Fundamental processes of dye chemistry

253 Pages·1949·7.293 MB·English

by  Fuerz-David H.E., Blangey L.

FUNDAMENTAL PROCESSES OF
DYE CHEMISTRY
By HANS EDUARD FIERZ-DAVID
and Louis BLANGEY
Eidgenossische Technische Hochschule, Zurich
Translated from the Fifth Austrian Edition
By PAUL W. VITTUM
Eastman Kodak Company, Rochester, New York
Published and distributed in the public interest with the
consent of the Attorney-General under License No. A-1360
1949
INTERSCIENCE PUBLISHERS, INC., NEW YORK
INTERSCIENCE PUBLISHERS LTD., LONDON
43G39
Translated from Grundlegende Operationen der Farbenchemie,
Siebente Unveranderte Auflage, Springer-Verlag, Wien, 1947.
The sixth (1946) and seventh (1947) Austrian editions are
unchanged reprints of the fifth (1943) Austrian edition.
Preface to the Fifth Austrian Edition
Copyright, 1922, Springer-Verlag OHG., Berlin. Copyright, This fifth edition of Grundlegende Operationen der Farbenchemie
1938, 1943, Springer-Verlag OHG., Vienna. Copyright vest- constitutes an expansion of the fourth edition. Since the appearance of
ed in the Alien Property Custodian, 1944, pursuant
the first edition in 1920, so many new processes of dye chemistry have
to law. Copyright, 1949, Interscience Publishers, Inc.
been discovered that it appeared necessary to rework or enlarge various
sections. In particular, the preparation of several important intermedi-
ates has been resurveyed.
The book is intended principally to introduce to the beginner the
methods of dye chemistry, and not merely to present a collection of
ALL RIGHTS RESERVED
recipes. To this end, the chapter on the practical work in the organic
industrial laboratory has been reworked and enlarged in order to clarify
This translation or any part thereof must not
all the important points. The chapter on analysis of dyes has been re-
be reproduced without permission of the pub-
vised so that the student may gain some insight into this difficult field.
lishers in writing. This applies specifically
Also, the section on the determination of light fastness has been re-
to photostatic and microfilm reproductions.
written, and we are grateful to Dr. Ris (Basel) for his contributions to
this subject. These additions have increased the scope of the book. We
hope that they have also increased its usefulness.
H. E. Fierz-David
Louis Blangey
Zurich, November 3, 1942
Chem.-Techn. Laboratorium der
Eidgenossischen Technischen
INTERSCIENCE PUBLISHERS, INC. Hochschule
215 Fourth Avenue, New York 3, N. Y.
For Great Britain and Northern Ireland:
INTERSCIENCE PUBLISHERS LTD.
2a Southampton Row, London, W. C. 1
PRINTED IN THE UNITED STATES OF AMERICA
OFFSET BY NEW YORK LITHOGRAPHING CORP., NEW YORK
COMPOSED BY GRAPHIC PRODUCTION CORP., NEW YORK
Preface to the Translation
Twenty-eight years have elapsed since the publication of the first
edition of Grundlegende Operationen der Farbenchemie. In the mean-
time the technology of dyestuff intermediates and the dyes obtained
from them has developed widely, and the processes described in 1920
are very well known today.
Editions subsequent to the first (up to the seventh edition, published
in Vienna in 1947) were expanded considerably in collaboration with
L. Blangey. The main aim was always to explain the fundamental prin-
ciples of dye chemistry to the student; and, since it was the endeavor
of the authors to write a laboratory book and not an encyclopedia, in
general only simple examples were given in this work. The preface to
the first edition indicated that the processes described were perhaps
not the best, but that by following the instructions exactly the results
stated would be obtained. In dye chemistry, as is well known, many
roads lead to the same goal.
The present edition is not intended to compete with more compre-
hensive books such as that of P. H. Groggins, Unit Processes in Organic
Synthesis (1947). The latter is a textbook, while Grundlegende Opera-
tionen der Farbencherhie, like Gattermann's book Praxis des Organ-
ischen Chemikers, is primarily a laboratory manual. The reprinting of
the fifth Austrian edition in the United States — without the consent of
the authors — indicated recognition of the need for such a volume.
