Azo dyes, their preparation and their use

Azo dyes comprising at least one structural unit of the formula (1) ##STR1## The azo dyes according to the invention are particularly suitable for dyeing cotton and wool and produce dyeings with good allround properties.

The present invention relates to novel azo dyes, processes for their 
preparation and their use. 
The practice of dyeing has recently lead to increased requirements 
regarding the quality of the dyeings and the profitability of the dyeing 
process. There consequently continues to be a demand for novel, readily 
accessible dyes which have good properties, in particular in respect of 
application. 
In the case of fibre-reactive dyes, those dyes, for example, which have an 
adequate substantivity and at the same time a good ease of washing off 
unfixed portions are required nowadays. They should furthermore have a 
good tinctorial yield and a high reactivity, and in particular dyeings 
with high degrees of fixing should be delivered. These requirements are 
not met with regard to all the properties by the known dyes. 
The present invention is therefore based on the object of discovering novel 
azo dyes, in particular for dyeing and printing fibre materials, which 
have the qualities characterized above to a high degree. They should 
produce dyeings with good allround properties, for example light and wet 
fastness properties. 
The present invention thus relates to azo dyes containing at least one 
structural unit of the formula (1) 
##STR2## 
The azo dyes according to the invention can belong to various classes of 
dye, according to their tinctorial use. These classes of dye are 
described, for example, in Venkataraman "The Chemistry of Synthetic Dyes" 
Volume 1, pages 268-303, Academic Press, New York, London 1952 and Volume 
6, pages 1-4, Academic Press, New York, London 1972. The azo dyes 
according to the invention are preferably acid, direct or reactive dyes 
for dyeing cotton, wool, leather, paper and wood, and in particular 
reactive dyes for dyeing cotton and wool, i.e. they contain at least one, 
and preferably at least two, fibre-reactive groups and are capable of 
reacting with the hydroxyl groups of cellulose or with the reactive 
centres of natural and synthetic polyamides to form covalent chemical 
bonds. 
The azo dyes according to the invention preferably have the formula (2), 
(3) or (4) 
##STR3## 
in which A is oxygen, sulfur or a radical --NR'-- and R' is hydrogen or 
C.sub.1 -C.sub.12 alkyl which is substituted or unsubstituted or may be 
interrupted by oxygen, 
B is an aliphatic or aromatic bridge member, 
D.sub.1, D.sub.2 and D.sub.3 independently of one another are each the 
radical of a diazo component of the benzene or naphthalene series, 
D.sub.4 is the radical of an aromatic tetrazo component and 
R is hydrogen or an aliphatic or aromatic radical, or the radicals R and 
R', together with the nitrogen atom, form a heterocyclic radical. 
C.sub.1 -C.sub.12 Alkyl, preferably C.sub.1 -C.sub.6 alkyl, and in 
particular C.sub.1 -C.sub.4 alkyl, as R' which is substituted or 
unsubstituted or may be interrupted by oxygen is straight-chain or 
branched and is, for example, methyl, ethyl, n- or isopropyl, n-, iso-, 
sec- or tert-butyl, n-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, 
n-nonyl, n-decyl, n-undecyl or n-dodecyl. The alkyl radicals mentioned can 
be interrupted by 1, 2 or 3 oxygen atoms and are unsubstituted or 
substituted by C.sub.2 -C.sub.4 alkanoylamino, for example acetylamino or 
propionylamino; C.sub.1 -C.sub.4 alkoxy, for example methoxy or ethoxy; 
hydroxyl; sulfo; sulfato; carboxyl; cyano; or carbamoyl, sulfamoyl, 
.beta.-sulfatoethylsulfonyl or .beta.-chloroethylsulfonyl. Preferred 
substituents of the alkyl radicals R' are hydroxyl, sulfo, carboxyl or 
sulfato, in particular hydroxyl or sulfato, and especially hydroxyl. 
Examples of the substituted alkyl radicals and the alkyl radicals 
interrupted by oxygen are: .beta.-hydroxyethyl, 
2-(.beta.-hydroxyethoxy)ethyl, 2-[2-(.beta.-hydroxyethoxy)ethoxy]ethyl, 
2-(.beta.-chloroethylsulfonyl)ethyl, 2-(.beta.-sulfatoethylsulfonyl)ethyl, 
.beta.-sulfatoethyl, .beta.-sulfoethyl, carboxymethyl or 
.beta.-carboxyethyl. 
R' is preferably hydrogen. 
An aliphatic bridge member B is, for example, a C.sub.2 -C.sub.12 alkylene 
radical, in particular a C.sub.2 -C.sub.6 alkylene radical, which can be 
interrupted by 1, 2 or 3 members from the group consisting of --NH--, 
--N(CH.sub.3)-- and, in particular, --O-- and is unsubstituted or 
substituted by hydroxyl, sulfo, sulfato, cyano or carboxyl. Preferred 
substituents of the alkylene radicals B are hydroxyl, sulfo or sulfato, in 
particular hydroxyl. 
Aliphatic bridge members B are furthermore, for example, C.sub.5 -C.sub.9 
cycloalkylene radicals, such as, in particular, cyclohexylene radicals. 
The cycloalkylene radicals mentioned can be unsubstituted or substituted 
by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.2 -C.sub.4 
alkanoylamino, sulfo, halogen or carboxyl, in particular by C.sub.1 
-C.sub.4 alkyl. Aliphatic bridge members B are furthermore 
methylene-cyclohexylene, ethylene-cyclohexylene or 
methylene-cyclohexylene-methylene radicals which are unsubstituted or 
substituted in the cyclohexylene ring by C.sub.1 -C.sub.4 alkyl, in 
particular methyl. 
An aromatic bridge member B is, for example, C.sub.1 -C.sub.6 
alkylenephenylene, for example methylenephenylene, C.sub.1 -C.sub.4 
alkylenephenylene-C.sub.1 -C.sub.4 alkylene, for example 
methylenephenylenemethylene, or phenylene which are unsubstituted or 
substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.2 
-C.sub.4 alkanoylamino, sulfo, halogen or carboxyl, or a radical of the 
formula 
##STR4## 
in which the benzene rings I and II are unsubstituted or substituted by 
C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.2 -C.sub.4 
alkanoylamino, sulfo, halogen or carboxyl and L is the direct bond or a 
C.sub.2 -C.sub.10 alkylene radical, which can be interrupted by 1, 2 or 3 
oxygen atoms, or L is a bridge member of the formula --CH.dbd.CH--, 
--N.dbd.N--, --NH--, --CO--, --NH--CO--, --NH--SO.sub.2 --, 
--NH--CO--NH--, --O--, --S-- or --SO.sub.2 --. The aromatic bridge members 
B mentioned are preferably unsubstituted or substituted by sulfo. 
If A is oxygen in the dye of the formula (3), an aromatic bridge member B 
is preferably a radical of the formula (5) in which the benzene rings I 
and II are unsubstituted or substituted as defined above and L is as 
defined and preferred above. Preferably, the benzene rings I and II are 
unsubstituted and L is isopropylene. 
B is preferably a C.sub.2 -C.sub.12 alkylene radical, in particular a 
C.sub.2 -C.sub.6 alkylene radical, which can be interrupted by 1, 2 or 3 
members --O-- and is unsubstituted or substituted by hydroxyl or sulfato. 
Substituents of the radicals D.sub.1, D.sub.2 and D.sub.3 are the 
substituents customary for azo dyes. Examples are the following: C.sub.1 
-C.sub.4 alkyl, which is to be understood as meaning methyl, ethyl, n- or 
iso-propyl, n-, iso-, sec- or tert-butyl; C.sub.1 -C.sub.4 alkoxy, which 
is to be understood as meaning methoxy, ethoxy, n- or iso-propoxy or n-, 
iso-, sec- or tert-butoxy; hydroxy-C.sub.1 -C.sub.4 alkoxy; phenoxy; 
C.sub.2 -C.sub.6 -alkanoylamino which is unsubstituted or substituted in 
the alkyl moiety by hydroxyl or C.sub.1 -C.sub.4 alkoxy, for example 
acetylamino, hydroxyacetylamino, methoxyacetylamino or propionylamino; 
benzoylamino which is unsubstituted or substituted in the phenyl moiety by 
hydroxyl, sulfo, halogen, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 
alkoxy; C.sub.1 -C.sub.6 alkoxycarbonylamino which is unsubstituted or 
substituted in the alkyl moiety by hydroxyl, C.sub.1 -C.sub.4 alkyl or 
C.sub.1 -C.sub.4 alkoxy; phenoxycarbonylamino, which is unsubstituted or 
substituted in the phenyl moiety by hydroxyl, C.sub.1 -C.sub.4 alkyl or 
C.sub.1 -C.sub.4 alkoxy; amino; N--C.sub.1 -C.sub.4 alkyl- or 
N,N-di-C.sub.1 -C.sub.4 alkylamino which are unsubstituted or substituted 
in the alkyl moiety by hydroxyl, C.sub.1 -C.sub.4 alkoxy, carboxyl, cyano, 
halogen, sulfo, sulfato, phenyl or sulfophenyl, for example methylamino, 
ethylamino, N,N-dimethylamino, N,N-diethylamino, .beta.-cyanoethylamino, 
.beta.-hydroxyethylamino, N,N-di-.beta.-hydroxyethylamino, 
.beta.-sulfoethylamino, .gamma.-sulfo-n-propylamino, 
.beta.-sulfatoethylamino, N-ethyl-N-(3-sulfobenzyl)amino or 
N-(.beta.-sulfoethyl)-N-benzylamino; cyclohexylamino; N-phenylamino or 
N-C.sub.1 -C.sub.4 alkyl-N-phenylamino which are unsubstituted or 
substituted in the phenyl moiety by nitro, C.sub.1 -C.sub.4 alkyl, C.sub.1 
-C.sub.4 alkoxy, carboxyl, halogen or sulfo; C.sub.1 -C.sub.4 
alkoxycarbonyl, for example methoxy- or ethoxycarbonyl; tifluoromethyl; 
nitro; cyano; halogen, which is generally to be understood as meaning, for 
example, fluorine, bromine or, in particular, chlorine; ureido; hydroxyl; 
carboxyl; sulfo; sulfomethyl; carbamoyl; carbamido; sulfamoyl; 
N-phenylsulfamoyl or N--C.sub.1 -C.sub.4 alkyl-N-phenylsulfamoyl which are 
unsubstituted or substituted in the phenyl moiety by sulfo or carboxyl; 
and methyl- or ethylsulfonyl. 
Fibre-reactive radicals are also possible substituents of the radicals 
D.sub.1, D.sub.2 and D.sub.3. 
Fibre-reactive radicals are to be understood as meaning those which are 
capable of reacting with the hydroxyl groups of cellulose, the amino, 
carboxyl, hydroxyl and thiol groups in wool and silk, or with the amino 
and possibly carboxyl groups of synthetic polyamides, to form covalent 
chemical bonds. The fibre-reactive radicals are as a rule bonded to the 
dye radical directly or via a bridge member. Suitable fibre-reactive 
radicals are, for example, those which contain at least one substituent 
which can be split off on an aliphatic, aromatic or heterocyclic radical, 
or in which the radicals mentioned contain a radical which is capable of 
reaction with the fibre material, for example a vinyl radical. 
