Disazo dyes with a vinylsulfonyl type fiber-reactive radical substituted diazo component and a 2-sulfophenylene middle component carrying a fiber-reactive radical in the 5-position

Reactive dyes of the formula ##STR1## where A, K and Z are each as defined in the claims, are especially useful for dyeing or printing cellulosic fiber materials, producing dyeings and prints having good fastness properties in a high yield.

The present invention relates to novel reactive dyes, processes for 
preparing them and their use for dyeing and printing fiber materials. 
The industrial experience of dyeing with reactive dyes has in recent years 
led to increased expectations of the quality of the dyeings and the 
economics of the dyeing process. Consequently there continues to be a 
demand for novel reactive dyes with improved properties, especially in 
respect of application. 
The dyeing of cellulosic materials such as cotton these days calls for 
reactive dyes which combine adequate substantivity with ease of removal of 
the unfixed portions by washing. They shall further be highly reactive and 
in particular yield dyeings having high degrees of fixation. Known dyes do 
not meet these requirements in all properties. 
The present invention therefore has for its object to provide novel, 
improved reactive dyes for the dyeing and printing of cellulosic fiber 
materials which possess the above-characterized qualities to a high 
degree. The novel dyes shall be notable in particular for high yields of 
fixation and high fiber-dye bond stabilities. Also, the portions not fixed 
on the fiber shall be easy to wash off. They shall further produce dyeings 
having good allround fastness properties, for example light and wet 
fastness properties. 
It has been found that this object is substantially achieved by the novel 
reactive dyes defined hereinafter. 
The present invention accordingly provides reactive dyes of the formula 
##STR2## 
where 
A is a fiber-reactive radical --NR'--A.sub.1, 
R' is hydrogen or C.sub.1 -C.sub.4 alkyl, 
A.sub.1 is a halopyrimidinyl, haloquinoxalinecarbonyl or triazinyl radical 
or a radical of the formula 
--CO--CH.sub.2 --X (2a) 
--CO--(CH.sub.2).sub.n --SO.sub.T Y (2b), 
--COCHX.sub.1 --CH.sub.2 X.sub.1 (2c) 
or 
--COCX.sub.1 =CH.sub.2 (2d), 
where Y is vinyl or --CH.sub.2 --CH.sub.2 --U and U is a leaving group, X 
and X.sub.1 are each independently of the other chlorine or bromine, and n 
is an integer from 1 to 6, 
K is the radical of a coupling component, and 
Z is the radical of a diazo component of the benzene or naphthalene series 
which carries at least one fiber-reactive radical of the formula 
--SO.sub.2 --Y (3a), 
--CONH--(CH.sub.2).sub.n --SO.sub.2 --Y (3b), 
--CONH--(CH.sub.2).sub.ml --O--(CH.sub.2).sub.m --SO.sub.2 --Y (3c), 
--(O).sub.p --(CH.sub.2).sub.q --CONH-- (CH.sub.2).sub.m --SO.sub.2 --Y 
(3d), 
--NH--CO--CHX.sub.1 --CH.sub.2 X.sub.1 (3e) 
or 
--NH--CO--CX.sub.1 =CH.sub.2 (3f) 
where X.sub.1 and Y are each as defined above, p is 0 or 1, and m, m.sub.1 
and q are each independently of the others an integer from 1 to 6. 
C.sub.1 -C.sub.4 Alkyl is generally methyl, ethyl, n-propyl, isopropyl, 
n-butyl, isobutyl, sec-butyl or tert-butyl; C.sub.1 -C.sub.4 alkoxy is 
generally methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, 
sec-butoxy or ten-butoxy; halogen is generally for example fluorine, 
bromine or in particular chlorine; examples of substituted or 
unsubstituted C.sub.2 -C.sub.4 -alkanoylamino are acetylamino, 
propionylamino and hydroxyacetylamino. C.sub.1 -C.sub.4 -Alkoxycarbonyl is 
generally methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, 
isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, 
sec-butoxycarbonyl or tert-butoxycarbonyl, preferably methoxycarbonyl or 
ethoxycarbonyl. Examples of C.sub.2 -C.sub.5 alkanoyloxy are acetyloxy and 
propionyloxy. Examples of C.sub.1 -C.sub.4 alkylthio are methylthio and 
ethylthio. 