It seems apropriate, however, to publish a new, American edition in
which several reactions are described that have not appeared in pre-
vious editions and which corrects minor errors discovered in the Aus-
trian edition on which the translation is based. These are the only
changes considered necessary.
After the present translation had been printed, the allied reports
on German and Japanese industry were made public. The authors noted
to their satisfaction that the processes they described corresponded
closely in many cases with those of the German dye factories. Certain
large-scale industrial reactions can be reproduced only with difficulty
in the laboratory with the small amounts of material at the chemist's
disposal. In our opinion, for example, it is practically impossible in the
via PREFACE TO THE TRANSLATION
laboratory to fractionate and crystallize out at low temperatures the
mixtures of chlorotoluenes as described in BIOS Final Report No. 1145.
On the other hand, we would like to point out here that 1-naphthyl-
amine-3-sulfonic acid can be separated easily from the mixture of the
1,6-, 1,7-, and 1,8- acids by precipitating carefully with acid, according
to FIAT Final Report No. 1016. The other processes correspond so
closely with those we present that there is no need for further amend-
CONTENTS
ments.
We want to thank Dr. Paul W. Vittum for a translation that corre-
sponds so well with the sense of the original German. We hope that this
American edition will fulfill its purpose and be cordially received. Preface to the Austrian edition v
Preface to the translation vii
H. E. Fierz-David Index of reactions , xix
Louis Blangey List of figures xxvii
List of tables xxix
Zurich, December 1, 1948
Swiss Federal Institute of Technology The foundations of the dye industry 1
I. INTERMEDIATES
General discussion 3
The various operations of intermediate chemistry 6
Sulfonation 6
Nitration 6
Reduction 7
Introduction of the hydroxyl group 7
Introduction of amino and alkoxy groups 8
Oxidation methods 8
Introduction of halogen 9
Practical work in the industrial organic laboratory 10
General 10
Proportions and weighing 13
Laboratory journals and reports 14
Apparatus 14
Stirring apparatus 15
Filtration 18
Distillation 21
Distillation under ordinary pressure 21
Vacuum distillation 25
Steam distillation 25
Separation of reaction products 27
Basic substances 27
Acidic substances 30
Purification of products 34
Testing the product for purity 40
Orientation rules 50
Orientation in the benzene series 50
Orientation in the naphthalene series 53
Orientation in the anthraquinone series 56
Orientation in the carbazole series 60
X CON-TCNTS CONTENTS XI
A. Compounds of the benzene series 62 Derivatives of aniline 126
Sulfanilic acid from aniline (baking process) 126
Chlorobenzene 62
The baking process in general 127
Halogenation in general 65
1- (p-Sulfophenyl) -3-methyl-5-pyrazolone from
Nitrobenzene 68
sulfanilic acid 128
Nitration in general 69
Phenylhydrazine-p-sulfonic acid 128
The Lunge nitrometer 72
p-Sulfophenyl-3-methyl-5-pyrazolone 129
