fundamental processes of dye chemistry

f
f


FUNDAMENTAL PROCESSES OF

DYE CHEMISTRY
By H A N S E D U A R D F I E R Z - D A V I D

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

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.

Copyright, 1922, Springer-Verlag OHG., Berlin. Copyright,
1938, 1943, Springer-Verlag OHG., Vienna. Copyright vested in the Alien Property Custodian, 1944, pursuant
to law. Copyright, 1949, Interscience Publishers, Inc.

ALL RIGHTS

RESERVED

This translation or any part thereof must not
be reproduced without permission of the publishers in writing. This applies specifically
to photdstatic and microfilm reproductions.

INTERSCIENCE PUBLISHERS,

INC.

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 U N I T E D STATES O F A M E R I C A
OFFSET BY N E W YORK LITHOGRAPHING C O R P . , N E W YORK
COMPOSED BY GRAPHIC PRODUCTION C O R P . , N E W

YORK


Preface to the Fifth Austrian Edition
This fifth edition of Grundlegende Operationen der Farbenchemie
constitutes an expansion of the fourth edition. Since the appearance of
the first edition in 1920, so many new processes of dye chemistry have
been discovered that it appeared necessary to rework or enlarge various
sections. In particular, the preparation of several important intermediates 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
recipes. To this end, the chapter on the practical work in the organic
industrial laboratory has been reworked and enlarged in order to clarify
all the important points. The chapter on analysis of dyes has been revised so that the student may gain some insight into this difficult field.
Also, the section on the determination of light fastness has been rewritten, 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
Hochschule

v

Preface to the Translation
Twenty-eight years have elapsed since the publication of the first
edition of Grundlegende Operationen der Farbenchemie. In the meantime 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 principles 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 comprehensive books such as that of P. H. Groggins, Unit Processes in Organic
Synthesis (1947). The latter is a textbook, while Grundlegende Operationen der Farbencherhie, like Gattermann's book Praxis des Organischen 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 previous editions and which corrects minor errors discovered in the Austrian 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
Vll


viii

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-naphthylamine-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 amendments.
We want to thank Dr. Paul W. Vittum for a translation that corresponds so well with the sense of the original German. We hope that this
American edition will fulfill its purpose and be cordially received.
H. E. Fierz-David
Louis Blangey
Zurich, December 1, 1948
Swiss Federal Institute of Technology


CONTENTS
Preface to the Austrian edition
Preface to the translation
Index of reactions
List of figures
List of tables
The foundations of the dye industry

v
vii
xix
xxvii
xxix
1

I. INTERMEDIATES
General discussion
The various operations of intermediate chemistry
Sulfonation
Nitration
Reduction
Introduction of the hydroxyl group
Introduction of amino and alkoxy groups
Oxidation methods
Introduction of halogen
Practical work in the industrial organic laboratory
General
Proportions and weighing
Laboratory journals and reports
Apparatus
Stirring apparatus
Filtration
Distillation
Distillation under ordinary pressure
Vacuum distillation
Steam distillation
Separation of reaction products
Rasic substances

Acidic substances
Purification of products
Testing the product for purity
Orientation rules
Orientation in the benzene series
Orientation in the naphthalene series
Orientation in the anthraquinone series
Orientation in the carbazole series
ix

3
6
6
6
7
7
8
8
9
10
10
13
14
14
15
18
21
21
25
25

27
27
30
34
40
50
50
53
56
60


X

CONTENTS

A. Compounds of the benzene series
Chlorobenzene
Halogenation in general
Nitrobenzene
Nitration in general
The Lunge nitrometer
Aniline from nitrobenzene
Reduction in general
Benzenesulfonic acid
Sulfonation in general
Phenol
Alkali fusion in general
Derivatives of chlorobenzene
o- and p-Nitrochlorobenzene

p- and 0-Nitroaniline from p- and o-nitrochlorobenzene
p-Nitrophenyloxamic acid and p-aminophenyloxamic
acid
p-Nitrophenylhydrazine
o-Nitroanisole from o-nitrochlorobenzene
p-Nitrochlorobenzene-o-sulfonic acid and p-nitroanilineo-sulfonic acid from p-nitrochlorobenzene
Diaminodiphenylaminesulfonic acid
Aminodiphenylaminesulfonic acid (III), and
aminophenyltolylaminesulfonic acid
2,4-Dinitrochlorobenzene from chlorobenzene
m-Phenylenediaminesulfonic acid from 2,4-dinitrochlorobenzene
Aniline-2,5-disulfonic acid from chlorobenzene
2-Nitrochlorobenzene-4-sulfonic acid
from chlorobenzene
Nitrobenzene-2,5-disulfonic acid
Aniline-2,5-disulfonic acid
4-Chloro-2-aminophenol from p-dichlorobenzene . . . .
Nitro-p-dichlorobenzene from p-dichlorobenzene . . .
4-Chloro-2-nitrophenol from nitro-p-dichlorobenzene
4-Chloro-2-aminophenol from 4-chloro-2-nitrophenol
Derivatives of nitrobenzene
m-Dinitrobenzene from nitrobenzene
m-Nitroaniline from m-dinitrobenzene
Partial reductions in general
m-Phenylenediamine from m-dinitrobenzene
m-Chloronitrobenzene from nitrobenzene
2-Chloro-4-dimethylaminobenzaldehyde
p-Tolyhydroxylaminesulfonic acid
2-Chloro-4-dimethylaminobenzaldehyde
m-Nitrobenzenesulfonic acid and metanilic acid