R' is preferably hydrogen, methyl or ethyl, particularly preferably 
hydrogen. 
A halopyrimidinyl or haloquinoxalinecarbonyl radical A.sub.1 can be for 
example 2,4-dichloropyrimidin-6-yl, 2,4,5-trichloropyrimidin-6-yl, 
2,4-dichloro-5-nitro- or -5-methyl- or-5-carboxymethyl- or -5-carboxy- 
or-5-cyano- or-5-vinyl- or-5-sulfo- or -5-mono-, -di- or-trichloromethyl- 
or-5-carboalkoxy-pyrimidin-6-yl, 2,6-dichloropyrimidine-4-carbonyl, 
2,4-dichloropyrimidine-5-carbonyl, 2-chloro-4-methylpyrimidine-5-carbonyl, 
2-methyl-4-chloropyrimidine-5-carbonyl, 
2-methylthio-4-fluoropyrimidine-5-carbonyl, 
6-methyl-2,4-dichloropyrimidine-5-carbonyl, 
2,4,6-trichloropyrimidine-5-carbonyl, 2,4-dichloropyrimidine-5-sulfonyl, 
2-chloroquinoxaline-3-carbonyl, 2- or 3-monochloroquinoxaline-6-carbonyl, 
2,3-dichloroquinoxaline-6-carbonyl, 2-fluoro-4-pyrimidinyl, 
2,6-difluoro-4-pyrimidinyl, 2,6-difluoro-5-chloro-4-pyrimidinyl, 
2-fluoro-5,6-dichloro-4-pyrimidinyl, 2,6-difluoro-5-methyl-4-pyrimidinyl, 
2,5-difluoro-6-methyl-4-pyrimidinyl, 
2-fluoro-5-methyl-6-chloro-4-pyrimidinyl, 
2-fluoro-5-nitro-6-chloro-4-pyrimidinyl, 5-bromo-2-fluoro-4-pyrimidinyl, 
2-fluoro-5-cyano-4-pyrimidinyl, 2-fluoro-5-methyl-4-pyrimidinyl, 
2,5,6-trifluoro-4-pyrimidinyl, 
5-chloro-6-chloromethyl-2-fluoro-4-pyrimidinyl, 
2,6-difluoro-5-bromo-4-pyrimidinyl, 
2-fluoro-5-bromo-6-methyl-4-pyrimidinyl, 
2-fluoro-5-bromo-6-chloromethyl-4-pyrimidinyl, 
2,6-difluoro-5-chloromethyl-4-pyrimidinyl, 
2,6-difluoro-5-nitro-4-pyrimidinyl, 2-fluoro-6-methyl-4-pyrimidinyl, 
2-fluoro-5-chloro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-4-pyrimidinyl, 
2-fluoro-6-chloro-4-pyrimidinyl, 
6-trifluoromethyl-5-chloro-2-fluoro-4-pyrimidinyl, 
6-trifluoromethyl-2-fluoro-4-pyrimidinyl, 2-fluoro-5-nitro-4-pyrimidinyl, 
2-fluoro-5-trifluoromethyl-4-pyrimidinyl, 2-fluoro-5-phenyl 
or-5-methylsulfonyl-4-pyrimidinyl, 2-fluoro-5-carbonamido-4-pyrimidinyl, 
2-fluoro-5-carbomethoxy-4pyrimidinyl, 
2-fluoro-5-bromo-6-trifluoromethyl-4-pyrimidinyl, 
2-fluoro-6-carbonamido-4-pyrimidinyl, 
2-fluoro-6-carbomethoxy-4-pyrimidinyl, 2-fluoro-6-phenyl-4-pyrimidinyl, 
2-fluoro-6-cyano-4-pyrimidinyl, 
2,6-difluoro-5-methylsulfonyl-4-pyrimidinyl, 
2-fluoro-5-sulfonamido-4-pyrimidinyl, 
2-fluoro-5-chloro-6-carbomethoxy-4-pyrimidinyl, 
2,6-difluoro-5-trifluoromethyl-4-pyrimidinyl, 
6-fluoro-5-chloropyrimidin-4-yl, 6-fluoro-5-trifluoromethylpyrimidin-4-yl, 
6-fluoro-2-methylpyrimidin-4-yl, 6-fluoro-5-chloro-2-methylpyrimidin-4-yl, 
5,6-difluoropyrimidin-4-yl, 
6-fluoro-5-chloro-2-trifluoromethylpyrimidin-4-yl, 
6-fluoro-2-phenylpyrimidin-4-yl, 6-fluoro-5-cyanopyrimidin-4-yl, 
6-fluoro-5-nitropyrimidin-4-yl, 6-fluoro-5-methylsulfonylpyrimidin-4-yl or 
6-fluoro-5-phenylsulfonylpyrimidin-4-yl. 