Aniline from nitrobenzene 75
p-Aminoacetanilide from aniline 129
Reduction in general 77
Acetanilide from aniline 130
Benzenesulfonic acid 80
p-Nitroacetanilide from acetanilide 131
Sulfonation in general 82
p-Aminoacetanilide from p-nitroacetanilide 132
Phenol 86
Dimethylaniline (diethyl- and ethylbenzylanilines) . . . 133
Alkali fusion in general 88
Ethylbenzylanilinesulfonic acid 136
Derivatives of chlorobenzene 90
Tetramethyl-p,p'-diaminodiphenylmethane from
o- and p-Nitrochlorobenzene 90 dimethylaniline and formaldehyde 137
p- and 0-Nitroaniline from p- and o-nitrochlorobenzene 92 Tetramethyl-p,p'-diaminobenzohydrol (Michler hydrol) 138
p-Nitrophenyloxamic acid and p-aminophenyloxamic Tetramethyl-p,p'-diaminobenzophenone
acid 93
(Michler ketone) 139
p-Nitrophenylhydrazine 95
Diphenylamine from aniline and aniline salt 140
o-Nitroanisole from o-nitrochlorobenzene 97
Acetoacetanilide 142
p-Nitrochlorobenzene-o-sulfonic acid and p-nitroaniline-
Derivatives of benzenesulfonic acid 143
o-sulfonic acid from p-nitrochlorobenzene 99
Benzene-m-disulfonic acid 143
Diaminodiphenylaminesulfonic acid 99
Resorcinol 144
Aminodiphenylaminesulfonic acid (III), and
aminophenyltolylaminesulfonic acid 100 Derivatives of phenol 145
2,4-Dinitrochlorobenzene from chlorobenzene 101 o- and p-Chlorophenol from phenol 145
m-Phenylenediaminesulfonic acid from 2,4-dinitro- Chloranil 146
chlorobenzene 103 o- and p-Nitrophenols and their ethers 147
Aniline-2,5-disulfonic acid from chlorobenzene 104 Alkylation of nitrophenols 148
2-Nitrochlorobenzene-4-sulfonic acid Trinitrophenol (picric acid) 150
from chlorobenzene 104 Picramic acid 152
Nitrobenzene-2,5-disulfonic acid 106 2-Aminophenol-4,6-disulfonic acid from phenol 153
Anilme-2,5-disulfonic acid 106 Salicylic acid from phenol 154
4-Chloro-2-aminophenol from p-dichlorobenzene .... 108 p-Aminosalicylic acid 156
Nitro-p-dichlorobenzene from p-dichlorobenzene ... 108 Preparation of the azo dye 156
4-Chloro-2-nitrophenol from nitro-p-dichlorobenzene 109 Reduction 157
4-Chloro-2-aminophenol from 4-chloro-2-nitrophenol 110 Derivatives of toluene 158
Derivatives of nitrobenzene Ill Benzal chloride and benzaldehyde from toluene .... 158
m-Dinitrobenzene from nitrobenzene Ill Benzal chloride 158
m-Nitroaniline from m-dinitrobenzene 113 Benzaldehyde 158
Partial reductions in general 114 2,6-Dichlorobenzaldehyde from o-nitrotoluene 160
m-Phenylenediamine from m-dinitrobenzene 115 Chloronitrotoluene from o-nitrotoluene 160
m-Chloronitrobenzene from nitrobenzene 116 2,6-Chlorotoluidine 161
2-Chloro-4-dimethylaminobenzaldehyde 118 2,6-Dichlorotoluene 161
p-Tolyhydroxylaminesulfonic acid 118 2,6-Dichlorobenzal chloride 162
2-Chloro-4-dimethylaminobenzaldehyde 119 2,6-Dichlorobenzaldehyde 162
m-Nitrobenzenesulfonic acid and metanilic acid Benzidine-3,3'-dicarboxylic acid from o-nitrobenzoic acid 16.4
from nitrobenzene 120 2-Nitro-4-aminotoluene from p-toluidine 165
2,2'-Benzidinedisulfonic acid from nitrobenzene 123 Dinitrostilbenedisulfonic acid and diaminostilbenedisul-
