 Anisol, 291 Anol, 380 Anthracene, 404 Anthracenecarbonic Acid, 410 Anthranilic Acid, 330 Anthraquinone, 406 Antiarin, 456 Antimonyethyl, see Stib- ethyl. Antitartaric Acid, 185 Apomorphine, 438 Apophyllic Acid, 440 Aposorbic Acid, 187 Arabin, see Gum. Arachidic Acid, 100 Arbutin, 419 Archil, 308 Aricine, 441 Aromatic Compounds, 251 Arsenicethyl, 60 Arsenicmethyl, 40 Asparagin, 160 Aspartic Acid, 160 Athamantin, 456 Atropic Acid, 376 Atropine, 452 Azaleine, 279 Azela'ic Acid, 164 Azo-Compounds and Di- azo-Compounds, see the original compounds, e. g., Azobenzeiie, see Ben zene, etc. Azoxybenzene, 268 Azulmic Acid, 209 . DALSAMS, 476 J3 Barbituric Acid, 239 Bassorin, see Vegetable Mucus. Behenolic Acid, 135 Behenoxylic Acid, 135 Benic Acid, 100 Benzamide, 327 Benzene, 253 Benzenesulphurous Acid, 270 Benzhydrol, 316 Benzhydroxamic Acid, 327 Benzhydrylbenzoic Acid, 322 Benzidine, 271 Benzil, 321 Benzilic Acid, 321 Benzoic Acid, 325 Benzoin, 320 Benzol, see Benzene. Benzonitrile, 256 Benzophenone, 335 Benzoylbenzoic Acid,' 322 Benzoyl-Compounds, 327ff. Benzyl Alcohol, 312 Benzylbenzene, 282 Benzylbenzoic Acid, 322. Benzyl-Compounds,274 ff.- 312 ff. Benzylic Aldehyde, 317 Bouzylphouol, 301 Beuzyltoluene, 282 524 INDEX. Bevberi ne, 447 Betaorcin, 309 Betausnic Acid, 429 Betulia, 473 Bezoar, 425 Bile, 501 Biliary Coloring Matters 481 Biliary Compounds, 477 Bilifusciu, 482 Bilibumiu, 483 Biliprasin, 483 Bilirubin, 482 Biliverdin, 482 Bismuthethyl, 61 Bitter Principles, 455 Biuret, 221 Blood, 493 Bones, 506 Borethyl, 61 Borneenc, 470 Borneo-Camphor, 469 Borneol, see Borneo-Cam phor. Brain, 513 Brasilia, 456 Brassic Acid=Erucic Acid. Brassidic Acid, 127 Brassy lie Acid, 165 Brorniil, 10(j Brombydrine, 170 Bromine-Compounds, see the original compounds, e g., Ethyl bromide, see Ethyl-Compounds, etc. Bromoform, 36 Brornopicrin, see Nitrobro- moform. Brucine, 445 Butalinin, 97 Butter, 518 • Butyl Alcohol, 67 Butyl-Compounds, 67 ff. Butylene, 116 Butylene Alcohol, 143 Butyleueglycol, 143 Butylenehydrate, 63 Butyl Hydride, 29 Butyllactiuic Acid, see Oxyisobutyric Acid. Butyraldin, 432 Butyric Acid, 92 Butyric Aldehyde, 107 Butyroacetic Acid, 94 Butyrone, 111 PACODYL, 40 \J Caffeiic Acid, 378 Ciiffeidine, 449 Caffeine, 448 Caifetaunic Acid, 428 Caincein, 422 Ca'incic Acid, see Caincin Camcigeuin, 422 Cainciu, 422 Camphenos, see Terpenes. Camphic Acid, 466 Camphilene. 461 Camphocarbonic Acid, 468 Camphol, see Borneo-Cam plior. Campholic Acid, 467 Camphor, 466 Camphoric Acid, 468 Camplioronic Acid, 468 Camphresiuic Acid, 468 Cane-Sugar, 197 Cantharidic Acid, 457 Cantharidiu, 457 Caoutchouc, 475 Capric Acid, 99 Caproic Acid, 97 Caproic Aldehyde, 108 Caproyl Alcohol, see Hexy' Alcohol. Capryl Alcohol, see Octy Alcohol. Caprylic Acid, 99 Caramel, 199 Carbacetoxylic Acid, 176 Carballylic Acid, see Tri- carballylic Acid. Carbamic Acid, 226 Carbamide, 227 Carbazol, 271 Carbohydrates, 193 Carbohydrociuiuonic Acid, 357 Carbolic Acid, see Phenol. Carbonaphtholic Acid, see Oxynaphthoic Acid. Carbon bisulphide, 223 Carbonic Acid, Deriva tives, 222 Carbon sulphoxide, 