A fibre-reactive radical contained in D.sub.1, D.sub.2 and D.sub.3 
preferably has the formula (6a), (6b), (6c), (6d), (6e), (6f) or (6g) 
EQU --SO.sub.2 --Y (6a), 
EQU --NH--CO--(CH.sub.2).sub.l --SO.sub.2 --Y (6b), 
EQU --CONR.sub.2 --(CH.sub.2).sub.m --SO.sub.2 --Y (6c), 
EQU --NH--CO--CH(Hal)--CH.sub.2 --Hal (6d), 
EQU --NH--CO--C(Hal).dbd.CH.sub.2 (6e), 
##STR5## 
in which Hal is chlorine or bromine; 
X.sub.1 is halogen, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl; 
T.sub.1 independently has the meaning of X.sub.1, or is a substituent which 
is not fibre-reactive or a fibre-reactive radical of the formula (7a), 
(7b), (7c), (7d), (7e) or (7f) 
##STR6## 
in which R.sub.1, R.sub.1a and R.sub.1b independently of one another are 
each hydrogen or C.sub.1 -C.sub.4 alkyl, 
R.sub.2 is hydrogen, C.sub.1 -C.sub.4 alkyl which is unsubstituted or 
substituted by hydroxyl, sulfo, sulfato, carboxyl or cyano or a radical 
##STR7## 
R.sub.3 is hydrogen, hydroxyl, sulfo, sulfato, carboxyl, cyano, halogen, 
C.sub.1 -C.sub.4 alkoxycarbonyl, C.sub.1 -C.sub.4 alkanoyloxy, carbamoyl 
or the group --SO.sub.2 --Y, 
alk and alk.sub.1 independently of one another are linear or branched 
C.sub.1 -C.sub.6 alkylene, arylene is a phenylene or naphthylene radical 
which is unsubstituted or substituted by sulfo, carboxyl, C.sub.1 -C.sub.4 
alkyl, C.sub.1 -C.sub.4 alkoxy or halogen, 
Q is a radical --O-- or --NR.sub.1 --, in which R.sub.1 is as defined 
above, 
W is a group --SO.sub.2 --NR.sub.2 --, --CONR.sub.2 -- or --NR.sub.2 CO--, 
in which R.sub.2 is as defined above, 
Y is vinyl or a radical --CH.sub.2 --CH.sub.2 --U and U is a group which 
can be split off under alkaline conditions, 
Y.sub.1 is a group --CH(Hal)--CH.sub.2 --Hal or --C(Hal).dbd.CH.sub.2 and 
Hal is chlorine or bromine and l and m independently of one another are an 
integer from 1 to 6 and n is the number 0 or 1; and 
X.sub.2 is halogen or C.sub.1 -C.sub.4 alkylsulfonyl; 
X.sub.3 is halogen or C.sub.1 -C.sub.4 alkyl and 
T.sub.2 is hydrogen, cyano or halogen. 
A group U which can be split off under alkaline conditions is, for example, 
--Cl, --Br, --F, --OSO.sub.3 H, --SSO.sub.3 H, --OCO--CH.sub.3, 
--OPO.sub.3 H.sub.2,--OCO--C.sub.6 H.sub.5, --OSO.sub.2 --C.sub.1 -C.sub.4 
alkyl or --OSO.sub.2 --N(C.sub.1 -C.sub.4 alkyl).sub.2. U is preferably a 
group of the formula --Cl, --OSO.sub.3 H, --SSO.sub.3 H, --OCO--CH.sub.3, 
--OCO--C.sub.6 H.sub.5 or --OPO.sub.3 H.sub.2, in particular --Cl or 
--OSO.sub.3 H, and particularly preferably --OSO.sub.3 H. 
Examples of suitable radicals Y are accordingly vinyl, .beta.-bromo- or 
.beta.-chloroethyl, .beta.-acetoxyethyl, .beta.-benzoyloxyethyl, 
.beta.-phosphatoethyl, .beta.-sulfatoethyl and .beta.-thiosulfatoethyl. Y 
is preferably vinyl, .beta.-chloroethyl or .beta.-sulfatoethyl, and in 
particular vinyl or .beta.-sulfatoethyl. 
R.sub.1, R.sub.1a and R.sub.1b independently of one another are each 
preferably hydrogen, methyl or ethyl, and particularly preferably 
hydrogen. 
R.sub.2 is preferably hydrogen or C.sub.1 -C.sub.4 alkyl, such as methyl, 
ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, and 
particularly preferably hydrogen, methyl or ethyl. R.sub.2 is particularly 
preferably hydrogen. 
R.sub.3 is preferably hydrogen. 
l and m independently of one another are preferably the number 2, 3 or 4, 
and particularly preferably the number 2 or 3. 
Especially preferably, l is the number 3 and m is the number 2. 
Substituents T.sub.1 which are not fibre-reactive are, for example, the 
following radicals: 
hydroxyl; 
C.sub.1 -C.sub.4 alkoxy, for example methoxy, ethoxy, n- or isopropoxy or 
n-, sec-, iso- or tert-butoxy, in particular methoxy or ethoxy; the 
radicals mentioned are unsubstituted or substituted in the alkyl moiety, 
for example by C.sub.1 -C.sub.4 alkoxy, hydroxyl, sulfo or carboxyl; 
C.sub.1 -C.sub.4 alkylthio, for example methylthio, ethylthio, n- or 
isopropylthio or n-butylthio; the radicals mentioned are unsubstituted or 
substituted in the alkyl moiety, for example by C.sub.1 -C.sub.4 alkoxy, 
hydroxyl, sulfo or carboxyl; 
amino; 
N-mono- or N,N-di-C.sub.1 -C.sub.6 alkylamino, preferably N-mono- or 
N,N-di-C.sub.1 -C.sub.4 alkylamino; the radicals mentioned are 
unsubstituted, uninterrupted or interrupted in the alkyl moiety by oxygen 
or substituted in the alkyl moiety, for example by C.sub.2 -C.sub.4 
alkanoylamino, C.sub.1 -C.sub.4 alkoxy, hydroxyl, sulfo, sulfato, 
carboxyl, cyano, carbamoyl or sulfamoyl; examples are N-methylamino, 
N-ethylamino, N-propylamino, N,N-di-methylamino or N,N-di-ethylamino, 
N-.beta.-hydroxyethylamino, N,N-di-.beta.-hydroxyethylamino, 
N-2-(.beta.-hydroxyethoxy)ethylamino, 
N-2-[2-(.beta.-hydroxyethoxy)ethoxy]ethylamino, 
N-.beta.-sulfatoethylamino, N-.beta.-sulfoethylamino, 
N-carboxymethylamino, N-.beta.-carboxyethylamino, 
N-.alpha.,.beta.-dicarboxyethylamino, 
N-.alpha.,.gamma.-dicarboxypropylamino, N-ethyl-N-.beta.-hydroxyethylamino 
or N-methyl-N-.beta.-hydroxyethylamino; 
C.sub.5 -C.sub.7 cycloalkylamino, for example cyclohexylamino, which 
includes both the unsubstituted radicals and the radicals substituted in 
the cycloalkyl ring, for example by C.sub.1 -C.sub.4 alkyl, in particular 
methyl, or carboxyl; 
phenylamino or N--C.sub.1 -C.sub.4 alkyl-N-phenylamino, which includes both 
the unsubstituted radicals and the radicals substituted in the phenyl 
ring, for example by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, 
C.sub.2 -C.sub.4 alkanoylamino, carboxyl, carbamoyl, sulfo or halogen, for 
example 2-, 3- or 4-chlorophenylamino, 2-, 3- or 4-methylphenylamino, 2-, 
3- or 4-methoxyphenylamino, 2-, 3- or 4-sulfophenylamino, 
disulfophenylamino or 2-, 3- or 4-carboxyphenylamino; 
naphthylamino which is unsubstituted or substituted in the naphthyl ring, 
for example by sulfo, preferably the radicals substituted by 1 to 3 sulfo 
groups, for example 1- or 2-naphthylamino, 1-sulfo-2-naphthylamino, 
1,5-disulfo-2-naphthylamino or 4,8-disulfo-2-naphthylamino; or 
benzylamino which is unsubstituted or substituted in the phenyl moiety, for 
example by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy , carboxyl, 
sulfo or halogen. 
A radical T.sub.1 which is not fibre-reactive is preferably C.sub.1 
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylthio, hydroxyl, amino, N-mono- or 
N,N-di-C.sub.1 -C.sub.4 alkylamino which are optionally substituted in the 
alkyl moiety by hydroxyl, sulfato or sulfo, morpholino, phenylamino or 
N--C.sub.1 -C.sub.4 alkyl-N-phenylamino which are unsubstituted or 
substituted in the phenyl ring by sulfo, carboxyl, acetylamino, chlorine, 
methyl or methoxy and in which the alkyl is unsubstituted or substituted 
by hydroxyl, sulfo or sulfato, or naphthylamino which is unsubstituted or 
substituted by 1 to 3 sulfo groups. 
Particularly preferred radicals T.sub.1 which are not fibre-reactive are 
amino, N-methylamino, N-ethylamino, N-.beta.-hydroxyethylamino, 
N-methyl-N-.beta.-hydroxyethylamino, N-ethy-N-.beta.-hydroxyethylamino, 
N,N-di-.beta.-hydroxyethylamino, morpholino, 2-, 3- or 
4-carboxyphenylamino, 2-, 3- or 4-sulfophenylamino or N--C.sub.1 -C.sub.4 
-alkyl-N-phenylamino. 
X.sub.1 is preferably halogen, for example fluorine, chlorine or bromine, 
and particularly preferably chlorine or fluorine. 
Halogen T.sub.2, X.sub.2 and X.sub.3 are, for example, fluorine, chlorine 
or bromine, in particular chlorine or fluorine. 
C.sub.1 -C.sub.4 Alkylsulfonyl X.sub.2 is, for example, ethylsulfonyl or 
methylsulfonyl, and in particular methylsulfonyl. 
C.sub.1 -C.sub.4 alkyl X.sub.3 is, for example, methyl , ethyl, n- or 
iso-propyl or n-, iso or tert-butyl, and in particular methyl. 
X.sub.2 and X.sub.3 independently of one another are preferably chlorine or 
fluorine. 
T.sub.2 is preferably cyano or chlorine. 
Hal is preferably bromine. 
alk and alk.sub.1 independently of one another are, for example, a 
methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or 
1,6-hexylene radical or branched isomers thereof. 
alk and alk.sub.1 independently of one another are preferably each a 
C.sub.1 -C.sub.4 alkylene radical, and particularly preferably an ethylene 
radical or propylene radical. 
arylene is preferably a 1,3- or 1,4-phenylene radical which is 
unsubstituted or substituted, for example by sulfo, methyl, methoxy or 
carboxyl, and particularly preferably an unsubstituted 1,3- or 
1,4-phenylene radical. 
Q is preferably --NH-- or --O--, and particularly preferably --O--. 