Benzidine from nitrobenzene 124 fonic acid from p-nitrotoluene (simultaneous oxida-
tion of two molecules) 167
CONTENTS xiii
xii CONTENTS
Dinitrostilbenedisulfonic acid 167 l-Naphthylamine-3,6-disulfonic acid (Freund acid) 209
Reduction to diaminostilbenedisulfonic acid 168 l-Amino-8-naphthol-3,6-disulfonic acid (H acid) 211
2-Chloro-5-aminobenzoic acid 169 l-Naphthylamine-3,6,8-trisulfonic acid (Koch acid) 211
Gallamide and gallic acid from tannin 170 l-Amino-8-naphthol-3,6-disulfonic acid (H acid) . . 213
Benzene derivatives from naphthalene 171 l-Naphthylamine-5- and -8-sulfonic acids 214
Phthalic anhydride from naphthalene by l-Aminonaphthalene-4,8-disulfonic acid, 2-aminonaphthalene-
catalytic oxidation 171 4,8-disulfonic acid, and l-aminonaphthalene-3,8-disul-
Preparation of the catalyst 171 fonic acid 219
Performing the reaction. Apparatus 172 Naphthalene-l,4,5,8-tetracarboxylic acid from pyrene 221
Phthalimide from phthalic anhydride 173 Tetrachloropyrene 221
Anthranilic acid from phthalimide 174 Naphthalenetetracarboxylic acid 222
B. Compounds of the naphthalene series 175 C. Compounds of the anthraquinone series 224
a-Nitronaphthalene and a-naphthylamine 175 Anthraquinone 224
Phenyl-a-naphthylamine 179 Method 1: oxidation of anthracene 224
o-Naphthol from a-naphthylamine 180 Method 2: from phthalic anhydride and benzene 225
Naphthionic acid from a-naphthylamine 180 o-Benzoylbenzoic acid 225
Preparation of the acid sulfate 180 Anthraquinone 226
Baking process 181 l-Amine>-2-methylanthraquinone 227
l-Naphthol-4-sulfonic acid (Nevile-Winther acid) from 2-Methylanthraquinone 227
naphthionic acid (Bucherer reaction) 182 l-Nitro-2-methylanthraquinone 227
The sulfonic acids of naphthalene 183 l-Amino-2-methylanthraquinone 228
1,6- and 1,7-Naphthylaminesulfonic acids (Cleve acids) 184 2-Aminoanthraquinone . 228
Naphthalene-/3-sulfonic acid and £-naphthol 187 Sodium anthraquinone-2-sulfonate ("silver salt") . . . 228
Sulfonation of /3-naphthol 191 2-Amin9anthraquinone 229
2-Naphthol-6-sulfonic acid (Schaeffer acid) 1-Aminoanthraquinone and 1,4-diaminoanthraquinone 230
(R acid and G acid) 194 Anthraquinone-1 -sulfonic acid 230
2-Naphthol-6,8-disulfonic acid (G acid) and 1-Aminoanthraquinone 231
2-naphthol-3,6-disulfonic acid (R acid) 197 1-Anthraquinonyloxamic acid 231
2-Naphthylamine-l-sulfonic acid (Tobias acid) 4-Nitro-l-anthraquinonyloxamic acid 232
from /3-naphthol 198 1,4-Diaminoanthraquinone 232
2-Naphthol-l-sulfonic acid from j3-naphthol 199 1,5- and 1,8-Dihydroxyanthraquinone, and 1,5-dichloro-
2-Naphthylamine-l-sulfonic acid from anthraquinone 234
2-naphthol-l-suJfonic acid 200 Anthraquinone-1,5- and -1,8-sulfonic acid 234
l-Amino-2-naphthol-4-sulfonic acid from j8-naphthol 1,5- and 1,8-Dihydroxy anthraquinone 236
Preparation of an aminonaphtholsulfonic acid from 1,5-Dichloroanthraquinone 236
the hydroxynitroso compound (quinonemon- 1,5-Dinitroanthraquinone and 1,5-diaminoanthraquinone . . . 236
oxime) 201 1,5-Dinitroanthraquinone 237
/3-Naphthylamine from /3-naphthol 203 Reduction to 1,5-diaminoanthraquinone 237
2,8,6- and 2,5,7-Aminonaphtholsulfonic acids (Gamma