223 Carbon tetrabromide, 36 Carbon tetrachloride, 35 Carbon trichloride, 46 Carbonyl chloride, 222 Carbonyldisulphethyl,226 Carbotripheuyltrianiine, 265 Carbyl sulphate, 142 Carmine-red, 423 Carmiuic Acid, 422 Carotin, 457 Carthamin, 457 Cartilage, 508 Casein, 487 Catechin, 426 Catechuic Acid, see Cate- chia. Catcchutannic Acid, 425 Cellulose, 201 Cerebriu, 5] 5 Cerotic Acid, 101 Ceryl Alcohol, 74 Cetraric Acid, 429 Cetyl Alcohol, 74 Chelidonic Acid, 431 Cheuocholic Acid, 480 Chenotanrocbolic Acid, 4SO Chinoidine, 444 Chinoline, 454 Chitin, 504 Chloral, 105 Chlorauile, 302 Chloranilic Acid, 302 Chlorcarbonic Acid, 222 Chlordracylic Acid, 329 Chlorformic Acid, see Chlorcarbouic Acid. Chlorhydriue, 169 Chlorine-Compounds, see the original compounds, e. ff., Chloracetic Acid, see Acetic Acid, etc. Chloruitrocarboii, 115 Chloroform, 35 Chlorophyl, 458 Chloropicriu, see Nitro- chloroforrn. Chlorsalylic Acid, 32S Cholesterin, 480 Cholestrophane, 236 Cholic Acid, 478 Choliue, 140 Chondrin, 508 Chrysainmic Acid, 409 Chrysanilin, 280 Chryseue, 411 Chrysophanic Acid, 409 Chrysoquinone, 411 Chyle, 499 Cimicic Acid, 126 Cinchonicine, 444 Ciuchonidine, 444 Cinchouiue, 443 Ciunarneue, 372 Cinnamic Acid, 374 Cinuatriic Aldehyde, 373 Citracouic Acid, 1(^7 Citramalic Acid, 178 Citric Acid, 185 Cocaine, 452 Coccinin, 423 Codamiue, 441 Codeine, 440 Colchiceine, 454 Colchicine, 454 Collidine, 130 Colophony, 471 Colostrum, 518 Columbin, 458 Comenic Acid, 4.31 Conhydrine 433 Conine, 432 Conquiniue, see Quinidine. Couvolvulic Acid, 421 Couvolvulin, 420 Convolvulinol, 421 Convolvulinolic Acid, 421 Conylcne, 433 Copaiba-BaLsam, 472 Copaiba-Resin, 472 Copaivic Acid, 472 Copal, 473 Corindine, 131 Corium, 503 Cotarnic Acid, 440 Cotaruiue, 439 Coumarin, 377 Cournaric Acid, 378 Creatine, 248 Creatiniue, 249 reosol, 309 Cresols, 298 Cresotic Acids, see Oxy- toluic Acids. Crotou Chloral, 129 Crotonic Acid, 123 INDEX. 525 Crotonlc Aldehyde, 129 Crotonylene, 133 Cryptidine, 454 Cryptopine, 441 Cudbear, 307 Cumene, see Propylben- zene. Cumidinic Acid, 367 Cumine Alcohol, 316 Carainic Acid, 343 Cuminic Aldehyde, 325 Cuminol, see Cuminic Al dehyde. Cumylic Acid, see Durylic Acid. Curcumin, 45t> Cyamelide, 212 Cyanamide, 217 Cyanhydric Acid, 209 Cyanine, 455 Cyanic Acid, 211 Cyanogen, 208 Cyanogen-Compounds, 208 see also the original com pounds, e. p.. Ethyl Cya nide, see Ethyl Com pounds, etc. Cyanogen Sulphide, 216 Cyanuramide 218 Cyanuric Acid, 216 Cymene, 289 Cymophenol, 301 Cystine, 175 DAMMARA Resin, 473 Daphnetin, 420 Daphnin, 420 Daturin, see Atropin. Decatyl Alcohol, 74 Decatylene, 119 Decay, 19 Desoxybenzoin, 320 Dextrin, 207 Dextrinic Acid, 191 Diacetamide, 89 Diacetenylphenyl, 379 Diallyl, 133 Diallylhydrate, 143 Dialuric Acid, 238 Diamylene, 119 Diastase, 490 Diazobenzene, 266 Dibenzhydroxamic Acid 327 Dibenzyl, 282 Dibromhydrine, 170 Dichlorhydrine, 170 Dicyanamidic Acid, 218 Dicyano-diamide, 217 Dicyano-diamine, 218 Diethoxalic Acid, see Is leucic Acid. Diethyl, 29 Diethylacetic Acid, 93 Diethylbenzene, 289 Diethylketone, 110 Diethylmethylcarbinol, 7 Diethyl protocatechuic Acid, 357 Diothylsulphon, 54 Digitalin, 424 thylamyl, 31 Digitalretin, 424 Diglycolamidic Acid, 86 Diglycolic Acid, 146 Dihexylene, 119 Diisopropyl, 30 Ethylbenzene, 285 Sthylbenzoic Acid, 341 Sibyl-Compounds, 45 ff. Ethylcrotonic Acid, 125 Ethyldimcthylcarbinol, 71 Dilituric Acid, 240 Ethylene, 113 Mmethoxalic Acid, see Oxyisobutyric Acid. Hmethylbenzenes, 283 Ethylene Alcohol, 136 Ethylene-Compounds,! 