POLYAZO DYESTUFFS, THEIR PRODUCTION AND THEIR USE

COLORANTS POLYAZOIQUES

English Abstract

NEW POLYAZO DYESTUFFS, THEIR PRODUCTION AND THEIR USE
Abstract of the Disclosure
Process for the production of polyazo dyestuffs
of the formula
<IMG>
wherein coupling components of the formulae K1H and
K2H are coupled with tetrazo compounds from diamines
of the formula
<IMG>
and obtained diazo intermediate products or coupling end
products further coupled with coupling components or
with diazo components of the aromatic or heterocyclic
series, wherein
-X- = -N= or -NO=;
I = a benzene, naphthalene, pyridine or pyrimidine ring
of which the nitrogen atoms are in the 4- or
6-position with respect to the triazole nucleus,

J = the atoms necessary to form a 5 or 6-membered
aromatic or heterocyclic ring optionally containing
an aromatic or alicyclic ring bound by condensation,
K1 and K2 = radicals of coupling components of the aromatic
or heterocyclic series, or of azo dyestuffs
having at least one position capable of coupling,
whereby they can be identical or different,
and whereby
I and J are unsubstituted, or substituted with water-
solubilising groups and alkyl, hydroxy, alkoxy,
aryloxy, alkanoyl, aroyl, alkyl or arylsulphonyl,
alkanoylamino, unsubstituted or N-substituted
carbamoyl or sulphamoyl, alkoxycarbonyl, alkoxy-
sulphonyl, nitro, cyano or trifluoromethyl
groups, and all above mentioned alkyl, alkoxy
or alkanoyl groups contain 1 to 4 carbon atoms,
Ra and Ra' = a radical of the aromatic or heterocyclic series,
m = 1, 2 or 3 and
p = 1, 2, whereby m + p is less than 5.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Process for the production of polyazo dyestuffs of the formula
<IMG>
wherein coupling components of the formulae K1H and K2H are coupled with
tetrazo compounds from diamines of the formula
<IMG> ;
and obtained diazo intermediate products or coupling end products further
coupled with coupling components or with diazo components of the aromatic
or heterocyclic series, wherein
-X- = -N= or -NO=,
I = a benzene, naphthalene, pyridine or pyrimidine ring of which the
nitrogen atoms are in the 4- or 6-position with respect to the
triazole nucleus,
J = the atoms necessary to form a 5- or 6-membered aromatic or heterocyclic
ring optionally containing an aromatic or alicyclic ring bound by
condensation,

K1 and K2 = radicals of coupling components of the aromatic
or heterocyclic series, or of azo dyestuffs
having at least one position capable of coupling,
whereby they can be identical or different,
and whereby
I and J are unsubstituted, or substituted with water-
solubilising groups and alkyl, hydroxy, alkoxy,
aryloxy, alkanoyl, aroyl, alkyl or arylsulphonyl,
alkanoylamino, unsubstituted or N-substituted
carbamoyl or sulphamoyl, alkoxycarbonyl, alkoxy-
sulphonyl, nitro, cyano or trifluoromethyl
groups, and all above mentioned alkyl, alkoxy
or alkanoyl groups contain 1 to 4 carbon atoms.
2. Process according to Claim 1 for the production
of disazo dyestuffs, wherein coupling components of the
formulae K1H and K2H defined in Claim 1 are coupled with
tetrazo compounds from diamines of the formula
<IMG>
wherein I' and J' can be substituted with chlorine or
bromine atoms, -OH, -SO3H, -COOH, methyl, ethyl, methoxy,
86

ethoxy, phenoxy, .beta.-hydroxyethyl, hydroxymethoxy, carboxymethoxy, acetyl,
benzoyl, methyl or ethylsulphonyl, acetylamino, methoxy or ethoxycarbonyl,
nitro, cyano, trifluoromethyl groups, or groups of the formula
<IMG>
whereby -Y- = -CO- or -SO2-,
R1 = a hydrogen atom, an alkyl or a hydroxyalkyl group,
R2 = a cyclohexyl, phenyl, benzyl, benzoyl or phenylsulphonyl group or
has one of the meanings given for Rl. and the phenyl ring of the
above mentioned benzyl, phenyl, benzoyl or phenylsulphonyl groups
can be substituted with chlorine or bromine atoms or with an alkyl
group containing 1 to 4 carbon atoms.
3. Process according to Claim 2, wherein coupling components of the
formulae A1H and A2H are used as components K1H or K2H, whereby
A1 and A2 a) = phenyl, alkylphenyl or naphthyl radical which is substituted
with at least one halogen atom or a -COOH, -SO3H, hydroxy,
alkoxy, -NO2, -NH2, N-alkyl, N-aryl or N,N-dialkylamino,
alkanoylamino, -NH-CO-COOH, arylsulphonyloxy group, or
with an alkylamino group containing a -COOH, SO3H or
hydroxy group, or with a fibre-reactive group,
b) = a naphthyl radical which is substituted with a phenylamino,
naphthylamino, benzoylamino,
87

phenylsulphonylamino, (p- or m-benzoyl-
amino)-benzoylamino, -NH-CO-NH2 or -NH-CO-
NH-aryl group, which can carry a fibre-
reactive radical, or bound by condensation to
a bivalent radical of the formula
<IMG> or <IMG>
whereby -U- = -S- or -NH-, and the mentioned
phenylamino, benzoylamino or phenylsulphonyl-
amino groups can carry on the phenyl nucleus
-OH, -NH2, -COOH, alkyl or alkoxy groups,
c) = a radical of the formula
<IMG>
whereby Z is a hydrogen atom or an -NH2,
-NO2, SO3H- or aminophenylcarbonamide group
or a fibre-reactive group;
or of the formula
<IMG>
whereby Z' is a hydrogen or chlorine atom or an -NH2,
SO3H, alkyl, hydroxy or COOH group, or a fibre-reactive group;
88

or of the formula
<IMG>
whereby n is 1 or 2; or of the formula
<IMG> or <IMG>
whereby Y' can be substituted by an SO3H group; or of the formula
<IMG>
whereby in the above given formulae the alkyyl, alkoxy or alkanoyl groups
contain 1 to 4 carbon atoms, and A1 and A2 can represent identical or
different radicals.
4. Process for the production of tris- or tetrakisazo dyestuffs,
wherein coupling components of the formulae A1H and A2H defined in Claim 3
are coupled with tetrazo compounds from diamines of the formula
<IMG>
89

wherein A? = B, B-N=N-B or C-N=N-D if p = 1
= B if p = 2, whereby
B = a phenylene radical which is unsubstituted or
substituted with alkyl, alkoxy, NH2, -SO3H,
-NH-CO-COOH or carboxyalkylamino groups, or with
fibre-reactive groups,
= a naphtylene radical which is unsubstituted or
substituted with hydroxy, alkoxy or SO3H-groups,
or
= -aryl-NH-CO-phenyl, naphthyl-NH-CO-phenyl-CO-NH-phenyl
or
<IMG>
C = a phenylene, naphthylene, diphenylenemethane,
diphenyleneurea, dinaphtylenemethane or di(p-phenylene-
1-pyrazolon-4-yl)urea radical substituted with alkyl,
hydroxyalkyl, H2N-, HO, HO3S-, HO2C-groups or with
fibre-reactive groups,
= (hydroxynaphthylene -CO-NH)2-L or (hydroxynaphthylene-
NH-CONH)2-L, whereby L = diphenylene or phenylene
radical which can be substituted by alkoxy, alkyl or
HO3S-groups,
D = a phenylene radical unsubstituted or substituted with
a chlorine atom, an alkyl, alkoxy, hydroxy or SO3H-
group,
- 90 -

= a naphthylene radical unsubstituted or substituted with an SO3H-group, or
= a diphenylene or -phenylene-V-phenylene radical unsubstituted or substi-
tuted with a chlorine atom, a nitro, hydroxy, -COOH, -SO3H, alkyl, alkoxy or
carboxyalkoxy group, with -V- = -NH-, -O-, -S-, -CH(cyclohexyl)-, -CH(phenyl)-,
-CH(chlorophenyl)-, -CH2-CH2-, -CH2-, -CO-NH-, -NH-CO-NH-, NH-CS-NH- or
-NO=N-, and X has the meaning given in Claim 1, and I' and J' have the mean-
ings given in Claim 2.
5. Process according to Claim 1 for the production of tri- or tetra-
kisazo dyestuffs, wherein tetrazo compounds from diamines of the formula
<IMG>
are coupled, if p = 1 or 2, both with a coupling component of the formula
A1H wherein A1 is phenyl, alkylphenyl or naphthyl radical which is substi-
tuted with at least one halogen atom or a -COOH, -SO3H, hydroxy, alkoxy, -NO2,
-NH2, N-alkyl, N-aryl or N,N-dialkylamino, alkanoylamino, -NH-CO-COOH, aryl-
sulphonyloxy group, or with an alkylamino group containing a -COOH, SO3H
or hydroxy group, or with a fibre-reactive group,
= a naphthyl radical which is substituted with a phenylamino,
naphthylamino, benzoylamino, phenylsulphonylamino, (p- or m-benzoyl-amino)-
benzoylamino, -NH-CO-NH2 or -NH-CO-NH-aryl group, which can carry a fibre-
reactive radical, or bound by condensation to a bivalent radical of the formula
<IMG> or <IMG>
whereby -U- = -S- or -NH-, and the mentioned phenylamino, benzoylamino or
phenylsulphonylamino groups can carry on the phenyl nucleus -OH, -NH2, -COOH,
alkyl or alkoxy groups and with a coupling component of the formula HB-N=N-A1
or HC-N=N-E, or, if p=1, both with A1H and with a coupling component of the
91

formula HB-N=N-B-N=N-A1, HB-N=N-C-N=N-E, HC-N=N-B-N=N-E or HC-N=N-D-N=N-A1,
or on both sides with coupling components of the formula HB-N=N-A1 or
HC-N=N-E, wherein B is a phenylene radical which is unsubstituted or substi-
tuted with alkyl, alkoxy, -NH2, -SO3H, -NH-CO-COOH or carboxyalkylamino
groups, or with fibre-reactive groups,
= a naphtylene radical which is unsubstituted or substituted with hydroxy,
alkoxy or SO3H-groups, or
= -aryl-NH-CO-phenyl, naphthyl-NH-CO-phenyl-CO-NH-phenyl or
<IMG>
C= a phenylenel naphthylene, diphenylenemethane, diphenyleneurea,
dinaphthylenemethane or di(p-phenylene-1-pyrazolon-4-yl)urea radical
substituted with alkyl, hydroxyalkyl, H2N-, HO-, HO3S-, HO2C-groups or with
fibre-reactive groups,
=(hydroxynaphthylene -CO-NH)2-L or (hydroxynaphthylene-NH-CONH)2-L, whereby
L = diphenylene or phenylene radical which can be substituted by alkoxy,
alkyl or HO3S-groups,
D= a phenylene radical unsubstituted or substituted with a chlorine atom, an
alkyl, alkoxy, hydroxy or SO3H- group,
= a naphthylene radical unsubstituted or substituted with an SO3H-group, or
= a diphenylene or -phenylene-V phenylene radical unsubstituted or substituted
with a chlorine atom, a nitro, hydroxy, -COOH,-SO3H, alkyl, alkoxy or
carboxyalkoxy group, with -V- = -NH-, -O-, -S-, -CH(cyclohexyl)-, -CH(phenyl)-,
-CH(chlorophenyl)-, -CH2-CH2 , -CH2-, -CO-NH-, -NH-CO-NH-, NH-CS-NH-or -NO=H-,
I' and J' can be substituted with chlorine or bromine atoms, -OH, -SO3H,
-COOH, methyl, ethyl, methoxy, ethoxy, phenoxy, .beta.-hydroxyethyl, hydroxymethoxy,
carboxymethoxy, acetyl, benzoyl, methyl or ethylsulphonyl acetylamino, methoxy
or ethoxycarbonyl, nitro, cyano, trifluoromethyl groups, or groups of the
formula
92

<IMG>
whereby -Y- = -CO- or -SO2-,
R1 - a hydrogen atom, an alkyl or a hydroxyalkyl group,
R2 = a cyclohexyl, phenyl, benzyl, benzoyl or phenylsulphonyl group or has
one of the meanings given for R1, and the phenyl ring of the above mentioned
benzyl, phenyl, benzoyl or phenylsulphonyl groups can be substituted with
chlorine or bromine atoms or with an alkyl group containing 1 to 4 carbon atoms,
X has the meanings given in Claim 1, and E = a phenyl radical unsubstituted
or substituted with chlorine atoms, O2N-, H2N-, N,N-dialkylamino, sulpho-
alkylamino, phenylamino, benzoylamino, acetylamino, hydroxy, HO2C-, HO3S-,
sulphamoyl, alkoxy, alkyl, phenylaminocarbonyl, phenoxy groups or fibre-
reactive groups, or = a naphthyl radical unsubstituted or substituted with
93

H2N-, O2N-, hydroxy or HO3S-groups or fibre-reactive groups.
6. Process according to Claim 1 for the production of tri- or tetra-
kisazo dyestuffs, wherein tetrazo compounds from diamines of the formula
<IMG>
are coupled, if p = 1 or 2, with coupling components AlH, BH or CH, and
further coupled with coupling components A1H or with diazo components from
amines E-NH2, or, if p = 1, coupled both with A1H and with BH or CH, and
further coupled with coupling components HB-N=N-A1 or AC-N=N-E or with dia-
zotised amines A1-N=N-D-NH2 or E-N=N-B-NH2, or coupled with HB-N=N-B, HB-N=N-C,
HC-N=N-D or HC-N=NB and further coupled with AlH or diazotised amines E-NH2,
whereby X has the meanings given in Claim 1,
I' and J' can be substituted with chlorine or bromine atoms, -OH,
-SO3H, -COOH, methyl, ethyl, methoxy, ethoxy, phenoxy, .beta.-hydroxyethyl, hy-
droxymethoxy, carboxymethoxy, acetyl, benzoyl, methyl or ethylsulphonyl,
acetylamino, methoxy or ethoxycarbonyl, nitro, cyano, trifluoromethyl groups,
or groups of the formula
<IMG>
whereby -Y- = -CO- or -SO2-,
R1 = a hydrogen atom, am alkyl or a hydroxyalkyl group,
R2 = a cyclohexyl, phenyl, benzyl, benzoyl or phenylsulphonyl group
or has one of the meanings given for R1, and the phenyl ring of the above
mentioned benzyl, phenyl, benzoyl or phenylsulphonyl groups can be substitu-
ted with chlorine or bromine atoms or with an alkyl group containing 1 to 4
carbon atoms
A1 is phenyl, alkylphenyl or naphthyl radical which is substituted
with at least one halogen atom or a -COOH, -SO3H, hydroxy, alkoxy, -NO2,
-NH2, N-alkyl, N-aryl or N,N-dialkylamino, alkanoylamino, -NH-CO-COOH,
94

arylsulphonyloxy group, or with an alkylamino group containing a -COOH, SO3H
or hydroxy group, or with a fibre-reactive group,
= a naphthyl radical which is substituted with a phenylamino,
naphthylamino, benzoylamino, phenylsulphonylamino, (p- or m-benzoylamino)-
benzoylamino, -NH-CO-NH2 or NH-CO-NH-aryl group, which can carry a fibre-
reactive radical, or bound by condensation to a bivalent radical of the
formula
<IMG> or <IMG>
whereby -U- = -S- or -NH-, and the mentioned phenylamino, benzoylamino or
phenylsulphonylamino groups can carry on the phenyl nucleus -OH, -NH2, -COOH,
alkyl or alkoxy groups,
= a radical of the formula
<IMG>
whereby Z is a hydrogen atom or an -NH2, -NO2, SO3H- or aminophenylcarbon-
amide group or a fibre-reactive group; or of the formula
<IMG>
whereby Z' is a hydrogen or chlorine atom or an NH2, SO3H, alkyl, hydroxy or
COOH group, or a fibre-reactive group;
or of the formula
<IMG>

whereby n is 1 or 2; or of the formula
<IMG> or <IMG>
whereby Y' can be substituted by an SO3H group; or of the formula
<IMG>
whereby in the above given formulae the alkyl, alkoxy or alkanoyl groups
contain 1 to 4 carbon atoms, .beta. is a phenylene radical which is unsubstituted
or substituted with alkyl, alkoxy, -NH2, -SO3H, -NH-CO-COOH or carboxyalkyl-
amino groups, or with fibre-reactive groups,
= a naphthylene radical which is unsubstituted or substituted with
hydroxy, alkoxy or SO3H-groups, or
= -aryl-NH-CO-phenyl, naphthyl-NH-CO-phenyl-CO-NH-phenyl or
<IMG>
C = a phenylene, naphthylene, diphenylenemethane, diphenyleneurea, dinaphthyl-
enemethane or di(p-phenylene-1-pyrazolon-4-yl)urea radical substituted with
alkyl, hydroxyalkyl, H2N-, HO-, HO3S-, HO2C-groups or with fibre-reactive
groups,
= (hydroxynaphthylene -CO-NH)2-L or (hydroxynaphthylene-NH-CONH)2-L, whereby
L = diphenylene or phenylene radical which can be substituted by alkoxy,
alkyl or HO3S-groups,
D = a phenylene radical unsubstituted or substituted with a chlorine atom,
an alkyl, alkoxy, hydroxy or SO3H- group,
96

= a naphthylene radical unsubstituted or substituted with an SO3H-group, or
= a diphenylene or -phenylene-V-phenylene radical unsubstituted or substi-
tuted with a chlorine atom, a nitro, hydroxy, -COOH, -SOH, alkyl, alkoxy
or carboxyalkoxy group, with -V- = -NH-, -O-, -S-, -CH(cyclohexyl)-,
-CH(phenyl)_, -CH(chlorophenyl)-, -CH2-CH2-, -CH2-, -CO-NH-, -NH-CO-NH-,
NH-CS-NH- or -NO=N-, and
E = a phenyl radical unsubstituted or substituted with chlorine atoms, O2N-,
H2N-, N,N-dialkylamino, sulphoalkylamino, phenylamino, benzoylamino, acetyl-
amino, hydroxy, HO2C-, HO3S-, sulphamoyl, alkoxy, alkyl, phenylaminocarbonyl,
phenoxy groups or fibre-reactive groups, or = a naphthyl radical unsubsti-
tuted or substituted with H2N-, O2N-, hydroxy or HO3S-groups or fibre-
reactive groups, and the last coupling can be effected on the fibres.
7. Process according to Claims 5 and 6, wherein coupling or diazo
components are used in which the azo radicals B-N=N-B, C-N=N-D, C-N=N-E,
B-N=N-A, B-N=N-C, B-N=N-E and D-N=N-A have metallisable positions in the
ortho-position with respect to the azo bridge.
8. Process according to Claims 5 and 6, wherein coupling or diazo
components are used in which the azo radicals of the starting materials are
metallised with CT, CO, Ni or Cu.
9. Dyestuffs of the formula
<IMG>
wherein
-X- = -N= or -NO=,
I = a benzene, naphthalene, pyridine or pyrimidine ring of which the nitrogen
atoms are in the 4- or 6-position with respect to the triazole nucleus,
J = the atoms necessary to form a 5- or 6-membered aromatic or heterocyclic
97

ring optionally containing an aromatic or alicyclic ring bound by condensa-
tion,
K1 and K2 = radicals of coupling components of the aromatic or heterocyclic
series, or of azo dyestuffs having at least one position capable of coupling,
whereby they can be identical or different, and whereby,
I and J are unsubstituted or substituted with water-solubilising groups and
alkyl, hydroxy, alkoxy, aryloxy, alkanoyl, aroyl, alkyl or arylsulphonyl,
alkanoylamino, unsubstituted or N-substituted carbamoyl or sulphamoyl, al-
koxycarbonyl, alkoxysulphonyl, nitro, cyano or trifluoromethyl groups, and
all above mentioned alkyl, alkoxy or alkanoyl groups contain 1 to 4 carbon
atoms.
10. Dyestuffs according to Claim 9, of the formula
<IMG>
wherein K1 and K2 have the meanings given in Claim 9 I' and J' can be substi-
tuted with chlorine or bromine atoms, -OH, -SO3H, -COOH, methyl, ethyl, me-
thoxy, ethoxy, phenoxy, .beta.-hydroxyethyl, hydroxymethoxy, carboxymethoxy,
acetyl, benzoyl, methyl or ethylsulphonyl, acetylamino, methoxy or ethoxycar-
bonyl, nitro, cyano, trifluoromethyl groups or groups of the formula
<IMG>
whereby
-Y- = the -CO- or -SO2-bridge,
R1 - a hydrogen atom, an alkyl or hydroxyalkyl group,
R2 = a cyclohexyl, phenyl, benzyl, benzoyl or phenylsulphonyl group, or has
one of the meanings given for R1, and the phenyl ring of the above mentioned
benzyl, phenyl, benzoyl or phenylsulphonyl groups can be substituted with-
chlorine or bromine atoms, or with an alkyl group having 1 to 4 carbon atoms.
11. Dyestuffs according to Claim 9, of the formula
98