W is preferably a group of the formula --CONH-- or --NHCO--, in particular 
a group of the formula --CONH--. 
n is preferably the number 0. 
The reactive radicals of the formulae (7a) to (7f) are preferably those in 
which W is a group of the formula --CONH--, R.sub.1, R.sub.2 and R.sub.3 
are each hydrogen, Q is the radical --O-- or --NH--, alk and alk.sub.1 
independently of one another are each ethylene or propylene, arylene is 
phenylene which is unsubstituted or substituted by methyl, methoxy, 
carboxyl or sulfo, Y is vinyl or .beta.-sulfatoethyl, Y.sub.1 is 
--CHBr--CH.sub.2 Br or --CBr.dbd.CH.sub.2 and n is the number 0. 
A fibre-reactive radical contained in D.sub.1, D.sub.2 and D.sub.3 is 
particularly preferably a radical of the formula (6a), (6c), (6d), (6e) or 
(6f), in which Y is vinyl, .beta.-chloroethyl or .beta.-sulfatoethyl, Hal 
is bromine, R.sub.2 and R.sub.1a are hydrogen, m is the number 2 or 3, 
X.sub.1 is halogen, T.sub.1 is C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 
alkylthio, hydroxyl, amino, N-mono- or N,N-di-C.sub.1 -C.sub.4 alkylamino 
which are unsubstituted or substituted in the alkyl moiety by hydroxyl, 
sulfato or sulfo, morpholino, phenylamino or N--C.sub.1 -C.sub.4 
alkyl-N-phenylamino which are unsubstituted or substituted in the phenyl 
ring by sulfo, carboxyl, acetylamino, chlorine, methyl or methoxy and in 
which the alkyl is unsubstituted or substituted by hydroxyl, sulfo or 
sulfato, or naphthylamino which is unsubstituted or substituted by 1 to 3 
sulfo groups, or a fibre-reactive radical of the formula (7a'), (7b'), 
(7c'), (7d') or (7f') 
EQU --NH--(CH.sub.2).sub.2-3 --SO.sub.2 Y (7a'), 
EQU --NH--(CH.sub.2).sub.2-3 --O--(CH.sub.2).sub.2-3 --SO.sub.2 Y(7b'), 
##STR8## 
in particular (7c') or (7d'), in which Y is as defined above and 
Y.sub.1 is a group --CH(Br)--CH.sub.2 --Br or --C(Br).dbd.CH.sub.2, 
In the case of the radicals of the formulae (7a') and (7b'), Y is 
preferably .beta.-chloroethyl. In the case of the radicals of the formulae 
(7c') and (7d'), Y is preferably vinyl or .beta.-sulfatoethyl. 
A particular embodiment of the present invention relates to dyes in which a 
radical contained in D.sub.1, D.sub.2 and D.sub.3 has the formula (6h) 
##STR9## 
in which R.sub.1a and X.sub.1 are as defined and preferred above and 
T.sub.3 is a monoazo- or disazoamino radical of the formula (8) or (9) 
EQU D--N.dbd.N--(M--N.dbd.N).sub.u --K--NR.sub.1 -- (8) 
or 
EQU --NR.sub.1 --D--N.dbd.N--(M--N.dbd.N).sub.u --K (9) 
in which 
D is the radical of a diazo component of the benzene or naphthalene series, 
M is the radical of a middle component of the benzene or naphthalene 
series, 
K is the radical of a coupling component of the benzene, naphthalene, 
pyrazolone, 6-hydroxypyrid-2-one or acetoacetic acid arylamide series, 
R.sub.1 is as defined and preferred above and 
u is the number 0 or 1, where D, M and K can carry the substituents 
customary in azo dyes. 
The term "substituents customary in azo dyes" means both fibre-reactive 
substituents and substituents which are not fibre-reactive, for example 
the substituents defined above for D.sub.1, D.sub.2 and D.sub.3. 
Substituents for D, M and K in T.sub.3 which are not fibre-reactive are 
preferably C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy which are 
unsubstituted or further substituted by hydroxyl, sulfo or sulfato, 
halogen, carboxyl, sulfo, nitro, cyano, trifluoromethyl, sulfamoyl, 
carbamoyl, amino, ureido, hydroxyl, sulfomethyl, C.sub.2 -C.sub.4 
alkanoylamino, benzoylamino which is unsubstituted or substituted in the 
phenyl ring by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, halogen or 
sulfo or phenyl which is unsubstituted or substituted by C.sub.1 -C.sub.4 
alkyl, C.sub.1 -C.sub.4 alkoxy, halogen, carboxyl or sulfo. 
The monoazo- or disazoamino radicals of the formula (8) or (9) preferably 
contain at least one sulfo group. 
Preferred monoazo- or disazoamino radicals T.sub.3 are the radicals of the 
formula (10a), (10b), (10c), (10d), (10e), (10f), (10g), (10h), (10i), 
(10j), (10k), (10l), (10m), (10n), (10o) or (10p) 
##STR10## 
in which (R.sub.4).sub.0-3 is 0 to 3 identical or different substituents 
from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 
alkoxy, halogen, carboxyl and sulfo, 
(R.sub.5).sub.0-3 is 0 to 3 identical or different substituents from the 
group consisting of halogen, nitro, cyano, trifluoromethyl, sulfamoyl, 
carbamoyl, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy which is 
unsubstituted or substituted by hydroxyl, sulfato or C.sub.1 -C.sub.4 
alkoxy, amino, C.sub.2 -C.sub.4 alkanoylamino, ureido, hydroxyl, carboxyl, 
sulfomethyl, C.sub.1 -C.sub.4 alkylsulfonylamino and sulfo and 
Z.sub.1 is a radical of the formula (6a), (6c), (6d), (6e), (6f) or (6g), 
preferably (6a), (6c), (6d) or (6e), and in particular (6a), where the 
radicals mentioned are as defined and preferred above, 
##STR11## 
in which R.sub.6 is C.sub.2 -C.sub.4 alkanoyl or benzoyl, 
##STR12## 
in which (R.sub.7).sub.0-3 is 0 to 3 identical or different substituents 
from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 
alkoxy, halogen, carboxyl and sulfo, 
##STR13## 
in which R.sub.8 and R.sub.10 independently of one another are hydrogen, 
C.sub.1 -C.sub.4 alkyl or phenyl and R.sub.9 is hydrogen, cyano, carbamoyl 
or sulfomethyl, 
##STR14## 
in which (R.sub.4).sub.0-3, (R.sub.5).sub.0-3 and (R.sub.7).sub.0-3 in 
each case are as defined above, 
(R.sub.11).sub.0-3 and (R.sub.12).sub.0-3 independently of one another are 
0 to 3 identical or different substituents from the group consisting of 
C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, halogen, carboxyl and 
sulfo and Z.sub.1 is as defined and preferred above. 
The numbers on the naphthyl rings of the radicals of the formulae (10a), 
(10b), (10c), (10d), (10e), (10g) and (10h) identify the possible bonding 
positions. 
(R.sub.4).sub.0-3 in the disazoamino radicals of the formulae (10n) and 
(10p) is preferably 0 to 3 sulfo groups. 
Particularly preferred monoazo- or disazoamino radicals T.sub.3 are the 
radicals of the formula (10a), (10b), (10d), (10e), (10f), (10k) or (10m), 
in particular (10b), (10k) or (10m). 
Preferably, a radical of the formula (6h) in which R.sub.1a, X.sub.1 and 
T.sub.3 are as defined and preferred above is contained in only one of the 
radicals D.sub.1, D.sub.2 and D.sub.3, in particular in D.sub.1. 
Radicals D.sub.1, D.sub.2 and D.sub.3 of a substituted or unsubstituted 
diazo component of the benzene or naphthalene series independently of one 
another are, for example, phenyl or naphthyl, which is unsubstituted or 
substituted, for example by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 
alkoxy, halogen, sulfo, nitro, carboxyl or a fibre-reactive radical of the 
formulae (6a), (6b), (6c), (6d), (6e), (6f) or (6g), in particular (6a), 
(6c), (6d), (6e) or (6f), in which the fibre-reactive radicals mentioned 
are as defined and preferred above. 
Radicals D.sub.1, D.sub.2 and D.sub.3 of a substituted or unsubstituted 
diazo component of the benzene or naphthalene series independently of one 
another also include monoazo radicals, for example those of the formula 
(11) or (12) 
EQU --D*--N.dbd.N--K* (11) 
or 
EQU D*--N.dbd.N--K**-- (12), 
preferably of the formula (12), in which D* is the radical of a diazo 
component of the benzene or naphthalene series, K* is the radical of a 
coupling component of the benzene, naphthalene, pyrazolone, 
6-hydroxypyrid-2-one or acetoacetic acid arylamide series and K** is the 
radical of a coupling component of the benzene or naphthalene series, 
where D*, K* and K** can carry substituents customary in azo dyes. 
Substituents which are not fibre-reactive D*, K* and K** are preferably 
C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy which are unsubstituted 
or further substituted by hydroxyl, C.sub.1 -C.sub.4 alkoxy, sulfo or 
sulfato, halogen, carboxyl, sulfo, nitro, cyano, trifluoromethyl, 
sulfamoyl, carbamoyl, amino, ureido, hydroxyl, sulfomethyl, C.sub.2 
-C.sub.4 alkanoylamino, C.sub.1 -C.sub.4 alkylsulfonylamino, benzoylamino 
which is unsubstituted or substituted in the phenyl ring by C.sub.1 
-C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, halogen or sulfo or phenyl which 
is unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 
-C.sub.4 alkoxy, halogen, carboxyl or sulfo. 
Fibre-reactive substituents for D*, K* and K** are preferably the radicals 
of the formulae (6a), (6c), (6d), (6e) or (6f), in particular (6a), in 
which the radicals mentioned are as defined and preferred above. 
The monoazo radicals of the formula (11) or (12) preferably contain at 
least one sulfo group. 
Preferred monoazo radicals D.sub.1, D.sub.2 and D.sub.3 of the formula (12) 
are the radicals of the formula (12a), (12b), (12c), (12d), (12e), (12f), 
(12g), (12h), (12i) or (12j) 
##STR15## 
in which (R.sub.4).sub.0-3 is 0 to 3 identical or different substituents 
from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 
alkoxy, halogen, carboxyl and sulfo and Z.sub.1 is a fibre-reactive 
radical of the formula (6a), (6c), (6d), (6e), (6f) or (6g), preferably 
(6a), (6c), (6d) or (6e), and in particular (6a), in which the 
fibre-reactive radicals mentioned are as defined and preferred above, 
##STR16## 
in which (R.sub.4).sub.0-3 is as defined above, (R'.sub.5).sub.0-3 is 0 to 
3 identical or different substituents from the group consisting of 
halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C.sub.1 
-C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy which is unsubstituted or 
substituted by hydroxyl, sulfato or C.sub.1 -C.sub.4 alkoxy, amino, 
C.sub.2 -C.sub.4 alkanoylamino, ureido, hydroxyl, carboxyl, sulfomethyl, 
C.sub.1 -C.sub.4 alkylsulfonylamino, sulfo and a fibre-reactive radical of 
the formula (6f), in which the radicals R.sub.1a, T.sub.1 and X.sub.1 are 
as defined and preferred above, and Z.sub.1 is as defined and preferred 
above. 