Quinizarin from p-chlorophenol 237
and J acids) from £-naphthylamine 204
2,6,8- and 2,5,7-Naphthylaminedisulfonic acids from
/3-Naphthylamine. 205 II. DYES
2-Amino-8-naphthol-6-sulfonicacfd (Gamma acid) . . 207
D. Azo dyes 239
2-Amino-5-naphthol-7-sulfonic acid (J acid, iso-
Laboratory preparation of azo dyes 239
Gamma acid) 207
Fundamental considerations 239
From 2-naphthol-6,8-disulfonic acid 208
Diazotization 241
From G acid and 2,8-dihydroxynaphthalene-6-
sulfonic acid 208 Examples 243
Phenyl-gamma acid 209
xiv CONTENTS CONTENTS XV
Coupling 249
E. Di- and triphenylmethane dyes 298
Theoretical . . . . 249
Practical 252 Auramine OO 298
Isolation of dyes 257 Malachite green 299
Dyes without sulfo or carboxyl groups 257 Leuco malachite green 299
Dyes with sulfo or carboxyl groups 258 Oxidation of the leuco base to the dye 300
Xylene blue VS 301
Technical diazotization procedures 259
Toluenedisulfonic acid 302
Aniline 259
Benzaldehydedisulfonic acid 303
p-Nitroaniline 260
Condensation to the leuco dye 303
a-Naphthylamine 260
Oxidation to the dye 304
Sulfanilic acid 261
Wool blue 5B 305
Benzidine 261
Victoria blue B 306
Coupling reactions 262
Wool green S 307
Single coupling reactions with hydroxy compounds .... 262
Acid orange A*or orange II 262 F. Oxazine and thiazine dyes 308
Acetyl-H acid and amidonaphthol red G 263 Gallamine blue from gallamide 308
Fast light yellow G (Bayer) 265 Nitrosodimethylaniline 308
Hansa yellow G 266 Gallamine blue 309
Permanent red 2G 267 Methylene blue from dimethylaniline » 311
Helio Bordeaux BL 268 p-Aminodimethylaniline 311
Preparation of the sodium salt 268 Thiosulfonic acid of Bindschadler green 312
Preparation of the calcium lake 269
Single coupling reactions with amines 270 C. Anthraquinone dyes 314
p-Aminoazobenzene from aniline 270 Mordant dyes 314
Tropaeoline or orange IV and azo yellow from sulfanilic Alizarin 314
acid and diphenylamine 273
Acid dyes 317
Tropaeoline or orange IV 274
Quinizarin green or alizarin cyanine green G 317
Azo yellow (Indian yellow, helianthine, etc.) .... 275
Alizarin saphirol B and SE 319
Secondary disazo and polyazo dyes 277
Sulfonation and nitration 319
Naphthylamine black D 277
Reduction 320
Benzo light blue 2 GL or sirius light blue G 279
Splitting out of one sulfo group : . . . 320
Aniline-2,5-disulfonic acid. a-Naphthylamine 279
Vat dyes 321
Aniline-2,5-disulfonic acid. a-Naphthylamine.
Indanthrene blue RS from /9-aminoanthraquinone .... 321
l-Naphthylamine-7-sulfonic acid 280
Indanthrene yellow GK 322
Preparation of the trisazo dye 281
Disazo and polyazo dyes from diamines 282 H. Indigoid dyes 323
Bismarck brown G and R 282
Indigo 323
Bismarck brown R (Vesuvine R, etc.) 282
Heumann synthesis 323
Chrysophenine G 283
Phenylglycine-o-carboxylic acid 323
Benzidine dyes 285
Indoxylcarboxylic acid 324
The intermediate from benzidine and salicylic acid
Indigo 324
(or from o-tolidine and o-cresotinic acid) 285
Traugott Sandmeyer synthesis 324
Dianil brown 3 GN 286
Thiocarbanilide 326
Diamine green B 288
Hydrocyanocarbodiphenylimide 326