from nitrobenzene
2,2'-Benzidinedisulfonic acid from nitrobenzene
Benzidine from nitrobenzene

62
62
65
68
69
72
75
77
80
82
86
88
90
90
92
93
95
97
99
99
100
101
103
104
104
106

106
108
108
109
110
Ill
Ill
113
114
115
116
118
118
119
120
123
124


CONTENTS

Derivatives of aniline
Sulfanilic acid from aniline (baking process)
The baking process in general
1- (p-Sulfophenyl) -3-methyl-5-pyrazolone from
sulfanilic acid
Phenylhydrazine-p-sulfonic acid
p-Sulfophenyl-3-methyl-5-pyrazolone
p-Aminoacetanilide from aniline
Acetanilide from aniline

p-Nitroacetanilide from acetanilide
p-Aminoacetanilide from p-nitroacetanilide
Dimethylaniline (diethyl-and ethylbenzylanilines) . . .
Ethylbenzylanilinesulfonic acid
Tetramethyl-p,p'-diaminodiphenylmethane from
dimethylaniline and formaldehyde
Tetramethyl-p,p'-diaminobenzohydrol (Michler hydrol)
Tetramethyl-p,p'-diaminobenzophenone
(Michler ketone)
Diphenylamine from aniline and aniline salt
Acetoacetanilide
Derivatives of benzenesulfonic acid
Benzene-m-disulfonic acid
Resorcinol
Derivatives of phenol
o- and p-Chlorophenol from phenol
Chloranil
o- and p-Nitrophenols and their ethers
Alkylation of nitrophenols
Trinitrophenol (picric acid)
Picramic acid
2-Aminophenol-4,6-disulfonic acid from phenol
Salicylic acid from phenol
p-Aminosalicylic acid
Preparation of the azo dye .
Reduction
Derivatives of toluene
Benzal chloride and benzaldehyde from toluene . . . .
Benzal chloride
Benzaldehyde

2,6-Dichlorobenzaldehyde from o-nitrotoluene
Chloronitrotoluene from o-nitrotoluene
2,6-Chlorotoluidine
2,6-Dichlorotoluene
2,6-Dichlorobenzal chloride
2,6-Dichlorobenzaldehyde
Benzidine-3,3'-dicarboxylic acid from o-nitrobenzoic acid
2-Nitro-4-aminotoluene from p-toluidine
Dinitrostilbenedisulfonic acid and diaminostilbenedisulfonic acid from p-nitrotoluene (simultaneous oxidation of two molecules)

xi

126
126
127
128
128
129
129
130
131
132
133
136
137
138
139
140
142
143

143
144
145
145
146
147
148
150
152
153
154
156
156
157
158
158
158
158
160
160
161
161
162
162
1644
165
167


xii

CONTENTS

Dinitrostilbenedisulfonic acid
Reduction to diaminostilbenedisulfonic acid
2-Chloro-5-aminobenzoic acid
Gallamide and gallic acid from tannin
Benzene derivatives from naphthalene
Phthalic anhydride from naphthalene by
catalytic oxidation
Preparation of the catalyst
Performing the reaction. Apparatus
Phthalimide from phthalic anhydride
Anthranilic acid from phthalimide
B. Compounds of the naphthalene series
a-Nitronaphthalene and a-naphthylamine
Phenyl-a-naphthylamine
a-Naphthol from a-naphthylamine
Naphthionic acid from a-naphthylamine
Preparation of the acid sulfate
Baking process
l-Naphthol-4-sulfonic acid (Nevile-Winther acid) from
naphthionic acid (Bucherer reaction)
The sulfonic acids of naphthalene
1,6- and 1,7-Naphthylaminesulfonic acids (Cleve acids)
Naphthalene-/3-sulfonic acid and £-naphthol
Sulfonation of /3-naphthol
2-Naphthol-6-sulfonic acid (Schaeffer acid)
(R acid and G acid)
2-Naphthol-6,8-disulfonic acid (G acid) and