The numbers on the naphthyl rings of the radicals of the formulae (12a), 
(12b), (12e) and (12f) identify the possible bonding positions. 
The radicals D.sub.1, D.sub.2 and D.sub.3 in the dyes of the formulae (2) 
or (3) according to the invention and the radicals D.sub.1 and D.sub.2 in 
the dyes of the formula (4) according to the invention are identical or 
are not identical. 
An aromatic tetrazo component D.sub.4 is, for example, phenylene or 
naphthylene which are unsubstituted or substituted by C.sub.1 -C.sub.4 
alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.2 -C.sub.4 alkanoylamino, sulfo, 
halogen or carboxyl, or a radical of the formula (5), where the radical of 
the formula (5) is as defined above. 
An aromatic tetrazo component D.sub.4 is also a radical of the formula (5') 
##STR17## 
Preferably, D.sub.4 is a naphthylene which is substituted by 1 to 3, 
preferably 2, sulfo groups, a radical of the formula (5') or a radical of 
the formula (5), in which the benzene rings I and II are unsubstituted or 
substituted by 1 or 2 sulfo groups and L is a direct bond, a C.sub.2 
-C.sub.4 alkylene radical or a bridge member of the formula --CH.dbd.CH--, 
--NH--, --CO--, --NH--CO--, --NH--SO.sub.2 --, --NH--CO--NH--, --O--, 
--S-- or --SO.sub.2 --. 
An aliphatic radical R is, for example, the radicals defined above for 
C.sub.1 -C.sub.12 alkyl R' which is substituted or unsubstituted or 
interrupted by oxygen. Further examples of R are the following radicals: 
2,5-di-(.beta.-chloroethylsulfonyl)pentyl, 
2-[2-(.beta.-chloroethylsulfonyl)ethoxy]ethyl or 
2-[2-(.beta.-sulfatoethylsulfonyl)ethoxy]ethyl. 
Aliphatic radicals R are furthermore, for example, C.sub.5 -C.sub.7 
cycloalkyl radicals, such as, in particular, cyclohexyl radicals. The 
cycloalkyl radicals mentioned can be unsubstituted or substituted by 
C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.2 -C.sub.4 
alkanoylamino, sulfo, halogen or carboxyl, in particular by C.sub.1 
-C.sub.4 alkyl. Aliphatic radicals R are furthermore methylene-cyclohexyl 
or ethylene-cyclohexyl radicals which are unsubstituted or substituted in 
the cyclohexyl ring by C.sub.1 -C.sub.4 alkyl, in particular methyl. 
An aromatic radical R is, for example, phenyl or naphthyl which are 
unsubstituted or substituted, which include both the unsubstituted 
radicals and the radicals substituted by C.sub.1 -C.sub.4 alkyl, for 
example methyl or ethyl; C.sub.1 -C.sub.4 alkoxy, for example methoxy or 
ethoxy; C.sub.2 -C.sub.4 alkanoylamino; carboxyl; carbamoyl; sulfo or 
halogen, for example chlorine or bromine; or a fibre-reactive radical of 
the formula (6a), (6b), (6c), (6d), (6e), (6f) or (6g), where the 
fibre-reactive radicals of the formulae (6a), (6b), (6c), (6d), (6e), (6f) 
and (6g) are as defined and preferred above. Examples are the following 
radicals: o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, o-, m- or 
p-methoxyphenyl, o-, m- or p-sulfophenyl, disulfophenyl, o-, m- or 
p-carboxyphenyl, 1- or 2-naphthyl, 1-sulfo-2-naphthyl, 
1,5-disulfo-2-naphthyl, 4,8-disulfo-2-naphthyl or 
4-(.beta.-sulfatoethylsulfonyl)phenyl. 
Substituted or unsubstituted phenyl or naphthyl R furthermore is, for 
example, a monoazo or disazo radical of the formula (13) or (14) 
EQU D--N.dbd.N--(M--N.dbd.N).sub.u --K-- (13) 
or 
EQU --D--N.dbd.N--(M--N.dbd.N).sub.u --K (14), 
in which D, M, K and u are as defined above under the formulae (8) and (9). 
Monoazo radicals R are, for example, the radicals of the formula (10a), 
(10b), (10c), (10d), (10e), (10f), (10g), (10h), (10i), (10j), (10k), 
(10l), (10m), (10n), (10o) or (10p) defined above, if the group --NH-- in 
the particular formula is replaced by a direct bond. 
A heterocyclic radical formed by the radicals R and R', together with the 
nitrogen atom, is, for example, morpholine. 
In a preferred embodiment of the azo dyes of the formula (2), (3) or (4) 
according to the invention, A is oxygen or a radical --NR'--. 
If A in the dyes of the formula (2) or (4) according to the invention is a 
radical --NR'--, R' is preferably hydrogen and R is preferably hydrogen, a 
C.sub.1 -C.sub.4 alkyl which is unsubstituted or substituted by hydroxyl, 
sulfo, carboxyl or sulfato, in particular hydroxyl or sulfato, and 
especially hydroxyl, or 2-(.beta.-sulfatoethylsulfonyl)ethyl. 
If A in the dyes of the formula (2) or (4) according to the invention is 
oxygen, R is preferably hydrogen or C.sub.1 -C.sub.4 alkyl which is 
unsubstituted or substituted by hydroxyl, and in particular hydrogen. 
In the dyes of the formula (3) according to the invention, A is preferably 
a radical --NR'--, in which R' is hydrogen, methyl or ethyl, and 
especially hydrogen. 
In a particularly preferred embodiment of the azo dyes of the formula (2) 
or (4) according to the invention, A is oxygen and R is hydrogen. 
The azo dyes of the formula (2) or (4) according to the invention, and in 
particular of the formula (2), are preferred. 
The radicals D.sub.1, D.sub.2 and D.sub.3 independently of one another are 
preferably each a radical of the formula (15) or (16) 
##STR18## 
in which K is the radical of a coupling component of the formula (17a) or 
(17b) 
##STR19## 
and Z and Z.sub.1 independently of one another are a radical of the 
formula (6a), (6c), (6d), (6e) or (6f), in which 
R.sub.1a and R.sub.2 are hydrogen, 
Hal is bromine, 
Y is vinyl, .beta.-chloroethyl or .beta.-sulfatoethyl, 
T.sub.1 is C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylthio, hydroxyl, 
amino, N-mono- or N,N-di-C.sub.1 -C.sub.4 alkylamino which are 
unsubstituted or substituted in the alkyl moiety by hydroxyl, sulfato or 
sulfo, morpholino, phenylamino or N--C.sub.1 -C.sub.4 alkyl-N-phenylamino 
which are unsubstituted or substituted in the phenyl ring by sulfo, 
carboxyl, acetylamino, chlorine, methyl or methoxy and in which the alkyl 
is unsubstituted or substituted by hydroxyl, sulfo or sulfato, 
naphthylamino which is unsubstituted or substituted by 1 to 3 sulfo 
groups, or a fibre-reactive radical of the formula (7c') or (7d') 
##STR20## 
and Y is as defined above, 
X.sub.1 is chlorine or fluorine, 
m is the number 2 or 3, 
(R.sub.4).sub.0-3 and (R.sub.13).sub.0-3 independently of one another are 0 
to 3 identical or different substituents chosen from the group consisting 
of halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, carboxyl and 
sulfo, 
R'.sub.5 is hydrogen, sulfo or C.sub.1 -C.sub.4 alkoxy which is 
unsubstituted or substituted in the alkyl moiety by hydroxyl or sulfato 
and 
R'.sub.5a is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, 
C.sub.2 -C.sub.4 alkanoylamino, ureido or a radical of the formula (6f), 
in which radicals R.sub.1a, T.sub.1 and X.sub.1 are as defined above. 
C.sub.1 -C.sub.4 Alkyl R.sub.4, R'.sub.5a and R.sub.13 independently of one 
another are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 
sec-butyl, tert-butyl or isobutyl, preferably methyl or ethyl, and in 
particular methyl. 
C.sub.1 -C.sub.4 -Alkoxy R.sub.4, R'.sub.5, R'.sub.5a and R.sub.13 
independently of one another are, for example, methoxy, ethoxy, n-propoxy, 
isopropoxy, n-butoxy or isobutoxy, preferably methoxy or ethoxy, and in 
particular methoxy. R'.sub.5 is unsubstituted or may be substituted in the 
alkyl moiety by hydroxyl or sulfato. 
Halogen R.sub.4 and R.sub.13 independently of one another are, for example, 
fluorine, chlorine or bromine, preferably chlorine or bromine, and in 
particular chlorine. 
C.sub.2 -C.sub.4 -Alkanoylamino R'.sub.5a is, for example, acetylamino or 
propionylamino, in particular acetylamino. 
A radical R'.sub.5a of the formula (6f) is preferably a radical in which 
R.sub.1a is hydrogen, 
T.sub.1 is amino, N-mono- or N,N-di-C.sub.1 -C.sub.4 alkylamino which are 
unsubstituted or substituted in the alkyl moiety by hydroxyl, sulfato or 
sulfo, morpholino, phenylamino or N--C.sub.1 -C.sub.4 alkyl-N-phenylamino 
which are unsubstituted or substituted in the phenyl ring by sulfo, 
carboxyl, acetylamino, chlorine, methyl or methoxy and in which the alkyl 
is unsubstituted or substituted by hydroxyl, sulfo or sulfato or 
naphthylamino which is unsubstituted or substituted by 1 to 3 sulfo groups 
and 
X.sub.1 is fluorine or chlorine. 
In the radical of the coupling component of the formula (17b), the sulfo 
group in the ring ii is preferably bonded in the 3- or 4-position. If the 
ring ii contains a sulfo group, the radical of the formula (17b) is 
preferably bonded to the ring ii in the 1-, 2- or 3-position. If no sulfo 
group is present in the ring ii, the radical of the formula (17b) is 
preferably bonded to the ring ii in the 2- or 3-position. 
The radicals D.sub.1, D.sub.2 and D.sub.3 independently of one another are 
particularly preferably each a radical of the formula (15a), (15b), (15c), 
(15d) or (16a) 
##STR21## 
in which R'.sub.5 is hydrogen, sulfo or ethoxy which is unsubstituted or 
substituted in the alkyl moiety by hydroxyl or sulfato, 
R'.sub.5a is hydrogen, methyl, ethyl, methoxy, ethoxy, acetylamino, 
propionylamino or ureido, 
(R.sub.13).sub.0-2 is 0 to 2 identical or different substituents chosen 
from the group consisting of halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 
-C.sub.4 alkoxy and sulfo, in particular methyl, methoxy and sulfo, 
Y.sub.1 is a group --CH(Br)--CH.sub.2 --Br or --C(Br).dbd.CH.sub.2, 
Y is vinyl, .beta.-chloroethyl or .beta.-sulfatoethyl, in particular vinyl 
or .beta.-sulfatoethyl, and 
m is the number 2 or 3, in particular 2. 