Direct deep black EW 29]
"Thioamide" 327
Congo red 293
a-Isatinanilide 327
Acid anthracene red G and chromocitronine R 294 t
a-Thioisatin and indigo '. 329
Special methods 295
Eriochrome flavine A 295 Thioindigo 330
Sun yellow G from p-nitrotoluene 296 o-Carboxyphenylthioglycolic acid (O acid) 330
3-Hydroxythionaphthene 331
XVI CONTENTS CONTENTS xvii
Determination of amines 386
I. Sulfur fusions 332
Direct determination 386
Primuline 332
Indirect determination 387
Chloramine yellow FF (naphthamine yellow NN
Determination of naphthols 387
and thiazole yellow 332
Separation of the melt 334 /3-Naphthol 387
Naphthamine yellow NN (also FF) a-Naphthol 388
and thiazole yellow 335 Dihydroxynaphthalenes (molecular weight 160) 388
Naphthamine yellow NN 335 Determination of aminosulfonic acids 388
Thiazole yellow or Clayton yellow 336
Determination of aminonaphtholsulfonic acids 389
Sulfur black T from dinitrochlorobenzene 337
H acid. l-Amino-8-naphthol-3,6-disulfonic acids 389
J. Phthalocyanines 338 Determination of naphtholmono- and -disulfonic acids
Monastral fast blue BS, heliogen blue B . . . 338 and dihydroxynaphthalenemono- and -disulfonic acids 390
Example: Nevile-Winther acid (l-naphthol-4-sulfonic
acid) (molecular weight 224) 390
III. TECHNICAL DETAILS
Determination of 2-naphthylamine-5,7-disulfonic acid in the
K. Vacuum distillation in the laboratory and plant 341 presence of 2-naphthylamine-6,8-disulfonic acid .... 391
Volumetric determination of dyes by the Edmund Knecht
L. The filter press 348
reduction method 392
M. The construction and use of autoclaves 350 Principle of the Knecht method 392
General rules on the use of pressure vessels 361 Preparation of the titanium trichloride solution 393
Titration of methylene blue 393
N. Construction materials for dye chemistry 362 Azo dyes 394
Metals 362 Triphenylmethane dyes 394
Nonmetals 365 The common test papers 395
Materials of organic origin 367
Solution for spot tests on filter paper 396
O. Technical details of factory management 369 Evaluation of zinc dust , . . . . 396
Charges 372 Evaluation of lead peroxide paste 397
Steam consumption 372
Compressed air and vacuum 373 V. THE ANALYSIS OF COMMERCIAL DYES
Function of the plant chemist 373
Manufacturing 373 Polar brilliant red 3B and B 404
Sample dyeing 375 Polar brilliant red 3B 404
Grinding 377 Benzo light grey BL 407
Brilliant sulfo flavine (I.G.) 409
P. Calculation of costs for a simple dye 378
Literature on analysis of dyes 410
Orange II or acid orange A 378
0-Naphthol 378 VI. THE DETERMINATION OF LIGHT FASTNESS
Sodium ]3-naphthalenesulfonate 378
Fusion of the sodium salt 379
Sulfanilic acid 380
TablesItoXXI 417-465
Nitrobenzene ". 380
Reduction of nitrobenzene 380 Subject Index
467
Sulfonation of aniline 380
Preparation of the dye from sulfanilic acid and 0-naphthol 381
IV. ANALYTICAL SECTION
Preparation of standard titrimetric substances 384
Preparation of pure sulfanilic acid 384
Preparation of 1 N sodium nitrite solution 385
Preparation of 0.1 N phenyldiazonium solution 385
INDEX OF REACTIONS
1. Halogenation
General 9, 65