2-naphthol-3,6-disulfonic acid (R acid)
2-Naphthylamine-l-sulfonic acid (Tobias acid)
from £-naphthol
2-Naphthol-l-sulfonic acid from jS-naphthol
2-Naphthylamine-l-sulfonic acid from
2-naphthol-l-suJfonic acid
l-Amino-2-naphthol-4-sulfonic acid from jS-naphthol
Preparation of an aminonaphtholsulfonic acid from
the hydroxynitroso compound (quinonemonoxime)
/3-Naphthylamine from /3-naphthol
2,8,6- and 2,5,7-Aminonaphtholsulfonic acids (Gamma
and J acids) from £-naphthylamine
2,6,8- and 2,5,7-Naphthylaminedisulfonic acids from
/3-Naphthylamine.
2-Amino-8-naphthol-6-sulfonicacfd (Gamma acid) . .
2-Amino-5-naphthol-7-sulfonic acid (J acid, isoGamma acid)
From 2-naphthol-6,8-disulfonic acid
From G acid and 2,8-dihydroxynaphthalene-6sulfonic acid
Phenyl-gamma acid

167
168
169
170
171
171
171
172
173
174

175
175
179
180
180
180
181
182
183
184
187
191
194
197
198
199
200

201
203
204
205
207
207
208
208
209


CONTENTS

l-Naphthylamine-3,6-disulfonic acid (Freund acid)
l-Amino-8-naphthol-3,6-disulfonic acid (H acid)
l-Naphthylamine-3,6,8-trisulfonic acid (Koch acid)
l-Amino-8-naphthol-3,6-disulfonic acid (H acid) . .
l-Naphthylamine-5- and -8-sulfonic acids
l-Aminonaphthalene-4,8-disulfonic acid, 2-aminonaphthalene4,8-disulfonic acid, and l-aminonaphthalene-3,8-disulfonic acid
Naphthalene- 1,4,5,8-tetracarboxylie acid from pyrene
Tetrachloropyrene
Naphthalenetetracarboxylic acid

xiii

209
211
211
213
214
219
221
221
222

C. Compounds of the anthraquinone series
224
Anthraquinone
224
Method 1: oxidation of anthracene
224
Method 2: from phthalic anhydride and benzene

225
o-Benzoylbenzoic acid
225
Anthraquinone
226
l-Amino-2-methylanthraquinone
227
2-Methylanthraquinone
227
l-Nitro-2-methylanthraquinone
227
l-Amino-2-methylanthraquinone
228
2-Aminoanthraquinone
228
Sodium anthraquinone-2-sulfonate ("silver salt") . . . 228
2-Aminoanthraquinone
229
1-Aminoanthraquinone and 1,4-diaminoanthraquinone
230
Anthraquinone-1-sulfonic acid
230
1-Aminoanthraquinone
231
1-Anthraquinonyloxamic acid
231
4-Nitro-l-anthraquinonyloxamic acid
232
1,4-Diaminoanthraquinone
232

1,5- and 1,8-Dihydroxyanthraquinone, and 1,5-dichloroanthraquinone
234
Anthraquinone-1,5- and -1,8-sulfonic acid
234
1,5- and 1,8-Dihydroxyanthraquinone
236
1,5-Dichloroanthraquinone
236
1,5-Dinitroanthraquinone and 1,5-diaminoanthraquinone . . . 236
1,5-Dinitroanthraquinone
237
Reduction to 1,5-diaminoanthraquinone
237
Quinizarin from p-chlorophenol
237
II. DYES
D. Azo dyes
Laboratory preparation of azo dyes
Fundamental considerations
Diazotization
Examples

239
239
239
241
243


xiv

CONTENTS

Coupling
Theoretical
Practical
Isolation of dyes
Dyes without sulfo or carboxyl groups
Dyes with sulfo or carboxyl groups
Technical diazotization procedures
Aniline
p-Nitroaniline
a-Naphthylamine
Sulfanilic acid
Benzidine
Coupling reactions
Single coupling reactions with hydroxy compounds . . . .
Acid orange A'or orange II
Acetyl-H acid and amidonaphthol red G
Fast light yellow G (Bayer)
Hansa yellow G
Permanent red 2G
Helio Bordeaux BL
Preparation of the sodium salt
Preparation of the calcium lake
Single coupling reactions with amines
p-Aminoazobenzene from aniline
Tropaeoline or orange IV and azo yellow from sulfanilic
acid and diphenylamine
Tropaeoline or orange IV

Azo yellow (Indian yellow, helianthine, etc.) . . . .
Secondary disazo and polyazo dyes
Naphthylamine black D
Benzo light blue 2 GL or sirius light blue G
Aniline-2,5-disulfonic acid. a-Naphthylamine
Aniline-2,5-disulfonic acid. a-Naphthylamine.
l-Naphthylamine-7-sulfonic acid
Preparation of the trisazo dye
Disazo and polyazo dyes from diamines
Bismarck brown G and R
Bismarck brown R (Vesuvine R, etc.)
Chrysophenine G
Benzidine dyes
The intermediate from benzidine and salicylic acid
(or from o-tolidine and o-cresotinic acid)
Dianil brown 3 GN
Diamine green B
Direct deep black EW
Congo red
Acid anthracene red G and chromocitronine R
Special methods
Eriochrome flavine A
Sun yellow G from p-nitrotoluene

249
249
252
257
257
258

259
259
260
260
261
261
262
262
262
263
265
266
267
268
268
269
270
270
273
274
275
277
277
279
279
280
281
282
282
282

283
285
285
286
288
291
293
294
295
295
296


CONTENTS

xv

E.

