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422 LITBKATUEB OF OKGANIC CHBMISTKY suitable. Unfortunately, owing to the vast amount of subject matter, some of its parts are unpleasantly out of date. An excellent reference work for preparations of technical interest is provided by the ten volumes of F. Ullmann's Enzyhlopddie der technischen Chemie, arranged alphabetically. In the four volumes of Die Methoden der organischen Chemie of Houben and Weyl, all the methods used in organic laboratories are systematically collected and described, whilst the comprehensive book by Hans Meyer, Analyse und Konstitutionsermittlung organischer Verbindungen, is more concerned with analytical requirements. PREPARATIONS FROM THE ORIGINAL LITERATURE As a conclusion to his preparative course the student should undertake several preparations, for which he has to look up the appropriate methods in scientific journals, instead of finding them worked out in minute detail in a manual of laboratory instruction. In so doing he will learn, with the aid of the directions given above, how to consult the literature, and how to make use of the chemical library ; most of all, however, these more difficult preparations will serve to test his capacity for laboratory work. When synthesising a compound in several stages it is absolutely essential to test and consolidate each separate stage by means of test-tube experiments before the whole of the substance is risked. Whoever fails to observe this rule will pay dearly for his neglect by loss of material and time. The choice of difficult preparations will often be regulated by the requirements and desiderata resulting from the scientific work of the institute ; that the interests of the person who carries out the preparation must take precedence in this matter need not be emphasised. The following short list of preparations has proved suitable for the reasons given : Pinacone, Pinacoline O-Methylhydroxylamine Allyl Alcohol Styrene Stilbene Phenacyl Bromide Diphenyl Ethylene Oxide Choline Dithioglycollic Acid Oxalyl Chloride Nitrourea Nitramide Ethyl Orthoformate Pumaric Acid Glutaric Acid Adipic Acid Pimelic Acid Cyanamide /3-Phenylethyl Alcohol Pyruvic Acid Oxalylacetic Acid Dihydroxytartaric Acid Dihydroxymaleic Acid Acetonedicarboxylic Acid (ethyl ester) Muconio Acid
PKBPAKATIONS FKOM THE LITBKATUEB 423 Cadaverine Triphenylamine Fulminuric Acid Ethyl Azodicarbozylate y-Dinitrobenzene Aldol Crotonio aldehyde Phenylacetaldehyde Benzildioxime Phenylalanine Methylcyclohexenone y-Diketocyclohexane Diacetyl Mesitylene Acetonylacetone Antipyrine Carbon Suboxide Coumarin Allocinnamio Acid Xanthone Acridine Anthranol Di-biphenylene-ethylene /3-Nitronaphthalene Diphenylketene Camphorquinone Violuric Acid Veronal Phenylnitramine m-Toluidine m-Nitrophenol y-Nitrophenylhydrazine Fuchsone Hexahydroxybenzene Inositol o-Benzoquinone Quinol Hydroxyquinol Tetraphenylxylylene Dimethylaminobenzaldehyde Phenanthraquinone Biphenylene-ethylene Diphenylhydrazine Triphenylhydrazine and Hexaphenyltetrazane Tolane Mercury Diphenyl Dimethylpyrone 1 : 5-Dibromopentane Diphenylnitric Oxide Thioindigotin Thioindigo Scarlet Isatin (Sandmeyer's method) Thymolphthalein Sodium Triphenylmethyl Dimethylpyrrole Mellitic Acid Methyliminazole from glucose a- and /3-Methylglucosides ttt-Camphor from pinene Cystine Hydrolysis of protein (according to E. Fischer and Dakin) Dihydroxyphenylalanine Glutamic Acid Glycyglycine Adrenaline Mannose Diacetoneglucose Dulcitol from galactose Sylvane from furfural Guanine Xanthine Uric Acid (synthetic) Camphoric Acid Camphoronic Acid o-Esdragole from phenylallyl ether Ionone Vanillin from iso-eugenol Tartrazine Auramine Tetraphenyl Lead Boron Triphenyl Phorone Ninhydrin Ethyl Chloro-iminocarbonate Diphenyldiazomethane Phenylacetylene Piperidine Piperylene Ethyl Cyclopentanone Carboxylate Picrolonic Acid os-Diphenylethylene Amylene from acetone Xylose Glyoxal Furfuryl Alcohol and Cinnamyl Alcohol (Meerwein's method) Glutathione
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L A B O R A T O R Y M E T H O D S O
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PEEFACE TO THE TWENTY-FOUKTH EDITIO
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PEEFACE TO THE EEVISED (NINETEENTH)
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CONTENTS A. SOME GENERAL LABORATORY
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CONTENTS x III. NlTBO-COMPOUNDS AND
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CONTENTS xiii B. Aromatic Diazo-Com
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CONTENTS xv PAGE 5. Lactose and cas
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A. SOME GENERAL LABORATORY RULES Re
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PUKIFICATION OF OEGANIC SUBSTANCES
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CHOICE OF SOLVENT 5 The choice of t
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DISSOLVING THE SUBSTANCE then be di
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ISOLATION OF CEYSTALS 9 The steam-h