<IMG>
wherein K1 and K2 have the meanings given in Claim 9, and I' and J' have
the meanings given in Claim 10.
12. Dyestuffs according to Claim 9 of the formula
<IMG>
wherein I' and J' have the meanings given in Claim 10, and wherein A1 and
A2 can represent identical or different radicals:
a) a phenyl, alkylphenyl or naphthyl radical which is substituted
with at least one halogen atom or a -COOH, -SO3H, hydroxy, alkoxy, -NO2,
-NH2, N-alkyl, N-aryl or N,N-dialkylamino, alkanoylamino, -NH-CO-COOH,
arylsulphonyloxy group, or with an alkylamino group containing a -COOH,
-SO3H or hydroxy group, or with a fibre-reactive group,
b) a naphthyl radical which is substltuted with a phenylamino,
naphthylamino, benzoylamino, phenylsulphonylamino, (p- or m-benzoylamino)-
benzoylamino, -NH-CO-NH2 or -NH-CO-NH-aryl group, which can carry a fibre-
reactive radical, or bound by condensation to a bivalent radical of the
formula
<IMG>
whereby -U- = -S- or -NH- and the mentioned phenylamino, benzoylamino or
phenylsulphonylamino groups can carry on the phenyl nucleus -OH, -NH2, -COOH,
alkyl or alkoxy groups,
c) a radical of the formula
99

<IMG>
whereby Z is a hydrogen atom or an -NH2, -NO2, SO3H- or aminophenylcarbon-
amide group, or a fibre-reactive group; or of the formula
<IMG>
whereby Z; is a hydrogen or chlorine atom or an NH2, -SO3H, alkyl, hydroxy
or COOH-group or a fibre reactive group; or of the formula
<IMG>
whereby n is 1 or 2; or of the formula
<IMG> or <IMG>
whereby Y' san be substituted by an SO3H-group; or of the formula
<IMG>
whereby in the above given formulae the alkyl, alkoxy or alkanoyl groups
contain 1 to 4 carbon atoms.
13. Dyestuffs according to Claim 9 of the formula
<IMG>
100

wherein I' and J' can be substituted with chlorine or bromine atoms, -OH,
-SO3H, -COOH, methyl, ethyl, methoxy, ethoxy, phenoxy, .beta.-hydroxyethyl, hy-
droxymethoxy, carboxymethoxy, acetyl, benzoyl, methyl or ethylsulphonyl,
acetylamino, methoxy or ethoxycarbonyl, nitro, cyano, trifluoromethyl
groups or groups of the formula
<IMG>
whereby
-Y- = the -CO- or -SO2-bridge,
R1 = a hydrogen atom, an alkyl or hydroxyalkyl group,
R2 = a cyclohexyl, phenyl, benzyl, benzoyl or phenylsulphonyl group, or has
one of the meanings given for R1, and the phenyl ring of the above mentioned
benzyl, phenyl, benzoyl or phenylsulphonyl groups can be substituted with
chlorine or bromine atoms, or with an alkyl group having 1 to 4 carbon atoms,
and A1 and A2 can represent identical or different radicals:
a) a phenyl, alkylphenyl or naphthyl radical which is substituted
with at least one halogen atom or a -COOH, -SO3H, hydroxy, alkoxy, -NO2,
-NH2, N-alkyl, N-aryl or N,N-dialkylamino, alkanoylamino, -NH-CO-COOH,
arylsulphonyloxy group, or with an alkylamino group containing a -COOH,
-SO3H or hydroxy group, or with a fibre-reactive group,
b) a naphthyl radical which is substituted with a phenylamino,
naphthylamino, benzoylamino, phenylsulphonylamino, (p or m-benzoylamino)-
benzoylamino, -NH-CO-NH2 or -NH-CO-NH-aryl group, which can carry a fibre-
reactive radical, or bound by condensation to a bivalent radical of the
formula
<IMG> or <IMG>
whereby -U- = -S- or -NH- and the mentioned phenylamino, benzoylamino or
phenylsulphonylamino groups can carry on the phenyl nucleus -OH, -NH2,
101

-COOH, alkyl or alkoxy groups,
c) a radical of the formula
<IMG>
whereby Z is a hydrogen atom or an -NH2, -NO2, SO3H- or aminophenylcar-
bonamide group, or a fibre-reactive group; or of the formula
<IMG>
whereby Z' is a hydrogen or chlorine atom or an -NH2, -SO3H, alkyl, hydroxy
or COOH-group or a fibre reactive group; or of the formula
<IMG>
whereby n is 1 or 2; or of the formula
<IMG> or <IMG>
whereby Y' can be substituted by an SO3H-group; or of the formula
<IMG>
whereby in the above given formulae the alkyl, alkoxy or alkanoyl groups
contain 1 to 4 carbon atoms, and wherein
B = a phenylene radical which is unsubstituted or substituted with alkyl,
alkoxy, -NH2, -SO3H, -NH-CO-COOH or carboxyalkylamino groups, or with fibre-
reactive groups, or
= a naphthylene radical which is unsubstituted or substituted with hydroxy,
102

alkoxy or SO3H-groups, or
= -aryl-NH-CO-phenyl, naphthyl-NH-CO-phenyl-CO-NH-phenyl or
<IMG>
whereby the azo dyestuff radical -B-N=N-A2 can be metallised with Cr, Co, Ni
or Cu.
14. Dyestuffs according to Claim 9 of the formula
<IMG>
wherein I' and J' can be substituted with chlorine or bromine atoms, -OH,
-SO3H, -COOH, methyl, ethyl, methoxy, ethoxy, phenoxy, .beta.-hydroxyethyl, hy-
droxymethoxy, carboxymethoxy, acetyl, benzoylm methyl or ethylsulphonyl, ace-
tylamino, methoxy or ethoxycarbonyl, nitro, cyano, trifluoromethyl groups
or groups of the formula
<IMG>
whereby
-Y- = the -CO- or -SO2-bridge,
R1 = a hydrogen atom, an alkyl or hydroxyalkyl group,
R2 = a cyclohexyl, phenyl, benzyl, benzoyl or phenylsulphonyl group, or has
one of the meanings given for R1, and the phenyl ring of the above mentioned
benzyl, phenyl, benzoyl or phenylsulphonyl groups can be substituted with
chlorine or bromine atoms, or with an alkyl group having 1 to 4 carbon atoms,
A1 as a phenyl, alkylphenyl or naphthyl radical which is substituted
with at least one halogen atom or a -COOH, -SO3H, hydroxy, alkoxy, -NO2,
-NH2, N-alkyl, N-aryl or N,N-dialkylamino, alkanoylamino, -NH-CO-COOH, aryl-
sulpnonyloxy group, or with an alkylamino group containing a -COOH, -SO3H
103

or hydroxy group, or with a fibre-reactive group,
a naphthyl radical which is substituted with a phenylamino, naph-
thylaminoa benzoylamino, phenylsulphonylamino, (p- or m-benzoylamino)-
benzoylamino, -NH-CO-NH2 or -NH-CO-NH-aryl group, which can carry a fibre-
reactive radical, or bound by condensation to a bivalent radical of the
formula
<IMG> or <IMG>
whereby the mentioned phenylamino, benzoylamino or
phenylsulphonylamino groups can carry on the phenyl nucleus -OH, -NH2,
COOH, alkyl or alkoxy groups,
a radical of the formula
<IMG>
whereby Z is a hydrogen atom or an -NH2, -NO2, SO3H- or aminophenylcarbona-
mide group, or a fibre-reactive group; or of the formula
<IMG>
whereby Z; is a hydrogen or chlorine atom or an -NH2, -SO3H, alkyl, hydroxy
or COOH-group or a fibre reactive group; or of the formula
<IMG>
whereby n is 1 or 2; or of the formula
<IMG> or <IMG>
104

whereby Y' can be substituted by an SO3H-group; or of the formula
<IMG>
whereby in the above given formulae the alkyl, alkoxy or alkanoyl groups
contain 1 to 4 carbon atoms, B is a phenylene radical which is unsubstituted
or substituted with alkyl, alkoxy, -NH2, -SO3H, -NH-CO-COOH or carboxyalkyl-
amino groups, or with fibre-reactive groups, or
= a naphthylene radical which is unsubstituted or substituted with hydroxy,
alkoxy or SO3H-groups, or
= -aryl-NH-CO-phenyl, naphthyl-NH-CO-phenyl-CO-NH-phenyl or
<IMG>
whereby C is a phenylene, naphthylene, diphenylenemethane, diphenyleneurea, di-
naphthylenemethane or di(p- phenylene-1-pyrazolon-4-yl)urea radical substitu-
ted with alkyl, hydroxyalkyl, H2N-, HO, HO3S-, HO2C-groups or fibre-reactive
groups,
= (-hydroxynaphthylene-CO-NH)2-L, or (-hydroxynaphthylene-NH-CO-NH)2-L, whereby
L = a diphenylene or a phenylene radical which can be substituted by alkoxy,
alkyl or HO3S-groups,
E = a phenylene radical unsubstituted or substituted with chlorine atoms, 02N-,
H2N-, N,N-dialkylaminoJ sulphoalkylamino, phenylamino, benzoylamino, acetyl-
amino, hydroxy, HO2C-, HO3S-, sulphamoyl, alkoxy, alkyl, phenylaminocarbonyl,
phenoxy groups or fibre-reactive groups, or
= a naphthyl radical unsubstltuted or substituted with H2N-, O2N-, hydroxy
or HO3S-groups or fibre-reactive groups, whereby the mentioned phenylamino and
phenylaminocarbonyl groups can carry on the phenyl nucleus HO2C-, hydroxy or
alkyl groups, all alkyl and alkoxy groups contain 1 to 4 carbon atoms, and
the azo dyestuff radical C-N=N-E can be metallised with Cr, Co, Ni or Cu,
105

15. Dyestuffs according to claim 9 of the formula
<IMG>
wherein I' and J' can be substituted with chlorine or bromine atoms, -OH,
-SO3H-, -COOH, methyl, ethyl, methoxy, ethoxy, phenoxy, .beta.-hydroxyethyl,
hydroxymethoxy, carboxymethoxy, acetyl, benzoyl, methyl or ethylsulphonyl,
acetylamino, methoxy or ethoxycarbonyl, nitro, cyano, trifluoromethyl
groups or groups
106

of the formula
<IMG>
whereby
-Y- = the -CO- or -SO2-bridge,
R1 = a hydrogen atom, an alkyl or hydroxyalkyl group,
R2 = a cyclohexyl, phenyl, benzyl, benzoyl or phenylsulphonyl group, or has
one of the meanings given for R1, and the phenyl ring of the above mentioned
benzyl, phenyl, benzoyl or phenylsulphonyl groups can be substituted with
chlorine or bromine atoms, or with an alkyl group having 1 to 4 carbon atoms,
and A1 is a phenyl, alkylphenyl or naphthyl radical which is substituted
with at least one halogen atom or a -COOH9 -SO3H, hydroxy, alkoxy, -NO2,
-NH2, N-alkyl, N-aryl or N,N-dialkylamino, alkanoylamino, -NH-CO-COOH, aryl-
sulphonyloxy group, or with an alkylamino group containing a -COOH, -SO3H
or hydroxy group, or with a fibre-reactive group,
a naphthyl radical which is substituted with a phenylamino, naph-
thylamino, benzoylamino, phenylsulphonylamino, (p- or m-benzoylamino)-ben-
zoylamino, -NH-CO-NH2 or NH-CO-NH-aryl group, which can carry a fibre-reac-
tive radical, or bound by condensation to a bivalent radical of the formula
<IMG>
whereby the mentioned phenylamino, benzoylamino or
phenylsulphonylamino groups can carry on the phenyl nucleus -OH, -NH2,
-COOH, alkyl or alkoxy groups,
a radical of the formula
<IMG>
whereby Z is a hydrogen atom or an -NH2, -NO2, SO3H- or aminophenylcarbonamide
107

group, or a fibre-reactive group; or of the formula
<IMG>
whereby Z1 is a hydrogen or chlorine atom or an -NH2, -SO3H, alkyl, hydroxy
or COOH-group or a fibre reactive group; or of the formula
<IMG>
whereby n is 1 or 2; or of the formula
<IMG> or <IMG>
whereby Y' can be substituted by an SO3H-group; or of the formula
<IMG>
whereby in the above given formulae the alkyl, alkoxy or alkanoyl groups
contain 1 to 4 carbon atoms, and A3 denotes a diazo component corresponding
to one of the following formulae:
-B1-N=N-B2-N=N-A2
-B-N=N-C-N=N-E,
-C-N=N-B-N=N-E or
-C-N=N-D-N=N-A2
wherein A2 is identical or different from A1 and is a phenyl, alkylphenyl or
naphthyl radical which is substituted with at least one halogen atom or a
-COOH, -SO3H, hydroxy, alkoxy, -NO2, -NH2, N-alkyl, N-aryl, or N,N-dialkyl-
amino, alkanoylamino, -NH-CO-COOH, arylsulphonyloxy group, or with an alkyl-
amino group containing a -COOH, -SO3H or hydroxy group, or with a fibre-
reactive group,
108

a naphthyl radical which is substituted with a phenylamino,
naphthylamino, benzoylamino, phenylsulphonylamino, (p- or m-benzoylamino)-
behzoylamino, -NH-CO-NH2 or -NH-CO-NH-aryl group, which can carry a fibre-
reactive radical, or bound by condensation to a bivalent radical of the
formula
<IMG> or <IMG>
whereby the mentioned phenylamino, benzoylamino or
phenylsulphonylamino groups can carry on the phenyl nucleus -OH, -NH2, -COOH,
alkyl or alkoxy groups,
a radical of the formula
<IMG>
whereby Z is a hydrogen atom or an -NH2, -NO2, SO3H- or aminophenylcarbona-
mide group, or a fibre-reactive group; or of the formula
<IMG>
whereby Z' is a hydrogen or chlorine atom or an -NH2, -SO3H, alkyl, hydroxy
or COOH-group or a fibre reactive group; or of the formula
<IMG>
whereby n is 1 or 2, or of the formula
<IMG> or <IMG>
109

whereby Y' can be substituted by an SO3H-group; or of the formula
<IMG>
whereby in the above given formulae the alkyl, alkoxy or alkanoyl groups
contain 1 to 4 carbon atoms, B is a phenylene radical which is unsubstituted
or substituted with alkyl, alkoxy, -NH2, -SO3H, -NH-CO-COOH or carboxyalkyl-
amino groups, or with fibre-reactive groups, or a naphthylene radical which
is unsubstituted or substituted with hydroxy, alkoxy or SO3H-groups, or
-aryl-NH-CO-phenyl, naphthyl-NH-CO-phenyl-CO-NH-phenyl, or
<IMG>
whereby the azo dyestuff radical A3 can be metallised with Cr, Co,
Nl or Cu, C is a phenylene, naphthylene, diphenylenemethane, diphenyleneurea,
dinaphthylenemethane or di(p-phenylene-1-pyrazolon-4-yl)urea radical substitut-
ed with alkyl, hydroxyalkyl, H2N-, HO-, HO3S, HO2C-groups or fibre-reactive
groups, (-hydroxynaphthylene-CO-NH)2-L, or (-hydroxynaphthylene-NH-CO-NH)2-L,
whereby L= a diphenylene or a phenylene radical which can be substituted by
alkoxy, alkyl or HO3S-groups, E = a phenylene radical unsubstituted or sub-
stituted with chlorine atoms, O2N-, H2N, N,N-dialkylamino, sulphoalkylamino,
phenylamino, benzoylamino, acetylamino, hydroxy, HO2C-, HO3S-, sulphamoyl,
alkoxy, alkyl, phenylaminocarbonyl, phenoxy groups or fibre-reactive groups;
or a naphthyl radical unsubstituted or substituted with H2N-, O2N-, hydroxy
or HO3S-groups or fibre-reactive groups, whereby the mentioned phenylamino
and phenylaminocarbonyl groups can carry on the phenyl nucleus ho2C-, hydroxy
or alkyl groups, all alkyl and alkoxy groups contain 1 to 4 carbon atoms,
whereby B1 and B2 each have one of the meanings given for B, and wherein D =
a phenylene radical unsubstituted or substituted with a chlorine atom, an
110

alkyl, alkoxy, hydroxy or SO3H-group, a naphthylene radical unsubstituted or
substituted with an SO3H-group, or a diphenylene or phenylene-V-phenylene
radical unsubstituted or substituted with a chlorine atom, a nitro, hydroxy,
-COOH-, -SO3H, aIkyl, alkoxy or carboxyaIkoxy group, with -V- = -NH, -O-,
-S-, -CH(cyclohexyl)-, -CH(phenyl)-, -CH(chlorophenyl)-, -CH2-CH2-, -CH2-,
-CO-NH-, -NH-CO-NH-, NH-CS-NH- or -NO=N.
16. Dyestuffs according to claim 9 of the formula
<IMG>
wherein I' and J' can be substituted with chlorine or bromine atoms, -OH,
-SO3H, -COOH, methyl, ethyl, methoxy, ethoxy, phenoxy, .beta.-hydroxyethyl, hydroxy-
methoxy, carboxymethoxy, acetyl, benzoyl, methyl or ethyl sulphonyl, acetylamino,
methoxy or ethoxycarbonyl, nitro, cyano, trifluoromethyl groups or groups of
the formula
<IMG>
whereby Y- = the -CO- or -SO2-bridge, R1 = a hydrogen atom, an alkyl or
hydroxyalkyl group, R2 = a cyclohexyl, phenyl, benzyl, benzoyl or phenylsul-
phonyl group, or has one of the meanings given for R1, and the phenyl ring
of the above mentioned benzyl, phenyl, benzoyl or phenylsulphonyl groups can
be substituted with chlorine or bromine atoms, or with an alkyl group having
1 to 4 carbon atoms, wherein A4 and A5 which can be identical or different,
represent monoazo components which correspond to one of the formulae -B-N=N-A1
or C-N=N-E, whereby A1 is a phenyl, alkylphenyl or naphthyl radical which is
substituted with at least one halogen atom or a -COOH, -SO3H, hydroxy, alkoxy,
-NO2, -NH2, N-alkyl, N-aryl or N,N-dialkylamino, alkanoylamino, -NH-CO-COOH,
arylsulphonyloxy group, or with an alkylamino group containing a -COOH, -SO3H
or hydroxy group, or with a fibre-reactive group, a naphthyl radical which is
substituted with a phenylamino, naphthylamino, benzoylamino, phenylsulphonyl-
amino, (p- or m-benzoylamino)-benzoylamino, -NH-CO-NH2 or -NH-CO-NH-aryl group,
which can carry a fibre-reactive radical, or bound by condensation to a bi-
111

valent radical of the formula
<IMG> or <IMG>
whereby -U- = -S- or -NH- and the mentioned phenylamino, benzoylamino or phenyl-sulphonylamino groups can carry on the phenyl nucleus -OH, -NH2, -COOH, alkyl
or alkoxy groups, a radical of the formula
<IMG>
whereby Z is a hydrogen atom or an -NH2, -NO2, SO3H- or aminophenylcarbonamide
group, or a fibre-reactive group; or of the formula
<IMG>
whereby Z' is a hydrogen or chlorine atom or an -NH2, -SO3H, alkyl, hydroxy
or COOH-group or a fibre reactive group; or of the formula
<IMG>
whereby n is 1 or 2; or of the formula
<IMG> or <IMG>
whereby Y' can be substituted by an SO3H-group; or of the formula
112