Di- and triphenylmethane dyes
Auramine OO
Malachite green
Leuco malachite green
Oxidation of the leuco base to the dye
Xylene blue VS
Toluenedisulfonic acid
Benzaldehydedisulfonic acid
Condensation to the leuco dye
Oxidation to the dye
Wool blue 5B

Victoria blue B
Wool green S

298
298
299
299
300
301
302
303
303
304
305
306
307

F.

Oxazine and thiazine dyes
Gallamine blue from gallamide
Nitrosodimethylaniline
Gallamine blue
Methylene blue from dimethylaniline »
p-Aminodimethylaniline
Thiosulfonic acid of Bindschadler green

308
308
308

309
311
311
312

G. Anthraquinone dyes
Mordant dyes
Alizarin
Acid dyes
Quinizarin green or alizarin cyanine green G
Alizarin saphirol B and SE
Sulfonation and nitration
Reduction
Splitting out of one sulfo group
: . . .
Vat dyes
Indanthrene blue RS from /9-aminoanthraquinone . . . .
Indanthrene yellow GK
H. Indigoiddyes
Indigo
Heumann synthesis
Phenylglycine-o-carboxylic acid
Indoxylcarboxylic acid
Indigo
Traugott Sandmeyer synthesis
Thiocarbanilide
Hydrocyanocarbodiphenylimide
'Thioamide"
a-Isatinanilide
a-Thioisatin and indigo

Thioindigo
o-Carboxyphenylthiogly colic acid (O acid)
3-Hydroxythionaphthene

314
314
314
317
317
319
319
320
320
321
321
322
323
323
323
323
324
324
324
326
326
327
327
329
330
330

331


xvi

I.

CONTENTS

Sulfur fusions
Primuline
Chloramine yellow FF (naphthamine yellow NN
and thiazole yellow
Separation of the melt
Naphthamine yellow NN (also FF)
and thiazole yellow
Naphthamine yellow NN
Thiazole yellow or Clayton yellow
Sulfur black T from dinitrochlorobenzene

J. Phthalocyanines
Monastral fast blue BS, heliogen blue B

332
332
332
334
335
335
336

337
338
338

III. TECHNICAL DETAILS
K. Vacuum distillation in the laboratory and plant
L. The filter press
M. The construction and use of autoclaves
General rules on the use of pressure vessels

341
348
350
361

N.

362
362
365
367

Construction materials for dye chemistry
Metals
Nonmetals
Materials of organic origin

O. Technical details of factory management
Charges
Steam consumption

Compressed air and vacuum
Function of the plant chemist
Manufacturing
Sample dyeing
Grinding

369
372
372
373
373
373
375
377

P. Calculation of costs for a simple dye
Orange II or acid orange A
/3-Naphthol
Sodium j8-naphthalenesulfonate
Fusion of the sodium salt
Sulfanilic acid
Nitrobenzene
*.
Reduction of nitrobenzene
Sulfonation of aniline
Preparation of the dye from sulfanilic acid and 0-naphthol

378
378
378

378
379
380
380
380
380
381

IV. ANALYTICAL SECTION
Preparation of standard titrimetric substances
Preparation of pure sulfanilic acid
Preparation of 1 N sodium nitrite solution
Preparation of 0.12V phenyldiazonium solution

384
384
385
385


CONTENTS

xvii

Determination of amines
Direct determination
Indirect determination
Determination of naphthols
/3-Naphthol
a-Naphthol

Dihydroxynaphthalenes (molecular weight 160)
Determination of aminosulfonic acids
Determination of aminonaphtholsulfonic acids
H acid. l-Amino-8-naphthol-3,6-disulfonic acids
Determination of naphtholmono- and -disulfonic acids
and dihydroxynaphthalenemono- and -disulfonic acids
Example: Nevile-Winther acid (l-naphthol-4-sulfonic
acid) (molecular weight 224)
Determination of 2-naphthylamine-5,7-disulfonic acid in the
presence of 2-naphthylamine-6,8-disulfonic acid . . . .
Volumetric determination of dyes by the Edmund Knecht
reduction method
Principle of the Knecht method
Preparation of the titanium trichloride solution
Titration of methylene blue
Azo dyes
Triphenylmethane dyes
The common test papers
Solution for spot tests on filter paper
Evaluation of zinc dust
, . . . .
Evaluation of lead peroxide paste