The numbers in the radicals of the formulae (15a), (15c) and (15d) identify 
the possible bonding positions of the fibre-reactive radical. 
D.sub.1, D.sub.2 and D.sub.3 independently of one another are in each case 
preferably a radical of the formula (15a), (15b) or (16a). 
In the particular embodiment of the present invention defined above, in 
which a radical contained in D.sub.1, D.sub.2 and D.sub.3 has the formula 
(6h), D.sub.1 is preferably a radical of the formula (18) 
##STR22## 
in which X.sub.1 is chlorine or fluorine, in particular chlorine, and 
T.sub.3 is a monoazo- or disazoamino radical of the formula (10a), (10b), 
(10d), (10e), (10f), (10k) or (10m), in which the radicals 
(R.sub.4).sub.0-3, (R.sub.5).sub.0-3, R.sub.8, R.sub.10, R.sub.9 and 
(R.sub.11).sub.0-3 are as defined above, and 
Z.sub.1 is a radical of the formula (6a), (6c'), (6d') or (6e') 
EQU --SO.sub.2 --Y (6a), 
EQU --CONH--(CH.sub.2).sub.2-3 --SO.sub.2 --Y (6c'), 
EQU --NH--CO--CH(Br)--CH.sub.2 --Br (6d') 
or 
EQU --NH--CO--C(Br).dbd.CH.sub.2 (6e'), 
preferably (6a), in which Y is vinyl, .beta.-chloroethyl or 
.beta.-sulfatoethyl, in particular vinyl or .beta.-sulfatoethyl; and the 
radicals 
D.sub.2 and D.sub.3 independently of one another are each a radical of the 
formula (15a), (15b), (15c) or (15d), in which the radicals 
(R.sub.13).sub.0-2, Y, Y.sub.1 and m are as defined above. 
Preferred dyes are those of the formula (2a) 
##STR23## 
in which D.sub.1, D.sub.2 and D.sub.3 independently of one another in each 
case are a radical of the formula (15a), (15b), (15c), (15d) or (16a), 
preferably (15a), (15b) or (16a), where at least one of the radicals 
D.sub.1, D.sub.2 and D.sub.3 contains a fibre-reactive group; or 
D.sub.1 is a radical of the formula (18), in which 
X.sub.1 is chlorine and T.sub.3 is a radical of the formula (10a), (10b), 
(10d), (10e), (10f), (10k) or (10m), preferably (10b), (10k) or (10m), and 
D.sub.2 and D.sub.3 independently of one another in each case are a radical 
of the formula (15a), (15b), (15c) or (15d), preferably (15a) or (15b), 
where at least one of the radicals D.sub.2 and D.sub.3 contains a 
fibre-reactive group. 
Preferably, at least two of the radicals D.sub.1, D.sub.2 and D.sub.3 in 
the dye of the formula (2a) contain a fibre-reactive group. 
The present invention furthermore relates to a process for the preparation 
of the azo dyes according to the invention, which comprises coupling one 
or more than one diazotized amine together or in any desired sequence to a 
compound containing at least one structural unit of the formula (19) 
##STR24## 
such that an azo dye which contains at least one structural unit of the 
formula (1) is obtained. 
More than one diazotized amine means, for example, 2 or 3 diazotized 
amines. 
Amines which are suitable for the preparation of the azo dyes according to 
the invention are, for example, aromatic amines of the benzene or 
naphthalene series which can be diazotized and are capable of coupling in 
accordance with processes known per se, such as are described, for 
example, in Venkataraman "The Chemistry of Synthetic Dyes" Volume 1, pages 
210-214 and 409-441, Academic Press, New York, London 1952. 
The amines are diazotized, for example, with a nitrite, for example with an 
alkali metal nitrite, such as sodium nitrite, in a mineral acid medium, 
for example in a hydrochloric acid medium, at temperatures of, for 
example, -5 to 40.degree. C., and preferably at -5 to 10.degree. C. 
Coupling to the coupling components of the formula (19) is carried out in a 
manner known per se at an acid or neutral to weakly alkaline pH, for 
example a pH of 1 to 10, and at temperatures of, for example, -5 to 
40.degree. C., preferably 0 to 30.degree. C. 
The coupling reaction is advantageously first carried out in a strongly 
acid medium, for example at pH 1, and the pH of the reaction mixture is 
increased slowly, for example to pH 5 to 8, as the reaction progresses. 
Azo dyes of the formula (2) in which A is oxygen and R is hydrogen and 
D.sub.1 =D.sub.2 .noteq.D.sub.3 or D.sub.2 =D.sub.3 .noteq.D.sub.1 are 
obtained, for example, by first reacting about 1 molar equivalent of a 
diazotized amine of the formula (20a) 
EQU D.sub.1 --NH.sub.2 (20a) 
in an acid medium with about 1 molar equivalent of a compound of the 
formula (19a) 
##STR25## 
to give a compound of the formula (21a) 
##STR26## 
and allowing the compound of the formula (21a) to react at an increased pH 
with about 2 molar equivalents of a diazotized amine of the formula (20b) 
EQU D.sub.2 --NH.sub.2 (20b) 
in which D.sub.1 and D.sub.2 are as defined and preferred above. 
Azo dyes of the formula (2) in which A is oxygen, sulfur or a radical 
--NR'-- and R is an aliphatic or aromatic radical and D.sub.1 =D.sub.2 
.noteq.D.sub.3 or D.sub.2 =D.sub.3 .noteq.D.sub.1 are obtained, for 
example, by reacting about 1 molar equivalent of a compound of the formula 
(22a) 
##STR27## 
with about 1 molar equivalent of a compound of the formula (23) 
EQU R--AH (23) 
in a manner known per se to give a compound of the formula (22b) 
##STR28## 
reducing the compound of the formula (22b) to a compound of the formula 
(19c) 
##STR29## 
in a manner known per se and then further reacting the compound of the 
formula (19c) stepwise with the diazotized amines of the formulae (20a) 
and (20b) analogously to the procedure described above, where R' and R are 
as defined and preferred above. 
Azo dyes of the formula (3) in which D.sub.1 =D.sub.2 .noteq.D.sub.3 or 
D.sub.2 =D.sub.3 .noteq.D.sub.1 are obtained, for example, by reacting 
about 2 molar equivalents of a compound of the formula (22a) with about 1 
molar equivalent of a compound of the formula (24) 
EQU HA--B--AH (24) 
in a manner known per se to give a compound of the formula (22c) 
##STR30## 
reducing the compound of the formula (22c) to a compound of the formula 
(19d) 
##STR31## 
in a manner known per se and then further reacting the compound of the 
formula (19d) stepwise with the equivalent amount of the diazotized amines 
of the formulae (20a) and (20b) analogously to the procedure described 
above, where A and B are as defined and preferred above. 
The conditions for the reduction of the compounds of the formulae (22b) and 
(22c) are advantageously chosen such that any functional groups present in 
R, R' or B are not reduced. Such selective reduction reactions are known 
and are widely described in the relevant literature. 
Those dyes of the formulae (2) and (3) according to the invention in which 
D.sub.1 .noteq.D.sub.2 .noteq.D.sub.3 can be obtained if the procedure 
described above is followed, except the equimolar amount of a mixture of, 
for example, two diazotized amines D.sub.2 --NH.sub.2 and D.sub.3 
--NH.sub.2 in a molar ratio of, for example, 1:1 is used in place of a 
diazotized amine D.sub.2 --NH.sub.2. As a rule, these dyes are obtained as 
mixtures. 
Azo dyes of the formula (4) in which A is oxygen and R is hydrogen and 
D.sub.1 =D.sub.2 are obtained, for example, by first reacting about 1 
molar equivalent of a tetrazotized diamine of the formula (20c) 
EQU H.sub.2 N--D.sub.4 --NH.sub.2 (20c) 
in a hydrochloric acid medium with about 2 molar equivalents of a compound 
of the formula (19a) to give a compound of the formula (21b) 
##STR32## 
and allowing the compound of the formula (21b) to react at an increased pH 
with about 4 molar equivalents of a diazotized amine of the formula 
D.sub.1 --NH.sub.2, where D.sub.1 and D.sub.4 are as defined and preferred 
above. 
Azo dyes of the formula (4) in which A is oxygen, sulfur or a radical 
--NR'-- and R is an aliphatic or aromatic radical and D.sub.1 =D.sub.2 are 
obtained, for example, if the procedure described above is followed, 
except that the equimolar amount of a compound of the formula (19c) is 
used in place of the compound of the formula (19a). 
Those dyes of the formulae (4) according to the invention in which D.sub.1 
.noteq.D.sub.2 can be obtained if the procedure described above is 
followed, except that an equimolar amount of a mixture of, for example, 
two diazotized amines D.sub.1 --NH.sub.2 and D.sub.2 --NH.sub.2 in a molar 
ratio of, for example, 1:1 is used in place of a diazotized amine D.sub.1 
--NH.sub.2. As a rule, the dyes are obtained as mixtures. 
The compounds of the formulae (19a), (20a), (20b), (20c), (22a), (23) and 
(24) are known or can be obtained in a manner known per se. 
Valuable direct dyes can be obtained from the dyes according to the 
invention which contain exclusively one or more halogenotriazinyl radicals 
of the formula (6f) as the fibre-reactive radical and in which X.sub.1 is 
chlorine or fluorine and T.sub.1 is a radical which is not fibre-reactive, 
by further reacting the dye with an amount equivalent to the amount of 
halogenotriazinyl of, for example, a compound of the formula T.sub.1 --H, 
in which T.sub.1 is as defined above, excluding a fibre-reactive radical. 
In particular, T.sub.1 --H is ammonia, an amine which is unsubstituted or 
substituted as defined above or morpholine. Such reactions can be carried 
out by processes known per se. 
The dyes according to the invention are suitable for dyeing and printing 
the most diverse materials, in particular fibre materials containing 
hydroxyl groups or containing nitrogen. Examples are paper, silk, leather, 
wool, polyamide fibres and polyurethanes, and in particular all types of 
cellulosic fibre materials. Such fibre materials are, for example, the 
natural cellulose fibres, such as cotton, linen and hemp, as well as pulp 
and regenerated cellulose. The dyes according to the invention are also 
suitable for dyeing or printing fibres containing hydroxyl groups which 
are contained in blend fabrics, for example mixtures of cotton with 
polyester fibres or polyamide fibres. 
The present invention therefore furthermore relates to the use of compounds 
of the formula (1) for dyeing or printing fibre materials containing 
hydroxyl groups or containing nitrogen, in particular containing cotton. 
The dyes according to the invention can be applied to the fibre material 
and fixed to the fibre in various ways, in particular in the form of 
aqueous dye solutions and printing pastes. They are suitable both for the 
exhaust method and for dyeing by the padder method, can be employed at low 
dyeing temperatures and require only short steaming times in the pad-steam 
process. The degrees of fixing are high and the unfixed portions can 
easily be washed off, the difference between the degree of exhaustion and 
degree of fixing being remarkably small, i.e. the soaping loss is very 
low. The dyes according to the invention are also suitable for printing, 
in particular on cotton, but likewise also for printing fibres containing 
nitrogen, for example wool, silk or blend fabrics containing wool. 