<IMG>
whereby in the above given formulae the alkyl, alkoxy or alkanoyl groups
contain 1 to 4 carbon atoms, B is a phenylene radical which is unsubstituted or
substituted with alkyl, alkoxy, -NH2, -SO3H, -NH-CO-COOH or carboxyalkylamino
groups, or with fibre-reactive groups, or a naphthylene radical which is
unsubstituted or substituted with hydroxy, alkoxy or SO3H-groups, or -aryl-
NH-CO-phenyl, naphthyl-NH-CO-phenyl-CO-NH-phenyl or
<IMG>
whereby the azo dyestuff radical <IMG> can be metallised with Cr, CO,
Ni or Cu, C is a phenylene, naphyhylene, diphenylenemethane, diphenyleneurea,
dinaphthylenemethane or di(p-phenylene-1-pyrazolon-4-yl)urea radical
substituted with alkyl, hydroxyalkyl, H2N-, HO-, HO3S-, HO2C-groups or fibre-
reactive groups, (-hydroxynaphthylene-CO-NH)2-L, or (-hydroxynaphthyIene-NH-CO-
NH)2-L, whereby L = a diphenylene or a phenylene radical which can be
substituted by alkoxy, alkyl or HO3S-groups, E= a phenylene radical unsubstituted
or substituted with chlorine atoms, O2N-, H2N-, N,N-dialkylamino, sulpho-
alkylamino, phenylamino, benzoylamino, acetylamine, hydroxy, HO2C-, HO3S-,
sulphamoyl, alkoxy, alkyl, phenylaminocarbonyl, phenoxy groups or fibre-
reactive groups, or a naphthyl radical unsubstituted or substituted with H2N-,
O2N-, hydroxy or HO3S-groups or fibre-reactive groups, whereby the mentioned
phenylamino and phenylaminocarbonyl groups can carry on the phenyl nucleus
HO2C-, hydroxy or alkyl groups, all alkyl and alkoxy groups contain 1 to 4
carbon atoms, and the azo dyestuff radical C-N=N-E can be metallised with
Cr, Co, Ni or Cu.
113

17. Dyestuffs according to claim 12, of the formula
<IMG>
wherein I' and J' can be substituted with chlorine or bromine atoms, -OH, -SO3H,
-COOH, methyl, ethyl, methoxy, ethoxy, phenoxy, .beta.-hydroxyethyl, hydroxymethoxy,
carboxymethoxy, acetyl, benzoyl, methyl or ethylsulphonyl, acetylamino,
methoxy, or ethoxycarbonyl, nitro, cyano, trifluoromethyl groups or groups
of the formula
<IMG>
whereby -Y- = the -CO- or -SO2-bridge, R1 = a hydrogen atom, an alkyl or
hydroxyalkyl group, R2 = a cyclohexyl, phenyl, benzyl, benzoyl or phenyl-
sulphonyl group, or has one of the meanings given for R1, and the phenyl
ring of the above mentioned benzyl, phenyl, benzoyl or phenylsulphonyl
groups can be substituted with chlorine or bromine atoms, or with an
alkyl group having 1 to 4 carbon atoms wherein A? and A? = a) a
naphthyl radical carrying at least one HO- or H2N-group, which can be substituted
with further HO-, H2N-, HO3S- or carboxy groups or with chlorine atoms, or
b) a phenyl radical carrying at least one HO- or H2N-group, which can
be substituted with further HO-, H2N-, HO3S- carboxy, nitro, -NHCOCOOH, methyl,
methoxy, ethoxy, phenyl or tolylsulphonyloxy, acetylamino, phenyl or tolylamino,
carboxyalkylamino, N-mono- or N,N-dialkylamino groups, or c) a naphthyl radical
substituted with a carboxyalkylamino, alkylamino or arylamino group, or d) a
hydroxynaphthyl radical carrying at least one sulpho group, which is
substituted with alkylamino, carboxylalkylamino, acetylamino, benzoylamino,
phenyl or tolylsulphonylamino or phenylamlno groups, which can carry on
the phenyl nucleus methyl, methoxy, carboxy or HO-groups, or e) a 3-methyl-,
3-carboxy- or 3-carboxyethoxy-1-phenyl- or -1-sulphonaphthyl-5-pyrazolone
radical, or a 5-amino-3-methyl-1-phenyl-2-pyrazoline radical, which can carry
on the phenyl nucleus -SO3H, HO-, nitro, carboxy or methyl groups or chlorine
atoms.
114

18. Dyestuffs according to claim 13, of the formula
<IMG>
wherein I' and J' can be substituted with chlorine or bromine atoms, -OH, -SO3H,
-COOH, methyl, ethyl, methoxy, ethoxy, phenoxy, .beta.-hydroxyethyl, hydroxymethoxy,
carboxymethoxy, acetyl, benzoyl, methyl or ethylsulphonyl, acetylamino,
methoxy or ethoxycarbonyl, nitro, cyano, trifluoromethyl groups or groups of
the formula
<IMG>
wherein -Y- = the -CO- or -SO2-bridge, R1 = a hydrogen atom, an alkyl or
hydroxyalkyl group, R2 = a cyclohexyl, phenyl, benzyl, benzoyl or phenyl-
sulphonyl group, or has one of the meanlngs given for R1, and the phenyl
ring of the above mentioned benzyl, phenyl, benzoyl or phenylsulphonyl
groups can be substituted with chlerine or bromine atoms, or with an alkyl
group having 1 to 4 carbon atoms and wherein A1 and A2 = a phenyl radical
carrying at least one HO- or H2N-group, which can be substituted with
further HO-, H2N-, HO3S-, carboxy, methyl, methoxy or carboxymethylamino
groups, a naphthyl radical carrying at least one HO- or H2N-group, which can
be substituted with further HO-, H2N-, HO3S- or phenylamino groups, carboxy,
methyl, methoxy or carboxymethylamino groups, whereby they can be identical
or different, B' = a phenylene radical substituted with methyl, methoxy or
NH-CO-COOH-groups, or a naphthylene radical which can be substituted with
HO- or HO3S-groups.
19. Dyestuffs according to claim 14 of the formula
<IMG>
115

wherein I' and J' can be substituted with chlorine or bromine atoms, -OH,
-SO3H, -COOH, methyl, ethyl, methoxy, ethoxy, phenoxy, .beta.-hydroxyethyl,
hydroxymethoxy, carboxymethoxy, acetyl, benzoyl, methyl or ethylsulphonyl,
acetylamino, methoxy or ethoxycarbonyl, nitro, cyano, trifluoromethyl groups
or groups of the formula
<IMG>
whereby -Y- = the -CO- or -SO2-bridge, R1 - a hydrogen atom, an alkyl or
hydroxyalkyl group, R2 = a cyclohexyl, phenyl, benzyl, benzoyl or phenyl
sulphonyl group, or has one of the meanings given for R1, and the phenyl ring
of the above mentioned benzyl, phenyl, benzoyl or phenylsulphonyl groups can
be substituted with chlorine or bromine atoms, or with an alkyl group having
1 to 4 carbon atoms, wherein A" is a naphthyl radical carrying at least one
HO- or H2N-group, which can be substituted with further HO-, H2N- HO3S or
carboxy groups or with chlorine atoms, or a phenyl radical carrying at least
one HO- or H2N-group, which can be substituted with further HO-, H2N-, HO3S-,
carboxy, nitro, NHCOCOOH, methyl, methoxy, ethoxy, phenyl or tolylsulphonyloxy,
acetylamino, phenyl or tolylamino, carboxyalkylamino, N-mono- or N, N-
dialkylamino groups, C' = a phenylene or naphthylene radical carrying at least
one HO- or H2N-group, which can be substituted with further HO- H2N-, HO3S-
or methyl groups, and E' = a phenyl radical which can carry HO3S-, HO-, H2N-,
carboxy, nitro, methyl, acetylamino or sulphamoyl groups or chlorine atoms,
whereby the azo dyestuff radical -C'-N=N-E' can be metallised with Cr, Co, Ni
and Cu.
20. Dyestuffs according to claim 16 of the formula
<IMG>
wherein I' and J' can be substituted with chlorine or bromine atoms, -OH, -SO3H,
-COOH, methyl, ethyl, methoxy, ethoxy, phenoxy, .beta.-hydroxyethyl, hydroxymethoxy,
carboxymethoxy, acetyl, benzoyl, methyl or ethylsulphonyl, acetylamino,
116

methoxy or ethoxycarhonyl, nitro, cyano, trifluoromethyl groups or groups of
the formula
<IMG>
whereby -Y- = the -CO- or -SO2-bridge, R1= a hydrogen atom, an alkyl or
hydroxyalkyl group, R2 = a cyclohexyl, phenyl, benzyl, benzoyl or phenyl-
sulphonyl group, or has one of the meanings given for R1, and the phenyl ring
of the above mentioned benzyl, phenyl, benzoyl or phenylsulphonyl groups can
be substituted with chlorine or bromine atoms, or with an alkyl group having
1 to 4 carbon atoms, wherein A? and A? = -B'-N=N-A? or -C'-N-N=E" and can be
identical or different, whereby B' and A? have the meanings given in claim 18,
and C' and E' the meanings given in claim 19.
21. Dyestuffs according to claim 12 of the formula
<IMG>
wherein J" carries, in the o-position to the azo bridge, a metallisable HO-,
carboxy, methoxy, ethoxy, hydroxymethoxy or carboxymethoxy group, and K? a
metallisable HO-, H2N-, methoxy or -NHCOCOOH, in the o-position to the azo
bridge, I' can be substituted with chlorine or bromine atoms, -OH, -SO3H,
-COOH, methyl, ethyl, methoxy, ethoxy, phenoxy, .beta.-hydroxyethyl, hydroxymethoxy,
carboxymethoxy, acetyl, benzoyl, methyl or ethylsulphonyl, acetylamino, methoxy
or ethoxycarbonyl, nitro, cyano, trifluoromethyl groups or groups of the
formula
<IMG>
whereby -Y- = the CO- or -SO2-bridge, R1 = a hydrogen atom, an alkyl or
hydroxyalkyl group, R2 = a cyclohexyl, phenyl, benzyl, benzoyl or phenyl-
sulphonyl group, or has one o the meanings given for R1, and the phenyl ring
of the above mentioned benzyl, phenyl, benzoyl or phenylsulphonyl groups can be
substituted with chlorine or bromine atoms, or with an alkyl group having 1 to 4
117

carbon atoms, K? is a naphthyl radical carrying at least one HO- or H2N-group,
which can be substituted with further HO-, H2N-, HO3S- or carboxy groups or
with chlorine atoms, or b) a phenyl radical carrying at least one HO- or H2N-
group, which can be substituted with further HO-, H2N-, HO3S-, carboxy, nitro,
-NHCOCOOH, methyl, methoxy, ethoxy, phenyl or tolylsulphonyloxy, acetylamino,
phenyl or tolylamino, carboxyalkylamino, N-mono or N, N-dialkylamino groups,
or c) a naphthyl radical substituted with a carboxyalkylamino, alkylamino or
arylamino group, or d) a hydroxynaphthyl radical carrying at least one sulpho
group, which is substituted with alkylamino, carboxylalkylamino, acetylamino,
benzoylamino, phenyl or tolylsulphonylamino or phenylamino groups, which can
carry on the phenyl nucleus methyl, methoxy, carboxy or HO-groups, or e) a
3-methyl-, 3-carboxy- or 3-carboxyethoxy-1-phenyl- or 1-sulphonaphthyl-5-
pyrazolone radical, or a 5-amino-3-methyl-1-phenyl-2-pyrazoline radical, which
can carry on the phenyl nucleus -SO3H, HO-, nitro, carboxy or methyl groups or
chlorine atoms, for -B'-N=N-A? where A? is a phenyl radical carrying at least
one HO- or H2N-group, which can be substituted with further HO-, H2N-, HO3S-,
carboxy, methyl, methoxy, or carboxymethylamino groups, a naphthyl radical
carrying at least one HO- or H2N-group, which can be substituted with further
HO-, H2N-, HO3S- or phenylamino groups, carboxy, methyl, methoxy or carboxy-
me-thylamino groups, whereby they can be identical or different, and B' is a
phenylene radical substituted with methyl, methoxy or NH-CO-COOH-groups, or a
naphthylene radical which can be substituted with HO- or HO3S-groups, where
J" can be substituted with chlorine or bromine atoms, -OH, -SO3H, -COOH, methyl,
ethyl, methoxy, ethoxy, phenoxy, .beta.-hydroxyethyl, hydroxymethoxy, carboxymethoxy,
acetyl, benzoyl, methyl or ethylsulphonyl, acetylamino, methoxy, or ethoxy-
carbonyl, nitro, cyano, trifluoromethyl groups or groups of the formula
<IMG>
whereby -Y- = the -CO- or -SO2-bridge, R1 = a hydrogen atom, an alkyl or
hydroxyalkyl group, R2 = a cyclohexyl, phenyl, benzyl, benzoyl or phenyl-
sulphonyl group, or has one of the meanings given for Rl, and the phenyl ring
118

of the above mentioned benzyl, phenyl, benzoyl or phenylsulphonyl groups can
be substituted with chlorine or bromine atoms, or with an alkyl group having
1 to 4 carbon atoms, K? is a naphthyl radical carrying at least one HO- or
H2N-group, which can be substituted with further HO-, H2N-, HO3S- or carboxy
groups or with chlorine atoms, or a phenyl radical carrying at least one HO-
or H2N-group, which can be substituted with further HO-, H2N- HO3S- carboxy,
nitro, -NHCOCOOH, methyl, methoxy, ethoxy, phenyl or tolylsulphonyloxy,
acetylamino, phenyl or tolylamino, carboxyalkylamino, N-mono- or N, N-
dialkylamino groups, a hydroxynaphthyl radical carrying at least one sulpho
group, which is substituted with alkylamino, carboxylalkylamino, acetylamino,
benzoylamino, phenyl or tolylsulphonylamino or phenylamino groups, which can
carry on the phenyl nucleus methyl, methoxy, carboxy or HO-groups, or a
3-methyl-, 3-carboxy- or 3-carboxyethoxy-1-phenyl- or -1-sulphonaphthyl-5-pyr-
azolone radical, or a 5-amino-3-methyl-1-phenyl-2-pyrazoline radical, which
can carry on the phenyl nucleus -SO3H, HO-, nitro, carboxy or methyl groups
or chlorine atoms or represents a radical of the formula
<IMG>
whereby n is 1 or 2, and A? is a phenyl radical carrying at least one HO- or
H2N- group, which can be substituted with further HO-, H2N-, HO3S-, carboxy,
methyl, methoxy or carboxymethylamino groups, a naphthyl radical carrying at
least one HO- or H2N-group, which can be substituted with further HO-, H2N-,
HO3S- or phenylamino groups, carboxy, methyl, methoxy or carboxymethylamino
groups, whereby they can be identical or different and C' is a phenylene or
naphthylene radical carrying at least one HO- or H2N-group, which can be
substituted with further HO-, H2N-, HO3S- or methyl groups and E' is a phenyl
radical which can carry HO3S-, HO-, H2N-, carboxy, nitro, methyl, acetylamino
or sulphamoyl groups or chlorine atoms, whereby the azo dyestuff radical
-C'-N=N-E' can be metallised with Cr, Co, Ni and Cu and metal complexes of
the said dyestuffs.
22. Dyestuffs according to claim 12 of the formula
119

<IMG>
wherein I" carries a metallisable HO-, carboxy, methoxy, ethoxy, hydroxymethoxy,
or carboxymethoxy group in the o-position with respect to the azo bridge,
J' can be substituted with chlorine or bromine atoms, -OH, -SO3H, -COOH, methyl,
ethyl, methoxy, ethoxy, phenoxy, .beta.-hydroxyethyl, hydroxymethoxy, carboxymethoxy,
acetyl, benzoyl, methyl or ethylsulphonyl, acetylamino, methoxy or ethoxycar-
bonyl, nitro, cyano, trifluoromethyl groups or groups of the formula
<IMG>
whereby -Y- = the -CO- or -SO2-bridge, R1 = a hydrogen atom, an alkyl or
hydroxyalkyl group, R2 = a cyclohexyl, phenyl, benzyl, benzoyl or phenyl-
sulphonyl group, or has one of the meanings given for R1, and the phenyl
ring of the above mentioned benzyl, phenyl, benzoyl or phenylsulphonyl groups
can be substituted with chlorine or bromine atoms, or with an alkyl group
having 1 to 4 carbon atoms, K? and K? have the meanings given in claim 21,
I" can be substituted with chlorine or bromine atoms, -OH, -SO3H, -COOH,
methyl, ethyl, methoxy, ethoxy, phenoxy, .beta.-hydroxyethyl, hydroxymethoxy, carboxy-
methoxy, acetyl, benzoyl, methyl or ethylsulphonyl, acetylamino, methoxy or
ethoxycarbonyl, nitro, cyano, trifluoromethyl groups or groups of the formula
<IMG>
whereby -Y- = the -CO- or -SO2-bridge, R1 = a hydrogen atom, an alkyl or
hydroxyalkyl group, R2 = a cyclohexyl, phenyl, benzyl, benzoyl or phenyl-
sulphonyl group, or has one of the meanings given for R1 and the phenyl ring
of the above mentioned benzyl, phenyl, benzoyl, or phenylsulphonyl groups
can be substituted with chlorine or bromine atoms, or with an alkyl group
having 1 to 4 carbon atoms and metal complexes of the said dyestuffs.
120

Description

so~
;; The present invention relates to a proc~ss for
t~e production of ne~ polyazo dyestu~s of the
. gen~ral formula
,. .
Kl - N=N - ------+- I ~ N - 4~ 2 (13
: S wherein
-X- = -N= or -NOa,
.: I = a benzene, naphthalene, pyridine or pyrimidine ring
of which the nitrogen atoms are in the 4- or ;~.
6-position with respect to the triazole nucleus,
J = the atoms necessary to form a 5- or 6-membered .
aromatic or heterocyclic ring optionally containing :~
an aromatic or alicyclic ring bound by condensation, ~ ~-
~ Kl and K2 = radicals of coupling components of the aromatic -~
f or heteroc.yclic series, or of azo dyestuffs having
. . .
- 15 at least one position capable of coupling, T~her~by
they can be identical or diferent, and ~hereby
I and J are unsubstituted, or substituted with water-
.~olubilising groups and with allcyl, hydroxy, alkoxy9
, . .
aryloxy, alkanoyl, aroyl, alkyl or arylsulphonyl, -~
alkanoylamino, unsubstituted or N-substituted carbamoyl
groups, or with sulphamoyl, alkoxycarbonyl, alkoxy-
sulphonyl~ nitro, cyano or trifluoromethyl groups, and
;~ all above-mentioncd a~kyl, alkoxy or alkanoyl groups
contain 1 to 4 c~rbon atoms, ::
, ~ . .
, . . .

~L~495~7
as well as to the compounds of formula (1) and metal complexes thereof, by
~; whatever production process they may be obtainedO
I'he compounds of formula (I) exist in two tautomeric forms in respect
- of the benzotriazole-moiety of the molecule. These two forms are:
' ' ,
;~ ~ N ~ N=N-K2 (I)
and
K -N=N -~ N ~ J
r, ' :,
see Beilstein, Handbuch der organischen Chemie, 4. Aufl., Band 26, Hauptwerk,
page 38~ formulae II and III.
;~ ~
The present process comprises the coupling of a tetrazotised
. diamine of the formula
~';: ' '
_ 2
i -
' " : .
,' .: ';~
with coupling components of the formula KlH and K2H, wherein I, J, X, Kl and
, K2 have the meanings defined under formula (1).
¦ Within the present definition, the disazo compounds corresponding
1~ to the following formula in partiçular are of practical interest, as well
:' as their oxidation products, whereby a nitrogen atom in the 1- or 3~position
i f the triazole ring is replaced by the -NO-bridge, or their metal
complexes:
Al-N=N ~ ~ {~ z
~L-~)
3 -
, .