12 ff Ethylglycol, see Ethylene Dimethyldiethylformene, 31 Alcohol. Ethyl Hydride, 28 Dimethylketone, see Ace- tone. ithylidene bromide, 46 Sthylidene chloride, 46 Mmethylpropylcarbinol, 72 ithylideneoxichloride,10* Ethyl-isobutyl, 30 Mmethylprotocatechuic Acid, 356 Ethyl Mustard -oil, 214 Ethylnaphthalene, 396 Dimethylpseudopropylcar- binol, 72 Ethylphenol, SCO Ethylphenylketone, 336 Dinaphthyl, 396 Dioxindol, 388 Ethylpropylketone, 111 Sthylsulphocarbamide, Moxybenzoic Acid, 357 )ioxynaphthalene, 399 Moxynaphthoquinone, 401 )iphenyl, 270 231 Ethyltoluene, 288 Ethyl-urea, 230 Ethylxylene, 288 Hphenylamine, 262 Mphenylbenzene, 272 Mpropylketone, 111 Disulphetholic Acid, 141 Msulphobenzoic Acid, 334 Disulphobenzolic Acid, 270 Dithiobenzoic Acid, 335 Mtolyl, 282 Eucalyn, 201 Euchron, 371 Euchronic Acid, 371 Eugenic Acid, see Eugenol. Eugenol, 381 Euthiochronic Acid, 305 Euxanthon, 460 Euxanthonic Acid, 460 )ragon's Blood, 475 )ulcite, 189 Evernic Acid, 359 Everninic Acid, 359 )urene, see Tetramethyl- Excrements, 522 benzene. Excretin, 522 Durylic Acid, 342 Eye, 512 Dyslisin, 478 GONINE 452 TUTS, 171 ]h Egg, 515* JP Fatty Acids, 75 Ela'fc Acid, see Oleic Acid Fermentation, 43 Elaidic Acid, 127 Ferulic Acid, 382 Elavl, see Ethylene. Elemi, 473 Fibrin, 489 Fibrinogenous Substance, Ellagic Acid, 425 489 Emetine, 453 Fibrinoplastic Substance, Emulsiu, 413 489 Epichlorhydrine, 170 Epicyanhydrine, 170 Epidermis, 503 Fibroin, 510 Fichtelite, 411 Filixtanuic Acid, 427 Ericinol, 422 Fish Scales, 507 Erucic Acid, 127 Formic Acid, 76 Erythrin, 358 Formic Aldehyde, 101 Erythrite, 180 Erythroglucic Acid, 181 Erythroglucin, see Ery thrite. Formylamide, 78 Formvlsulphaldehyde, 102 Frang'ulic Acid, 41S Frangulin, 418 Eserine, 453 Fraxetin, 420 Ether, 47 Fraxin, 419 Ethereal Oils, 461 Fruit-Sugar, 196 Ethionic Acid, 142 Fuchsine, 279 Ethionic Anhydride, se Carbyl Sulphate. Ethomethoxalic Acid, se Fulminic Acid, 220 Fulminuric Acid, 221 Fumaric Acid, 165 Isoxyvaleric Acid. Ethyl Alcohol, 42 Furfuramide, 193 Furfurin, 193 Ethylallyl, 117 Furfurol, 193 526 INDEX. GALLOTANNIC Acid, 424 Helleboretin, 423 TDRIALIN, 411 ; Gallic Acid, 360 Helleboriu, 423 JL Imperatorin,see Peuce- Garancin, 419 Hemimellitic Acid, 368 dauin. Garlic-oil, 121 Hemipinic Acid, 382 Incense, see Olibanurn. Gastric Juice, 501 Heptau, see Heptyl Hy Indigo, 383 Gaultheria-oil, 344, 462 dride. Indigo-Blue, 383 Gelatin, Tissues yielding, Heptyl Alcohol, 73 Indigo-Carmine, 386 508 Heptylene, 119 Indigo-White, 385 Gentianic Acid, see Gen Heptyl Hydride, 31 Indin, 390 tian in. Herapathite, 443 Indol, 389 Globulin, 490 Hesperidene-Sugar, 189 Inosic Acid, 506 Glucic Acid, 190 Hexamethylcneamine, 