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408 SUBSTITUTED PYRROLES CC CC2-Hg HgC.C II II II II HC CH , H3C.C CH COOH, NH NH 3 : 4-Methylethylpyrrole Haemopyrrole carboxylic acid H3C.C C.CH2.CH2 H3C.C C.CH2.CH2 || || COOH, || || COOH. HC C.CHg H3C.C C.CHg \ / V NH NH Cryptopyrrole carboxylic acid Phyllopyrrole carboxylic acid All these degradation products have also been obtained synthetically, chiefly by H. Fischer. On oxidation, haemin yields derivatives of maleic imide (W. Kuster) corresponding to the fact that pyrrole itself can be oxidised to this substance. CH—CH CH=CH II II I I CH CH —>- CO CO. NH NH Thus the imide of methylethylmaleic acid (I) corresponds to the pyrroles, and the so-called haematinic acid (II) to the carboxylic acids formulated above: H3C.C==C.C2H5 H3C.C=C.CH2.CH2.COOH I OC CO , II OC CO NH NH As will be seen later, C—C bonds of substituents in the a-position are broken on hydrogenation and so the various pyrrole units are set free. The porphyrins are pigments of this group, which have been freed from iron ; they are closely related to haemin, and iron in complex union can be reintroduced into them. Similar porphyrins are also derived from chlorophyll. Two natural porphyrins, uroporphyrin C40H38O16N4 and coproporphyrin C36H38O8N4, have acquired great importance in connection with the question of constitution. These substances tyere first isolated by Hans Fischer from the urine and faeces of a patient sufEering from deranged porphyrin metabolism; they are also formed in traces during normal metabolism. Uroporphyrin is an octa-, coproporphyrin a tetracarboxylic acid. Both are converted by thermal decarboxylation into the oxygen-free aetioporphyrin C32H38N4, a substance which Willstatter had obtained from haemin. With the synthesis of haemin (H. Fischer, 1929) our knowledge of the
PKOTOPOKPHYKIN 409 chemistry of the coloured components of the blood pigment has been made complete. The iron-free parent substance of haemin, protoporphyrin, has the following structure : CH CH CO2H CO2H (b) (a) Protoporphyrin The starting material for the synthesis was the iron compound of deuteroporphyrin in which c and d = H. By means of the Priedel-Crafts reaction (SnCl4 in place of A1C13), acetyl groups were introduced at c and d, the diketone formed was reduced to the glycol (haematoporphyrin, c and d =CH0H.CH3), and the latter converted into protoporphyrin with elimination of water. Fundamentally the synthesis of the porphyrins consists in condensation (by fusion) of two suitable " pyrromethines " with elimination of HBr and simultaneous dehydrogenation. The formulae represent this process in the case of deuteroporphyrin : CH CH2.CH2.CO2H CH2.CH2.CO2H
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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
Page 371 and 372: FIXATION OF DIPHENYLNITKOGEN 357 go
Page 373 and 374: QUADKIVALBNT NITROGEN 359 sponding
Page 375 and 376: CHAPTBK X HETEEOCYCLIC COMPOUNDS 1.
Page 377 and 378: KNOEVENAGEL'S SYNTHESIS E JH II /-
Page 379 and 380: a-AMINOPYKIDINB 365 rH2 I 2 I -+ I
Page 381 and 382: QUINALDINB 367 the liberated quinol
Page 383 and 384: 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: HABMIN FKOM OX BLOOD 407 12. HAEMIN
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 436 and 437: 422 LITBKATUEB OF OKGANIC CHBMISTKY
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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