~495~7
wherein I' and J' can be substituted with chlorine or bromine atoms,
-OH, -SO3H, -COOH, methyl, ethyl, methoxy, ethoxy, phenoxy, ~-hydroxyethyl,
hydroxymethoxy, carboxymethoxy, acetyl, benzoyl, methyl- or ethylsulphonyl, ~
, ', , ,
;~ ~
., . .. :
~
~''':
' '
' ,''~,: ~' '
,~, ~'.
.. . .
.'
.'
., '~- :
: :.
i~ "
:.
' ~; "
.: :
~ 3
. ~ .
, ., ~: , . , .~ , :

ace~yl.ar,lino, me~ho~y or etho~yc~lrbonyl~ n.itro, cyano,
trifluoro~lethyl groups, or groups o:E the formul.a y ~< 1
. wherein R2
~! Y - - - CO - or S02 ,
Rl = a hydrogen atom, an alkyl or hyclroxyalkyl group,
R2 = a cyclohexyl, phenyl, benæyl, benzoyl or phenyl
, . .
. sulphonyl group, or has one of the meanings given
... .
for R.l, and the phenyl ring of the above men-tioned
benzyl, phenyl, benzoyl or phenylsulphonyl groups
can be substltuted with chlorine or bromine atoms
or with an alkyl group containing 1 to 4 carbon atoms,
. .
Al and A2 = a) a phenylg alkylphenyl or naphthyl radical
` substituted with a~ least one halogen a-tom9 or with
:- a -C0011, -S03H~ hydroxy, alkoxy, -N02, -NH2, .
.~ 15 N-alkyl~ N-aryl or N,N-dialkylamino group, or an - ~
.~ alkanoylamino, -NH-C0-COOH or arylsulphonyloxy group, .~.
`'' or with an alkylamino group containing a -COOH,
~: -S03H or hydroxy group, or with a fibre-reac~ive
. .
` group,
.` 20 b) a naphthyl radical which is substituted
with a phenylamino~ naphthylamino, benzoylamino,
::i
phenylsulphonylamino, (p- or m-benzoylamino)-
benzoylamino, ~NH-C0-NH2 or NH-C0-NH-aryl group
which can carry a fibre-reactive radical, or bound
by condensation to a bivalent radical of the formula
-- 4 --

~ 9S~ :
N l~T
whereby -IJ- = -S- or -~1-, and the mentioned
phenylamino, benzoylamino or phenylsulphonylamino
groups can carry on ~he phenyl nucleus -OH,
-~12, -COOI-I, alkyl or alkoxy groups,
c) a radi.cal of the formula
HO
~_ C~
COOH
wher~in Z is a hydrogen atom or an -NH2j -N02, SO3H-
or aminophenylcarbon~mide group, or a fibre-reactive group;
or of the formula
HO
~1 1 ~z i , :
- ~ N . ':
,i . .
~, .
CH~ r -
wherein æ ~ is a hydrogen or chlorine atom~ or an -NH2,
-SO3H, alkyl, hydroxy or COOH group, or a fibre reactive
group; or of the ~ormula
HO
~ - N ~ (SO~H)n
: ~ N . 1 .
., ~ .
3 . .
wherein n is 1 or 2;
,, .
~,

or o~ the formula
OII - ~
wherein Y' can be substituted by an SO31l-group;
or of the ~ormula
H N
~rlN--O , .
CH~ `
.I whereby in the above formulae the alkyl, alkoxy or
. alkanoyl groups contain 1 to 4 carbon atomS~ and Al
and A2 can represent identical or different radicals.
~ Within the present definition, triazole compounds
li 10 corresponding to the following ~ormulae in particular
-~ are of practical interest, as well as their oxidation
products, whereby a nitrogen atom in the 1- Dr 3~position
I o~ the triazole ring is replaced by the =NO-bridge,
.~ or their metal complexes :
.~ .
~ =N ~ ~ ~\ ~ N= ~ - - - (4)
-/ . B-N=N-A2
or
- 6 -
, ~

~0~95~
.. . . . . . . .
A ~ ~ N~N
~ / - C-N=N-~
wherein I', J', Al and A~ have the meanin~s given in the
explanation of formula (3),
B = a phenylene radical which is unsubstituted or
substituted with alkyl, alkoxy, -~2~ S3H~
-NH-CO-COOH or carboxyalkylamino groups, or with
fibre-reactive groups,
= a naphthylene radical which is unsubstituted or
substituted with hydroxy~ alkoxy or S03H-groups, or
-aryl-NHCO-phenyl, naphthyl-~ CO-phenyl-CO-~1-phenyl
or HO
lr I c2 - .
~ ~ N
. _ COOH
C ~ a phenylene, naphthyLene, diphenylenemethane,
diphenyleneurea, dinaphthylenemethane or di(p-
lS pheny1ene-l-pyraæolon-4-yl)urea radical substituted
with alkyl, hydroxyalkyl, H~N-, HO-, H03S-,
H02C-groups or with fibre-reactive groups,
~ (-hydroxynaphthylene-CO-~1)2-L or (-hydroxy-
naphthylene-NH-CO-NH)2-L, whereby
L = a diphenylene radical or a phenylene radical which
can be substituted by alkoxy) alkyl or H03S-groups,
E = a phenyl radical unsubstituted or substituted with
; .
~' , . . .
!
~ ~ ' ", ; ~ , " ' ' ' ' ', '.

`--
S~
chlori.ne atoms, O~N-, lf~N-, N,M dialk~ alino, sulpho-
alkylamino, phenylarll:ino, ben~oylamirlo) acetylamLno,
hydroxy, H02C-, H03S-, sulphamoyl, alkoxy, alkyl,
phenylaminocarbonyl, phenoxy groups or Eibre-
reac~ive groups, or
c a naphthyl radical unsubstit-lted or substituted
with H2N-9 02N-, hydroxy or H03S-groups or fibre- .
reactive groups, whereby the mentioned phenylamino
and phenylaminocarbonyl groups can carry on the
phenyl nucleus H02C-, hydroxy o~ alkyl groups, all
al'~yl and alkoxy groups contain 1 to 4 carbon atoms, ~
~ and the azo dyestuff radicals B-N-N-A2 and -
-C-N=N-E can be metallised with Cr, Co, Ni
. and particularly Guo
Within the present definition, the tetrazo compounds of the
. . ~
^ following formulae in particular are of practical interest, as
.~ well as their oxidation products, whereby a nitrogen atom in
i~ the 1- or 3 position of the triazole ring is replaced by the
=NO-bridge, or their metal complexes:
~ ~ ~ A~ A~ (
,
A~--N=N
. . ~ N/ ~ - N A5 (7)
.. ..... .... .. . . . . . .
. . , i.
wherein A3 = -Bl-N=N-B2-N N A2,.
-B -N=N-C-N=N-E,
-C-N=N-B-N--N-E or ~
-C-N=N-D-N=N-A2 s
-- $ --
,~ .
, . ~.

S~7
and A4 and A5 = -B-NsN-A2 or
. C-N=N-E,
whereby
I', J', Al and A2 have the meanings giver. in the explanation -of formula (3), B, Bl and B2 the meanings given in the
explanation of for~ula (4), C and E the ~,eani.ngs given
in the explanation of ormula (5), and A4 and A5 as
well as Bl and B2 can be identicaL or different, and
D = an unsubstituted phenylene radical, or a phenylene
radical substituted with a chlorine atom, an alkyl,
alkoxyg hydroxy or S03H-group,
a naphthylene radical unsubstituted, or substituted
with an S03H-group, or
diphen~lene- or -phenylene-V-phenylene radical
15. unsubstituted or substituted with a chlorine atom, a
nitro, hydroxy, -COOH, -S03H, alkyl, alkoxy or carboxy-
.
: alkoxy group, wherein -V- = -NH-, -O-, -S-, -CH(cyclo-
hexyl)-, -CH(phenyl)~, -CH(chlorophenyl)-, -CH2-CH2-,
-CH2, -CO-NH-, -NH-CO-~E-, NH-CS-NH- or -NO=N-group.
Particularly valuable disazo dyestuffs are those
of the formula
Al - N-N
(8)
.
. , .: , : . . -
..

5 0 7
wherein Al and A2
a) a naph~hyl radical carrying at least one ~lO- or
H2N-group, which can be substituted with further
HO-, H2N-, H03S or carboxy groups or with
chlorine atoms, or
b) a phenyl radical carrying at least one HO- or
H2N group, which can be substituted with further
HO-, H2N , H03S-, carboxy, nitro, -NHCOCOOH,
methyl, methoxy, ethoxy, phenyl or tolylsulphonyloxy,
acetylamino, phenyl or tolylamino, carboxyalkyl-
amino, N-mono or N,N-dialkylamino groups, or
c) a naphthyl radical substituted with a carboxy-
alkylamino, alkylamino or arylamino group,
or d) a hyd~oxynaphthyl radical carrying at least one
sulpho group, which is substituted with alkylamino,
carboxyalkylamino, acetylamino, benzoylamino,
phenyl or tolylsulphonylamino or phenylamino groups,
which can carry on the phenyl nucleus methyl,
methoxy, carboxy or HO-groups, or
e) a 3-methyl, 3-carboxy or 3-carboxyethoxy-1-phenyl
or -l-sulphonaph~hyl-5-pyrazolone radical, or a
5-amino-3-methyl-1-phenyl-2-pyrazoline radical,
which can carry on the phenyl nucleus -S03H> HO-,
nitro, carboxy or methyl groups or chlorine atoms,
wherein I' and J' can carry the substituents given in the
~ 10 - .

explarlation o :Eormula (3), ~nd whereby ~1 and ~2 can
be identical or di.fferent.
; Particwlarly valuable trisazo dyestu~fs are those
oJ~ the formula
_ _ ~ :
_ -N=N ~ N N = N
A~
or .
_ ~ . -.,
ï -N--N\ N N = N~-- _
N ~ . -C'--N--N-E' (10)
wherein
I' and J' can carry the substituents given in the
e,xplanation of formula (3),
10 A", A"l can 'nave one of the meanings given for Al and
A2 in the explanation of foxmula (8) under
- paragraphs a) and b), or
', = a hydroxy or aminonaphthyl radical carrying a !~ -
phenylamino group, whereby they can be identical
or different,
; B' = a phenylene radical substituted with methyl~
methoxy or NH-CO-COOH-groups, or
= a naphthylene radical which can be substituted ~:
with HO- or HO3S groups,
C' = a phenyl~ne or naphthylene radical carrying at
- - .
,.
, .
'

s~
least one M0- or H2N-group, ~/hlch can be substituted
with furt:her H0-, H2N~, H03S- or methyl. groups,
E' = a phenyL radical which can carry H03S-~ H0-,
H2N-~, carboxy~ nitro, methyl~ acetylamino or
sulphamoyl groups or chlorine a~oms, or
= a naphthyl radical which can carry ~103S-, H0- or
carboxy groups~ whereby the azo dyestuff radicals
-B'-N-N-A2 and C-N=N-E' can be bound in complex
linkage (metallised) with Cr, Co~ Ni and Cu.
Particularly valuable tetrakisazo dyestuffs are those
of the formula
, .. .. . . .
: N
A4---N= ~ N~T_ ~-A5 (11)
wherein A4 and A5 can be ldentical or different, A'2~ -
E', B' and C' have the meanings given in the explanation
of ~ormulae (8) and (9), and I' and J' have the meanings
given in the explanation of formula (3).
Besides the metal-complex dyestuffs mentioned in the
definitions of formulae (4), (5), (9) and (lO), there are
also the particularly valuable ones obtained by the
metallisation of azo dyestuffs of the following
formulae ,
J 1~2--N=~ ~ `N ~ N=N-Kl (12)
. . . . . .. .
- 12 -

so~ :
~ Dr K~ `"~3 ~ ~ K2
wherein K' = A' .
, 1 1 , .
; -C'-N=N-E' or
~ ~ ?~ ~ - N=~-A2
K~ = Ai
- -B'-N=N-A2 or -C'-N=N-E', whereby n = 1 or 2, .
B' and A2 have the meanings given under ~ormula (9)9
: C' and E' " " : " (10),
I' and J' " 11 . l' (3),
I" and J" carry an H0-, carboxy, methoxy, ethoxy, hydroxy-
methoxy or carboxymethoxy group which can be
metallised, and
Kl carries a metallisable H0-, H2N-, methoxy or ..
-NHCOCOOH-group in the o-position ~7ith respect
to the azo bridge, whereby I" and T~l can be further
substituted with the substituents given for I' and
J' in the definition of formula (3).
The coupling components KlH and K2H used in the present :
production process can be monoazo and even disazo dyestuffs
capable of being coupled, as well as metal-complex :
dyestuffs; they can carry fibre-reactive radicals, i.e.
radicals which react with the hydroxyl groups of the celulose
~: '
' -' '
; ' '
., ~

-` ~0495(~7
or with the amino groups of polyamides ~rith the formation
of one or more covalent bonds.
The same final products are obtained by the coupling
of a diazotised diamine of formula (2) with coupling
components which are diazotisable, or ~hich have a
further coupling position, or which are substituted
with metallisable groups, with free -~m2-groups, or
with substituents convertible into such a group, e.g.
with a reducible -N02 group or a saponifiable acylamino
group. They can thus be subsequently further couplPd
with diazo or coupling components, and/or metallised,
in a kno~m manner, by means of agents rele~sing
chromium, copper, nickel or cobalt; and/or fibre-
reactive groups can be introduced.
lS The triazolediamines of formula (2) serving as
~tarting materials are produced by methods kno~m per se
in that, for example, correspondingly substituted
o-aminoazo subs~ances of the formulae
~, ' ' , - . . .
2 ~ 2
are subjected to oxidation.
The following may be mentioned, for example, as
diamines of formula (23 suitable for diazotisa~ion
and coupling:
- 14 -
' ' .
. . .

~ S~ 7
2'~5~diamlno-2~phenylberlzotriaYole,
3',5-d:i.amino 2-phenylbenzc3triazole,
2',5-diamino 4'~-chloro 2-phenylbenzotr:Lazole7
3',5~diamino-6-chloro-2 phenylbenæotriazole~
2',5-diamino~ methyl-2-phenylbenæotriazole,
3',5 diamino~2'~methyl-2-phenylbenzotriazole,
3',5-diamino-4-methyl~2~-phenylbenzotriazole,
3',5-diamlno--6-methyl-2-phenylbenzotriaæole,
3',5-diamino~7-methyl~2-phenylbenzotriazole,
1.0 3',5-diamino~ ',6-dime-thyl~2-phenylbenzotriazole,
3',5-diamino~2',6-dimethyl-2-phenyLbenzo~riazole,
3',5-diamino-4,4'-dimethyl-2--phenylbenzotriazole,
3',5-diamino-2',7-dimethyl 2-phenylbenzotriazole, .
2'~5-diamino-4'-methoxy-2-pheny~Lbenzotriazole,
3',5~diamino--6~methoxy-2-phenylbenzotriazole,
3',5-diamino-6,6' dimethoxy-2 phenylbenzotriazole,
3',5-diamino~6'-methoxy-2~phenylbenzotriazole,
3',5-diamino~ methyl 6-chloro-2-phenylbenæotri~zole,
3',5-diamino-6'-methyl-6-chloro-2-phenylbenzotriazole,
3',5-dlamino-6' me~hoxy-6-chloro-2-phenylbenzotriazole,
- 3',5-diamino-6'-methyl-6-methoxy-2-phenylbenzotriazole,
3'~5-diamino-6-methyl-6'-methoxy-2-phenylbenzotriazole,
3',5-diamino-2'-methyl-5'-methoxy-2-phenylbenzotriazole,
3',5-diamino-4-chloro-4'-metho~y-2-phenylbenzotriazole, . I
3i,5-diamino-2'-methyl-4'-methoxy-4-nitro 2-phenylbenzo
triazole,
'. .
- 15 - ~
1 .

1~ S~07
2-(4l-aminophenyl)-5-amino-benzotriazole, which is not
further substituted, or is substituted in the 3'- and
6-position by two carboxy, sulpho, carboxymethoxy,
hydroxy, methyl or methoxy groups or by two chlorine
S atoms, in the 3'- or 6-position by a sulpho; carboxy or
ethoxy group or by tT~o chlorine atoms,
4',5-diamino-3'-chloro-2-phenylbenzotri~zole,
4'~5-diamino-5-chloro-2-phenylbenzotriazol2,
4',5-diamino-2'-methyl-2-phenylbenzotriazole,
4',5-diamino-3'-methyl-2-phenylbenzotriazole,
4',5 diamino-2',5'-dimethyl-2-phenylbenzotriazole,
4',5-diamino-2',5',6-trimeth~1-2-phenylben~otriazole,
.~ 4'g5-diamino-3'-methoxy-2-phenylbenzotriazole,
4',5~diamino-6-met'noxy-2-phenylbenzotriazole,
lS 4',5-diamino-2'~5'-dimethoxy~2-phenylbenzotriazole,
4'95-diamino-2',6,5'-tr;methoxy-2-phenylbenzotriazole,
4',5-diamino-6'-methyl-6-chloro-2-phenylbenzotriazole,
4'95-diamino-3'-meth~yl-6-chloro-2-phenylbPnæotriazole,
`~ 4',5-diamino-6-methyl-3'-chloro-2-phenylbenzotriazole,
4',5-diamino-7-methyl-5'-chloro-2-phenylbenzotriazole,
4'95-diamino 3'-methoxy-6-chloro-2-phenylbenzotriazole,
4',5-diamino-6-methoxy-3'-chloro-2-phenyLbenzotriazole,
4',5-diamino-2'-methyl-S'-methoxy-2-phenylbenzotriazole,
4',5-diamino-6-methyl-3'-methoxy-2-phenylbenzotriazole,
4',5-diamino-3'-methyl-6-methoxy-2-phenylbenzotria7O1e,
. 4'jS-diamino-2'-methyl-6-methoxy-2-phenylbenzotriazole,
- 1 6 - ~
.
.
: .
. . .
.
. ~ ... .. .
.: . . . .
.

;~
~o~s~
4',5-diamino-7-methyl-3'-me~hoxy-2-phenylb~nzotriazole,
4',5-diamino-2',5'-dimethyl-6-methoxy-2-phcnylbenzotriazole,
4',5-diamino-6-methyl-2',5~-dim2thox~-2-phenyl~enzotriazole,
4',5-di~mino-7-methyl-2',5'-dimetlloxy-2-phenylbenzotr;azole,
4',5-diamino-2'-methyl-6,5'-dimethoxy-2-p'nenylbenzotriazole, -
2-(3'-methyl-4'-amino-6'-sulphophenyl)-5-amino-6-methyl-,
2 (3'-methoxy-4'-amino-6'-sulphophenyl)-5-amino~6-methoxy-
benzotriazole9 as well as their derivatives N-oxidised
on the nitrogen atom in the 1- or 3-position.
The following may be mentioned as exa~Qples of applicable
: coupling components denoted in the above description as KlH and K2H
; 2-amino-, 2,7-diamino, l,N-carboxymethylamino or 2,N- :
phenylamino-na~hthalene,
1-amino-naphthalene-4- or -5-sulphonic acid,
2-amino-naphthaLene-6- or -7-sulphonic acid or -5,7- or
. -3,6-disulphonic acid,
2,N-methyl- or 2,N-ethylamino-naphthalene-7-sulphonic acid,
3,6-diamino-naphthalene-2,7-disulphonic acid,
l-naphthol-5-sulphonic acid, -4,7-, -3,8-, -4,8- or
-3,6-disulphonic acid or -2,6,8trisulphonic acid,
l-naphthol-4-sulphonic acid (Nevile-Winther acid)~
2-naphthol, ..
2-naphthol-6-sulphonic acid (Schaeffer acid),
2-naphthol-8-sulphonic acid, -3-carboxylic acid or
-3,7-disulphonic acid,
2-naphthol-3,6-disulphonic acid (R acid),
- 17 -
'
.
: , ,. . , ,..... ~

~ S0 7
2 naph~hol-6,8-d:k3ulpl~onic acLd (G acLd),
2,7 dihydroxy~naphthalerl2,
4~7-dihydroxy-naphthalene~-2-sulphonic acid~ -
4,6-dihyclroxy~naphthalene-1 sulphonic acid, -l~sulpho 3'-
carboxylic acid or -2~sulpho-7-carboxylic acid,
l-naphtol-8-chloro-5-sulphonic acid or -376--clisulphonic
acid or -3,6 disulphonic acid,
l-naphthol-8-ethoxy-3,6-disulphonic acid,
7-amino-2-naph-thol,
5-amino- or 6 amino-5-chloro 1-naphthol-3-sulphonic acid,
8-amino-1-naphthol-5,7-disulphonic acid,
3-amino-2-naphthol-7 sulphonic acid,
6,N-ethyl-, 6~carboxymethyl-, 6-phenyl-, 6,p-tolyl-,
6,p-methoxyphenyl-, 6-benæoyl , 6,m-carboxyphenyl-, 6-(2,4
dimethoxyphenyl)-, 6-(3-carboxy-4-hydroxyphenyl)-
l~naphthol-3-sulphonic acid, 6-(1-hydroxy-3-sulpho-naphth-
6-yl)-amino-1-naphthol-3-sulphonic acid (di J acid),
7,N-methyl-, ethyl-, phenyl-, acetyl-, benzoyl- or
7,N,N-dimethylamino-l-naphthol-3-sulphonic acid,
8~N-benzoylamino-l-naphthol 5-sulphonic acid,
8-N-acetyl~nino-l-naphthol-3,5-disulphonic acid,
3-methyl-1-phenyl-, (p-tolyl)-, (p- or m-sulphophenyl)-,
(4-sulpho-o-tolyl)-, (3-carboxy-2-hydroxy-S-sulphophenyl)-,
(6-sulphonaphth-2-yl)-, (2-chloro-5- or 6-sulphoph~nyl)-,
(4,8- or 5,7 disulphonaphth-2-yl)-5-pyrazolone3
3-carboxy-1-(m-nitro- or p-sulphophenyl)-6-pyrazolones,
- 18 -
, ~
,
.
: : . . . . . ..
~ . . . .