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FILTKATION 11 In order to remove th
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VACUUM DESICCATOKS 13 The consisten
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DISTILLATION 15 filter tube filled
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BATHS AND CONDENSEKS 17 may be allo
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FKACTIONAL DISTILLATION 19 The near
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VACUUM DISTILLATION 21 during vacuu
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HEATING 23 The two pieces of appara
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EFFECT OF PEESSUEE ON BOILING POINT
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DISTILLATION WITH STEAM 27 retorts,
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THEOKY OF STEAM DISTILLATION 29 On
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EVAPOKATION IN A VACUUM 31 to the p
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DEYING OF SOLUTIONS 33 determined b
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EXTKACTION APPAEATUS 35 The extract
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HEATING UNDEK PEESSUEE 37 in hydrog
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STIEEING AND SHAKING 39 reaction lo
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SINTEKING 41 the middle of the merc
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B. ORGANIC ANALYTICAL METHODS DETEC
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BBILSTBIN'S TEST 45 case remove gla
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DETEKMINATION OF NITKOGEN 47 rapid-
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FILLING THE COMBUSTION TUBE 49 Fill
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THE DUMAS METHOD 51 FIG. 34 CARRYIN
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THE DUMAS METHOD 53 bulb lowered fo
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DETEKMINATION OF CAKBON AND HYDEOGB
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THE DEYING APPAEATUS 57 cotton wool
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FILLING THE COMBUSTION TUBE 59 amou
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THE ABSOKPTION APPAEATUS 61 grease
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CAEEYING OUT THE COMBUSTION 63 Duri
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THE COMBUSTION 65 ously been specia
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THE COMBUSTION 67 the tube immediat
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DETERMINATION OF HALOGEN, SULPHUR,
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HALOGEN BY THE CAEIUS METHOD 71 out
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DETEKMINATION OF CHLOKINE AND BROMI
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DETEKMINATION OF CHLOKINE AND BROMI
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DETEKMINATION OF SULPHUE 77 tube. B
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DETEKMINATION OP HALOGEN 79 solutio
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DETEKMINATION OF THE METHOXY GEOUP
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DETEKMINATION OF THE ACETYL GKOUP 8
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DETEKMINATION OF ACTIVE HYDKOGEN 85
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DETEKMINATION OF MOLECULAK WEIGHT 8
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PKEVENTION OF ACCIDENTS 89 stances
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EQUIPMENT EEQUIEED BY THE BEGINNEE
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CHAPTBE I THE REPLACEMENT OF HYDROX
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ETHYL IODIDE FKOM ETHYL ALCOHOL 95
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EBPLACBMBNT OF HYDKOXYL BY HALOGEN
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EBPLACBMENT OF HYDKOXYL BY HALOGEN
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BENZYL CHLOKIDE FKOM TOLUENE 101 Us
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BKOMOBENZENE 103 The intermediate p
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BKOMOBENZENE 105 Grignard reaction
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PKEPAKATION OF AN OLEFINE 107 HC1 H
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PKEPAKATION OF AN OLEFINE 109 the c
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EBACTIONS OF OLEFINES 111 Thus ethy
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DIBNB SYNTHESIS' OF DIBLS 113 and,
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GLYCOL FKOM BTHYLBNB DIBKOMIDE 115
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ISOAMYL BTHBE 117 formaldehyde are
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HALOGEN CAEEIBES 119 The introducti
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CHAPTBE II CARBOXYLIC ACIDS AND THE
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ACID CHLOKIDES 123 The course of th
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BENZOYL PEKOXIDE 125 Experiments.