Direct chlorination:
With chlorine:
Chlorobenzene and dichlorobenzene from benzene 62
m-Chloronitrobenzene from nitrobenzene 116
Trichlorophenol from phenol 145
Benzal chloride from toluene 158
2-Nitro-6-chlorotoluene from o-nitrotoluene 160
2,6-Dichlorobenzaldehyde from 2,6-dichlorotoluene 162
Tetrachloropyrene from pyrene 221
With sulfuryl chloride:
o- and p-Chlorophenol from phenol 145
Indirect introduction of chlorine:
Replacement of — SO H by — Cl:
3
1,5-Dichloroanthraquinone from anthraquinone-l,5-disulfonic acid 236
Replacement of —NH2 by —Cl (Sandmeyer reaction):
2,6-Dichlorotoluene from 2-amino-6-chlorotoluene 161
Oxidative chlorination with aqua regia:
Chloranil from trichlorophenol 146
Bromination:
2,4-Dibromo-l-aminoanthraquinone from 1-aminoanthraquinone . . 233
2. Nitration
General 6, 69
Nitrobenzene 68
m-Dinitrobenzene from nitrobenzene Ill
o- and p-Nitrochlorobenzene 90
2,4-Dinitrochlorobenzene from chlorobenzene 101
Nitro-p- dichlorobenzene 108
2-Nitrochlorobenzene-4-sulfonic acid 104
p-Nitroacetanilide 131
o- and p-Nitrophenol 147
Picric acid from phenol 150
2-Nitrophenol-4,6-disulfonic acid 153
2-Nitro-4-aminotoluene 165
3-Nitro-6-chlorobenzoic acid 169
Azo yellow G from tropaeoline 276
a-Nitronaphthalene 175
l-Nitronaphthalene-5- and 8-sulfonic acid 215
l-Nitronaphthalene-6- and 7-sulfonic acid 184
l-Nitronaphthalene-3,6-disulfonic acid 209
l-Nitronaphthalene-3,8- and 4.8-disulfonic acid, and
2-nitronaphthalene-4,8-disulfonic acid 219
KX INDEX OF REACTIONS INDEX OF REACTIONS xxi
l-Nitronaphthalene-3,6,8-trisiilfonic acid 211 —N=N+C1- to —NH—NH:
2
1,5-Dinitroanthraquinone from anthraquinone 237 «- and o-Nitrophenylhydrazine from p- and o-nitroaniline
l-Nitro-2-methylanthraquinone 227 (Na S0 + NaHSOa) 95
4-Nitro-l-anthraquinonyloxamic acid 232 Phenylh2ydr3azinesulfonic acid^ (NaSOa) 128
4,8-Dinitro-l,5-dihydroxyanthraquinone-2,6-disulfonic acid 319 2
Other reductions:
Methylene green from methylene blue 313
Thiosalicylic acid from dithiosalicylic acid (Fe) 331
Leuco quinizarin from quinizarin (SnCl ) 318
3. Nitrosation 2
Modem violet from galfamine blue (NaS) 310
2
p-Nitrosodimethylaniline from dimethylaniline 308 o-Thioisatin from isatinanilide (NaSH) 329
l-Nitroso-2-naphthol from /3-naphthol 201
Nitrosotropaeoline from tropaeoline 275 5. Oxidation
General 8
4. Reduction Phthalic anhydride from naphthalene (air) 171
General 7, 77 Benzaldehyde-2,4-disulfonic acid from toluenedisulfonic acid (MnO2) 303
—NO to —NH: v p'-Dinitrostilbenedisulfonic acid from p-nitrotoluene-o-sulfonic acid
2 2
Reduction of all the nitro groups present: (NaOCl) 167
Naphthalene-1,4,5,8-tetracarboxylic acid from tetrachloropyrene (HNOa) 222
Aniline (Fe) 75
Anthraquinone from anthracene (CrOa) 224
m-Phenylenediamine from nitrobenzene (Fe) 115
Tetramethyldiaminobenzhydrol (Michler hydrol) from
Metanilic acid (Fe) 121
tetramethyldiaminodiphenylmethane (PbO ) 138
Aniline-2,5-disulfonic acid (Fe) 106 2
Malachite green from the leuco base (PbO ) 300
m-Phenylenediaminesulfonic acid (Fe) 103 2
Xylene blue VS from the leuco compound (PbO ) 304