386
386
387
387
387
388
388

388
389
389
390
390
391
392
392
393
393
394
394
395
396
396
397

V. THE ANALYSIS OF COMMERCIAL DYES
Polar brilliant red 3B and B
Polar brilliant red 3B
Benzo light grey BL
Brilliant sulfo flavine (I.G.)
Literature on analysis of dyes

404
404
407
409
410

VI. THE DETERMINATION OF LIGHT FASTNESS
TablesItoXXI
Subject Index

417-465
467



INDEX OF REACTIONS
1. Halogenation
9
General
> 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 —SO3H by —CI:
1,5-Dichloroanthraquinone from anthraquinone-1,5-disulfonic acid 236
Replacement of —NH2 by —CI (Sandmeyer reaction):
2,6-Dichlorotoluene from 2-amino-6-chlorotoluene
161
Oxidative chlorination with aqua regia:
Chloranil from trichlorophenol
146
Bromination:
2,4-Dibromo- 1-aminoanthraquinone from 1-aminoanthraquinone . . 233

2. Nitration
General
Nitrobenzene
m-Dinitrobenzene from nitrobenzene
0- and p-Nitrochlorobenzene
2,4-Dinitrochlorobenzene from chlorobenzene
Nitro- p- dichlorobenzene
2-Nitrochlorobenzene-4-sulfonic acid
p-Nitroacetanilide
0- and p-Nitrophenol
Picric acid from phenol
2-Nitrophenol-4,6-disulfonic acid
2-Nitro-4-aminotoluene
3-Nitro-6-chlorobenzoic acid
Azo yellow G from tropaeoline

a-Nitronaphthalene
l-Nitronaphthalene-5- and 8-sulfonic acid
l-Nitronaphthalene-6- and 7-sulfonic acid
l-Nitronaphthalene-3,6-disulfonic acid
l-Nitronaphthalene-3,8- and 4.8-disulfonic acid, and
2-nitronaphthalene-4,8-disulfonic acid
xix

6, 69
68
Ill
90
101
108
104
131
147
150
153
165
169
276
175
215
184
209
219


X

INDEX OF REACTIONS

l-Nitronaphthalene-3,6,8-trisulfonic acid
1,5-Dinitroanthraquinone from anthraquinone
l-Nitro-2-methylanthraquinone
4-Nitro-l-anthraquinonyloxamic acid
4,8-Dinitro-l,5-dihydroxyanthraquinone-2,6-disulfonic acid
Methylene green from methylene blue
3. Nitrosation
p-Nitrosodimethylaniline from dimethylaniline
l-Nitroso-2-naphthol from 0-naphthol
Nitrosotropaeoline from tropaeoline

211
237
227
232
319
313
308
201
275

4. Reduction
General
__N0 2 to —NH 2 :
Reduction of all the nitro groups present:
Aniline (Fe)
m-Phenylenediamine from nitrobenzene (Fe)

Metanilic acid (Fe)
Aniline-2,5-disulfonic acid (Fe)
m-Phenylenediaminesulfonic acid (Fe)
p-Aminoacetanilide (Fe)
p-Aminophenyloxamic acid (Fe)
4-Chloro-2-aminophenol (Fe)
2-Aminophenol-4,6-disulfonic acid (Na 2 S)
6-Chloro-2-aminotoluene (Fe)
p,p'-Diaminostilbenedisulfonic acid (Fe)
6-Chloro-3-aminobenzoic acid (Zn)
a-Naphthylamine (Fe)
1.5- and 1,8-Naphthylaminesulfonic acid (Fe)
1.6- and 1,7-Naphthylaminesulfonic acid (Fe)
l-Naphthylamine-3,6-disulfonic acid
l-Naphthylamine-3,8- and 4,8-disulfonic acid and
2-naphthylamine-4,8-disulfonic acid (Fe)
l-Naphthylamine-3,6,8-trisulfonic acid (Fe + H 2 S0 4 )
l-Amino-2-methylanthraquinone (Na 2 S)
1,4-Diaminoanthraquinone (Na 2 S)
1,5-Diaminoanthraquinone (Na 2 S)
Alizarin saphirol B (NaSH)
^
Reduction of only one of several nitro groups (partial reduction):
General
m-Nitroaniline from m-dinitrobenzene (NaSH)
Picramic acid from picric acid (Na 2 S)
—N0 2 to —NHOH:
p-Tolylhydroxylamine-o-sulfonic acid (Zn)
—N0 2 to —NH—NH—, followed by benzidine rearrangement:
Benzidine from nitrobenzene (Zn)

Benzidine-2,2/-disulfonic acid (Zn)
Benzidine-3,3'-dicarboxylic acid (Zn)
—NO to —NH 2 :
p-Aminodimethylaniline (Zn)
l-Amino-2-naphthol-4-sulfonic acid (simultaneous
sulfonation, with S0 2 )
—N=N— to —NH 2 :
p-Aminosalicylic acid (Na2S204>
Reductive splitting of polar brilliant red 3B (Na2S2C>4)
Reductive splitting of polar brilliant red 3B (SnCl 2 )
Reductive splitting of benzo light grey BL (SnCl 2 )