S~amlno- 3~me~hyl- l ~phe-~n5~1.pyra~oline,
2-methyl.inclole,
2,4-quinolinediol,
: ethoxy~, phenylsu~phoxy or (p-methylphenyl)sulphoxybenzene,
2-methyl-, 2~(o-methylphe-nylamino)-~ 3-phenylarnino- or
3 amino-6 chloro-phenol,
salicylic acid,
phenol-2- or 3-sulphonic acid,
5- or 6-methyl phenol-2-carboxylic acid,
3~amino~phenol-4- or 6-sulphonic acid,
- o- or m-to].uidine,
:, m~ethylaminoacetanilide,
m-carboxymethylamino-aniline or -p-methylaniLine
4-nitro-, chloro- or methoxy-m-phenylenediamine,
~ 15 2-methyl- or 2-methoxy-5-acetylamino-aniline,
,~ 2-methoxy-aniline,
3,5-diamino-4-chloro- or 2,4-diamino-5-methyl-benzene-1-
sulphonic acid;
as well as the following diazotisable coupling components:
l-amino-naphthalene~
l-amino-naphthalene-6- or -7-sulphonic acid,
7- or 8-amino-1-naphthol-3,6-disulphonic acid ~H acid)~
:! 8-amino-1-naphthol-5-sulphonic acid3
6-amino-1-naphthol-3-sulphonic acid (J acid),
3-amino- or 3-amino-4-methyl-oxanilic acid, .:
3-me~hyl-6-methyl- or -6-methoxy-aniline;
,i . ,
- 19 -
.
, :
..

0 7
as well as ~he ~ollowing couplin~ components havinp a
~ n~:
1,8-dih~drocy-n~.phthalene-4-sulphonic acid,
1,8-dihydro.~y-naphthalene-3,6-disulphonic acid (chromotropic acid);
8-amino-1-naphthol-5-sulphonic acid or 3,6-, or 4,6-
disulphonlc acid,
~-amino-l-naphthol-3,5-disulphonic acid (K acid),
6-amino-1-naphthol-3-sulphonic acid (~ acid)~
resorcin,
phenol 9
1,3-phenylenediamine,
4-sulpho-9 4-methyl- or 5-sulpho-2-methyl-1,3-phenylene-
cliamine; :
as well as the followin~ monoazo compo-mds:
4-(4'-sulpho-, 4'-acetylamino-, 2',4'-disulpho-phenylazo)-1,3-
phenylenediamine,
4-(4'- or 2'~hydroxy-3'-carboxy-phenylazo)-1,3-ph~nylene-
diamine,
6-sulpho-4-phenylazo- or 6-m~thyl-4(4'-sulphop'nenylazo)-
1,3-phenylenediamine,
4-[4'-sulphonaphthyl-(1)'-azol-, 4-[8'-hydroxy-6'-sulpho- or
.' 3,6'-disulphonaphthyl-(2~'-azo~-1,3-phenylenediaMine,
6-methyl-4-[4'-sulphonaphthyl-(1)'-azo]- or 4-~6',8'- or
3,6'-disulphonaphthyl (2)'-azo~-1,3-phenylenediamine, :
5-sulpho-2-methyl-4-[8'-hydroxy-6'-sulphonaphthyl-(2)'-azo]-
. 1,3-phenylenediamine, -
- 20 -
.. . . . .

~0~95~)7
4-(3'-sulphoplLenylazo) or 4-~5'-sulphonaphthyl-(1)']-
resorcinol,
the copper complex of 4 (2'-hydroxy- or 1'-hydroxy-2'-
carbo~y-5'-sulphopheltylazo)- or 4-(2'-hydroxy-5'-
S sulphaD~oylphen~lazo)-resorcinol,
5-hydroxy-3-[4'-aminonaphth~Jl-(l)'-azo]-ll~phthalene-2,7-
disulphonic acid,
4,5-dihydroxy-3-~4'~sulp'nonaphthyl-(1)'-azo]-naphthalene-1-
sulphonic acid or 2,7-disulphollic acid,
S-hydroxy-4-amino-3[2'-chloro-2'- or 4'-nitro-, 2',5'-
dichloro- or 4'-sulpho-phenylaæo~-3-[2'-chloro-4'- or
- 5l-nitro-phenglazo~ or -3[2'-methyl-5'-nitrophenylazol-
naphthalene~2,7-disulphonic acid,
5-hydroxy-4-amino-3[4'-sulphophenylaæo]- or 4-hydroxy-5-
amino-6[4'-nitrophenylazo] naphthalene 2,8-disulphonic acid,
5-hydroxy-4-arltino~3(phenylazo)-, -3(4'-sulpho-, 2',5'-
disulpho- or 4'-chloro-3'-sulpho-phen~lazo)-naphthalene-1-
sulphonic acid, 4-hydroxy-6(2',4'-diamino-3'-methyl-6'-
`~ sulphophenylazo)- or -7-amino-8(3'- or 4'-nitrophellylazo
;~ 20 or 2'-chloro-4'-suLphophenylazo)-naphthalene-2-sulphonic
acid, whereby all nitro groups present can be subsequently
red~lced, e.g. by a treatment with sodium sulphide,
as well as disazo compounds such as, e.g., 1,3-di(2',4'-
` diaminophenylazo)-benæene.
The above mentioned coupling components and monoazo
compounds can also be coupled with intermediates capable
~ 21 -
. , . '' ~.
-:

~ 5~ 7
o:E ef~ec~lng the present dyestuE~ formcl~ion; for ~xample,
these -~Jhich are formed by the coupllng of a di.amine
of formula (2) with diaæotisable coupling components.
As components with a double coupling position
that react with two equivalents o~ a dia~o component,
mention may be made, for example, o~ compounds 8-LCh
as 4,4'~methylenediphenol and 3,3'-diaminocarbanilide.
Examples of applicable diazotisabl~ components,
deno~ed in the above description as E~N~12, are:
sulphanilic~ metanilic, 3-chlorosulphanilic or 6-
chlorosulphanili.c acid, ..
6-amino benzene-1,3- or 1,4-disulphonic acid,
., .
aniline, o-chloro~ or o,m or p-nitroaniline, 2-chloro-
4-nitro-, 2~5-dichloro- or 2-methyl-5-nitro-aniline,
p-aminooxanilic acid~
p-aminoacetanilide, ::~
2-amino-5-nitro-benæenecarboxylic or -sulphonic acid, ~ .
.
3- or 5-amino- or 3-amino-5-sulpho-salicyclic acid,
2-amino-1-phenol-4-sulphonic aci.d or -4-su].phonamide, -~
l-amino-naphthalene,
l-amino-naphthalene-4-, 5-, 6- or 7-sulphonic acid, j`
2-amino-naphthalene-6,8-disulphonic acid,
.
2-~mino~8-hydroxy-naphthalene-6-sulphonic or 3,6-di- ', :
sulphonic acid,
5-amino-~H-1,2,4-triazole-3-carboxylic acid, t
~:
':
- 22 - ~ ~
.,

S~
or, as a compollent having a clouble cliazotisab:Le posit:i.on
~ilich reac~s with ~wo equivalents of a coup:li.ng component: :
4,8-diamlno-naphthalene-2,6-disulphonlc acid.
Large numbers of fibre-reactive groups are kno~rn
from the literature. The foll.owing groupings represent,
therefore, only a select:ion of possible fibre-reactive
groups: .~.
; A) Such suitable groups include those which contain at least one fibre-reactive substituent bound to a
5- or 6-membered heterocyclic ring having, optionally,
one or more rings of aromatic nature bound by condensation. .
Among the fibre reactive substituents bound on the
heterocycle, the following are, for example, to be mentioned: :~
halogen (such as chlorine, bromine or fluorine), ammonia
(including hydrazinium), sulphoni~tm, sulphony]., azido (N3),
rhodamido, th;o (such as thiocyano or radicals of the
formula S-C-N or -S-C- ), thlo- and oxyether containing
; S N-
one electronegative substituent (such as a sulpho or nitro
group), sulphinic acid, sulphonic acid and e~hyleneimino.
The men~ioned 5- or 6-membered heterocyclic rings
can also contain non-~ibre-reactive substituents; the
following are given as examples of such substituents:
primary amlno and hydroxyl groups, also mono- or di-
substituted amino groups, e-therified hydroxyl groups and
'~
- 23 -
.
.. . , ~

95Q~
;
etheri~ied mercap~o groups; the class of subst-L~tlted
amino groups embraces, for example, mono- and di-
alkylamino groups in which the alkyl groups contain
~; preferably at mos~ 4 carborl a~oms and wh-ich can also
contain substituentsg e.g. hydro~yl or alkoxy groups,
as well as phenylamino and naphthylamino groups which --
.~ preferably contain sulphonic acid substi~uents; the class
of etherified hydroxyl and mercapto groups includes, for : -
example, al.koxy and alkylthio groups, pre~erably ~such
groups having low mo].ecular weight, i.e. with Up to 4
; carbon atoms, as well as phenoxy, phenylthio, naphthoxy ;~.
... or naphthylthio groups. Chlorine atoms or cyano, nitro,
;.~ carboxyl or carbalkoxy groups in the S-position of a
pyrimidinyl radical likewise fall into the category of
nonreactive substi~uents. Alkyl or acyl groups bound
direct on the heterocycle can also be included.
Particularly pre~erred dyestuffs in the range of the
!~ new dyes~u~fs are those on which the ~ibre-reactive
: group is a 6-membered diazine or triazine ring in which :
a carbon atom is bound on the dyestuf radical by means of
a -0-, -NH-, -NCH3-, -N-C0- or -N-S02-bridge, ànd which
contains at least one fibre-reactive substituent such .
as a halogen atom or a sulphonyl group. .
Of ou~standing interest among these are:
1~ .
;; - 24 -
1'.
.~,, j .
. : . ,, ,- .
.. .. .. ... ...

9507
'
1. Triazine grou~, symboli~Qd as ~ N-Rel, such as
N=<S/u
a) wherein G = F, Cl, Br,
: -Su = a primary, seconda~y or tertiary
amino group, such as
~NH2, ~NHC~-r3; ~IHC2H5~ -~HC3H7j -N~C~ g,
~I hex~l-, NH-eyclohexyl, -N(CH )2~
( 2 5)2~ -NHC~2C~H20H, ~r(CH2CH20H)2J
2 20SO~H, -NHC~I2CH20CE~3; -~HCH CH C~
-NEICH2~CH(OH)2~ C~2C;~~so3HJ MrPhlin~J'
piperidino, hydrazino, N-methylhydrazino, ~-phenyl, -NH(2-,
~ 3- or 4-sulphophenyl), NH(2-, 3 or 2,4- or 2,5-- or 4,5-
;: or 3,5-disulphophenyl), -NH~0-9 m- or p me~hyl-phen~l),
-NH-carboxyphenyl, -NH-benzyl, -~(0.0'-dimethyl-phenyl),
~NH(0-carboxy-sulphophenyl), N~I(m-carbo~y-p-llydro.~yphenyl),
-NH-sulphonaphthyl, -N(CH3)CH2CH2CN, -N(CH2CH2CN)2,
-N(CH3)-CH2CH2S03H, -N(CH3)phenyl, -N(CH3)sulphophenyL,
-N(CII2CH20H)-sulphophenyl, -N(CH2S03H)phenyl9 NHCN,
n(CH3)CN9 -aminoacetic acid, thioacetamido-9 -NH
S02-NH-CH2S03H, or such as amino groups oE the formulae ~ -
'
.
- 25 -

; ., ~04951U7
-N11 ~ - N~ - ~ I or -N1~C = M
~ S0311 N~ < . ~ ¦
-. ~ -SO~I
;. , . I . :
EI~
- (whereby Ra = alkoxy, aryloxy, thioalkoxy or thioaryloxy),
- an ether-Lfied hydro~yl or marcapto group, such as
3, C2115, QC3~7, OC4Hg, phenyloxy-, -SH, -SCH
. 5 -SC2H5, -SCH2C~120I1, -OCH2S02-phenyl, OCE12CH20CH3, -S-phenyl, ~: .
-SCH2COOH, -SCSN(CH3)2, whereby the above mentioned
.phenyl rings can be substituted by chlorine~ methyl
1 ' ' ~ ~ '
or methoxy groups.
o an alkyl or aryl group 5uch as tL~e phenyl group,
. lO which can be substituted by chlorine, bromine, methyl,
. ~ hydroxy, methoxy, cyano, sulpho, carbo~y or nitro groups,
a methyl or trichlorome~hyl group, or
= a fibre-reactive substit-lent, such a~ Cl, Br, F, ~:
-S02-carbo~yphen7l, -S02-sulphophenyl, -OS03H, -SCM, nitro-
or sulp'nophenyloxy-, -S-nitro- or su1phophenyl, or
b) wherein -G = -Su = S02-phenyl, -S02-car'~oxyphenyl, -S02-
: trichloromethylphenyl or -S02-(~-sulphoethyl), or
~ . .
c) wherein -G = S02CIi3 and
Su = trichloroethylo~y~, phenoxy-, -NH-sulpho-
phenyl, --N(CII3)pllenyl, or
- ~
: ' '.. ' ,. ,
- 26 -

95~)7
d) wherein -G = -S = nitro- or sulphophenoxy, nitro- or
suLpho-thiophenoxy, -SCN, -OSO3H, -N , -SCSN(Rb)Rc or
-SC(Rd) = N(Re) whereby Rb and Rc = alkyl, cycloalkyl,
aryl or aralkyl groups, and Rd and Re = H, alkyl, aryl
or aralkyl groups, or
e) wherein-G = -N(CH3)3, -N(CH3)2-NH2, ~N 1~ /N ~ ~ :
N~r-- ~/ \\ 6g I NH2 :
N~ /N or -NUN ' AND
-Su = -NH-phenyl, -NH-sulphophenyl or -N(CH2CH20H)2; i~
2. 4-pyrimidine ~roup, symbolised as ~ N-Re2 or-0-Re2, such as
Su G
~N ~ N wherein Gl and G2 = F, Cl or Br
and ~Su = -H, -F, -Cl, -Br, -NO2, -CH3, -CH2COOH, -COOH,
-CN, SO3H, -CH2Cl, -CHC12, -CC13, -CBr3, -CF3 , ~.
-COOCH3, -COOC2H5 -CH=CH2-halogenovinyl- or
-allyl, such as
N02 CH3 Sul S~ SU2
<Cl > \~ ~ / ~ \F
wherein -Sul = -NO2, 6COOH, -COOCH3 or -COOC2H5,
ISu2 = -Su, excepting -NO2 and SO3H, allyl-, -CONH2 ;~
and -SO2NH2 optionally N-substituted, -SO2phenyl,
ISO2-methyl, -SO2-ethyl or -SO2-chlorophenyl,
. .
- 27 -

~0~95(~7
,
., . .. . .. .. . ... . .. .. .. . ...... . . .. . . .. .. . ... .. . . . ... ... .. . . . . .. ;
-Su3 - Su2, N02 or SO~I, such as
Su5 S--~ Sv.5 G4 . G
I~G ~ ~ G ~SO CH
, ~<S02CIIS , .. ...
,~ . wherein
' '
G 5 -- S02CH~ $02C2H5) -S02CH2COOH, -SO2CH2CH2SO;~,EI, -S02Cl_
-SO;~-phenyl . ::
-Su~ C~3~ ,"Hs, ~CH2Cl or OCH3 and
-Su5 = -H, -Cl, -Br, ~1`~0.2, -C1~3 or C~
1~. - 03 or = Cl, Br, COOH or CH2COOH,
-Su6 = -H, -Cl,
'' )'
G5 = SO3~ or COOH, such as
Su7 F
C' H' '''~
I whcre~n -Su7 = ~ tl, -Br~ t~3 2 5;
,3. 2-pyrimidine group symbolised as >N-Re'2, such as
.
Cl . . Sv.2
>l~ so3~ or >N~N ~Su3
Cl . ~T~

wherein Su2 and Su3 have the_above given meaning;
,.
_ _ _ . _ . _ _ _ .. _ _ _ . _ _ _ _ . . _ _ _ _ , . _ . _ . _ .. _ _ _ _ _ _ .. .... .. . .
- ' . '
:, . . .
- 28 -
..

11~4~507
4. 4-carbony'l-_or sulphonyl-~yrimidine ~roue, symbolised
as ~Y-Re3, such as S 8 G7 Su8 Su9
G6 ~ >N-Y
N N --~
'G6 G7 G8
,
wherein
Y -CO- or S02-,
G6 and G6 -Cl, -Br, -S02CH3 or -S2c2H5~ .
G7 and G7 -S03H) -Cl or -Br,
" -Su8 -H~ 3 -Br or -Cl, ~'
-Su9 -Alkoxy, -Aryloxy, NH2, -NHalkyl, -Ntalkyl)2,
.' -NHphenyl~ -NH(sulfophenyl) or -NHtdisulfophenyl);
' G8 -Ammonium;
5. -5-carbonyl- or sulphony'lpyrimidin'e ~'roup, symbolised
as N Y Re'3, such as
.i
N-~ ~ ~ G9 ' wherein
. Gg or Gg ~ Cl or S02CH3 and the other _ CH3, such as :
' SulO Cl 10
N~ lo >N Y~ 6 > ji~ Y-~6
G'l ~, u 9
or
'
.
~ - 29 -

. . , '1~4g~7
>~-Y ~ ~ SCII~ ~herein G~ o and Glo - G6 or G7, and
~,?~,
SulO = ~ or C~l~. .
..
6. Further diazines such as
2-chloro- or bromoquinoxaline -(3)- or (6)-Y-N~
3-chloro- or bromoquinoxaline -(6)-Y-N~
2,3-dichloro- or dibromoquinoxaline -(5)- or (6)-Y-N~
2,4-dichloro- or dibromoquinazol~ne -(6)- or (7)-Y-N~ :
dichloro or dibromophthalaæine -(6)-Y-N
2,4,6-trichloroquinazoline -(7)- or.(8)-Y-N ~
2,4~7- or 2,4,8-trichloroquinazoline -(6)-Y-N ~ , or groups
of the formulae
S ~ y_~< ~ C~ c~I2c~I2--Y--~<or
Cl o . O
......
~T/ ~ :
~ ~ ~ N~ s~nbolised as >~--Y-Re ~, -
whereby Y = -CO- or -SO~-, or such as
2-methylsulphonyl-quinazolinyl -(4)-N~
3-trichloromethylsulphonyl-pyridazinyl -(6) -N
3-phenylmethylsulphonyl-pyridazinyl -(6)-N_
3-methylsulphonyl-4-methyl-pyridazinyl -(6)-N -
3-methylsulphonyl-pyridazinyl -(6)-N
- 30 -
,. _

`" 11131~9507
-- ! 3,4,5-trichloro~pyridazinyl -(6)-N~
3,6-difluoro-pyridazinyl -(5) N
and the group of the formula
.
CH3SO2 ~ ~ i~T< , symbolised as >l~-Re2
2 3
-'
7. Othcr 5- or 6-membered he~erocycles ~7hich contain only
one nitrogen atom: :
2-chloro-, 2-bromo-, 2-sulpho-, 2-methylsulphonyl-, 2-ethyl-
sulphonyl- or 2-phenylsulphonyl-benzothiazole -S- or 6-
carbonyl or -sulphonyl, 2-chloro- or bromo-benzoxazole - or
1~ -benzimidazole -S- or 6-carbonyl or -sulphonyl, 2-chloro - 1 -
methyl-benzimidazole -5- or 6-Garbonyl or -sulphonyl,
2-chloro- or bromothiazole - or -4-methyl-thiazole-4- or
5-carbonyl or -sulphonyl, N-oxide of 4-chloro- or -nitro-
quinoline~5-car~onyl, 2-methylsulphonyl-4-carbo~y-pyridine~
2-trichloro- or 2-carboxymethylsulphonylquinoline.
B) Other suitable groups are unsaturated and/or halogena~ed
aliphatic or aromatic radicals of a sulphonic or
carboxylic acid chloride;
8) They can be bound by an amino group on the dyes~uff,
20 su~h as a group of the formula Re4-Y-N~
CIT C~I - CO-~r< or ~ <
H2~ 2C,_,,,_, _,__
- 31
.