A halopyrimidinyl or haloquinoxalinecarbonyl A.sub.1 is preferably 
2,4,5-trichloropyrimidin-6-yl, 2,4-dichloro-5-cyanopyrimidin-6-yl, 
2,4-difluoro-5-chloropyrimidin-6-yl 
2-fluoro-5-chloro-6-methylpyrimidin-4-yl or 
2,3-dichloroquinoxaline-6-carbonyl. 
A triazinyl A.sub.1 conforms for example to the formula 
##STR3## 
where T is chlorine, fluorine, bromine, 3-carboxypyridin-1-yl, 
3-carbamoylpyridin-1-yl or a reactive radical of the formula 
##STR4## 
R is hydrogen, unsubstituted or hydroxyl-, sulfo-, sulfato-, carboxyl- or 
cyano-substituted C.sub.1 -C.sub.4 alkyl or a radical 
##STR5## 
R.sub.1 is hydrogen, hydroxyl, sulfo, sulfato, carboxyl, cyano, halogen, 
C.sub.1 -C.sub.4 alkoxycarbonyl, 
C.sub.2 -C.sub.5 alkanoyloxy, carbamoyl or the group --SO.sub.2 --Y, 
R.sub.2 is hydrogen or C.sub.1 -C.sub.4 alkyl, alk and alk' are each 
independently of the other C.sub.1 -C.sub.6 alkylene, arylen is an 
unsubstituted or sulfo-, carboxyl-, hydroxyl-, C.sub.1 -C.sub.4 alkyl-, 
C.sub.1 -C.sub.4 alkoxy- or halogen-substituted phenylene or naphthylene 
radical, 
Y.sub.1 is a group --CHX.sub.1 --CH.sub.2 X.sub.1 or --CX.sub.1 =CH.sub.2, 
and X.sub.1 is chlorine or bromine, 
B is the radical --O-- or --NR.sub.2 --, and 
t is 0 or 1, and 
V independently has the meaning of T or is a non-reactive radical selected 
from the group consisting of hydroxyl, C.sub.1 -C.sub.4 alkoxy, phenoxy, 
C.sub.1 -C.sub.4 alkylthio, morpholino and substituted or unsubstituted 
amino. 
Suitable leaving groups U include for example --Cl, --Br, --F, --OSO.sub.3 
H, --SSO.sub.3 H, --OCO--CH.sub.3, --OPO.sub.3 H.sub.2, --OCO--CCl.sub.3, 
--OCO--CHCl.sub.2, --OCO-- CH.sub.2 Cl, --OSO.sub.2 --Cl --C.sub.4 alkyl, 
--OSO.sub.2 --N(C.sub.1 -C.sub.4 alkyl).sub.2 or --OCO--C.sub.6 H.sub.5. 
Preferably U is a group of the formula --Cl, --OSO.sub.3 H, --SSO.sub.3 H, 
--OCO--CH.sub.3, --OCO--C.sub.6 H.sub.5 or --OPO.sub.3 H.sub.2, in 
particular --Cl or --OSO.sub.3 H, preferably --OSO.sub.3 H. 
Y is preferably vinyl, .beta.-chloroethyl, .beta.-sulfatoethyl, 
.beta.-thiosulfatoethyl, .beta.-acetoxyethyl, .beta.-phenoxyethyl or 
.beta.-phosphatoethyl, particularly preferably .beta.-sulfatoethyl or 
vinyl. 
X.sub.1 is preferably bromine. 
alk and alk' are each independently of the other for example a methylene, 
ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexylene 
radical or branched isomers thereof. 
Preferably alk and alk' are each independently of the other a C.sub.1 
-C.sub.4 alkylene radical, particularly preferably an ethylene radical or 
propylene radical. 
Preferably arylen is an unsubstituted or for example sulfo-, methyl-, 
methoxy- or carboxyl-substituted 1,3- or 1,4-phenylene radical, 
particularly preferably an unsubstituted 1,3- or 1,4-phenylene radical. 