7, 77
75
115
121
106
103
132
94
110
154
161
168
169
176
215
186
210
219

212
228
232
237
320
114
113
152
118
124
123
164
311
201
157
404
404
407


INDEX OF REACTIONS

xxi

—N=N+C1- to —NH—NH 2 :
p- and o-Nitrophenylhydrazine from p- and o-nitroaniline
(Na 2 S0 3 + NaHS0 3 )
Phenylhydrazinesulfonic acioV (Na2S03)
Other reductions:
Thiosalicylic acid from dithiosalicylic acid (Fe)

Leuco quinizarin from quinizarin (SnCl2)
Modern violet from galfamine blue (Na 2 S)
o-Thioisatin from isatinanilide (NaSH)

95
128
331
318
310
329

5. Oxidation
General
Phthalic anhydride from naphthalene (air)
Benzaldehyde-2,4-disulfonic acid from toluenedisulfonic acid (Mn0 2 )
p p'-Dinitrostilbenedisulfonic acid from p-nitrotoluene-o-sulfonic acid
'(NaOCl)
Naphthalene-1,4,5,8-tetracarboxylic acid from tetrachloropyrene (HNO3)
Anthraquinone from anthracene (Cr0 3 )
Tetramethyldiaminobenzhydrol (Michler hydrol) from
tetramethyldiaminodiphenylmethane (Pb0 2 )
Malachite green from the leuco base (Pb0 2 )
Xylene blue VS from the leuco compound (Pb0 2 )
Wool green S from the leuco compound (Cr0 3 )
Bindscbedler green-thiosulfonic acid from dimethylaniline,
p-aminodimethylaniline, and thiosulfate (Cr0 3 )
Indigo from indoxylcarboxylic acid (air)
Thioindigo from 3-hydroxythionaphthene (S)
Naphthamine yellow NN from dehydrothiotoluidinesulfonic acid
(NaOCl)

Alizarin from anthraquinone-j8-sulfonic acid (NaOCl in alkali fusion;
simultaneous replacement of —SO3H by —OH)
6. Sulfonation
General
Direct sulfonation:
Benzenesulfonic acid (oleum)
Benzene-m-disulfonic acid (oleum)
Toluene-2,4-disulfonic acid (oleum)
p-Chlorobenzenesulfonic acid (oleum)
m-Nitrobenzenesulfonic acid (oleum)
p-Nitrochlorobenzene-o-sulfonic acid (oleum)
p-Nitrotoluene-o-sulfonic acid (oleum)
Sulfanilic acid (baking process)
The baking process in general
Ethylbenzylanilinesulfonic acid (oleum)
p-Aminoazobenzenedisulfonic acid (fast yellow) (oleum)
Azo flavine FF (100$ H 2 S0 4 )
Phenol-2,4-disulfonic acid (oleum)
Naphthalenesulfonic acids, general
Naphthalene-a-sulfonic acid (100% H 2 S0 4 )
Naphthalene-/3-sulfonic acid (H 2 S0 4 , 66° Be)
Naphthalene-1,5- and 1,6-disulfonic acid (oleum)
Naphthalene-2,7-disulfonic acid (100% H 2 S0 4 )
Naphthalene-l,3,6-trisulfonic acid (oleum)
0-Naphtholsulfonic acids, general
2-Naphthol-l-sulfonic acid (C1S0 3 H)
2-Naphthol-6-sulfonic acid (H 2 S0 4 , 66°'Be)
2-Naphthol-3,6- and 6,8-disulfonic acid (H 2 S0 4 , 66° Be;
oleum)
:

l-Naphthylamine-4-sulfonic acid (baking)

8
171
303
167
222
224
138
300
304
308
312
324
332
335
314
6, 82

80
143
302
104
120
99
167, 296
126
127
136
271

272
150, 153
183
215
184, 187
219
209
211
191
199
194
194, 197
181


xxii

INDEX OF REACTIONS

2-Naphthylamine-5,7- and 6,8-disulfonic acid (oleum)
Anthraquinone- 1-sulfonic acid (oleum + Hg)
Anthraquinone-2-sulfonic acid (oleum)
Anthraquinone-1,5- and 1,8-disulfonic acid (oleum -f Hg)
l,5-Dihychoxyanthraquinone-2,6-disulfonic acid (oleum)
Alizarin pure blue B from the dye base (oleum)
Quinizarin green from the dye base (oleum)
Dehydrothiotoluidinesulfonic acid (oleum)
Primuline from primuline base (oleum)
Indirect, replacement of —CI by —SO3H:
2,4-Dinitrobenzenesulfonic acid from 2,4-dinitrochlorobenzene . . .