D5107
whereinY ~ -CO- or SO2-
Re4 = ClCH2-, ClCH2CH2-, BrCH2CH2-, BrCH2CHBr~,
3 2 2 4 ' C2H5SO2C2H4-, HS3C2H4-, Hso3oc2H4so2c2H -
NO CH3 NO2
L ~ ,_
F ~ , F-/ ~ , Cl _ r~ ~ cl cH 2~ ~S 2 c 2H~
:~ N2 ~:
CH2=CH-, CH2=CBr-, CH2=CCl-, COOH-CH=CCl-, CH2=CH-CH2-S- ~ ,
Sn' t t Sn''~
F Snn ¦ CH=CH Sn~-
¦ ~ or _ ~ . ~ .
F G" F G"
i~ whereby Su" = H or Alkyl . :
Su"' = Su" or Aryl
G" = Cl or F.
b) They can be bound direct on the dyestuff, such as groups of . .
the formula Re5-SO2-, where Re5 = ClC2H4-, EISO3C2H4-, HPO3C2H4-,
:1 CHIV2:=CH-, ClCH2CH(OH)CH2-, BrCH2CH(OH)CH2-, HOCH2CH(OH)CH2NHC2H4-, ~.
., (C2H5)2NC2H4 , HS030C2H4MH-, ClcH2~HclcH2NH-~ Hso3sc2H4NH- or
HS030C2H4N(CH3) C3H6NH-, H2C -. .
:f ~ ~ -SO2-
; H2C
`::
'
.', . '
' '; .: ,'
_ 32 - ~
., ~ . .
. '
. '
: , . ~, .. . ... ~,

~ L049507
or c1l2----c~ cH2~so~-- -
, , ' '
C) Other suitable groups are, for example:
a) the CH2 - --C.I-CII2 M~ group,
\o/
wherein -M- = -N-, -0- or -S-
b) groups which are bound direct on the dyestuffs, such as
-S02~, p. . .. . .
~ and ~~ ~ o
I N02 Cl
.
Further suitable fibre-reactivP components are known
; :in large numbers from the literature, and therefore need
;~ no separate mention.
The tetrazotisation of the diamine of formula (2~ is
performed by methods known per se, e.g. with the aid of
sodium nitrite and hydrochloric acid The coupling wit~
the coupling components KlH and K2H, as well as the possibly
further required couylings, can likewise be performed by
lS a manner known per se in an acid to alkaline medium.
Like benzidine, the diamines of formula (2) are particularly
suitable Eor the production of unsymmetrical diazo
dyestuffs, since the two couplings proceed with an entirely
different energy requirement. The first coupling occurs also
in an acid medium very rapidly, whilst the disazo dyestuff
~ 33 -

forms only s:lo~,7ly.
According to one embodimen~ o~ tle abo-Je proce.ss,
~he diazotisation and/or coupling of a compound containing ~ -
a fibre-relctive substituent should be performed as
far as possible in acid medium or at most weakly alkaline
aqueous medium
According to a further embodiment, the coupling
component used is a monoazo compound con-~aining a metal
in the form of a complex. Such compounds can be obtained,
for example, by trea~ment with metal-releasing agents,
from a monoazo compo~md which contains a metalLisable
grouping, :Eor example~ an o,o"-dihydroxyazo grouping,
o--carboxy o'-hydroxyaæo grouping or o-amino-o'-hydroxy-
azo grouping. `
According to a further embodiment of the above
process, whereby metal-complex polyazo dyestuffs are
produced, metallisable compound containi.ng fibre-reactive
radicals are subjected to a treatment with a metal . .
releasing agent. This process, however, is preferably
restricted to the production of dyestuffs in which the
;, , .
fibre reactive substituent is stable to hydrolysis during
metallisation, which is the case, for example, when it
is a 2-chloro-4-amino, 2-chloro-4~(m-sulphophenyl)amino-, ! -~
2,4-dichloro- or 2-chl~ro-4~phenoxy-s-triazin-6~yl
radical.
f'.
'

95~7
The introduction of such fibre-reactive groups
during the above proces~ can be ef~ected in a manner
known per se. It can be performed, for example, by
condens~tion onto a free amino group -NH2 or -NnlCH3
S with an acid chloride supplying a f;bre-reactive
radical, oE the formula Re3-Y-Cl, Re73-Y-Cl or Re"3-
Y-Cl (see paragraphs A4, A5 and A6) or of the formula
Re4-Y-Cl (see paragraph B), or with the corresponding
acid anhydride.
It can also be effecte~ by azinylation oE an -N~2- :
vr -NnlCH3-group with cyanuric chloride, or with a
chlorine derivative of the formula Rel-Cl, Re2-Cl,
Re'2-Cl or R"2-Cl ~see paragraphs Al, A2, A3 and A6)
or, }f the radicals denoted by Rel, Re2, RP'2 or Re"2
eontain a sulphonyl group -S02-Q, with a ~ulphonyl
derivative oE the Eormula Rel-S02-Q, Re2-S02Q, Re'2-S02Q
- or Re"2-S02Q. If the radical symbolised by Re2 contain~
two fluorine atoms in the 2- and 6-position, it can also
by performed by reaction of a dyestuff or of an
in~ermediate product capable oE dyestufE formation,
which contains an H0-group, with a 2,4,6-trifluoro-
pyrimidine compound.
The introduction oE the ethylene radical can occur,
for example, by the reacting of the ethyleneimine with
a dyestuff containing a benzoylamino group or one of
the two fibre-reactive -N~l-C0-CH2Cl or ~S02F groups,
- 35 -
.

~ 0 ~9 5~ 7 :
- I 80 that the fibre-reac~ive groupings of the ~ormula
S 2 ~f -NII-C0- ~ , -NH-C0-CH2- ~ or
CH2
are obtained.
According to further embodiments of the present 5 process, further modifications can be efected, by
m~thods known per se, in fibre-reactive groupings
already present; such as, or example: the treatment
of am a,~-dihalogeno- or ~-halogenopropionyl g*oup
~Jith an agent splitting oEf hydrogen halide ~or the
:Eormation of an a-halogenoacryl or aryl group;
-the treatment of a ~-halogeno-~-hydroxypropyl-sulphonyl,
-amino-, -oxy- or -mercapto radical ~or the formation of a
-CH2-CH-CE12-group, which is bound on the dyestuff by
O '.
an -S0~-, -~I-, -So or -0-bridge;
-the treatment of a dibromo- or dichlorotriazine nucLeus
: with a~monia, with a primary or secondary amine or with :
an alcohol or thioalcohol for the repl~cement of a
halogen atom by another substituent;
-the treatment of a bromo- or chlorotriazine nucleu~ with
a tertiary amine for the formation of an ammonium group.
The obtained dyestuffs are used in the dyeing or
.printing of natural fibres, such as leather, wool or silk;
of synthetic pol.yamide or polyurethane materials; and
: - 36 -
.
-,. . .. , , .... . ., . _
. . . . .

/ `
~ 49 5~ ~
chiefly of natural or regenerated celluLose fibres.
The said dyestuffs produce a large variety of
dyeings, which in general have better fastness to wet
processing than that of the corresponding hitherto
knowm benzidine dyestuffs.
A5 in the case o~ the above mentioned benzidine
dyestuffs, dyeing can be performed from a neutral to
slightly soda-alkaline solution by intensification of
absorption onto the flbres by salt add;tions The
~emperature is slowly raised from 30 - 50C to the
; boiling pointO
In some cases, the dyed materi.al can receive an
aftertreatment, such as a development by means ~f a
; further d~azotisation and couplin~, a ~re~m nt ~:ith
formaldehyde (dyestuffs with resorcin, m-aminophenol
or m-phenylenediamine as end component) for ~he improvement
~- , - .
- of fastness to wet processing, or with copper or chromium
salts (in the case oE complex-forming dyestuffs) for
the improvement of fastness to light.
In addition to possess;ng better general fastness to
wet processing, the present dyest~lffs have a further r
advan~age compared with the correspondillg benzidine dyestuffs
; in that they do not exhibit the toxicity of the latter.
~nlere not otherwise stated in the following examples,
parts are given as parts by weight, percentages as per cent
by weight, and temperatures are in degrees Centigrade.
- 37 -
. ' :
~':
- . . .

109~35~7
..
Example I
,
8 9 Par~s o~ concentrated hydrochloric acid are mi~ed t7ith
31.6 parts of finely crushed ice and cooled in a
cooling bath to -10. I~hile stirring is maintained,
5.37 parts of a 4N sodium nitrite solution are plunged in.
To the formed bl~lish solution of nitrous acid
there is then added at -10 d--ring 15 mirlutes,
with vigorous stirring, a solution produced from
1 part of 2-(4'-aminophenyl)-5-amino-benzotriaz~le in
0.9 part of concentrated hydrochloric acid and
10.5 parts of water. After completed addition of the
diamine solution, stirring is continued ~or
a further 15 minutes at -10, and the excess
sodium nitrite decomposed by addition of
a solu~ion of ca.
1.6 parts of sulphamic acid in
20.0 parts of ~Jater. The strongly acid diazo solution is
,
cleared through a Hyflo-bed of the small
amount of insoluble matter.
For coupling ther~ is prepared a solution,
produced with conc. sodium hydroxide solution, of
1.35 parts of H-acid (100%) in
82.0 parts of water, with a pH-value of 10.5.
The diazo component is added to this solution
at 0 - 5 in the course of 15 minutes, the
- ' ' .
~ 38 -
. . .:

~4~5~7
pH-Yalue being maintained between 10 ~ and 10.5 by
the sim~l~.taneous addition oE a 10% aqueous sodium
hydro~ide solution. The solution i~nediateLy turns
violet and there is soon formed a fine dark blue
precipitate. After completion of the addition of
the diazo solution, stirring is continued ~or a further
5 minutes at 0 - 5, and a solution of
0.943 part of ~-acid (100%)~
0.55 part of conc. sodium hydroxide solution and
0.25 part of sodium carbonate in
8.4 parts of water then plunged into the reaction mixture.
The blue-violet suspension is alLoT7ed to react
completely at 20 ~ 25 overnight. There are then added
- 34.00 parts of sodium chloride, and stirring is carried
out ~or 5 hours at 35 ~ 40 and then overnight at
20 - 25; the reaction mixture is ~inall~J filtered
under suction and then dried to tllus obtain 5.3 par~s
of the dyestuf~ o~ formula I
H2N\~ {> N\~T~ ~/~
S0~ SO~H SO~H
I -
The dyestuff dyes cotton substantively in deep
blue shades.
If the coupling of tlle H-acid is performed with
'
;
'
:
. . : , : ~ .
, ... . .

so~
a pH-value of 2 4 - 3 and the coupling oE the ~-acid
as above with a pH-value of 10.2 - 10.5 7 then there
are obtained, after analogous p~ocessing of the
reaction mixture, 5 05 parts of the isomeric dyestu~
o~ formula II, wlich dyes cotton substantively, and
; wool from acid solution, in violet shades.
j ~2 ~
~2N~ \~N- ~r-~_ N/~ N~
S03H ~ N ~ ~O~H S0
II
Both dyestuf~s in the completely dye~ state on
cotton can be diazotised and further coupled ~ith
coupling components. If, for example, a blue cotton
cloth dyed wit~ the dyestuff of form~tla I is
treated with a diluted sulphuric acid sodium nitrite
- solution and subsequently rinsed with an aqueous
solution of m-phenylenediamine, then the cloth
obtained after thi~ treatment is dyed black.
If 1 part of 2-(4'-aminophenyl)-S-amino-benzotriazole
according to the data given in Example 1 is replaced by
equivalent amounts of a diamine of the formula
H2N
X ~ N / ~ N~2
, . X
wherein the two ~'s have the meanings given in column 2
- 40 -
,
.
,,"""~ ~
.

~9 50~
of. the :EoLlo~/iirlg ~abLe~ and ~he 1.,35 parts of H-ac.i.-l
~nd 0.9~3 part of ~-a(:i d replaced by e~qu; valeTlt arnounks
! ' of the coupling cornpon2nts given in colull1ns 3 and 4,
respec~ivelgg of Lhe following table I, then dyestuffs
are obtainecl which have equally good properties and
w~ich clye cot~on in the shades sho~m in column 5,
Some of these dyestuffs, like dyestuffs I and II,
can be diazo-cised in the dyed state on cotton and
further coupled wi.th coupling co~ponent,s~ Accordingly, .
che dyestuffs given in column 2 of Table II and numbered
according to Table I were diazotised and coupled with
; the respective coupl.ing component listed in column 3
to obtaln th~ dysings on cotton c oth 6ho~n in column 4.
,'.
,' . ''"
.~ ' :;
. ',
.. . ~.
". ,~', ~ .
, - 41 - ~

507
. .
. .
Tab l e
.
. .
_ ~
,~ a ~d o o o
. ~ r 1 ~1 ~ I r~
~ ~ r~ P ~Q r
~ '`'.
O I ~
l Q~
l a) ~ ~ ~ o ';`''
', l ~ tq o
C07 1
. l ~d C.~ ra .~.- I ~d
~I r -l ~ rC ~ t~
~ I a) b~) r ~ ~rl
;i- I rC ~ ~ ~ r~ X
~ I ~ ~ ~ rl I I caO ~ :
i trC C~ r--l ~I S-l C ::
rC O~
C~ rC ~
~) ~ rC r~ O O ~ C
rC rc~
.,~ a~c o~ a
~>~1 ~ C ~ rl C) r~
Z Z ~~
_ ~
~ 0 '~'
~ g
7 . ,, ~ -
d ~1
d~d I ~a ~o ' c ra ~.
1 ~ I c.)c) ~ 4 u
~)
~,, ,~ -a .
C t)
rC~ ~ I O
X
~- lrC r~ ~r l ~ rC ~IJ O
~~ ~d ,I Q~ ~ ~ ^ ~ ~, '~ O
rCrC~ ~ rl rC a ~)
C~1 ~ cq C~rl r-l ~ ~1 ~> C.)~rJ td rC~
_ . _ _. _ __ _
.1 ~ ~ ~ p~ :.,
~ ' ~ X X ~ ''
'I ^ "'l ~ O O O ~'
.1 ~ $ ~ rC
Q
_ - , .
. ~, .
; ~ o ~ .
--~ o ~ ~ I r-~
~_ ~Z; . I
.
;' '
- 42
.
` : , " ~ `. `
.

~o~sso7
(conti.nuat:i.on o~ Tahle I)
.
_
1-1 H H
H H H ~J
.
0 a) ~ n P
3 tl~ ~a O ~ O O
. ~ ~ p
tO u~
.
.
.,
C~
~/ 0
~ 3 0 ~.
~1 ~ ,G ~
~ t~ 1 ,G
~ E3
~ ~1 o ~a
r--l rG I Cl~

JJ J ~
~ O ~G rl1~ ~ (71 rl
.,1 ~ Cl ~ ~d X I ~J :
O ~ 3 ~ O ~ tG
h I ~ O X ~ l O
~~) a) O X ~G O rl r~lt~
4~1~; O Q
i ~) 3 ~ ^v~ ; G S~
0 0 I I ~ 3
x~ oo g
O I ~ . ,G-,I ~1-,l
' P~ O '
,S: N rl ~ u~ ,~ .
~O ~ 0 ~
a 'd O
00 C
.~ U ~3 td ` ~ ~ ~ ~ -~. :
O
~ '' ~3 ~ ~ G ~: ~ O
O I ~ ~~ ~,1 ~ ~ I ~ I ,1
~::.C O ~ 1 7 ~ O oo ,-1 ;:-~ G
rl ~ ~rl X T-l :~ O ,G .C: I ~I X O
E~ ~ ~ O P~ X ~ ~ ~ ~ o ;~ o .
~d CL O,L:I JJ O Q . ~ ~G ~: rl h
E3 G Q, ~ U ~ ~ rae., ~ ~ :
~ 3~ U~ G u3
I ~ 3 S-~ I C.~I I I
c~ Z Zoo ~ `~
~, ~ '
X X X ~ X ~ ',:
O O O ~G
J- ~1 ~ a~ ~ ~ o
~ o a~ ~
~ ~ e c~ cn e
~ ~ ~ o~ o
- '
: :
.
~ ~3 ~
.: ..- ~ , .
.. : . .

S~7
Table IL
(:l) (2) . (3) (O
______ ~ . ~~~___~ .~__.~ ~
L 5 3,5-diamino-p toluene blue
sulphonic acid
2 6 ll ,- bLue
~lack
3 7 2-naphthol ~lack
4 6 m-phenylenèdic;miIle ,l
14 2-naphthol blue
6 17 (aLk) N-p carboxyphenyl-~- 31ack
7 16 2,4-toluylenediamine .l
i . ,
'~ '

1~495~)7
Example 2a
Production o~ the starti.~ æ o~uc~ 2-(4' a~ phen~ 5-
amillob~nzt:ria~o1e-6-sulphonic acld
10 parts o~ acetyl-p-phenylenediamine (titer: 87%)
are diazotised by a ~no~n method. The congo-acid
S diazo solution is added at 10 in the course of one
hour to a neutral sol-ltion of 11.82 parts o 1,3-
phenylenedia~line-4-sulphonic acid (titer: ~2.1%) in
100 parts of water. By the simultaneous addition of
a 15% sodium carbonate solution, the pH-value is
maintained constant at between 6.1 ~nd 6,3 during the
entire coupling reaction. Stirring is continued for
a further 2 hours at 10; the pH-value is then adjusted
to 8.0 to 8.3 by the addition of sodium ca~bonate, and
the mixture heated at 75 for 5 hours to obtain a ;
lS clear dark-brown solution.
Additions are subsequently made to the solution of
the thus prepared azo dyestuff at 75 of 0.3 part of
IrgafoMal TP and then of 6 parts of concentra~ed aqueous
a~nonia. A solution of 2.9 parts of copper sulphate-
pentahydrate in 15 parts of water and 6 parts of conc.aqueous ~nonia is added; while vigorous stirring is
maintained, air is then passed through the solution in a
manner ensuring ~ good distribution of the gas in the
liquid. Oxidation is completed after the passage of gas
for ca. 4 1/2 hours near to the boiling temperature, with
- 45 -

~at4~507
the thin-layer chromatogram indicating no fur-ther
unoxidised dyes-tuff.
There are then added to this solution 1.4 parts
of sodium sulphide (65%) dissolved in 5 parts of water.
After 15 minutes' stirring, an addition is made in
portions of 11.6 parts of solid sodium hydroxide" and
refluxing subsequently performed for 4 hours. To effect
decolorisationg 0.3 part of sodium hydrosulphite is
added, and refluxing carried out for a further 20
lO. minutes. The precipitated copper sulphide is finally
separated by filtration; 20 parts of sodium chloride are
added -to the mcthen liquor and the solution is stirred
overnight. The formed precipitate is filtered off under
suction and subsequently washed with brine. After drying
there are obtained 20 parts of 2-t4'-aminophenyl)-5-
amino-benztriazole-6-sulphonic acid of the below given
formula III, in the form of a yellow crystal powder
having a nitrite value of 63.4%. `
H2N N
HO3S ~N~ NH2
- ' :' .
III
:: .
- 46 -
~.