102 Inosite, 197 Glucinic Acid, 195 Hexan,see'Hexyl Hydride Inulin, 206 Glucose, see Grape-Sugar. Hexoyleno, 133 Iodine-Compounds, see the Glucosides, 412 Hexyl Alcohols, 71 original compounds, e. Glue, 509 Hexylene, 118 g , Ethyl Iodide, see Glutamic Acid, 163 Hexylene Alcohol, 143 Ethyl-Compounds, etc. Glutaric Acid, 178 Hexyl Hydride, 30 Iodine-Green, 281 Glutin, 508 Hippuric Acid, 336 lodoforra, 36 Glyceric Acid, 174 Homocuminic Acid, 343 Isatic Acid, see Trioxindol. Glycerin, 168 Horny Tissues, 503 Isatin, 387 Glycin, see Glycocol. Hyseuic Acid, 100 Isatosulphuric Acid, 388 Glycocholic Acid, 477 Hydautoic Acid, 245 Isatropic Acid, 376 Glycocol, 84 Hydanto'ine, 244 Isatyde, 389 Glycooyarnidine, 248 Hvdracetamide, 104 Isethionic Acid, 140 Glycocyamiue, 248 H'ydratropic Acid, 342 Lsoamyl Alcohol, 70 Glycogen, 206 Hydrazobenzene, 2tJ9 Isoamylene, 118 GIvcolacetal, 157 Hydriudic Acid, see Diox- Isobutylacetic Acid, 98 Glvcolic Acid, 145 indol. Isobutyl Alcohol, 68 GIvcolid, 146 Hvdrobenzamide, 319 Isobutylbeuzene, 289 Glycols, 136 H'ydrobenzom, 320 Isobutylene, 117 Glvcoluric Acid, see Hy- Hydroberberiue, 448 Isobutvric Acid, 94 d an to ic Acid. HydrocaflVic Acid, 360 Isobutyric Aldehyde, 107 Glycolurile, 244 Hydrocarbons, 27 Isocaproic Acid, 98 Glycosine, 157 Hydrocarotiu, 457 Isocrotonic Acid, 124 Glycyrrhetin, 424 Hydrochloranilic Acid, see Isocyanuric Acid, 221 Glycyrrhizin, 423 Dichlortetroxy benzene. Isodiglycolethylenic Acid, Glyoxal, 156 Hydrochrysamide, 409 see Lactonic Acid. Glyoxalacetal, 157 Hydrociunamic Acid, 342 Isodulcite, 189 Glyoxaline, 157 Hydrocinuamide, 373 Isohydrobenzoin, 320 Glyoxylic Acid, 157 Hydrocotaruinc, 441 Isohydromellitic Acid, 371 Grape-Sugar, 194 Hydrocoumaric Acid, see Isoleucic Acid, 152 Guaincolj 305 Melilotic Acid. Isomerism, 16 Guaiacum, 474 Hydrocoumarin, 377 Isonaphtho'ic Acid, 402 Guaiaretic Acid, 474 Hydrocouvnarinic Acid, 377 Isonaphthol, 399 Guanidine, 219 Hydromeconic Acid, 430 Isophtalic Acid, 364 Guanine, 247 Hydrornellitic Acid, 371 Isopinic Acid, 382 Gum Arabic, 207 Hydroparacoumaric Acid, Isopropylacetic Acid, 95 Gum-benzoin, 474 35 * Isopropyl Alcohol, see G um-resins, 476 Hydrophloron, 309 Pseudopropyl Alcohol. Gum-lac, 474 Hydrophtalic Acid, 363 Isopurpuric Acid, see Pi- Gun Cotton, 203 Hydropiperic Acid, 383 crocyamic Acid. Gutta Percha, 476 Hydroprehnitic Acid, 369 Isosuccinic Acid, 162 Hydropyromellitic Acid, Isoxylene, 283 369 Isoxyvaleric Acid, 152 HAIRS, 504 Hydroquinone, 303 Isuvitic Acid, 367 Hajmatein, 459 Hydroxorbic Acid, 125 Itaconic Acid, 167 Hrematin, 495 Hydroterephtalic Acid, 366 Itamalic Acid, 178 Haematoidin, 496 Hydurilic Acid, 238 Hrcmatoglobulin, see Hae Hygrine, 452 moglobin. Hyocholic Acid, 479 Hsematoxvlin, 458 Hyoglycocholic Acid, 479 TALAPIN.421 Hrcmiri, 496 Hyosciue, 453 fj Jalapinol, 421 Hemoglobin, 494 Hyoscinic Acid, 453 Jervine, 447 Harmaline, 451 Hyoscyamine, 453 Harmine, 451 Hyotaurocholic Acid, 479 Heleuene, 459 Hypogncic Acid, 126 Helen! n, 459 Hyposulphiudigotic Acid, KERATIN, 504 Helicin, 415 386 Ketones, see Acetones. Hellebore! n, 423 Hypoxanthine, nee Sar- Kinotannic Acid, 426 Helleboresin, 423 ciue. Kynurenic Acid, 521 INDEX. 