The dyeings and prints produced with the dyes according to the invention, 
in particular the reactive dyes, have a high colour strength and a high 
fibre-dye bond stability both in the acid and in the alkaline range, and 
furthermore a good fastness to light and very good wet-fastness 
properties, such as fastness to washing, water, sea water, crossdyeing and 
perspiration. Dyeings which are level over the fibre and surface are 
obtained. 
The following examples serve to illustrate the invention. Temperatures are 
stated in degrees Celsius, parts are parts by weight and percentage data 
relate to % by weight, unless noted otherwise. Parts by weight bear the 
same relation to parts by volume as the kilogram to the liter.

EXAMPLE 1 
17.3 parts of an amine of the formula D.sub.10 --NH.sub.2, in which 
D.sub.10 is a radical of the formula 
##STR33## 
are introduced into 215 parts of water and the mixture is stirred 
thoroughly. 25 parts of a 4N sodium nitrite solution are added to the 
resulting solution at 0.degree. C. and 20 parts of concentrated 
hydrochloric acid are then slowly added dropwise at 0 to 5.degree. C. The 
mixture is stirred at this temperature for 1 hour. 
EXAMPLE 2 
56.2 parts of an amine of the formula D.sub.11 --NH.sub.2, in which 
D.sub.11 is a radical of the formula 
##STR34## 
are introduced into 220 parts of water and the mixture is stirred 
thoroughly. First 50 parts of a 4N sodium nitrite solution and then 90 
parts of a 31% naphthalenesulfonic acid solution are added to the 
resulting suspension at 10.degree. C. The mixture is then stirred at 15 to 
20.degree. C. for 3 hours. 
EXAMPLES 3 to 33 
The diazo compounds of the amines listed in Table 1 can be prepared 
analogously to the procedure described in Examples 1 or 2 if an equimolar 
amount of the amines of the formula D.sub.xy --NH.sub.2 listed in Table 1 
is used in place of the amines of the formula D.sub.10 --NH.sub.2 or 
D.sub.11 --NH.sub.2 mentioned in Examples 1 or 2. 
TABLE 1 
__________________________________________________________________________ 
Amine 
Exp. D 
.sub.xy -NH.sub.2 D.sub.xy 
__________________________________________________________________________ 
3 D.sub.12 -NH.sub.2 D.sub.12 = 
#STR35## 
- 4 D.sub.13 -NH.sub.2 D.sub.13 = 
#STR36## 
- 5 D.sub.14 -NH.sub.2 D.sub.14 = 
#STR37## 
- 6 D.sub.15 -NH.sub.2 D.sub.15 = 
#STR38## 
- 7 D.sub.16 -NH.sub.2 D.sub.16 = 
#STR39## 
- 8 D.sub.17 -NH.sub.2 D.sub.17 = 
#STR40## 
- 9 D.sub.18 -NH.sub.2 D.sub.18 = 
#STR41## 
- 10 D.sub.19 -NH.sub.2 D.sub.19 = 
#STR42## 
- 11 D.sub.20 -NH.sub.2 D.sub.20 = 
#STR43## 
- 12 D.sub.21 -NH.sub.2 D.sub.21 = 
#STR44## 
- 13 D.sub.22 -NH.sub.2 D.sub.22 = 
#STR45## 
- 14 D.sub.23 -NH.sub.2 D.sub.23 = 
#STR46## 
- 15 D.sub.24 -NH.sub.2 D.sub.24 = 
#STR47## 
- 16 D.sub.25 -NH.sub.2 D.sub.25 = 
#STR48## 
- 17 D.sub.26 -NH.sub.2 D.sub.26 = 
#STR49## 
- 18 D.sub.27 -NH.sub.2 D.sub.27 = 
#STR50## 
- 19 D.sub.28 -NH.sub.2 D.sub.28 = 
#STR51## 
- 20 D.sub.29 -NH.sub.2 D.sub.29 = 
#STR52## 
- 21 D.sub.30 -NH.sub.2 D.sub.30 = 
#STR53## 
- 22 D.sub.31 -NH.sub.2 D.sub.31 = 
#STR54## 
- 23 D.sub.32 -NH.sub.2 D.sub.32 = 
#STR55## 
- 24 D.sub.33 -NH.sub.2 D.sub.33 = 
#STR56## 
- 25 D.sub.34a -NH.sub.2 -D.sub.34r -NH.sub.2 D.sub.34a -D.sub.34r = 
#STR57## 
- 
T.sub.1: 
25a D.sub.34a -NH.sub.2 D.sub.34a 
#STR58## 
- 25b D.sub.34b -NH.sub.2 D.sub.34b 
#STR59## 
- 25c D.sub.34c -NH.sub.2 D.sub.34c 
#STR60## 
- 25d D.sub.34d -NH.sub.2 D.sub.34d 
#STR61## 
- 
25e D.sub.34e -NH2 
D.sub.34e --NHCH.sub.2 CH.sub.2 OH 
25f D.sub.34f -NH.sub.2 D.sub.34f --N(CH.sub.2 CH.sub.2 OH).sub.2 
25g D.sub.34g -NH.sub.2 D.sub.34g 
#STR62## 
- 25h D.sub.34h -NH.sub.2 D.sub.34h 
#STR63## 
- 
25i D.sub.34i -NH.sub.2 
D.sub.34i --NH--(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --OH 
25j D.sub.23j -NH.sub.2 D.sub.34j --NHCH.sub.2 CH.sub.2 SO.sub.3 H 
25k D.sub.34k -NH.sub.2 D.sub.34k 
#STR64## 
- 25l D.sub.34i -NH.sub.2 D.sub.34l 
#STR65## 
- 
25m D.sub.34m -NH.sub.2 
D.sub.34m --NH--(CH.sub.2).sub.2 --SO.sub.2 --(CH.sub.2).sub 
.2 --Cl 
25n D.sub.34n -NH.sub.2 D.sub.34n --NH--(CH.sub.2).sub.2 --O--(CH.sub.2) 
.sub.2 --SO.sub.2 --(CH.sub.2).sub.2 --Cl 
25o D.sub.34o -NH.sub.2 D.sub.34o 
#STR66## 
- 25p D.sub.34p -NH.sub.2 D.sub.34p 
#STR67## 
- 25q D.sub.34q -NH.sub.2 D.sub.34q 
#STR68## 
- 25r D.sub.34r -NH.sub.2 D.sub.34r 
#STR69## 
- 26 D.sub.35 -NH.sub.2 D.sub.35 = 
#STR70## 
- 27 D.sub.36 -NH.sub.2 D.sub.36 = 
#STR71## 
- 28 D.sub.37 -NH.sub.2 D.sub.37 = 
#STR72## 
- 29 D.sub.38 -NH.sub.2 D.sub.38 = 
#STR73## 
- 30 D.sub.39 -NH.sub.2 D.sub.39 = 
#STR74## 
- 31 D.sub.40a -NH.sub.2 -D.sub.40f -NH.sub.2 D.sub.40a -D.sub.40f = 
#STR75## 
- 
T.sub.3 : 
31a D.sub.40a -NH.sub.2 D.sub.40a 
#STR76## 
- 31b D.sub.40b -NH.sub.2 D.sub.40b 
#STR77## 
- 31c D.sub.40c -NH.sub.2 D.sub.40c 
#STR78## 
- 31d D.sub.40d -NH.sub.2 D.sub.40d 
#STR79## 
- 31e D.sub.40e -NH.sub.2 D.sub.40a 
#STR80## 
- 31f D.sub.40f -NH.sub.2 D.sub.40f 
#STR81## 
- 32 D.sub.41a -NH.sub.2 -D.sub.41u -NH.sub.2 D.sub.41a -D.sub.41u = 
#STR82## 
- 33 D.sub.42a -NH.sub.2 -D.sub.42u -NH.sub.2 D.sub.42a -D.sub.42u = 
#STR83## 
- 
D: 
32a/33a D.sub.41a/42a -NH.sub.2 D.sub.41a/42a 
#STR84## 
- 32b/33b D.sub.41b/42b -NH.sub.2 D.sub.41b/42b 
#STR85## 
- 32c/33c D.sub.41c/42c -NH.sub.2 D.sub.41c/42c 
#STR86## 
- 32d/33d D.sub.41d/42d -NH.sub.2 D.sub.41d/42d 
#STR87## 
- 32e/33e D.sub.41e/42e -NH.sub.2 D.sub.41e/42e 
#STR88## 
- 32f/33f D.sub.41f/42f -NH.sub.2 D.sub.41f/42f 
#STR89## 
- 32g/33g D.sub.41g/42g -NH.sub.2 D.sub.41g/42g 
#STR90## 
- 32h/33h D.sub.41h/42h -NH.sub.2 D.sub.41h/42h 
#STR91## 
- 32i/33i D.sub.41i/42i -NH.sub.2 D.sub.41i/42i 
#STR92## 
- 32j/33j D.sub.41j/42j -NH.sub.3 D.sub.41j/42j 
#STR93## 
- 32k/33k D.sub.41k/42k -NH.sub.2 D.sub.41k/42k 
#STR94## 
- 32l/33l D.sub.41l/42l -NH.sub.2 D.sub.41l/42l 
#STR95## 
- 32m/33m D.sub.41m/42m -NH.sub.2 D.sub.41m/42m 
#STR96## 
- 32n/33n D.sub.41n/42n -NH.sub.2 D.sub.41n/42n 
#STR97## 
- 32o/33o D.sub.41o/42o -NH.sub.2 D.sub.41o/42o 
#STR98## 
- 32p/33p D.sub.41p/42p -NH.sub.2 D.sub.41p/42p 
#STR99## 
- 32q/33q D.sub.41q/42q -NH.sub.2 D.sub.41q/42q 
#STR100## 
- 32r/33r D.sub.41r/42r -NH.sub.2 D.sub.41r/42r 
#STR101## 
- 32s/33s D.sub.41s/42s -NH.sub.2 D.sub.41s/42s 
#STR102## 
- 32t/33t D.sub.41t/42t -NH.sub.2 D.sub.41t/42t 
#STR103## 
- 32u/33u D.sub.41u/42u -NH.sub.2 D.sub.41u/42u 
##STR104## 
__________________________________________________________________________ 
EXAMPLE 34 
16 parts of the diamine of the formula H.sub.2 N--D.sub.43 --NH.sub.2, in 
which D.sub.43 is a radical of the formula 
##STR105## 
are dissolved in 160 parts of water under neutral conditions. 13 parts of 
concentrated hydrochloric acid and then 19.5 parts of a 4N sodium nitrite 
solution are slowly added at 0.degree. C. When the diamine has reacted to 
give the corresponding tetrazo compound, the excess nitrite is destroyed 
by addition of sulfamic acid. 
EXAMPLES 35 to 37 
The tetrazo compounds of the diamines listed in Table 2 can be prepared 
analogously to the procedure described in Example 34 if an equimolar 
amount of the diamines of the formula H.sub.2 N--D.sub.xy --NH.sub.2 
listed in Table 2 is used in place of the diamine of the formula H.sub.2 
N--D.sub.43 --NH.sub.2 mentioned in Example 34. 