R is preferably C.sub.1 -C.sub.4 alkyl or particularly preferably hydrogen. 
R.sub.1 is preferably hydrogen. 
R.sub.2 is preferably hydrogen, methyl or ethyl, in particular hydrogen. 
B is preferably --NH-- or --O--, particularly preferably --O--. 
t is preferably O. 
Preference for use as radicals of the formulae (5a) to (5g) is given to 
those where R, R.sub.1 and R.sub.2 are each hydrogen, B is --O-- or 
--NH--, alk and alk' are each independently of the other ethylene or 
propylene, arylen is unsubstituted or methyl-, methoxy-, chlorine-, 
hydroxyl-, carboxyl- or sulfo-substituted phenylene, Y is vinyl or 
.beta.-sulfatoethyl, Y.sub.1 is --CHBr--CH.sub.2 Br or --CBr=CH.sub.2 and 
t is 0. 
A non-reactive substituted or unsubstituted amino radical V can be for 
example amino, N--C.sub.1 -C.sub.4 alkylamino or N,N-di-C.sub.1 -C.sub.4 
alkylamino, in which case the alkyl may be for example, sulfo-, sulfato-, 
hydroxyl-, carboxyl- or phenyl-substituted, cyclohexylamino, N--C.sub.1 
-C.sub.4 alkyl-N-phenylamino or phenylamino or naphthylamino, in which 
case the phenyl or naphthyl may be for example C.sub.1 -C.sub.4 alkyl-, 
C.sub.1 -C.sub.4 alkoxy-, amino-, C.sub.2 -C.sub.4 alkanoylamino-, 
carboxyl-, sulfo- or halogen-substituted. 
Examples of suitable non-reactive radicals V are amino, methylamino, 
ethylamino, .beta.-hydroxyethylamino, N,N-di-.beta.-hydroxyethylamino, 
.beta.-sulfoethylamino, cyclohexylamino, morpholino, o-, m- or 
p-chlorophenylamino, o-, m- or p-methylphenylamino, o-, m- or 
p-methoxyphenylamino, o-, m- or p-sulfophenylamino, 2,4- or 
2,5-disulfophenylamino, o-carboxyphenylamino, 1- or 2-naphthylamino, 
1-sulfo-2-naphthylamino, 1,5-disulfo-2-naphthylamino, 
6,8-disulfo-2-naphthylamino, 3,6,8-trisulfo-2-naphthylamino, 
1,6-disulfonaphthylamino, N-ethyl-N-phenylamino, N-methyl-N-phenylamino, 
morpholino, methoxy, ethoxy, n-propoxy or isopropoxy and hydroxyl. 
A non-reactive radical V is preferably C.sub.1 -C.sub.4 alkoxy, C.sub.1 
-C.sub.4 alkylthio, hydroxyl, in particular amino, N-C.sub.1 -C.sub.4 
alkylamino, with or without hydroxyl, sulfato or sulfo substitution in the 
alkyl moiety, morpholino, phenylamino or N--C.sub.1 -C.sub.4 
alkyl-N-phenylamino, where the phenyl is in each case unsubstituted or 
sulfo-, carboxyl-, acetylamino-, methyl-, or methoxy-substituted, or 
sulfo-monosubstituted, -disubstituted or -trisubstituted 2-naphthylamino. 
Particularly preferred non-reactive radicals V are amino, N-methylamino, 
N-ethylamino, .beta.-sulfoethylamino, phenylamino, 2-, 3- or 
4-sulfophenylamino, 2,4- or 2,5-disulfophenylamino, mono-, di-or 
trisulfo-2-naphthylamino, N-C.sub.1 -C.sub.2 alkyl-N-phenylamino or 
morpholino. 
A further group of suitable amino radicals V conforms to the formula 
EQU --NR"--Fa, 
where Fa is a monoazo radical --(D--N=N--K.sub.1) or the radical of a 
formazan, R" is independently subject to the meanings and preferences 
mentioned for R', D is the radical of a diazo component of the benzene or 
naphthalene series or of the heterocyclic series, and K.sub.1 is the 
radical of a coupling component. Preferably, D is a phenyl or 1- or 
2-naphthyl radical which is substituted by from 1 to 3 substituents 
selected from the group consisting of methyl, methoxy, chlorine, sulfo and 
--SO.sub.2 --Y, where Y is as defined above, and K is the radical of 
1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (H-acid), the radical of 
K-, I- or J-acid, or a radical of the formula (6a), (6b), (6d) or (6e) 
given below. 