527 T AGTAMIDE, 150 Jj Lactic Acid, 147 Lactide, 147 Lactimide, 1.50 Lactonic Acid, 191 Lactose, 197 Lactucone, 473 Lactyl chloride, 149 Lanthopine, 441 Laserol 459 Laserpitin, 459 Laudauine, 441 Laudanosine, 441 Laurie Acid, 99 Lecanoric Acid, 358 Lecithin, 514 Legumin, 483 Lepargylic Acid, see Aze- IHIC Acid. Lepidiuc, 454 Leucauilin, 280 Leucic Acid, 152 Leucine, 98 Lichenstearic Acid, 429 Linoleic Acid, 128 Lithofellic Acid, 480 Litmus, 308 Liver, 501 Lophin, 319 Lutidiue, 130 Lymph, 500 MACHROMIN, 427 Macluriu, see Morin- tannic Acid. Madder, 418 Maleic Acid, 166 Malic Acid, 176 Malonic Acid, 157 Mandelic Acid, 352 Mannite, 188 Mannitan, 189 Mannitic Acid, 191 Mannitose, 188 Margaric Acid, 100 Mariguac's Oil, 37 Marsh Gas, 28 Mastic, 473 Mauve'ine, 281 Meconic Acid, 430 Meconidine, 441 Meconin, 382 Melamiiie, see Cyanura- mide. Melampyrin, see Dulcite. Melauilin, 265 Melezitose, 201 Melilotic Acid, 353 Melissic Acid, 101 Melito.se, 201 Mellimide, see Paramide. Mellitic Acid, 370 Mellophanic Acid, 369 Menaphthoxylic Acid, see Naphtho'ic Acid. Mentha-Camphor, 470 Menthene, 470 Menthol, see Mentha-Cain phor. Mercaptan, 54 Mercurynaphthyl, 396 Mercuryphenyl, 272 Mesaconic Acid, 167 Mesarnalic Acid, 178 Mesitylene, 286 Mesityleuic Acid, 340 Mesityl oxide, 109 Mesoxalic Acid, 158 Metacetone, 199 Metacinnamene, 372 Metacopaivic Acid, 472 Metacrolein, 128 Metaldehyde, 103 Metamorphine, 441 Metatartaric Acid, 182 Methacrylic Acid, 124 Methyl Alcohol, 33 Methyl Aldehyde, see For mic Aldehyde. Methylallyl,116 Methylamylketone, 112 Methylbenzopheuoue, 335 Methylbromncetol, 110 Methylbutylketoue, 111 Methylchloracetol, 110 Methyl-Compounds, 34 ff. Methylcrotonic Acid, 125 Methylene chloride, 35 Methyleue iodide, 36 Methylethylketone, 111 Methylhexylcarbiuol, 74 Methylhexylketone, 112 Methylnaphthalene, 396 Methylnouylketoue, 112 Methylpropylketone, 111 Milk, 517 Milk-Sugar, 200 Monoforrnin, 172 Mode Acid, see Moriu. Morin, 427 Morindin, 419 Moriudon, 419 Morintannic Acid, 426 Morphine, 437 Moss-Starch, 206 Mucic Acid, 191 Mucin, 512 Muconic Acid, 192 Mucus, 511 Murexan, see Uramile. Murexide, 242 Muscles, 505 Mustard- Oils, 214 Mycose, 200 Myosin, 491 Myricyl Alcohol, 75 Myribtic Acid. 99 Myronic Acid, 420 Myrosin, 420 ATAPHTHALENE, 391 IN Naphthalene-Yellow, 398 Naphthalic Acid, 400 Naphthalidiue, 394 Naphthazarin, see Dioxy- naphthoqninone. Naphthoic Acid, 402 Naphthol, 397 Naphthoquinone, 400 Naphthyl-Compounds, 392 fit. Narceine, 441 Narcotine, 439 Nervous System, 513 Neurine, 140 Nicotine, 434 Nitrobromoform, 37 Nitrocarbon,37 Nitro-Compounds, see the original compounds, e. g., Nitrobenzene, see Benzene, etc. Nitrochloroform, 37 Nitrococcusic Acid, 423 Nitroform, 36 Nonyl Alcohol, 74 Nonylene, 119 Nonyl Hydride, 31 Nonylic Acid, 99 fvAKBARK-TANNIC U Acid, 427 Oak- Red, 427 Octan, see Octyl Hydride. Octyl Alcohols, 73 Octyleae, 119 Octylene Alcohol, 144 Octyl Hydride, 31 CEuanthol, see OEnanthy- lic Aldehyde. CEnanthyl Alcohol, see Heptyl Alcohols. (Enauthylic