Nitrobenzene-2,5-disulfonic acid from 2-nitrochlorobenzene4-sulfonic acid . . . . . *
Simultaneous reduction and sulfonation by SO2:
l-Amino-2-naphthol-4-sulfonic acid from nitroso-j3-naphthol . . . .
7. Splitting out of sulfo groups
Alizarin saphirol SE from alizarin saphirol B
8. Introduction of hydroxyl groups
General
Replacement of —SO3H by —OH:
Phenol
Resorcinol
i9-Naphthol
2-Amino-8-naphthol-6-sulfonic acid
2-Amino-5-naphthol-7-sulfonic acid
l-Amino-8-naphthol-3,6-disulfonic acid
1,5- and 1,8-Dihydroxy anthraquinone
Alizarin from anthraquinone-£-sulfonic acid
Replacement of —CI by —OH:
4-Chloro-2-nitrophenol from nitro-p-dichlorobenzene
2,4-Dinitrophenol from 2,4-dinitrochlorobenzene
Azosalicylic acid (eriochrome flavine A) from
chloroaminobenzoic acid-azo-salicylic acid
Replacement of —NH2 by —OH:
a-Naphthol from a-naphthylamine
l-Naphthol-4-sulfonic acid from naphthionic acid
The Bucherer reaction in general
Direct introduction of —OH by oxidation
Alizarin from anthraquinone-^-sulfonic acid
9. Introduction of alkoxyl groups
General
Replacement of —CI by -o-alkyl:

o-Nitroanisole from o-nitrochlorobenzene
Alkylation of phenols (see 14)
10. Introduction of amino groups
General
Replacement of —SO3H by —NH2:
o-Aminoanthraquinone
/9-Aminoanthraquinone '
Replacement of —CI by —NH2:
p- and o-Nitroaniline
p-Nitroaniline-o-sulfonic acid

205
230
228
234
319
233
318
334
334
103
106
201
320
7, 88
86
144
188
207
207

213
236
314
109
337
295

x.

. .

180
182
182
314
8
97

8
231
229
92
99


INDEX OF REACTIONS

Replacement of -—OH by —NH 2 :
0-Naphthylamine from 0-naphthol
2-Naphthylamine-l-sulfonic acid

Replacement of —CONH2 by —NH2 (Hoffmann degradation):
Anthranilic acid from phthalimide
Reduction of —N0 2 , -—NO, or —N=N— (see 4)

xxiii

203
200
174

11. Introduction of arylamino groups
Replacement of halogen by arylamino:
4-Nitrodiphenylamine-2-sulfonic acid from
p-nitrochlorobenzene-o-sulfonic acid and p-phenylenediamine 100
4-Nitro-4'-aminodiphenylamine-2-sulfonic acid from p-nitrochlorobenzene-0-sulfonic acid and p-aminoazobenzene
99
Dinitrophenylaminoazobenzene from 2,4-dinitrochlorobenzene
and p-aminoazobenzene
272
4-p-Toluidine-2-bromo- 1-aminoanthraquinone from
2,4-dibromo-l-aminoanthraquinone and p-toluidine
233
Replacement of —OH by —NH aryl:
Quinizarin green base from leuco quinizarin and p-toluidine . . . . 317
12. Introduction of aldehyde groups
2-Chloro-4-dimethylaminobenzaldehyde from m-chlorodimethylaniline,
p-tolylhydroxylaminesulfonic acid and formaldehyde (see also 17) . . . 119
13. Introduction of carboxyl groups (Kolbe-Schmidt synthesis)
Salicylic acid from phenol

154

14. Alkylation
Of amines:
Dimethylaniline
Diethylaniline
Ethylbenzylaniline
Of phenols:
o- and p-Nitroanisole and -phenetole
Chrysophenine from brilliant yellow
15. Phenylation
Diphenylamine
Phenyl-o-napbthylamine
2-Phenylamino-8-naphthol-6-sulfonic acid (phenyl-Gamma acid) . . . .
16. Acylation
Acetylation
Acetanilide
l-Acetamino-8-naphthol-3,6-disulfonic acid (acetyl-H acid)
Oxalylation:
p-Nitrophenyloxamic acid
Anthraquinonyl-1-oxamic acid
Benzoylation:
Indanthrene yellow GK
17. Hydrolysis
P-Nitroaniline from p-nitroacetanilide
P-Phenylenediamine from p-aminoacetanilide
Benzaldehyde from benzal chloride
2,6-Dichlorobenzaldehyde from 2,6-dichlorobenzal chloride

133

134
134
148
284
140
179
209

130
263
93
231
322
132
133
159
162


xxiv

INDEX OF REACTIONS

2-Chloro-4-dirnethylaminobenzaldehyde from chlorodimethylaminobenzal-p-toluidinesulfonic acid
Isatin from isatin-a-anilide
18. Diazotization
General
Aniline
p-Chloroaniline
2,5-Dichloroaniline