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ACID ANHYDKIDES 127 an excess of ac
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ACBTAMIDB 129 The - intermediate pr
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ACETAMIDE 131 Owing to the acyi gro
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POTASSIUM CYANATB AND UEBA 133 cool
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UEBA AND UEIC ACID FKOM UEINB 135 s
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ACETONITKILE 137 5. NITRILES (a) AC
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KEACTIONS OF NITEILBS 139 CH3.CN +
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BSTBES 141 pouring into 50 c.c. of
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BSTBES 143 the temperature, whilst
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INFLUENCE OF THE CATALYST 145 form
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ETHYL NITEITB 147 solution and then
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SAPONIFICATION 149 increases contin
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IODINE AND SAPONIFICATION VALUES 15
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THE CUETIUS KEACTION 153 (b) THE CU
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THE HOFMANN AND CURTIUS EBACTIONS 1
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NITEOMETHANB 157 to those used to e
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SILVBE FULMINATE 159 concentrated s
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NITKOBENZENE 161 if the reaction pr
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METHODS OF NITEATION 163 Nitro-grou
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ANILINE 165 3. REDUCTION OF A NITRO
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KEACTIONS OF ANILINE 167 three drop
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DIPHEJSTYLTHIOUKEA 169 a result of
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MBTA-NITEANILINB 171 with an equal
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BASICITY OF THE NITEANILINBS 173 On
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A K Y L H Y D K O X Y L A M I N E S
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NITKOSOHYDKOXYLAMINES 177 CH3 CH3 H
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NITKOSOBENZENE 179 5. NITROSOBENZEN
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CONDENSATION OF NITEOSO-COMPOUNDS 1
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HYDKAZOBENZENE 183 I H5C6.N-N.C6H5,
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AZOBENZENE 185 (75 c.c. of 22V-sodi
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THE BBNZIDINB KBAKKANGBMBNT HH HH H
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AZOXYBBNZBNB TO HYDKAZOBENZENE 189
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CHAPTBK IV 8ULPH0NIC ACIDS 1. BENZE
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TOLUENE-^-SULPHONIC ACID 193 toluen
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SULPHANILIC ACID 195 paste when rub
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SULPHONATION 197 and the aliphatic
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SULPHONATION 199 That this is the c
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SULPHINIC ACIDS 201 V SO2.NH2 / \ S
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CHAPTBK V ALDEHYDES 1. FORMALDEHYDE
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DBTEKMINATION OF FOKMALDEHYDE 205 e
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ACBTALDBHYDB 207 just-boiling mixtu
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ACBTALDBHYDB FKOM ACETYLENE 209 (6)
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ALDEHYDES 211 The aromatic aldehyde
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AUTOXIDATION 213 Thus the autoxidat
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KBACTION WITH AMMONIA 215 of an ald
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PAKALDBHYDB 217 more rapidly on hea
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CONDENSATION 219 a-acrose (dl-iiuct
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CANNIZZAKO'S KBACTION 221 tracted b
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THE ACYLOIN CONDENSATION 223 duct.
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THE PINACOLINE KEAKKANGEMENT 225 Th
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MANDELIC ACID 227 diphenylketene by
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ALANINB 229 rfZ-mandelic acid. Howe
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MOLBCULAK ASYMMBTKY 231 The amygdal
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CAKOTBNOIDS 233 used, with lead oxi
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SALICYLALDBHYDB 235 ing. While stil
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MECHANISM OF THE SYNTHESIS 237 This
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CHAPTBK VI PHENOLS AND ENOL8. KETO-
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PHENOLS AND BNOLS 241 Simple ketone
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OH BKOMINATION OF PHENOL 243 HOBr T
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BTHBKS OF PHENOLS 245 acids (method
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NITKOPHBNOLS 247 concentrated on a
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SALICYLIC ACID 249 In trinitrochlor
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ETHEL ACETOACETATE 251 Salicylic ac
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ACBTYLACBTONB. BBNZOYLACBTONB 253 m
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DIBTHYL MALONATB 255 bath at 40°-5
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KBTO-BNOL TAUTOMBKISM 257 separates
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ANALOGIES TO ACETOACETATE SYNTHESIS
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BKOMINATION AND BNOL CONTENT 261 th
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ALIPHATIC NITKO-COMPOUNDS 263 In be
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ACBTOACBTATB AND MALONATB SYNTHESES
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DBHYDKACBTIC ACID 267 HgC.CO.CH.COO
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CHAPTBK VII THE DIAZO-COMPOUNDS GEN
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DIAZOMBTHANB 271 a base, the salt o
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EBACTIONS OF DIAZOMBTHANB 273 it is
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GLYCINE BSTBK HYDKOCHLOKIDB 275 The
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HIPPUKIC ACID 277 This procedure wa
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STEAM DISTILLATION IN A PAKTIAL VAC
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DIAZOTISATION OF ANILINE 281 Benzen
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IODOBBNZBNE FKOM ANILINE 283 For pr
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IODOXYBBNZBNB 285 into a test tube,
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SOLID PHENYLDIAZONIUM CHLOKIDE 287
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PHENYLDIAZONIUM PBKBKOMIDB 289 Phen
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^-TOLUNITKILE FKOM ^-TOLUIDINE 291
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THE SANDMBYEK KBACTION 293 By perma
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SALVAKSAN 295 hydroxide solution, a
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PHBNYLHYDKAZINB 297 out turbidity.