Acid, 99 CEnanthylic Aldehyde, 108 Oil of Bitter Almonds, see Benzylic Aldehyde. Jf* Oil of Cinnamon, 373 I Oil of Cloves, 381 Oil of Rue, 112 Oil of Turpentine, 462 Olofiant Gas, see Ethylene. Oleic Acid, 126 Olein, 174 Olibanum, 474 Opianic Acid, 382 Opianine, 441 Opinic Aci_d, 382 Opium, 435 Orce'in, 308 Orcin, 307 Oreoselin, 456 Oreoselone, 456 Orsellic Acid, 358 Orthocarbonic Ether, 37 Orthoformic Ether, 35 Oxalan, 236 Oxalantine, 237 Oxalic Acid, 153 Oxalic Aldehyde, see Gly- oxal. Oxaluric Acid, 236 Oxainethan, 156 Oxamic Acid, 156 Oxamide, 155 Oxanilic Acid, 263 Oxanilide, 262 Oxanthracene, see Anthra- quinoue. Oxatolylic Acid, 430. 528 INDEX. Oxetbyl-Ba^es, 139 Oxindol, 3S9 Oxyacanthine, 448 ' Oxyacetic Acid, see Gly- colic Acid. Oxyauthraquinone, 408 Oxybenzoic Acid, 346 Oxybutyric Acids, 151 Oxycamphor, 467 Oxycamphoronic Acid, 468 Oxycaproic Acids, 152 Oxycinchonine, 444 Oxyisobutyric Acid, 151 Oxymaloiiic Acid, see Tar- tronic Acid. Oxymesityleaic Acid, 352 Oxymethylene, 101 Oxymethylphenylformic Acid, 351 Oxymorphine, 438 Oxynaphthoic Acid, 403 OxynapMhoquinone, 400 Oxypheuic Acid, see Pyro- catechiu. Oxypicric Acid, 307 Oxypropionic Acids, 147 Oxypyrotavtaric Acids, 178 Oxyquinone, 361 Oxysalicylic Acid, 355 Oxtetraldin, 129 Oxytoluic Acids, 351 Oxyvaleric Acids, 151 PALMITIC ACID, 100 I Palmitic Aldehyde, 108 Palmitin, 173 Palmitolic Acid, 134 Palmitoxylic Acid, 135 Papaverine, 441 Parabanic Acid, 235 Paraconic Acid, 168 Paracouraaric Acid, 378 Paracyanogen, 208 Paradatiscetin, 418 Paraffin, 32 Paralactic Acid, see Sarco- lactic Acid. Paraldehyde, 103 Paramide, 371 Paranthraceue, 405 Paraoxybenzoic Acid, 317 Parapeptone, see Synto- niu. Paratolylic Aldehyde, 325 Para-xylylic Acid, 341 Parietic Acid, Chrysopha- nic Acid. Parvoline, 131 Patchouli-Camphor, 470 Paytiae, 441 Pelargonic Acid, 99 Peppermint-Camphor, see Mentha-Camphor. Pepsin, 501 Peptones, 501 Persio, 308 Perspiration, 505 Persulphocyanic Acid, 213 Peru-Balsam, 312 Petroleum, 30 Peucedanin, 459 Phaseotnanuite, BOO Ino- site. Phenaconic Acid, see Fu- maric Acid. Phenetol, 291 Phenols, 290 Phenylacetic Acid, see Al- phatoluic Acid. Phenylacetyleue, see Ace- tenylbenzeno. Phenylangelic Acid, 376 Pheuylcarbylamine, 256 Phenyl- Compounds. 253, ff., 290 ff. Phenylethyl Alcohol (pri mary), see Stiryl Alco hol. Phenylglycolic Acid, see Mandelic Acid. Phenyllactic Acid, 354 Phenylpropiolic Acid, 380 Phenylpropionic Acid, see Hydrocinnamic Acid. Phillygenin, 420 Phillyrin, 420 Phloramine, 311 Phloretic Acid, 353 Phloretin, 417 Phlorizein, 417 Phlorizin, 416 Phloroglucin, 311 Phlorol, 300 Phlorone, 303 Phoron, 109 Phosgene Gas, see Car- bouyl Chloride. Photosantouin, 461 Phtalic Acid, 362 Phycite, see Erythrite. Physostigmiue, 453 Picoline, 130 Picramic Acid, 294 Picric Acid, 293 Picrocyamic Acid, 294 Picroerythrin, 358 Picrotoxin, 459 Pimaric Acid, 472 Piuacoliue, 144 Pinacoue, 144 Pinipicriu, 422 Finite, 189 Piperic Acid, 383 Piperidine, 450 Piperine, 449 Piperonal, 324 Piperonylic Acid, 337 Populiu, 415 Porrisic Acid, 460 Prehnitic Acid, 369 Propargylic Ether, 