TABLE 2 
__________________________________________________________________________ 
Diamine 
Exp. H.sub.2 N-D.sub.xy -NH.sub.2 D.sub.xy 
__________________________________________________________________________ 
35 H.sub.2 N-D.sub.44 -NH.sub.2 D.sub.44 = 
#STR106## 
- 36 H.sub.2 N-D.sub.45 -NH.sub.2 D.sub.45 = 
#STR107## 
- 37 H.sub.2 N-D.sub.46 -NH.sub.2 D.sub.46 = 
##STR108## 
__________________________________________________________________________ 
EXAMPLE 38 
a) 1st coupling: a solution of 15.2 parts of 3,5-diaminobenzoic acid in 100 
parts of 2N hydrochloric acid is added at 0 to 5.degree. C. to the acid 
diazo compound suspension obtained according to Example 1. The pH of the 
reaction mixture is brought to 3.2 in the course of 4 hours with a 40% 
sodium acetate solution. The mixture is then stirred at 6 to 7.degree. C. 
for a further 30 minutes. A compound which, in the form of the free acid, 
has the formula (101) 
##STR109## 
is obtained. 
b) 2nd coupling: the acid diazo compound suspension obtained according to 
Example 2 is added at 7.degree. C. and pH 3.2 to the suspension, obtained 
according to a), of the compound of the formula (101). The pH of the 
reaction mixture is brought to 3.5 in the course of 45 minutes at 12 to 
15.degree. C. with a 40% sodium acetate solution and to 6.3 in the course 
of 1 hour at 15 to 19.degree. C. with sodium bicarbonate. The mixture is 
then stirred at about 25.degree. C. for a further 45 minutes. The 
resulting solution is treated with 450 parts of acetone, the pH is brought 
to 1.5 with concentrated hydrochloric acid and 4.6 parts of potassium 
chloride are added. The dye which has precipitated out is filtered off and 
washed with acetone. 70.1 parts of a compound which, in the form of the 
free acid, has the formula (102) 
##STR110## 
and dyes cotton and wool in orange colour shades with good allround 
properties are obtained. 
EXAMPLES 39 to 108 
The dyes of the following general formula (103) 
##STR111## 
in which D.sup.1.sub.xy and D.sup.2.sub.xy in each case are the radicals 
listed in Table 3 and these radicals are as defined in Examples 1 and 2 
and in Table 1 can be prepared from the diazo compounds described in 
Examples 1 to 33 analogously to the procedure described in Example 38. The 
dyes dye cotton and wool in the colour shades stated in Table 3 with good 
allround properties. 
TABLE 3 
______________________________________ 
D.sup.1.sub.xy 
D.sup.2.sub.xy 
Exp. 1st coupling 2nd coupling Colour shade 
______________________________________ 
39 D.sub.10 D.sub.12 orange 
40 D.sub.13 D.sub.11 orange 
41 D.sub.13 D.sub.12 orange 
42 D.sub.10 D.sub.13 orange 
43 D.sub.10 D.sub.14 orange 
44 D.sub.10 D.sub.15 orange 
45 D.sub.10 D.sub.16 orange 
46 D.sub.10 D.sub.17 orange 
47 D.sub.10 D.sub.18 orange 
48 D.sub.10 D.sub.32 orange 
49 D.sub.10 D.sub.33 orange 
50 D.sub.10 D.sub.19 orange 
51 D.sub.10 D.sub.20 orange 
52 D.sub.10 D.sub.21 orange 
53 D.sub.10 D.sub.22 orange 
54 D.sub.10 D.sub.29 orange 
55 D.sub.30 D.sub.11 orange 
56 D.sub.30 D.sub.12 orange 
57 D.sub.30 D.sub.13 orange 
58 D.sub.30 D.sub.14 orange 
59 D.sub.30 D.sub.15 orange 
60 D.sub.30 D.sub.16 orange 
61 D.sub.30 D.sub.17 orange 
62 D.sub.30 D.sub.18 orange 
63 D.sub.30 D.sub.19 orange 
64 D.sub.30 D.sub.20 orange 
65 D.sub.30 D.sub.21 orange 
66 D.sub.30 D.sub.22 orange 
67 D.sub.30 D.sub.29 orange 
68 D.sub.31 D.sub.11 orange 
69 D.sub.38 D.sub.11 brown 
70 D.sub.10 D.sub.23 orange 
71 D.sub.10 D.sub.24 orange 
72 D.sub.10 D.sub.25 orange 
73 D.sub.10 D.sub.26 orange 
74 D.sub.10 D.sub.27 orange 
75 D.sub.10 D.sub.28 orange 
76 D.sub.34a D.sub.13 brown-orange 
77 D.sub.34b D.sub.13 brown-orange 
78 D.sub.34c D.sub.13 brown-orange 
79 D.sub.34d D.sub.13 brown-orange 
80 D.sub.34e D.sub.13 brown-orange 
81 D.sub.34f D.sub.13 brown-orange 
82 D.sub.34g D.sub.13 brown-orange 
83 D.sub.34h D.sub.13 brown-orange 
84 D.sub.34i D.sub.13 brown-orange 
85 D.sub.34j D.sub.13 brown-orange 
86 D.sub.34k D.sub.13 brown-orange 
87 D.sub.34l D.sub.13 brown-orange 
88 D.sub.34m D.sub.13 brown-orange 
89 D.sub.34n D.sub.13 brown-orange 
90 D.sub.34o D.sub.13 brown-orange 
91 D.sub.34p D.sub.13 brown-orange 
92 D.sub.34q D.sub.13 brown-orange 
93 D.sub.34r D.sub.13 brown-orange 
94 D.sub.35 D.sub.13 brown-orange 
95 D.sub.36 D.sub.13 brown-orange 
96 D.sub.37 D.sub.13 brown-orange 
97 D.sub.35 D.sub.11 brown-orange 
98 D.sub.36 D.sub.11 brown-orange 
99 D.sub.37 D.sub.11 brown-orange 
100 D.sub.34a D.sub.11 brown-orange 
101 D.sub.34e D.sub.11 brown-orange 
102 D.sub.34f D.sub.11 brown-orange 
103 D.sub.34g D.sub.11 brown-orange 
104 D.sub.34h D.sub.11 brown-orange 
105 D.sub.39 D.sub.13 brown 
106 D.sub.39 D.sub.11 brown 
107 D.sub.40a D.sub.13 brown-orange 
108 D.sub.40a D.sub.11 brown-orange 
______________________________________ 
EXAMPLE 109 
a) 1st coupling: a solution of 15.2 parts of 3,5-diaminobenzoic acid in 100 
parts of 2N hydrochloric acid is added at 0 to 5.degree. C. to the acid 
tetrazo compound suspension obtained according to Example 34. The pH of 
the reaction mixture is brought to 3.2 in the course of 4 hours with a 40% 
sodium acetate solution. The mixture is then stirred at 6 to 7.degree. C. 
for a further 30 minutes. A compound which, in the form of the free acid, 
has the formula (104) 
##STR112## 
is obtained. 
b) 2nd coupling: the acid diazo compound suspension obtained according to 
Example 2 is added at 7.degree. C. and pH 3.2 to the suspension, obtained 
according to a), of the compound of the formula (104). The pH of the 
reaction mixture is brought to 3.5 in the course of 45 minutes at 12 to 
15.degree. C. with a 40% sodium acetate solution and to 6.3 in the course 
of one hour at 15 to 19.degree. C. with sodium bicarbonate. The mixture is 
then stirred at about 25.degree. C. for a further 45 minutes. 450 parts of 
acetone are added to the resulting solution, the pH is brought to 1.5 with 
concentrated hydrochloric acid and 4.6 parts of potassium chloride are 
added. The dye which has precipitated out is filtered off and washed with 
acetone. 68 parts of a compound which, in the form of the free acid, has 
the formula (105) 
##STR113## 
and dyes cotton and wool in brown-orange colour shades with good allround 
properties are obtained. 
EXAMPLES 110 to 113 
The dyes of the following general formula (106) 
##STR114## 
in which D.sup.1.sub.xy and D.sup.2.sub.xy in each case are the radicals 
listed in Table 4 and these radicals are as defined in Table 2 and in 
Examples 2 and 4, can be prepared from the tetrazo compounds described in 
Table 2 and the diazo compounds described in Examples 2 and 4 analogously 
to the procedure described in Example 109. The dyes dye cotton and wool in 
the colour shades stated in Table 4 with good allround properties. 
TABLE 4 
______________________________________ 
D.sup.1.sub.xy 
D.sup.2.sub.xy 
Exp. 1st coupling 2nd coupling Colour shade 
______________________________________ 
110 D.sub.44 D.sub.13 brown-orange 
111 D.sub.45 D.sub.13 brown-orange 
112 D.sub.46 D.sub.13 brown-orange 
113 D.sub.46 D.sub.11 brown-orange 
______________________________________ 
EXAMPLE 114 
A solution of 10.1 parts of 3,5-diaminobenzoic acid in 67 parts of 2N 
hydrochloric acid is added at 0 to 5.degree. C. to the acid diazo compound 
suspension obtained according to Example 2. The pH of the reaction mixture 
is brought to 3.2 in the course of one hour with a 40% sodium acetate 
solution, to 5.8 in the course of a further hour with sodium bicarbonate 
and to 7.8 in the course of 45 minutes with a 20% sodium carbonate 
solution. The resulting solution is brought to pH 0.8 with concentrated 
hydrochloric acid, and 80 parts of acetone and 112 parts of potassium 
chloride are added. The dye which has precipitated out is filtered off and 
washed with acetone. 64.6 parts of a compound which, in the form of the 
free acid, has the formula (107) 
##STR115## 
and dyes cotton and wool in orange colour shades with good allround 
properties are obtained. 
EXAMPLES 115 to 140 
The dyes of the general formula (108) 
##STR116## 
in which D.sub.xy in each case are the radicals listed in Table 5 and 
these radicals are as defined in Table 1, can be obtained from the diazo 
compounds described in Examples 3 to 5, 9 to 12, 14, 15, 20 and 23 to 25 
analogously to the procedure described in Example 114. The dyes dye cotton 
and wool in the colour shades stated in Table 5 with good allround 
properties. 