Suitable formazan radicals Fa conform for example to the formula 
##STR6## 
A fiber-reactive triazinyl radical A.sub.1 is preferably a radical of the 
above-indicated formula (4) where T is chlorine or fluorine and V is 
C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylthio, hydroxyl, amino, 
N-C.sub.1 -C.sub.4 alkylamino, with or without hydroxyl, sulfato or sulfo 
substitution in the alkyl moiety, morpholino, phenylamino or N-C.sub.1 
-C.sub.4 alkyl-N-phenylamino, where the phenyl is in each case 
unsubstituted or sulfo-, carboxyl-, acetylamino-, methyl- or 
methoxy-substituted, sulfo-monosubstituted, -disubstituted or 
-trisubstituted 2-naphthylamino or a reactive radical of the 
above-indicated formula (5a) to (5g). 
A fiber-reactive triazinyl radical A.sub.1 is particularly preferably a 
radical of the above-indicated formula (4) where T is chlorine or fluorine 
and V is amino, N-methylamino, N-ethylamino, .beta.-sulfoethylamino, 
phenylamino, 2-, 3- or 4-sulfophenylamino, 2,4- or 2,5-disulfophenylamino, 
mono-, di- or trisulfo-2-naphthylamino, N--C.sub.1 -C.sub.2 
alkyl-N-phenylamino or morpholino. 
A fiber-reactive triazinyl radical A.sub.1 can preferably also be a radical 
of the above-indicated formula (4) where T is chlorine or fluorine and V 
is a fiber-reactive radical of the formula 
##STR7## 
where Y is vinyl or .beta.-sulfatoethyl. 
A fiber-reactive radical A.sub.1 of the formula (2a) to (2d) is preferably 
a radical of this kind where X is chlorine, X.sub.1 is bromine, Y is vinyl 
or .beta.-sulfatoethyl, and n is 2, 3 or 4. Of particular interest in this 
connection are compounds of the formula (1) where A is the radical 
--NH--A.sub.1 and A.sub.1 is chloroacetyl. 
K is in particular the radical of a water-soluble coupling component of the 
series of the aminobenzenes or phenols, in particular of the sulfonated or 
carboxylated aminobenzenes or phenols; of the naphthylamines or naphthols, 
in particular of the sulfonated or carboxylated naphthylamines or 
naphthols; of the aminonaphthols, in particular of the sulfonated 
aminonaphthols; of the acylaminonaphthols, in particular of the sulfonated 
acylaminonaphthols having the acyl radical of an alkanoic or alkenoic acid 
in each case having 1 to 4, preferably 2 to 4, carbon atoms in the alkyl 
or alkenyl moiety; or of the series of the pyrazolones, pyridones or 
pyrimidines, and K, in addition to the substituents customary in dyes, may 
contain a further azo group and/or one or more fiber-reactive groups. 
Of the series of substituents on the radical K, there may be mentioned for 
example lower alkyl groups having 1 to 4 carbon atoms such as methyl, 
ethyl, propyl, isopropyl or butyl, alkoxy groups having 1 to 4 carbon 
atoms, such as methoxy, ethoxy, propoxy, isopropoxy or butoxy, 
hydroxy-C.sub.1 -C.sub.2 alkoxy, e.g. hydroxyethoxy, acylamino groups 
having 1 to 8 carbon atoms, in particular alkanoylamino groups, such as 
acetylamino, or propionylamino, or benzoylamino; phenylamino, 
N,N-di-.beta.-hydroxyethylamino, N,N-di-.beta.-sulfatoethylamino, 
sulfobenzylamino, N,N-disulfobenzoylamino; alkoxycarbonyl having 1 to 4 
carbon atoms in the alkoxy radical, such as methoxycarbonyl or 
ethoxycarbonyl; alkylsulfonyl having 1 to 4 carbon atoms, such as 
methylsulfonyl or ethylsulfonyl; trifluoromethyl, nitro, cyano, halogen, 
such as fluorine, chlorine or bromine; carbamoyl, N-alkylcarbamoyl having 
1 to 4 carbon atoms in the alkyl radical, such as N-methylcarbamoyl or 
N-ethylcarbamoyl; sulfamoyl, N-alkylsulfamoyl having 1 to 4 carbon atoms, 
such as N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, 
N-isopropylsulfamoyl or N-butylsulfamoyl; 
N-(.beta.-hydroxyethyl)sulfamoyl, N,N-di-(.beta.-hydroxyethyl)sulfamoyl, 
N-phenylsulfamoyl, ureido, hydroxyl, carboxyl, sulfomethyl, sulfo, 
benzoyl, C.sub.2 -C.sub.5 alkanoyl, e.g. acetyl or propionyl, phenylazo, 
which is further substituted by one or more radicals, for example from the 
group consisting of sulfo, methyl, methoxy, chlorine and reactive radical 
of the above-indicated formula (3a), (3b) or (4), or naphthylazo which is 
further substituted by one or more radicals selected from the group 
consisting of hydroxyl, amino, sulfo, and reactive radical of the 
above-indicated formula (3a) or (4). 