133 Propioue, 110 Propionic Acid, S9 Propionic Aldehyde, 107 Propionitrile, 47 Propylacetylene, 133 Propyl Alcohols, 05 Propylbenzene, 2S8 Propyl Compounds, 65 ff. Propyldiethylcarbiuol, 74 Propylene, 115 ropylene Alcohol, 142 Propyl Hydride, 29 Protagon, see Lecithin. Protein Compounds, 484 Protocatechuic Acid, 356 Protocatechuic Aldehyde, 324 Protopine, 441 Prussic Acid, see Cyanhy- dric Acid. Pseudoamyl Alcohol, 71 Pseudobutyl Alcohol, 69 Pseudobutylene, 117 Peeudobutyl Hydride, 29 Pseudocaproic Acid, 98 Pseudocumene, 287 Pseudomorphiue, see Oxy morphine. Pseudopropyl Compounds, 66,67 Pseudotolnidin, 277 Pseud ouric Acid, 243 Pseudoxanthine, 246 Ptyaline, 500 Purpuric Acid, 212 Purpurin, 409 Pus, 512 Putrefaction, 19 Pyrene, 410 Pyrenequinone, 410 Pyridine, 130 Pyridine-Bases, 130 Pyrocatechin, 385 Pyrocomenic Acid, 431 Pyrogallic Acid, see Pyro- gallol. Pyrogallol, 310 Pyroguaiacin, 474 Pyromellitic Acid, 368 Pyromucic Acid, 192 Pyroracemic Acid, 175 Pyrotartaric Acid, 162 Pyroterebic Acid, 125 Pyroxylin, see Gun Cot ton. Pyrrol, 192- Pyruvic Acid, see Pyrora cemic Acid. QUASSIN, 460 Quinhydrone, 302 Uuinic Acid, 361 Quiniciue, 444 Quinidine, 444 Quinine, 442 Quinone, 301 Qui no-Red, 427 Quinotaunic Acid, 427 Quinovic Acid, 422 Quinovin, 422 Quercetic Acid, 418 Quercimeric Acid, 418 Quercite, 189 Quercitiu, 418 Quercitrin, 417 INDEX. 529 RACEMIC Acid, 184 ] Ratanhia-tannic Acid, Stearic Acid, 100 Stearin, 173 Thymohydroquinone, 310 Thymol, 300 428 Stearolic Acid, 135 Tbymoquinone, 303 Resins, 470 Resorcin, 306 Stearoxylic Acid, 135 Stibethyl, 60 Thymotic Acid, 355 Thymotide, 355 Respiration, 498 Stilbene, 282 Tinethyl, 64 Retene, 411 Stiryl Alcohol, 316 Tintriethylphenyl, 273 Retistene, 411 Storax, 372 Tolan, 283 Rhe'ic Acid, see Chryso- phanic Acid. Rhodan Compounds, see Strychnine, 445 Styphuic Acid, see Oxypic- ric Acid. Tollylene Alcohol, 317 Tolu-Balsam, 312 Toluene, 274 Sulphocyanates. Rhodeoretin, see Convol- Styracin, 375 Styrol, see Ciunamene. Toluic Acids, 338 Toluidin, 277 vulin. Rhccadine, 441- Ricinela'idic Aciu, 128 Styryl Alcohol, 373 Styrylic Aldehyde, see Ciunamic Aldehyde. Toluol, see Toluene. Toluquinone, 303 Toluylene, see Stilbene Ricinic Acid, 128 Suberic Acid, 164 Toluylenhydrate, 321 Roccellic Acid, 165 Roman-caraway Oil, 289, 38") Substitution, 21 Succinamic Acid, 161 Succinamide, 161 Toluylenoxide, 320 Tolyl Alcohol, 315 Tolylic Aldehyde, 325 Roman-chamomile Oil, 124 Succinic Acid, 159 Tormentill-tannic Acid, Rosanilio, 278 Succinimide, 161 428 Rubianic Acid, 418 Succinyl Chloride, 161 Trehalose, see Mycose. Rubidine, 131 Sugar, 198 Triacetamide, 89 Rufigallic Acid, 361 Rutin, 418 Sulphobeuzide, 297 Sulphobeuzolic Acid, 269 Triamylene, 119 Tribenzhydroxylamine, Sulpho-Compouuds, see the original compounds, 328 Tricarballylic Acid, 179 OACCHARIC Acid, 191 U Salicin, 414 e. g., Sulphocyanic Acid, see Cyanic Acid, etc. Trichlorphenomalic Acid, see Fumaric Acid. Salicylic Acid, 343 Salicylic Aldehyde, 322 Salicylous Acid, see Salicy lic Aldehyde. Sulphophocnicic Acid, 386 Sulphopurpuric Acid, see Sulphophccnicic