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SYNTHESIS OF INDOLES 299 mentioned
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ANALYSIS OF AZO-DYBS 301 The coupli
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COUPLING OF ANILINE 303 Congo red i
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COUPLING KBACTION OF DIAZO-COMPOUND
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ANALOGOUS ACTION OF NITKOUS ACID 30
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CHAPTEK VIII QUINONOID COMPOUNDS 1.
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ANILINOQUINONE 0 0 The great affini
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2H '°> O=/~\=O + NH3 + H2N QUINONB
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^-NITKOSOBASES AND THBIK SALTS 315
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DETECTION OF NITKOSO-GKOUPS 317 mon
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QUINONBDIIMINBS 319 base (or of a s
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BINDSCHBDLBK'S GKEBN 321 disappear
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VI MBTHYLBNE BLUB 323 Methylene blu
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MALACHITE GKBBN 325 Oxidation of th
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TKIPHBNYLMBTHANB DYES 327 obtained
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TKIPHBNYLMBTHANB DYES 329 C,H,.NHj
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PHTHALBINS 331 of fuchsonimine. Thu
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COOH Since fluorescein is coloured
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QUINIZAKIN 335 collecting the subst
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CHAPTBK IX THE GEIGNAED AND FEIEDEL
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ACETOPHBNONB FKOM BKOMOBBNZBNE 339
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THE GRIGNARD KBACTION 341 Formaldeh
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BBNZOPHBNONB 343 necked bottle in s
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THE BBCKMANN KEAKKANGBMBNT 345 abou
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TKIPHBNYLCHLOKOMBTHANB 347 of 80 g.
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THE FKIEDEL-CKAFTS KBACTION 349 Whe
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THE FKIEDEL-CKAFTS KBACTION 351 H \
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HEXAPHENYLETHANE 353 a folded paper
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TBTKAPHBNYLHYDKAZINB 355 sibly as a
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FIXATION OF DIPHENYLNITKOGEN 357 go
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QUADKIVALBNT NITROGEN 359 sponding
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CHAPTBK X HETEEOCYCLIC COMPOUNDS 1.
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KNOEVENAGEL'S SYNTHESIS E JH II /-
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a-AMINOPYKIDINB 365 rH2 I 2 I -+ I
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QUINALDINB 367 the liberated quinol
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ATOPHAN. PHENYLGLYCINE 369 a-phenyl
Page 385 and 386: INDIGO FKOM o-NITKOBBNZALDBHYDB 371
Page 387 and 388: VAT DYEING 373 by reduction in alka
Page 389 and 390: ISATIN 375 The beautiful preparatio
Page 391 and 392: CATALYTIC HYDKOGBNATION 377 the sle
Page 393 and 394: USB OF NICKEL 379 Preparation of Pl
Page 395 and 396: CYCLOHEXANE 381 potassium carbonate
Page 397 and 398: CLEMMBNSEN'S METHOD 383 the higher
Page 399 and 400: ADIPIC ALDEHYDE FROM CYCLOHEXENE 38
Page 401 and 402: FURFURAL 387 product is complete. R
Page 403 and 404: HYDKOLYSIS OF CANE SUGAK 389 50 c.c
Page 405 and 406: LACTOSE AND CASEIN FKOM MILK 391 of
Page 407 and 408: d-GALACTOSE FKOM LACTOSE 393 Millon
Page 409 and 410: SOME KBMAKKS ON CAKBOHYDKATBS 395 n
Page 411 and 412: SOME KBMAKKS ON CAKBOHYDKATBS A hex
Page 413 and 414: I 0 III SOME KBMAKKS ON CAKBOHYDKAT
Page 415 and 416: SACCHAKIFICATION OF STAKCH 401 8. S
Page 417 and 418: MECHANISM OF FBKMBNTATION 403 ferme
Page 419 and 420: CAFFEINE FKOM TEA 405 cools the arg
Page 421 and 422: HABMIN FKOM OX BLOOD 407 12. HAEMIN
Page 423 and 424: PKOTOPOKPHYKIN 409 chemistry of the
Page 425 and 426: GLYCOCHOLIC ACID 411 plate to fit a
Page 427 and 428: DBSOXYCHOLIC ACID 413 the solid) is
Page 429 and 430: CHOLBSTBKOL 415 From a little alcoh
Page 431: BAKIUM DBSOXYCHOLATB 417 of desoxyc
Page 434 and 435: 420 LITBKATUKB OF ORGANIC CHEMISTKY
Page 438 and 439: TABLE FOR CALCULATIONS IN THE DETER
Page 441 and 442: SUBJECT INDEX (The page numbers whi
Page 443 and 444: Cannizzaro's reaction 220 Carbimide
Page 445 and 446: Fluorene 260 Fluorescein 326 Formal
Page 447 and 448: Nerolin 244 New fuchsine 329 Nickel
Page 449: Sublimation 26, 27 Substitution, ru
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