10495~7
EY.ample 2b
Production of a dyestuff from 2-(4'-aminophenyl)-5-
aminobenztriazole-6-sulphonic acid
Tetrazotisation:
10 Parts of -the above obtained 2-(4'-aminophenyl)-5-
aminobenztriazole-6-sulphonic acid are suspended in 150
parts of water, and an addition then made of 17 parts -
of 39% hydrochloric acid. While vigorous stirring is
maintained, 11.75 parts of a 4N sodium nitrite solut~on
are then plunged all at once into the suspension at 0.
10. 'r~he suspension, which has become orange in colour, is
subsequently fully stirred at 0 for 1/2 hour.
Coupling:
7.02 Parts of l-hydroxy-6-aminonaphthalene-3-
sulphonic acid (66%) are dissolved in 180 parts of water
with the addition of 2.52 parts of. conc. sodium hydroxide
solution. To this solution there is then added at 0,
in the course of 1~2 hour, the above prepared diazo
solution, the pH-value being maintained throughout at
be-tween 9.0 and 10.0 by the simultaneous addition of a 10%
20. sodium hydroxide solution. Immediately after completed
addition of the diazo solution, a solution of 9.54 parts
of l-naphthol-3,8-disulphonic acid in 150 parts of water
is plunged into the reaction mixture, and stirring continued
with pH 9 to 10 overnight. After acidification of the
- 47 -
: , . . , . , . :, ~ . . .
:, .. . . . , : . ~: . ~ :
. . .

~ ~ ~9 50 7
reaction mixture to p~l 3.5, the dyestuEf o the folloJing
formula IV, wl1ich dyes s-lbstantively cellulose rnat:eri~1.s
in bright bluish-red shades, can be îsolated by
filtration.
HO~S O~I r HO
b~ -N=N~ \~N=N--~
S03H H03S
IV
,
xample ?.c ~-
lO Parts of 2-(4'-aminophenyl)-5-aminobenztriazole-~-
sulphonic aoid (55.6%) are tetrazotised by t'ne method
described in Example 2b. There îs then added to the
tetrazo solution at 0, in the course of half an hour,
a solution o~ 7.3 parts of l-amino-8~ydroxynaphtha1ene-
3,6-disulphonic acid (80.9%) in L30 parts of ~7lter and
2.4 parts of conc. sodium hydroxide solutiGn, the pH-value
being m~intained constant at 2.0 to 2.5 by the simultaneous
addition o~ a 10% sodium hydrogen carbol1ate solution.
The partly precipitated solution, stirred overnight
at 0 to 5, is adjusted with sodium carbonate to give a
pH-value of 8.0 to 8.2; there ls subsequently added at
- ~8 -

5 [)~ ~
0 -to 5, in -the course oE half an hour, a solution of
4.89 parts of 1-hydroxy-7-aminonaph-thalene~3-sulphonic
acid in 130 parts of water, 2.4 parts of conc. sodium
hydroxide solution and 1.1 parts of solid sodium carbonate, :;
5 the pH-value being main-tained constant at 8.0 to 8.2 ~ :
throughou-t the coupling reaction by the simultaneous
addition of a 10~ sodium carbonate solution. The
dyestuff suspension is subsequently s-tirred overnight
at room temperature and -then for 5 hours at 40; there
is finally made an addition of 50 parts of sodium
chloride, whereupon the dyestuff of the below given
formula V can be isolated. :
.,.,, ~, ,.
H~ NIH2 _ _
~ ~ _ N=N-~y/ \N ~ N--N- ~ H0
H03 03H H03S~\N/ _
L 1 7 ~ v~
V . ':
The obtained dyestuff dyes substrates based on cellulose
substantively in claret shades.
- 49 - ~:
., ' ''',
, . .. : ~ -

~4g5(~7
Example 2d
Production of a reactive dyestu:Ff from 2-(4'-amino-
phenyl~-5-aminobenz-triazole-6-sulphonic acid
20 Parts of the dyestuff produced in Example 2b
(nitrite value: 47.4%) are dissolved in 800 par-ts of
water and the solution cooled -to O. After the solution
has been adjusted wi-th lN sodium hydroxide solution to have
a pH-value of 7.0, a solution of 1.9 parts of cyanuric
chloride in 20 parts of acetone is addéd all a-t once.
The pH-value is then maintained constant at 6 to 7 by
the continuous addition of lN sodium hydroxide solution.
After no further sodium hydroxide solu-tion is consumed,
the pH-value is adjùsted to 7 and a neutralised solution
of 4.1 parts of aniline-2,5-disulphonic acid in 30 parts
of water plunged in rapidly. The whole is heated to 40
to 50 and again continuously neutralised to pH 7.0 with
lN sodium hydroxide solution. After a standing time of
3 hours at 40 to 50, stirring is maintained overnight at ; ;
room temperature, and the solution finally salted out
wi-th 70 parts of sodium chloride. The isola-ted dyestuff
20 of the follo~ing formula VI dyes, by dyeing processes
normally used for reactive dyes-tuffs, cellulose-containing
materials in bluish-red shades, with high fixing and
exhaust values.
- 50 -

~)49S~7
[ \N ~ 5 H ~ H03S ~ \NH ~ -NH
b - S03H ~ ~-
':'
VI
If in Examples 2b and 2c the 2-(4'-aminophenyl)-5-
aminobenztriazole-6-sulphonic acid is replaced by an
equivalentamount of 2-(4'-aminophenyl~-5-aminobenz- ~ :
triazole-2', 6-disulphonic acid (produced, for example,
by the coupling of diazotised 4-nitroaniline-2-sulphonic
acid to 1,3-phenylenediamine-4-sulphonic acid, oxidation
of the ob-tained o-aminoazo dyestuff with copper sulphate
in water/ammonia to give 2-(4'-nitrophenyl)-5-aminobenz-
triazole-2',6-disulphonic acid and subsequent reduction
of the nitro group with sodium sulphide in water), then ` .
there are likewise obtained valuable dyestuffs having
similar properties and shades, but wi-th improved solubility.
If the 10 parts of 2-(4'-aminophenyl)-5-aminobenz- -
triazole-6-sulphonic acid according to Example 2B is
replaced by equivalent amounts of a diamine of the -
formula
~ ! ; ' '
y ~ / NH2
:
- 51 -
: ~ , . . .: . .

so~
wherein Y ha3 the meanings given :in co:lurml 2 oi- the
following tabLe, and the 7,02 par:ts of l hydroxy 6-
amlnonaph~halene-3-sulphonlc acicl ancl 9.5~ parts o~
l-nap'nthol-3,8-disulphonic acid are replaced b-y
equivalent amounts respectlvely of the coupling
components Listed in columns 3 and 4 of the following
Table III, then likewise -there are obtained dyestu~s
which dye cellulose ma~erials substantive].y and whicll ~ -
possess good general Eastness properties. The shades
of the dyeings on cotton are shown in col~nn 5 of
the table.
-
~
':
- 52 -
,, ~

5~
' a~ ',' ."
U~ U r-l . ,
r,; ) a.) ~_~
~ d ~ O
__._ ~
a~
C
r-l r-l
~d tll ,
rC rC
rC r~ . rC
~ T~l r ~ 0~ r-l
O O ~ .
~ ~,C ~
: `D c,)
I ~ rl ;:
P~ C O
O r( rlO r~
S.l Q' rC S~l S:L,
rC ~
I I ~'dl l
r l ~ 1~ r~l ~rl . ,: .
~ C',C~
H Il) al O O -.
H r-l -1 ,C ~1
1_1 rd ~d ~ ~d
rC rC
a~ ~) ~) ~~ .1.- . .
~_1 rC rC~ rC
,a ~ ~c~ G
~d ~
E~ . ,~. .;, :
?~, ~d O I . P~ t~) . -
X 1~ X . ,-
O C) ~ O ~
~) S~ ~r~
~_
. P~ O I ~ ~ O , .
rC rC ~O ~) I rC~ rC
I Q, I ~rl r~l I Q.
~ ~1 X O rC I J
O u I O rt ~ ~J O u~ .. .
~ rC 1~ ~r l . .
t~
I
r-l ~) ~-I ~~) r-l t~ ~1
_
'
X~
c~ ~ rC _ _
a)
~,1 Ei
~ , .
~ _ . . .. ___ .... _
. . . ~
u~ , .
- 53 -
.. ..
, . :, ~ , . - :.:

~0~9507
Example 2e
To produce the copper complex o~ the dl~estuff desi~nated
as No, 3 in Table ~II, 10 parts of dyestuf~ (nitrite
value: 44.6%) are heated with 120 parts of water, 15
parts of conc. ammonia and 1.8 parts of copper sulphate-
pentahydrate or 15 hours at 105 to 110 in a pressure
vesselG The still ~arm solution is filtered to remove
the small amount of insoluble substance, and then
concentrated by evaporation to dryness. The obtained
copper complex (8.5 p~rts) dyes cotton substantively,
and leather ~rom weakly acid solution, in bro~m-vlolet ;:
shades having good general ~astness properties,
~ 5~ -
` ' - '-~'IF
.. ~

~ 5~ 7
Example 3
~ solution oE
1 part of 2~(4'-aminophenyl)~5-amino-henzotriazole in
0.9 part of concentrated hydrochloric acid and
10.5 parts of water is diazoti~sed with tle aid of a
mixture, cooled to -10, of
5.37 parts of 4N aqueous sodium nitrite i.n
31.6 parts of Einely crushed ice and ~ :
8.9 parts of conc. hydrochloric acidJ ~J use of the
process described in Example 1.
After decomposition of ~he nitrite excess by
means o~ a soLution of ca.
1.6 parts of sulphamic acid in : .
parts of water, the diazo solution, purified through
a Hyflo-bed9 is added in the course of 10
minutes, with vigorous stirring, to a solution
.eooled to 0 - 5 and prepared with the aid of ca.
19 parts of a 7.5% aqueous sodium hydroxide solution of
0.638 part of salizylic acid (100%) in
42 parts of water~ with a pH-value of 12.6. By means of
a simultaneo-ls and controlled addition of a 7.5%
aqueou~ sodium hydroxide solution, the pl~-value
of the solution remains during coupling between
12 and 12.8. After completed additioll of the
diazo component, the brown-red solution, still at
0 - S, is further stirred for S minutes. There
- 55 -
. .. ~,. .
. , . . ., ~ .
. .
., : .

-
~ 7
ic ~hen pl~mged i.n a so:lutioll o
1..01. parts o~ ~~acld (:LOO'Y0) ln
10.1 parts of water and
1.27 parts o~ conc. sodlum hyclroxi.de solution. The second
co~lpling slow].y co~lences~ the solution
becomes clearly dark and cloudy~ and a~ter ca.
-three hours there i5 :Eormed a dark bro~m
precipitate. The reaction mix~ure is allowed
to fully react overnight at 20 - 2.5, and is
then stirred at 45 ~or a further 5 hours.
Finally, an addition is made o ;:
34 parts of sodium chlorlde, ~he whole stirred overnight ~ -
at 20 - 25~ then filtered under suction and
dried; there are thus obtained 2.75 parts of
the dyestuff of form~lla VII, which dyes cotton
substantively in warm bro~m shades.
.
~0 ~ ~ 2
_ S0
VII
If the mixture just described is acidi~ied after .
the first coupling to salicylic acid with
50% aqueous acetic acid to give a pH-value of 4,
an addition then made to it of a solu~ion .
(acidified with hydrochloric acid until a
slight acid reaction to litmus is shown) of ~-~
- 56 - t
: ' -

- ~0~9S07 .
1.01 parts of ~-aci.d (100%) i.n
20 parts oE water and
1.3 parts o~ conc. sodium hydroxide solution, and the
whole finally processed as in the case of
dyestufE VII, then there is obtained the
isomeric dyestuff of formula VIII, which dyes
cel~ulose-containing materials, such as cotton,
paper, viscose, etc., substantively in . .
red shades. .
~ ~ ~ N=N~
S0 H
VIII . 3
The dyes~uff VIII dyes wool with chrome mordants,
in consequence of the salicylic acid group
present~ fast to fulling. -.
;
~ If, instead of the 2-t4'-aminophenyl)-5-aminobenæo-
15 tria~ole, the salicylic acid and gamma-acid, there are
used corresponding amounts respectively of a diamine
of the formula
X ' ' ~ '
wherein the two X's have the meanings given in column 2 ::
......... ......................................................... .... ....... ..... .
20 of the folLowing Table IV, and corresponding amounts of one
the coupling components listed in columns 3 and 4, the
~'
. .
,
..
. , - . , , ., ~
: .

10 ~9 SQ7
procedure o~herwise being as d~scribed in Example 2,
then there are obtailled dyestuffs wh;ch possess si.milar
properties and which dye cellulose-containing ~.aterl~ls
in the shades sho~n in column 5.
~s can be seen from Table IV, dyestuffs produced ~,Jith
~he diamines and coupling ccmponents given in columns
3, 4 and 5 dye ~Jool with chroine or copper mordants
fast to fulling, in the shades listed in column 6.
' ` ''`''~ IK

'I'eble IV
. .
O _~ ~ bO
u~ ~ bO t G) bO S~
",~ o ~ Q P o O
. _ X ~
~ O ~0
O P
E~ ~ ~ ~ C ~ o a.
o ~ td , N cO 0~ ~C
~ td ~ , O
t~ I ~
o ~ td ~ ~ ~ o b 4
cr~ E3 ~ ~ td C) E3
~`I ~ Q' ~ `~ E~
u
td rl
~ ~ t~
~: .,~
. ~ o ~
0~ ~
o
~0 ~ J~ ~ U U ~ '
~,1 N S~
U t~E~
~:1 ,n I I ~ ~ ~Htd t~t~ I
O I~ ~I~ ~ ~rl O O I ,_~
U ~ 1 U ~ U U I ~1
l U t~l U t~
~d ~ ~d ~ ~ ~ X O
i 4 . I ~ 1~ t~ U U t~ td ; ' '
Q td O ,1 1~ ~ td ~ ~ U
, ~ dtd I :~
c~l t~ O O Z;tn tq t~ Q-
c m~ ~ x x V
_ . __ ..... . .
:
~, o ~ ~ ~ ~~ ~O 1~, CO' ~
,~
__. . . _ . . .
o U~
U~ ~ "
5 9
i

so~ ~
ntlnuat:l on of Tab~ e IV
__ ~
$
, ~u ~u
__
G
~U
G ~ alS~
~ ~ G
C) r-l N ~ O
~ l N
bl) cq ~ O C~
`J
,~ I I Cl. R.
~ O Ul I I
o o O ,~
~ I ~ I O
I ~) N ~1
_ _~
,
~0
1--I N i~ ~
:o~
`_ .,1 ~ O O ~
I N IJ
O p~ Q' O
t~
U ' '
M ~ I ~ O
~1 t) r~
~ C~ CU ~d O
.
I ~U I I O
~-~1 ~ O O .' ~`
. . _ ... _. . ___ __._ , . . -- .. -- .
~Z _ ' l .
_ _, . _ __ __ ~.. _ . .... _ .
60 - :
.
.

~95C~
* and afZ~rtreaZ-merlL with C~115-Cl in a socla-.llka:li.rle
solution :Eor :Eorrnation o~ an O-C2~1cj-group;
-'c* ~md aEtertreatm~nt with Cl S02 o -c~3 for
esteri.Eication of the hydroY~y group,
*** and sub~3equent reduction of the nitro group to ~ ;
an ~NH2 group.
- 61 -
.
, . , . ,. , . :
, ,, - ., .. , : . . .

Tabl.e V
_.____
a~
.~ o
~3 a) ~ , J
~D~ ~ ~ ~
, ,~ ~
_ __ _ ~
-1
~ ~ ~o
O ~ ,~
~ ~ t~
~3 O ~ ~ ~ O ,S'.
c~ 5~ 1 a) I s~ L)
~ r~
~ ~ O ra p~
.~ ~
.~r~l ~r-l ~ O t~ O ~ C~l I
U`) ~ U I .-1 td ,~
:~ ~ .ua) a
o ~ o ual
O ~ O I ~ r~ O ~ ~U
-I~) r-l r~ a~ ~
rci ~1 ~ I o ~ , o~, ~ o
~ P` Il] ~ I O N
O ,c~U ~ F~ O O
t.~ aJI ~r~rl r~ ,~ N
.~ u E3 .
I I I I I I I I .'~
æ
.~ ~
U I ~
0 r~ I I r~ O
.~
.L) C) ~ O I U~ ON
8 ~
o ~ ~ ~ ,~ X
~ x ~ a 5,~
. o ~q s~ ~ ~ ~,
u I a
.~ o ~ ~a
,~ ~ ~a ~' O U
~~ .~ oo ~ ~ ~ ~d ~ I ~
~ ^ ~
~ ~ I a) o
O r~l O 1~ ,Q
U O .C~ I O ~ I ~
,c S l O ,~ O O ~ cd ~-1
N ~ O U
u~ .~ c~ a .. ~ N I ~: -
s~ ~ I .. ~ au E3 cd cY7 a)
,~ cd ~ ~ ~d ~ rl h ~' ,~
~ ~ cd
~ æ ~, ~D ~ æ
X ~
~ o 8 o
O C~ ~: ~ X C~
.~ o
_ Q O O O
, ~ :.
C`~
s~ ~ c~
~ _ . .~----------
~ . :' "
~1 0 ~I C.~! ~ ~ n ~
_~z '~ :
._ ----- : :
O
- 62 -
-

~0~95~7
.
A solution o
1 part of 2-(4'-aminophenyl)-5-amino-benzotriazole in
0.9 part of conc. hydrocltloric acid and
10.5 parts of water i.s diazotised with the aid o~ a
mi~ture, cooled to -10, o
5.37 parts of ~N aqueous sodium nitrite in
31.6 parts of ~inely crushed ice and
8.9 parts of conc. hydrochloric acid, by use of the
process described in Example 1.
After decomposition of the nitrite excess by
mean.~ of a solution oE ca.
1.6 parts of sulphamic acid in
~0 parts of water, the mixture is adjusted by the
addition portionwise o~ c~. ~
7.7 parts of solid sodium bicarbon~te to p~ 2-3, and
the insoluble matter removed by filtration
through a Hyflo~bed. The clear diazo solution is
then added at 0 - 5, in t'ne course of 10
minutes, to .l solution of
2.2 parts of sodium naphthionate (100%) and
2.2 parts of sodium acetate in
17.6 parts of water~ whereby the p~l-value oE the coupling
mixture becomes ca. 5 and the claret red
dyestuff immediately precipitates.
- 63

~ ~9 50 7
The mixture is then further stirred fo~ 1 hour at 5,
for 5 hours at 20, for 24 hours at 35 and for 12
hours a~ 55,
The mixture i~s afterwards boiled, subsequently filt2red
under suction at ca. 50, pressed and dried; there are
thus obtained 2.S parts oE ~he dyestuff of formula IX,
which d7es cotton sul)stantively in brilliant shades.
~2 ~ NH~
N/ ~
SO~H IX SO~H
If there is used in Example 4, instead of 2-(4'-
aminophenyl)-5-a~inobenztriazole, 2-(4'-aminophenyl)-5-
aminobenztriazole-6,3'-disulphonic acid as the tetrazo-
tising component, then a red dyestuff is obtained which
dyes cellulose materials likewise with high substantivity.
Exam~
An amount o~ 0.605 part of p-nitraniline (100~/o) is
dissolved in 1.67 parts of conc. hydrochloric acid and in ~;
1.325 parts of water at 80 to 90. The clear solution is
poure~ in a fine stream, with good stirring, into a
mixture of 2.21 parts of water and 2.2.1 parts of finely
crushed ice. There are then quickly plunged into the
cold suspension (temperature: 0 to 5) 1.3 parts of
a 4N aqueous sodium nitrite solution.
- 64 -
~ ~ - . : . : ...... . . . .