^Nitroaniline
p-Nitroaniline
2,4-Dinitroaniline
2-Nitro-4-chloroaniline
3-Nitro-4-toluidine
p-Aminoacetanilide
p-Aminodiphenylamine
p-Aminoazobenzene
Sulfanilic acid
Aniline-2,5-disulfonic acid
Benzidine
Benzidine-2,2'-disulfonic acid
p,p'-'Diaminostilbenedisulfonic acid
Anthranilic acid
6-Chloro-3-aminobenzoic acid
a-Naphthylamine
l-Naphthylamine-3,6-disulfonic acid
l-Amino-2-naphthol-4-sulfonic acid
Dehydrothiotoluidinesulfonic acid

119
328

241
156, 243, 259, 270
244
244
97, 246
95, 246, 260
247

247
246
245
249
245
128, 248, 261, 262, 273
279
261
294
283
330
295
245, 260
277
248
336

19. Coupling
General
Aniline + aniline
•. . . .
Aniline -f- salicylic acid
Aniline -f acetyl-H acid
Aniline + p-sulfophenylmethylpyrazolone
p-Nitroaniline -h H acid
2,4-Dinitroaniline + /3-naphthol
3-Nitro-4-toluidine -f acetoacetanilide
Sulfanilic acid -f- m-phenylenediamine
Sulfanilic acid -f- diphenylamine
Sulfanilic acid 4- £-naphthol

Aniline-2,5-disulfonic acid + a-naphthylamine
6-Chloro-3-aminobenzoic acid -f salicylic acid
l-Naphthylamine-3,6-disulfonic acid + a-naphthylamine
Dehydrothiotoluidinesulfonic acid -f dehydrothiotoluidinesulfonic acid
m-Toluylenediamine -f- 2 m-toluylenediamine
Benzidine + salicylic acid
Benzidine -f 2 naphthionic acid
Benzidine -j- H acid
Benzidine-2.2'-disulfonic acid -f 2 /3-naphthol
Benzidine-2.2'-disulfonic acid + 2 salicylic acid
Diaminostilbenedisulfonic acid 4- 2 phenol
(See also Table of Contents, under Azo Dyes)
20. Condensation
Acetoacetanilide from aniline and acetoacetic .ester
Phenylglycine-o-carboxylic acid from anthranilic acid
and chloroacetic acid
Phenylthioglycolic acid-o-carboxylic acid from
thiosalicylic acid and chloroacetic acid

249
270
156
264
265
288
267
266
287
274
262

279
295
277
336
282
285
293
291
294
295
283

142
323
330


INDEX OF REACTIONS

Thiocarbanilide from aniline and carbon disulfide
Tetramethyldiaminodiphenylmethane from dimethylaniline
and formaldehyde
Tetramethyldiaminobenzophenone (Michler ketone)
from dimethylaniline and phosgene
p-Sulfophenylmethylpyrazolone from phenylhydrazinesulfonic acid
and acetoacetic ester
3-Hydroxythionaphthene from phenylthioglycolic acid-o-carboxylic acid
Indoxylcarboxylic acid from phenylglycine-o-carboxylic acid
a-Isatinanilide from thiooxamidodiphenylamidine
Indigo from a-thioisatin

o-Benzoylbenzoic acid and anthraquinone from phthalic anhydride
and toluene
Quinizarin from phthalic anhydride and p-chlorophenol
Sun yellow from p-nitrotoluene-o-sulfonic acid
Leuco malachite green from benzaldehyde and dimethylaniline
Leuco xylene blue VS from benzaldehydedisulfonic acid
and diethylaniline
Leuco wool green S from tetramethyldiaminobenzhydrol and R s a l t . . . .
Leuco wool blue 5B from o-chloro-p-dimethylaminobenzaldehyde and
ethylbenzylanilinesulfonic acid
Victoria blue B from Michler ketone and phenyl-a-naphthylamine . . . .
Gallamine blue from nitrosodimethylaniline and gallamide
Methylene blue from Bindschedler green-thiosulfonic acid
Indanthrene blue RS from /3-aminoanthraquinone

xxv

326
137
139
129
331
324
327
329
225
237
297
299
303

307
305
306
309
312
321

21. Introduction of sulfur
Dithiosalicylic acid from o-diazobenzoic acid
330
Thiooxamidodiphenylamidine from hydrocyanocarbodiphenylimide . . . 327
Dehydrothiotoluidine and primuline base from p-toluidine
332
Sulfur black T from 2,4-dinitrophenol
337
22. Miscellaneous
Phthalimide from phthalic anhydride
Auramine from tetramethyldiaminodiphenylmethane
Hydrocyanocarbodiphenylimide from thiocarbanilide
o-Thioisatin from a-isatinanilide
Gallic acid and gallamide from tannin

173
298
326
329
170