TABLE 5 
______________________________________ 
Exp. D.sub.xy 
Colour shade 
______________________________________ 
115 D.sub.12 
orange 
116 D.sub.13 orange 
117 D.sub.14 orange 
118 D.sub.18 orange 
119 D.sub.19 orange 
120 D.sub.20 orange 
121 D.sub.21 orange 
122 D.sub.23 orange 
123 D.sub.24 orange 
124 D.sub.29 orange 
125 D.sub.32 orange 
126 D.sub.33 orange 
127 D.sub.34a orange 
128 D.sub.34b orange 
129 D.sub.34c orange 
130 D.sub.34e orange 
131 D.sub.34f orange 
132 D.sub.34g orange 
133 D.sub.34i orange 
134 D.sub.34j orange 
135 D.sub.34l orange 
136 D.sub.34m orange 
137 D.sub.34n orange 
138 D.sub.34o orange 
139 D.sub.34q orange 
140 D.sub.34r orange 
______________________________________ 
EXAMPLE 141 
14.4 parts of 2-sulfo-4-(.beta.-sulfatoethylsulfonyl)aniline and 22.7 parts 
of 4-(.beta.-sulfatoethylsulfonyl)aniline are introduced into 120 parts of 
water and the mixture is stirred thoroughly. First 30 parts of a 4N sodium 
nitrite solution and then 50 parts of a 31% naphthalenesulfonic acid 
solution are added to the resulting suspension at 10.degree. C. The 
mixture is then stirred at 15 to 20 C. for 3 hours. A solution of 6.1 
parts of 3,5-diaminobenzoic acid in 40 parts of 2N hydrochloric acid is 
added to this suspension at 0 to 5.degree. C. The pH of the reaction 
mixture is brought to 3.2 in the course of one hour at 0 to 5.degree. C. 
with a 40% sodium acetate solution, to 5.8 in the course of a further hour 
with sodium bicarbonate and to 7.8 in the course of 45 minutes with a 20% 
sodium carbonate solution. The resulting solution is evaporated. 66.9 
parts of a product which essentially comprises a mixture of compounds 
which, in the form of the free acid, have the formulae (109), (110), 
(111), (112), (113) and (114) 
##STR117## 
in which D.sub.11, and D.sub.13 are as defined in Examples 2 and 4, are 
obtained. The dye mixture dyes cotton and wool in orange colour shades 
with good allround properties. 
EXAMPLE 142 
a) 22.3 parts of 2-aminonaphthalenesulfonic acid are introduced into 215 
parts of water and the mixture is stirred thoroughly. 25 parts of a 4N 
sodium nitrite solution are added to the resulting solution at 0.degree. 
C. and 20 parts of concentrated hydrochloric acid are then slowly added 
dropwise at 0 to 5.degree. C. The mixture is stirred at this temperature 
for 1 hour. 
b) 30.3 parts of 2-amino-1,5-naphthalenedisulfonic acid are introduced into 
215 parts of water and the mixture is stirred thoroughly. 25 parts of a 4N 
sodium nitrite solution are added to the resulting solution at 0.degree. 
C. and 20 parts of concentrated hydrochloric acid are then slowly added 
dropwise at 0 to 5.degree. C. The mixture is stirred at this temperature 
for 1 hour. 
c) 28.1 parts of 4-(.beta.-sulfatoethylsulfonyl)aniline are introduced into 
110 parts of water and the mixture is stirred thoroughly. First 25 parts 
of a 4N sodium nitrite solution and then 45 parts of a 31% 
naphthalenesulfonic acid solution are added to the resulting suspension at 
10.degree. C. The mixture is then stirred at 15 to 20.degree. C. for 3 
hours. 
d) 1st coupling: a solution 15.2 parts of 3,5-diaminobenzoic acid in 100 
parts of 2N hydrochloric acid is added at 0 to 5.degree. C. to the acid 
diazo compound suspension obtained according to a). The pH of the reaction 
mixture is brought to 3.2 in the course of 4 hours with a 40% sodium 
acetate solution. The mixture is then stirred at 6 to 7.degree. C. for a 
further 30 minutes. 
e) 2nd coupling: the acid diazo compound suspension obtained according to 
b) is added at 7.degree. C. and pH 3.2 to the suspension obtained 
according to d). The pH of the reaction mixture is brought to 4.5 in the 
course of 45 minutes with a 40% sodium acetate solution. The mixture is 
then stirred at about 15.degree. C. for a further 30 minutes. 
f) 3rd coupling: the acid diazo compound suspension obtained according to 
c) is added at 15.degree. C. and pH 4.5 to the suspension obtained 
according to e). The pH of the reaction mixture is brought to 6.3 in the 
course of one hour with sodium bicarbonate. The mixture is then stirred at 
about 25.degree. C. for a further 45 minutes. 450 parts of acetone are 
added to the resulting solution, the pH is brought to 1.5 with 
concentrated hydrochloric acid and 4.6 parts of potassium chloride are 
added. The product which has precipitated out is filtered off and washed 
with acetone. 72 parts of a product which essentially comprises a compound 
which, in the form of the free acid, has the formula (115) 
##STR118## 
and dyes cotton and wool in orange colour shades with good allround 
properties are obtained. 
EXAMPLES 143 to 192 
Dyes which essentially comprise a compound of the following general formula 
(116) 
##STR119## 
in which D.sup.1.sub.xy, D.sup.2.sub.xy and D.sup.3.sub.xy in each case 
are the radicals listed in Table 6 and these radicals are as defined in 
Example 2 and Table 1, can be prepared from the diazo compounds described 
in Examples 2, 4 and 29 to 33 analogously to the procedure described in 
Example 142. The dyes dye cotton and wool in the colour shades stated in 
Table 6 with good allround properties. 
TABLE 6 
______________________________________ 
D.sup.1.sub.xy 
D.sup.2.sub.xy 
D.sup.3.sub.xy 
Exp. 1st coupling 2nd coupling 3rd coupling Colour shade 
______________________________________ 
143 D.sub.38 D.sub.11 D.sub.13 
brown 
144 D.sub.39 D.sub.11 D.sub.13 brown 
145 D.sub.4Oa D.sub.11 D.sub.13 brown-orange 
146 D.sub.40b D.sub.11 D.sub.13 gold-orange 
147 D.sub.40c D.sub.11 D.sub.13 gold-orange 
148 D.sub.40d D.sub.11 D.sub.13 gold-orange 
149 D.sub.40e D.sub.11 D.sub.13 gold-yellow 
150 D.sub.40f D.sub.11 D.sub.13 gold-yellow 
151 D.sub.41a D.sub.11 D.sub.13 red 
152 D.sub.41b D.sub.11 D.sub.13 red 
153 D.sub.41c D.sub.11 D.sub.13 red 
154 D.sub.4ld D.sub.11 D.sub.13 red 
155 D.sub.41e D.sub.11 D.sub.13 red 
156 D.sub.41f D.sub.11 D.sub.13 red 
157 D.sub.41g D.sub.11 D.sub.13 red 
158 D.sub.4lh D.sub.11 D.sub.13 red 
159 D.sub.41i D.sub.11 D.sub.13 red 
160 D.sub.41j D.sub.11 D.sub.13 red 
161 D.sub.4lk D.sub.11 D.sub.13 red 
162 D.sub.41l D.sub.11 D.sub.13 red 
163 D.sub.41m D.sub.11 D.sub.13 red 
164 D.sub.41n D.sub.11 D.sub.13 red 
165 D.sub.41o D.sub.11 D.sub.13 red 
166 D.sub.41p D.sub.11 D.sub.13 red 
167 D.sub.41q D.sub.11 D.sub.13 red 
168 D.sub.41r D.sub.11 D.sub.13 red 
169 D.sub.41s D.sub.11 D.sub.13 red 
170 D.sub.41t D.sub.11 D.sub.13 red 
171 D.sub.41u D.sub.11 D.sub.13 red 
172 D.sub.42a D.sub.11 D.sub.13 orange 
173 D.sub.42b D.sub.11 D.sub.13 orange 
174 D.sub.42c D.sub.11 D.sub.13 orange 
175 D.sub.42d D.sub.11 D.sub.13 orange 
176 D.sub.42e D.sub.11 D.sub.13 orange 
177 D.sub.42f D.sub.11 D.sub.13 orange 
178 D.sub.42g D.sub.11 D.sub.13 orange 
179 D.sub.42h D.sub.11 D.sub.13 orange 
180 D.sub.42i D.sub.11 D.sub.13 orange 
181 D.sub.42j D.sub.11 D.sub.13 orange 
182 D.sub.42k D.sub.11 D.sub.13 orange 
183 D.sub.42l D.sub.11 D.sub.13 orange 
184 D.sub.42m D.sub.11 D.sub.13 orange 
185 D.sub.42n D.sub.11 D.sub.13 orange 
186 D.sub.42o D.sub.11 D.sub.13 orange 
187 D.sub.42p D.sub.11 D.sub.13 orange 
188 D.sub.42q D.sub.11 D.sub.13 orange 
189 D.sub.42r D.sub.11 D.sub.13 orange 
190 D.sub.42s D.sub.11 D.sub.13 orange 
191 D.sub.42t D.sub.11 D.sub.13 orange 
192 D.sub.42u D.sub.11 D.sub.13 orange 
______________________________________ 
The procedure described in Examples 38 to 108 and 114 to 192 is repeated, 
except that an equimolar amount of the compound of the formula (117), 
(118), (119), (120) or (121) 
##STR120## 
is used in place of 3,5-diaminobenzoic acid. Further valuable dyes which 
dye cotton and wool with good allround properties can be prepared. 
The procedure described in one of Examples 109 to 113 is repeated, except 
that an equimolar amount of the compound of the formula (117), (118) or 
(119) is used in place of 3,5-diaminobenzoic acid. Valuable dyes which dye 
cotton and wool with good allround properties can likewise be prepared. 
The compounds of the formulae (117), (118), (119), (120) and (121) are 
known or can be prepared analogously to known compounds. 
Dyeing Instructions I 
100 parts of cotton fabric are introduced at 60.degree. C. into 1500 parts 
of a dyebath which comprises 45 g/l of sodium chloride and 2 parts of the 
reactive dye obtained according to Example 38. After 45 minutes at 
60.degree. C., 20 g/l of calcined sodium carbonate are added. Dyeing is 
continued at this temperature for a further 45 minutes. Thereafter, the 
dyed goods are rinsed, soaped at the boil with a nonionic detergent for a 
quarter of an hour, rinsed again and dried. 
As an alternative to the instructions given, dyeing can also be carried out 
at 80.degree. C. instead of at 60.degree. C. 
Dyeing Instructions II 
0.1 part of the dye according to Example 38 is dissolved in 200 parts of 
water, and 0.5 part of sodium sulfate, 0.1 part of a levelling assistant 
(based on the condensation product of a higher aliphatic amine and 
ethylene oxide) and 0.5 part of sodium acetate are added. The pH is then 
brought to a value of 5.5 with acetic acid (80%). The dyebath is heated to 
50.degree. C. for 10 minutes and 10 parts of a woollen fabric are then 
added. The bath is heated to a temperature of 100.degree. C. in the course 
of about 50 minutes and dyeing is carried out at this temperature for 60 
minutes. Thereafter, the bath is allowed to cool to 90.degree. C. and the 
dyed goods are removed. The woollen fabric is washed with warm and cold 
water and then spun and dried. 
Printing Instructions 
3 parts of the dye obtained according to Example 141 are sprinkled with 
rapid stirring into 100 parts of a stop thickener comprising 50 parts of 
5% sodium alginate thickener, 27.8 parts of water, 20 parts of urea, 1 
part of sodium m-nitrobenzenesulfonate and 1.2 parts of sodium 
bicarbonate. A cotton fabric is printed with the printing paste thus 
obtained, dried, and the resulting printed material is steamed in 
saturated steam at 102.degree. C. for 2 minutes. The printed fabric is 
then rinsed, can be soaped at the boil and rinsed again, and is then 
dried.