One or more fiber-reactive groups on K will be customary aliphatic or 
heterocyclic radicals having detachable groups or atoms, for example a 
radical of the above-indicated formula (3a) or (3b), an above-indicated 
halopyrimidinyl or haloquinoxalinecarbonyl radical, or preferably a 
fiber-reactive triazinyl radical of the above-indicated formula (4). K is 
preferably a 1- or 2-naphthol radical with or without substitution by 
sulfo or by a radical --SO.sub.2 --Y, where Y is as defined above, or is a 
1- or 2-naphthylamine radical with or without substitution by hydroxyl, 
sulfo or a radical --SO.sub.2 --Y, where Y is as defined above, or is a 
radical of the formula 
##STR8## 
where 
(R.sub.3).sub.0-3 represents 0 to 3 radicals selected from the group 
consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, halogen, 
C.sub.1 -C.sub.4 alkoxy-C.sub.1 -C.sub.2 alkoxy, hydroxyl, hydroxy-C.sub.1 
-C.sub.2 alkoxy, C.sub.2 -C.sub.5 alkanoyloxy, C.sub.1 -C.sub.4 
alkylsulfonyl, C.sub.2 -C.sub.4 alkanoylamino, N--C.sub.1 -C.sub.4 
alkylsulfamoyl and sulfo, 
R.sub.4 is hydroxyl, C.sub.1 -C.sub.4 alkoxy or a radical --NR.sub.11 
R.sub.12 and R.sub.11 and R.sub.12 are each independently of the other 
hydrogen, C.sub.2 -C.sub.5 alkanoyl or unsubstituted or hydroxyl-, 
sulfo-or sulfato-substituted C.sub.1 -C.sub.4 alkyl, 
R.sub.5 is hydrogen, C.sub.2 -C.sub.5 alkanoyl, benzoyl or a radical of the 
above-indicated formula (4), 
R.sub.6 is C.sub.1 -C.sub.4 alkyl, 
R.sub.7 is carbamoyl, cyano or sulfomethyl, 
R.sub.8 is C.sub.1 -C.sub.4 alkyl or carboxyl, 
R.sub.9 is unsubstituted or halogen-, sulfo-, C.sub.1 -C.sub.4 alkyl- or 
C.sub.1 -C.sub.4 alkoxy-substituted phenyl or naphthyl, and 
R.sub.10 is hydroxyl or amino. 
K particularly preferably has the following meanings: 
##STR9## 
where (R.sub.13).sub.0-3 represents 0 to 3 identical or different 
substituents selected from the group consisting of methyl, methoxy, 
hydroxyl, chlorine and sulfo, R.sub.14 is hydrogen, methyl, methoxy, 
hydroxyl, chlorine, acetyl, acetylamino, hydroxyacetylamino, 
propionylamino, ureido or methyl- or ethylsulfonyl, R.sub.15 is hydrogen, 
methyl, methoxy, chlorine or C.sub.1 -C.sub.4 alkoxy-C.sub.1 -C.sub.2 
alkoxy, R.sub.16 and R.sub.17 are each independently of the other 
hydrogen, C.sub.1 -C.sub.4 alkyl, .beta.-hydroxyethyl or 
.beta.-sulfatoethyl, R.sub.18 is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 
-C.sub.4 alkoxy-C.sub.1 -C.sub.4 alkyl or phenyl, R.sub.19 is hydrogen, 
methyl, ethyl, .beta.-hydroxyethyl, .beta.-cyanoethyl or 
.beta.-sulfatoethyl, and R.sub.20 is acetyl, propionyl or a radical of the 
above-indicated formula (4). 