~4~50'7
The suspension becomes clear in a few minutes
except for small amounts of a residue. For -
decomposition of the nitrite excess present,
an addition is made, with stirring, of
0.1 part of solid sulphamic acid; as soon as the solution
no longer visibly blackens potassium iodide - '~
starch paper, it is filtered.
There are then added to the ice-cold clear
diazonium solution in the course of 20 minutes, ~' '
with thorough stirring to avoid the formation of ,
lumps,
1.435 parts of H-acid (100~) and
0.232 part of sodium carbonate in ;- '
4.3 parts of water. Stirring is continued overnight at
20 - 25; the brown suspension is then heated
to 50, and the dyestuff dissolved by the
addition of
0.842 part of conc. sodium hydroxide solution and
1.684 parts of solid sodium carbonate.
The sodium salt of the dyestuff is then
precipitated with '"
8.42 parts of sodium chloride, the suspension stirred
overnight, ,then filtered under suction and
pressed.
The filter cake is dissolved in ,
parts of water with the aid of
- 65 -

~495i~)7
1.68 parts of sodium carbonate at 80; the solution is allowed
to cool, with stirring, to 20, and is finally
cooled with ice to 0 - 5, whereby the blue-violet
sodium salt of the intermediate dyestuff again
precipitates in finely dispersed form.
~ solution of
l part of 2-(4'-aminophenyl)-5-amino-benzotriazole in
0.9 part of conc. hydrochloric acid and
10,5 parts of water is diazotised with the aid of a
mixture, cooled to -10, of
5.37 parts of 4N aqueous sodium nitrite in
31.6 parts of finely crushed ice and
8.9 parts of conc. hydrochloric acid, by use of the
process described in Example l.
After decomposition of the nitrite excess by
means of a solution of ca.
1.6 parts of sulphamic acid in
parts of water, the cold diazo solution, purified
through a Hyflo-bed, is added in the course of
20 minutes, with thorough stirring, to the -~
above produced alkaline suspension of the
sodium salt of the intermediately obtained dyestuff ~ -
p-nitraniline -azo -II-acid, the p~-value of the
coupling mixture being maintained between 8 and 9
by the simultaneous addition of 10% aqueous -
sodium hydroxide solution.
- fi6 -

~.045~5~7 :
After completed addition of the diazo solution,
the neutral blue coupling product precipitates
completely; a drop test on filter paper shows
a colourless outspread.
There are then quickly added, by plunging,
0.55 part of phenol, melted in " '
, 5 parts of water, whereupon the suspension assumes a
' dark green coloration.'It is allowed to fully
react overnight at room temperature; it is then
heated for 5 hours at 40 and for 3 hours at 60;
there is finally made an addition of
34 parts of sodium chloride, and the whole stirred
overnight; the mixture is filtered off under
suction, pressed and dried to thus obtain
4.9 parts of the dyestuff of formula X
NH2 ~H N
2~ O ~=~ ~ ~ ~
X
The dyestuff dyes cotton substantively in deep ~ ' -
brilliant green shades. ,
If 3,''~,6-dimethyl-2-(4'-aminophenyl)-5-aminobenztriazole
20 is used as tetrazotising component, the procedure being
otherwise analogous, then a dyestuff is obt'ained which ,'
likewise dyes cellulose fibres substantively, in bluish-
green shades, and which has improved fàstness to light.
- 67 -

~ ~9 S~ 7
Example 6
,
A solution of
1 part of 2-(4'-aminophenyl)-5-amino-berlzotriazole in
0.9 part o~ conc. hydrochloric acicl and
10.5 parts of water is diazotised ~ h the aid o a
mixture, cooled to -10~ o
5.37 parts of 4N aqueous sodium nitrite in
31.6 parts of finely crushed ice and
8.9 parts of conc. hydrochloric acLcl, by use of the
process described in Example 1.
~fter decomposition of the nitrite excess by
means of a solution of ca.
1.6 parts of sulphamic acid in
parts of water, and filtration of the solution through
a Hy~lo bed, ~here is added to the cold dia~.o
solution at 0 - 5 a 40% aqueous sodium ac2tate
solution until a pH-value of 2.5 is obtained.
A solution of
1.44 pqrts of H-acid (100%) and
0.233 part of sodium carbonate in
20 22 par~s of water is then added during 10 minutes to
the cold diazo solution, the pH-value of the
coupling nixture being maintained constant
between 2.5 and 2.8 by the simultaneous addition
of a 40% aqueous sodium acetate solution. After
~'
- 6~ -
. , , . ~_
'' ~ ' ~ ' ' '

~495~7
the completed addition, the violet suspension
i9 stirred overnight at 0 - 107 whereupon in
the colourless outspread of a drop test on
filter paper with alkaline H-acid solution no
unreacted diazo component could he detected,
and with diazotised p-nitraniline only traces
of the coupling component.
On the following day,
0.371 part of aniline is emulsified in
1021 parts of hot water and~ with stirring,
1.19 parts of conc. hydrochloric acid slowly added~ The
whole is cooled with ;ce to 0 and, with
vigorous stirring,
1.2 parts of a 4N aqueous sodium nitrite solution are
plunged in. After 5 minutes' diazotising, the
excess nitrite is decomposed by addition of
0.05 part of sulphamic acid, and the solution plunged
quickly, with stirring, into the previously
describéd violet suspension of the acid
coupling product - tetrazo - 2-~4'-aminophenyl)-5
amino-benzotriazole- H-acid at O - 10.' There
is subsequently added during 15 minutes 10~
aqueous sodium carbonate solution to the coupling
mixture to the extent that a pH-value of 7 is
established. Stirring is then continued for 20
minutes at 0-10 and the pH-value held constant
- 69 -

~495~7
at 7. The violet colour of the Eirst coupling
product change~ to grey, and ~he reaction oE
the diazoaniline to alkaline H-acid in the
colourless outspread of a drop sample oE the
coupling mixture disappears ~lmost completely.
An addition is then made of
0.466 part of the purest m~phenylenediamine dissolved in
40~ parts of water, and the ~Jhole stirred overnigllt at
room temperature. There are then added to - -
the mixture -
6.6 parts of sodium chloride; the whole is heated for 5
hours at 50, stirred finally overnight at
~0 - 25, filtered under suction, pressed and
dried. There are thus obtained 3.87 parts of
lS thc dyestuf~ of for~ula ~I, which dyes cotton
su~stantively in neutraL black shades.
OH
O ~ N~¦ ~T -O-N-N--~1~> ~H
: ~103 /~S03H L / ~ 2
XI
The dyestufE XI can also be used for the dyeing of
leather in clear black shades with good general fastness
properties.
. ' ' .
:. ~

~ ~ ~9 S~ 7
.If, instead of the 2~ arninophenyl)-5-2minobenzo-
triazole, phenol or m phen~Jlenediamine, H-acid, and
p-nitroaniline or aniline, given in Exam21es 4 or 5,
there are used corresponding, amounts of one of the
diamines given in column 2 of the following Table V,
and one of the coupling and diazo components listed in
columns 3, 4 and S, respectively, the procedure other~7ise
being as described in Examples 4 or 5, then there are
obtained trisazo dyestuffs which have similar properties
and which dye cotton substantively in the shades shown
in column 6 of the table.
The coupling of the dia7.0tised diaminobenzotriazole
compound on the one hand, and of a coupling component
on the other hand, with a monoaæo compound can be
lS performed also in a different sequence from that given
in Example 4. For example, the coupling with the diazo
end component ma~ be performe~ also as the final step.
(See Table V)

-
~0495~7
Table VI
2(4~-aminophenyl)-5-amino-benzotriazole _ A
3',6-dimethyl-2(4'-aminophenyl)-5-amino-benzotriazole =B
_ _ . . . ~ .
No Diamine Couplin~ Coupling Diazo Shade
component component ll]L
(2~ -diamine~ r[1l~ Lll¦
Sequence of coupl6in~s
l A o. cresole (alk) H aeid 2,5-dichlorc green
-aniline : :
2 B (alk) S acid 1~ 5-nitro-o- blue
(2~ toluidine(l)
Sequence of couplings : l~ -~diamine~l]
(as in Example 7)
' ~.
3 A 4-chloro- (acid) H ~ci)d aniline Black
. m-phenylene (alk)~
-diamine
4 11 4-methoxy- , .. ..
m-phenylene
diamine
5 ll m-carboxy- . .. ..
methylamino- :
p-methyl .
-aniline
72 -
,. . . ~ , .

-t ~ S ~
6 A 2,7-naphthylene (acid~H acid 2-amino-5- black
-diamine (1) ni-troben-
(alk) ~__ zenesulpho-
nic acid
7 " 5-amino-2- ll aniline
chlorophenol
8 ll 2,4-quinoline- ll sulphanilic
(1) acid (2)
Se~ uence of couplings: I < diamine _~ [II III~
9 A salicylic acid m-phenylene- 4-amino- I:bDown
diamine benzene-m-di-
sulphonic aci d
10 ........ H acid (alk) ll p-aminoacet- brown
anilide
11 ll 2-methyl- ll sulphanilic brown
phenol-6- acid
carboxylic acid
12 . salicyclic acid 2,4-diamino- aniline orange
sulphonic ac d
13 ll 3,5-diamino-4- 2,4-toluylen l-amino- brown
chlorobenzene- diamine(acid) naphthalene
sulphonic acid -4-sulphonic
'" '
,

)9l95()7
14 A (alk) H acid 375-diamino~ acid blu~-
p-toluene- black
sulphonic acid
15 .l l-naphthylamine 4,5-dihydroxy- l-amino-naph black :
naph-thalene-l- thalene-4-sul-
sulphonic acid phonic acid
16 . m-phenylene- chromotropic n black
diam~ne acid
(2)
17 ll phenol (alk) p-nitroaniline~ green ::~
K acid (acid)
18 " salicyclic acid (2) . . .
(alk) o-nltroanlllne green
K acid (acid) :
19 ., salicyclic acid (2)
talk) l-naphthyl- brown
H acid (acid) amine
20 B salicyclic acid (2)
(alk) 6-chloro- green ~ :
S acid (acid) metanilic acid
:,' .
"
~:~
: ' ~ .. .:

S1~7
(1) (2)
Sequence of couplings : I ~ ~ diamine
._ _ ~ . ___ ~_.......................................... ,
21 B 5-amino-1- resorcin 1-an~ino~naphtll- c1aret
. a1ene-~~sulp~l- shade
onic acid
* and aE~ertreatment witll sodium sulphite in order to reduce
the nitro group
,~ , "
- . ~ .
- - 7~ - .
, "

~49S()7 :~
Example 7
1 part of 2-aminophenol--4-sulpho~lic acid (100~/o)
is dissolved in ~ -
parts of ~jater with the aid of
0.68 part of sodium hydroxide solu~ion (30%) at 65.
Acidification is performed with
0.79 part of conc. hydrochloric acid, and the precipitated
suspension cooLed with ice to 3. There are
then added belou the surfac~, with stirring
and in the course of 10 minutes,
1.34 parts o a 4N sodium nitrite solution; the mixture
is subsequently di~æotised for 1/2 hour. Before
coupling, the sodium nitrite present in a
slight excess is decomposed by the addition of
sulphamic acid.
To effect coupling,
0.6 part of resorcin (100%) is dissolved in
3.15 parts of water, and an addition then made of
0.84 part of sodium hydroxide solution (conc.). The
solution is then conled with ice to 0, and
half the above described diazo component added.
Into the coupling mixture there is then plunged
0.58 part of conc. sodium hydroxide solution,
and thereupon the remainder o the diazo
component added. After 4 hours' stirring at
10 - 20 9 the mixture is heated for 1/2 hour ~o
- 76 -
'
, , :- , , . - . .

-- ~ (149507
35 , and to the clear solution additions are
made successively of
0.37 par-t of cryst. sodium acetate dissolved in a
small ~mount of water,
0.1 part of conc. hydrochloric acid,
.52 part of sodium chloride, and of a solution at 30-40 of
1.37 parts of cryst. copper sulphate in
4.7 p~rts of water. The intermediate of formula XII, which
precipitates within a few minutes, is salted
1.6 parts of sodium chloride and, after overnight stirring,~
filtered off under suction, washed with 10%
brine and dried.
H0 ~ N_N ~
S03H
XII
An alkaline solution of the intermediate compound of
formula XII is produced by tetrazotisation of
1 part of 2-(4'-aminophenyl)-5-amino-benzotriazole,
coupling with
0.638 part of salicylic acid ~100~) by the process
de cribed in Example 3
o ~ N= N ~ ~ ~ ~ N_N
XII a

aS07
To this salicylic acid combination there is
added a suspension of
1.58 par-ts (calculated on 100% pure substance) of the
above produced copper salt of formula XII in
9.3 parts of water at 5 - 10. The formed, initially
light-brown, solutlon becomes gradually dark.
It is stirred overnight at room temperature
and subsequently for 24 hours at 25 - 30; it
is then heated to 60 and
5.5 parts of sodium chloride are added; after cooling,
the whole is filtered under suction and the
obtained product dried.
There are obtained 2.55 parts of the dyestuff
of formula XII b, which dyes cotton substantively
in brown shades.
H0 ~ N.
XII
Ifs instead of the 2-(4~aminophenyl)-5-amino-benzo-
triazole given in Example 7 and the salicylic acid, ~ -
resorcin and 2-amino-phenol-4-sulphonic acid used there,
corresponding amounts of one of the diamines listed in
column 2 of the following Table VII and one of the coupling
end- and intermediate-components and diazo components -
- 78 -
. , ."

~(1 4950~
given in column3 3, 4 and 59 respectively, are used, the
procedure being other~7ise as described in Exam21e 7,
then trisazo-copper-complexes which possess similar
' properties and ~Jhich dye cotton substanti~ely in the
shades sho~m in col~nn 5.
' Tabl.e VII
~_ , __ , . , ,, . . ,.
(1) (2) (3) (4) ~5) (6)
. No. ~iam- Goupling Coupling Diazo component Shade ,
ine end compon- intermediate
ent- . component
_ , ,, _ . _ _ , , ~ , _ , , ._ _ , , __
1 A ' sal cylic resorcin 2-amino-1-phenol- bro~m
I l 1 14-sulphonsmide
.2 ~ ll resorcin 3,-amino-5- bro~m
I ~ ¦ sulphosalicylic ¦ ¦
- ,3 C ", J acid 5,-nitro-anthra- blac'~
. ~ (aci ) nilic acid
with A ~ 2(4'-aminophenyl)-5-amino-benzotriazole
C = 3',6-dimethoxy-2(4'-aminophenyl)-5-amino-benzotrlazole
- 79 -

;
10~9507
Example 8
10 Parts oE 2-(4'-aminonaphth-1-yl)-5-aminoben~o-
triazole t84.8%) (produced by coupling of diazotised
4-nitro-1-naphtllylamine to m-phenylenediamine, oxidation
of the obtained o-aminoazo dyestuEf with copper
5 sulphate in pyridine/water to ben~otriazole and
subsequent catalytic hydrogenation of the nitro group)
are tetrazotised in the manner described in Example 2b
for 2-(4'-aminophenyl)-5-aminobenzotriazole-6-
sulphonic acid.
There is then added to this tetrazo solution at
0 to 5 in the course of one hour, while the pH-value
is maintained constant at 2 to 2.5, a solution of 12.1
parts of l-amino-8-hydroxynaphthalene-3,6-disulphonic
acid (80.9%) and 4 parts of conc. sodium hydroxide
I5 solution in 200 parts of water, and ~he whole subsequently
stirred overnight at 0 to 5. The formed b]ue suspension
of the intermediate compound is then added a~ 0 to 5 to
a solution of l-hydroxy-6-aminonaphthalene-3-sulphonic
acid (90.5%) in 200 parts of water and 4 parts of conc.
~0 sodium hydroxide solution, the pH-value being maintained
at 9 to 9.5 by the addition of a 10% sodium carbonate
solution. The whole is stirred overnight at room temperature,
then heated during one hour to 40, and the dyestuff
finally precipitated by neutralisation of the reaction ~
mixture and addition of 100 parts of sodium chloride. The -
o 80 -

r -- ~
-
~(3 495~7
dyestu.Ef o~ the belo~7 given Eormula XIII dyes cotton
substant;vely, and substrates based on albumen (e.g
leather, wool) from sligh~ly acid solution, in
navy blue shades.
HO ~IH2- N
H03 ~ ~ ~ N/ ~ ~ 2
XIII
Example 9
10 Parts of 4-aza-2-(4'-aminophenyl)-5-aminoben~o-
triazole (50.4%) ~produced by the coupling of diazotised
4-aminoacetanilide with 2,6-diaminopyridine, the
.~ . oxidation of the obtained intermediate product wi~h
copper sulphate in waterlammonia, and ~he subs~quent
saponification of the acetylamino group) are tetrazotised
in the manner given in Example 2b for the te~razotising
of 2-(4'-aminophenyl)-5-aminobenzo~riazole-6-sulphonic acid.
The obtained tetrazo compound is coupled, in the
manner described in Example 8 (first coupling acid, se~ond
coupling alkaline), with 8.78 parts of 1-amino-8-hydroxy-
naphthalene-3,6-disulphonic acid (8~.9%) and then with
5.88 parts of 1-hydroxy-6-aminona.phthalene-3-sulphonic acid
81

~0495~)7
(90.5%), and the occurring dyestuEf precipitated and
isolated. The obtained dyestuff oE the belo~7 giVell
formula ~IV dyes cotton subs tantively itl warm bro~
shades with good fastness to lighto
.. . . .... .
~0 NH
ll03 ~ S03~ ~ N-N ~ ~ ~ =il ~ ~lO S
.
- XIV
~ '
Exa~ple 10
.
10 Parts of 2-(3'-aminophenyl)-5-aminobenzotriazole
are tetrazotised in the manner given in Example 2b
for tetrazotisation of 2-(4'-aminophenyl)-5-amino-
benzotriazole-6-sulphonic acid.
10The obtained tetrazo compound is coupled, in the
manner described in Example 8 (first coupling acid,
second coupling alkaline), ~Jith 15.75 parts of 1-~mino-8-
hydroxynaphthalene-3~6-disulphonic acid (80.9%), and
subsequently with 10.54 parts of 1-hydroxy-6-aminonaphthalene-
3-su~phonic acid (90.5%), and the occurring dyestuff
isolated by salting out. The dyestuff of the follo~7ing
formula XV dyes cotton substantively in bro~-violet
~ ~2 -
!. ~

~a37
~ shades.
. .
`:
H0 NH - :
~~ ~ N=N ~ \N < ~
XV ,,.
'~
10 Parts of 2-~3'-carboxy-4'-aminophenyl)-5-amino--
benzotriazole (82~/o) (produced by coupling of diaæotised
2-nitro-5~aminobenzoic acid to m-phenylenediamine,
subsequent oxidation of the intermediate product to ~:
benzotriazole with copper sulphate in wa~er/ammonia
and reduction of the ni~ro group with sodium sulphide
in water), are tetrazotLsed in the manner given in
Example 2b for the tetrazotising of 2-(4'-aminophenyl)-5-
aminobenzotriazole-6-sulphonic acid.
The obtained tetrazo compo~md is coupled, in the
manner described in Example 8 (first coupling acid,
second coupling alkaline), with 12 parts of 1-amino-8-
hydroxynaphthalene-3,6-disulphonic acid (80.9%), and
subsequently with 8.1 parts of 1-hydroxy-6-aminonaphthaLene-
3-sulphonic acid (90.5%), and the dyestuff of the
- 83 -

5~7
, ...... . ..
; below given formula ~YVI, which dyes co~ton substantively
in bro~-violet shades, isolated by the u.sual process.
XVI
-~ HO NH2 ~ _
}IO~S ~ .`~}1 ~ `I ~ ON
2 ''
. 3
XVI
If the aqueous solution of dyestuff ~YVI is treated
with 1 mole of copper suLphate in sLightly a~nonia-
alkaline medium, and the solution subsequent~y
concentrated by evaporation to dryness, then the ~ -
copper complex of compound XVI is obtained, which
dyes cotton substantively in brown shades.
'`- ~ .
- 84 -
~` - ' , .
.' : ' .~"' ' ' ' . ' ' ~ :
- . . . .