Acid. Svcoceryl Alcohol, 316 Triethylcarbinol, 73 Trigenic Acid, 221 Triglycolamidic Acid, 86 Trimellitic Acid, 368 Saligenin, 315 Salirelin, 315 Sylvic Acid, 472 Synanthrose, 201 Trimesic Acid, 367 Trimethylbenzene, 286 Saliva, 500 Syntonin, 491 Trimethylcarbinol, 69 Sandarac, 474 Trimethylformene, 29 Santalic Acid, 460 Trinitroacetonitrile, 221 Santalin, see Santalic Acid. Santonin, 460 rPANNIC Acids, 424 1 Tannin, see Gallotan- Trioxindol, 388 Trioxynaphthalene, 400 Sapogenin, 422 nic Acid. Tropic Acid, 354 Saponin, 421 Tartar Emetic, 183 Tropiue, 453 Sarcine, 246 Tartaric Acid, 181 Turpentine, 462 Sarcolactic Acid, 150 Tartronic Acid, 176 Turpethic Acid, 421 Sarcosine, 85 Tartrophtalic Acid, 364 Turpethin, 421 Scheererite, 411 Taurin, 141 Turpetholic Acid, 421 Scoparin, 461 Taurocholic Acid, 479 Tyrosin, 350 Sebacic Acid, 164 Teeth, 508 ;• . . . )16 Terebentilic Acid, 464 Sericin, 511 Terebic Acid, 464 TTMBELLIC Acid, 359 Serine, 175 Terebilene, 464 • U Umbelliferone, 307 Shell-lac, 474 Terephtalic Acid, 365 Uramile, 241 Siliciumethyl, 65 Terpenes, 462 Urea, see Carbamide. Silk, 510 Terpilene, 464 Uretlian, 226 Silk-Gelatin, 511 Terpine, 463 Urethylan, 226 Sinapic Acid, 381 Terpinol, 463 Uric Acid, 232 Sinapine, 450 Tetramethylbenzene, 2SS Urine, 518 Sinkaline, 140 Tetramethylformene, 29 Uroxanic Acid, 233 Skin, 503 Tetroxybenzene, 311 Usnic Acid, 429 Smilacin, 461 Thebame, 440 Uvitic Acid, 366 Solanidin, 414 Thebenine, 440 Uvitonic Acid, 176 Solanin, 413 The'ine, see Caffeine. Sorbic Acid, 134 Theobromine, 448 Sorbine, 197 Thiacetic Acid, 87 VALERIC Acids, 95 Sorbite, 190 Thialdine, 106 Valeric Aldehyde, 107 Spar t erne, 435 Thiobenzoic Acid, 334 Valeryleue, I:i3 Spermaceti, 172 Thiochronic Acid, 305 Vegetable Fibrin, 490 Spirits of Wine, 42 Thionuric Acid, 242 Vegetable Mucus, 208 Spirits of Wood, 33 Thioresorcin, 307 Veratric Acid, 359 Starch, 204 Tbymeue, 300 Veratrine, 446 45 530 Veratrol, 310 Violuric Acid, 241 Viridine, 131 Vitellin, 516 Vulpic Acid, 430 WOOD SPIRIT, see Me thyl Alcohol. YANTHIC OXIDE, seo A. Xanthine. Xanthine, 216 Xanthogenic Acid, 225 Xyleues, 2S3 Xylenols, 299 Xylidinic Acid, 367 Xyloi'dine, 205 Xylols, see Xylenes Xylylic Acid, 311 yEAST, 43 7INCETHYL, 61 L UFI7BESIT7 ERRATA. Page 106, line 3 from bottom, read "Thialdine " for " Trialdine " 133, line 10 from top, read " Propargylic" for " Propagylic.' 1 150, after paragraph on Lactamide, insert : Lactimide, C2H4 $ . is formed by heating alanin in a current of hy drochloric acid gas at 180-200°.— Colorless, transparent needles or lami na*. Fusing point, 275° ; easily soluble in water and alcohol. Page 195, line 7 from bottom, read " Glucinic"/or "Glucic." 316, " 5 from top, read "Stiryl" for " Styryl." 377, " IS from bottom, rend " Hydrocoumarinic" for " Hydrocoumaric." 453, " 7 from top, read "Physostigmine " for "Thysostigmiue." 465, erase the bottom line — " Loxenge oil," etc. 466, after Rosemary oil, insert " Hue-oil from Ruta-graveolens (p. 112)." 511, line 8 from top, read " Sericin " for "Seracin." 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