K can also preferably be a radical of the formula 
##STR10## 
where (R.sub.23).sub.1-2 represents 1 or 2 identical or different radicals 
selected from the group consisting of sulfo, methyl, methoxy and 
--SO.sub.2 --Y, where Y is as defined above, T is chlorine or fluorine, 
and V is amino, N--C.sub.1 -C.sub.4 alkylamino or N,N-di-C.sub.1 -C.sub.4 
alkylamino, the alkyl being unsubstituted or sulfo-, sulfato-, hydroxyl-, 
carboxyl- or phenyl-substituted, cyclohexylamino, N-C.sub.1 -C.sub.4 
alkyl-N-phenylamino or phenylamino or naphthylamino, the phenyl or 
naphthyl being unsubstituted or C.sub.1 -C.sub.4 alkyl-, C.sub.1 -C.sub.4 
alkoxy-, amino-, C.sub.2 -C.sub.4 alkanoylamino-, carboxyl-, sulfo- or 
halogen-substituted, a radical of the formula 
##STR11## 
or a monoazo radical --(D--N=N--K.sub.1), where D is a phenyl or 1- or 
2-naphthyl radical which is substituted by from 1 to 3 substituents 
selected from the group consisting of methyl, methoxy, chlorine, sulfo and 
--SO.sub.2 --Y, where Y is as defined above, and K is the radical of 
1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (H-acid), the radical of 
K-, I- or J-acid, or a radical of the above-indicated formula (6a), (6b), 
(6d) or (6e). 
Z is a phenyl or naphthyl radical which, in addition to fiber-reactive 
radicals, can contain the substituents customary in organic dyes. Examples 
of such substituents include C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 
alkoxy, acylamino groups having 1 to 8 carbon atoms, in particular 
alkanoylamino groups and alkoxycarbonylamino groups, such as acetylamino, 
propionylamino, methoxycarbonylamino, ethoxycarbonylamino or benzoylamino, 
phenylamino, N,N-di-.beta.-hydroxyethylamino, 
N,N-di-.beta.-sulfatoethylamino, sulfobenzylamino, N,N-disulfobenzylamino; 
alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, such as 
methoxycarbonyl or ethoxycarbonyl; alkylsulfonyl having 1 to 4 carbon 
atoms, such as methylsulfonyl or ethylsulfonyl; trifluoromethyl, nitro, 
cyano, halogen, such as fluorine, chlorine or bromine; carbamoyl, 
N-alkylcarbamoyl having 1 to 4 carbon atoms in the alkyl radical, such as 
N-methylcarbamoyl or N-ethylcarbamoyl; sulfamoyl, N-alkylsulfamoyl having 
1 to 4 carbon atoms, such as N-methylsulfamoyl, N-ethylsulfamoyl, 
N-propylsulfamoyl, N-isopropylsulfamoyl or N-butylsulfamoyl; 
N-(.beta.-hydroxyethyl)sulfamoyl, N,N-di-(.beta.-hydroxyethyl)sulfamoyl, 
N-phenylsulfamoyl, ureido, hydroxyl, carboxyl, sulfomethyl or sulfo. 
The reactive radicals of the above-indicated formula (3a) to (30 in Z are 
subject to the abovementioned definitions and preferences as regards 
X.sub.1 and Y.m.sub.1 and m are each preferably independently of the other 
2, 3 or 4, particularly preferably 2 or 3, very particularly preferably 2. 
p is preferably 0, and q is preferably 1, 2 or 3, particularly preferably 
1 or 2. 
The Z is preferably a phenyl radical which carries a fiber-reactive radical 
of the formula (3a) or (3b) and is further unsubstituted or sulfo-, 
methyl-, chlorine- hydroxyl- or methoxy-substituted, or is a 1- or 
2-naphthyl radical which carries a fiber-reactive radical of the formula 
(3a) and is further unsubstituted or sulfo-substituted. 