p-Aminoacetanilide (Fe) 132 2
p-Aminophenyloxamic acid (Fe) 94 Wool green S from the leuco compound (CrOa) 308
Bindscbedler green-thiosulfonic acid from dimethylaniline,
4-Chloro-2-aminophenol (Fe) 110
p-aminodimethylaniline, and thiosulfate (CrOa) 312
2-Aminophenol-4,6-disulfonic acid (Na2S) 154
Indigo from indoxylcarboxylic acid (air) 324
6-Chloro-2-aminotoluene (Fe) 161
Thioindigo from 3-hydroxythionaphthene (S) 332
p,p'-Diaminostilbenedisulfonic acid (Fe) 168
Naphthamine yellow NN from dehydrothiotoluidinesulfonic acid
6-Chloro-3-aminobenzoic acid (Zn) 169
(NaOCl) 335
a-Naphthylamine (Fe) 176
Alizarin from anthraquinone-j8-sulfonic acid (NaOCl in alkali fusion;
1.5- and 1,8-Naphthylaminesulfonic acid (Fe) 215
simultaneous replacement of —SOaH by —OH) 314
1.6- and 1,7-Naphthylaminesulfonic acid (Fe) 186
l-Naphthylamine-3,6-disulfonic acid 210 6. Sulfonation
l-Naphthylamine-3,8- and 4,8-disulfonic acid and
2-naphthylamine-4,8-disulfonic acid (Fe) 219 General 6, 82
l-Naphthylamine-3,6,8-trisulfonic acid (Fe + H SO ) 212 Direct sulfonation:
2 4
l-Amino-2-methylanthraquinone (NaS) 228 Benzenesulfonic acid (oleum) 80
2
1,4-Diaminoanthraquinone (NaS) 232 Benzene-m-disulfonic acid (oleum) 143
2
1,5-Diaminoanthraquinone (Na S) 237 Toluene-2,4-disulfonic acid (oleum) 302
2
Alizarin saphirol B (NaSH) -. 320 p-Chlorobenzenesulfonic acid (oleum) 104
Reduction of only one of several nitro groups (partial reduction): m-Nitrobenzenesulfonic acid (oleum) 120
General 114 p-Nitrochlorobenzene-o-sulfonic acid (oleum) 99
m-Nitroaniline from m-dinitrobenzene (NaSH) 113 p-Nitrotoluene-o-sulfonic acid (oleum) 167, 296
Picramic acid from picric acid (Na S) 152 Sulfanilic acid (baking process) 126
2 The baking process in general 127
_NO to —NHOH:
2 Ethylbenzylanilinesulfonic acid (oleum) 136
p-Tolylhydroxylamine-o-sulfonic acid (Zn) 118
p-Aminoazobenzenedisulfonic acid (fast yellow) (oleum) 271
—NO2 to —NH—NH—, followed by benzidine rearrangement: Azo flavine FF (100$ H2SO4) 272
Benzidine from nitrobenzene (Zn) 124 Phenol-2,4-disulfonic acid (oleum) 150, 153
Benzidine-2,2/-disulfonic acid (Zn) 123 Naphthalenesulfonic acids, general 183
Benzidine-3,3'-dicarboxylic acid (Zn) 164 Naphthalene-a-sulfonic acid (100% H SO ) 215
2 4
—NO to —NH : Naphthalene-/3-sulfonic acid (H SO , 66° Be) 184, 187
2 2 4
p-Aminodimethylaniline (Zn) 311 Naphthalene-1,5- and 1,6-disulfonic acid (oleum) 219
l-Amino-2-naphthol-4-sulfonic acid (simultaneous Naphthalene-2,7-disulfonic acid (100% H2SO4) 209
sulfonation, with SO ) 201 Naphthalene-1,3,6-trisulfonic acid (oleum) 211
2
—N=N— to —NH : /3-Naphtholsulfonic acids, general 191
2 2-Naphthol-l-sulfonic acid (C1SOH) 199
p-Aminosalicylic acid (Na S O ) 157 8
2 2 4 2-Naphthol-6-sulfonic. acid (H SO , 66°'Be) 194
Reductive splitting of polar brilliant red 3B (NaSO) 404 2 4
2 2 4 2-Naphthol-3,6- and 6,8-disulfonic acid (H SO , 66° Be;
Reductive splitting of polar brilliant red 3B (SnCl ) 404 2 4
2 oleum) : 194, 197
Reductive splitting of benzo light grey BL (SnCl ) 407
2 l-Naphthylamine-4-sulfonic acid (baking) 181