A preferred embodiment of the present invention concerns compounds of the 
formula (1) where Z is a fiber-reactive radical of the formula 
##STR12## 
where Y is subject to the abovementioned meanings and preferences, 
(R.sub.22).sub.0-2 represents 0 to 2 identical or different radicals 
selected from the group consisting of methyl, methoxy, chlorine, hydroxyl 
and sulfo, q is 1 or 2, and m is 2 or 3. 
Particularly preferably Z is a radical of the formula 
##STR13## 
where Y is vinyl or .beta.-sulfatoethyl. 
The compounds of the formula (1) have at least two, preferably two to 
eight, particularly preferably three to six, sulfo or sulfato groups; 
these can each be present in the form of the free acid or preferably in 
salt form, for example as sodium, lithium, potassium or ammonium salt. The 
compounds of the formula (1) can also be present as mixed salt, for 
example as sodium-lithium or sodium-lithium-ammonium salt. 
The compounds of the formula ( 1 ) are fiber-reactive. Fiber-reactive 
radicals are to be understood as meaning radicals capable of reacting with 
the hydroxyl groups of cellulose, the amino, carboxyl, hydroxyl and thiol 
groups in the case of wool and silk, or with the amino and possibly 
carboxyl groups of synthetic polyamides to form covalent chemical bonds. 
The process for preparing the reactive dyes of the formula (1) comprises 
diazotizing a compound of the formula 
##STR14## 
where A and Z are each as defined in the formula (1), and coupling the 
diazotization product with a coupling component K--H with or without a 
further conversion reaction, for example again diazotizing the 
intermediate product of the coupling reaction and coupling it with a 
further coupling component of the defined group K with or without further 
reaction, or coupling the intermediate product with a further diazo 
component. 
A further method comprises first preparing a dye which contains a precursor 
of the reactive radical and subsequently convening this precursor stage 
into the final stage, for example by esterification or an addition 
reaction. 
It is also possible for the synthesis to be followed by elimination 
reactions. For instance, a reactive dye of the formula (1) which contains 
sulfatoethylsulfonyl radicals can be treated with hydrogen halide 
eliminators, such as sodium hydroxide, to convert the sulfatoethylsulfonyl 
radicals into vinylsulfonyl radicals. 
The compounds of the formula (8) are likewise fiber-reactive and novel. A 
further part of the subject-matter of the present invention therefore 
comprises compounds of the formula 
##STR15## 
where A.sub.1 and Z are each subject to the abovementioned meanings and 
preferences. 
The compounds of the formula (8) or (8a) can be obtained for example by 
diazotizing a compound of the formula 
EQU Z--NH.sub.2 ( 9) 
in a conventional manner and coupling it with a compound of the formula 
##STR16## 
where A and Z are each as defined above. The compounds of the formulae (9) 
and (10) are known or can be prepared in a manner known per se. 
The reactive dyes of formula (1) and the compounds of formula (8) are 
suitable for dyeing and printing a very wide range of materials, such as 
silk, leather, wool, polyamide fibers and polyurethanes, and in particular 
cellulosic fiber materials of any kind. These fiber materials include for 
example the natural cellulose fibers, such as cotton, linen and hemp, and 
also pulp and regenerated cellulose. The reactive dyes of the formula (1) 
are also suitable for dyeing or printing hydroxyl-containing fibers 
present in blend fabrics, for example blends of cotton with polyester 
fibers or polyamide fibers. 
The dyes of the invention can be applied to and fixed on the fiber 
materials in various ways, in particular in the form of aqueous dye 
solutions and print pastes. They are suitable not only for the exhaust 
method but also for dyeing by the padding method, can be used at low 
dyeing temperatures, and require only short steaming times in pad-steam 
processes. The degrees of fixation are high, and the unfixed portions are 
easy to wash off, the difference between the degree of exhaustion and the 
degree of fixation being remarkably small, i.e. the loss on soaping being 
very small. The reactive dyes of the formula (1) are also suitable for 
printing, especially on cotton, but also for printing nitrogen-containing 
fibers, for example wool, silk or wool-containing blend fabrics. 
The dyeings and prints on cellulose fiber materials prepared with the dyes 
of the invention have a high colour strength and a high fiber-dye bond 
stability not only in the acid but also in the alkaline range, also good 
light fastness and very good wet fastness properties, such as wash, water, 
seawater, cross-dyeing and perspiration fastness properties, and also good 
fastness to pleating, fastness to hot pressing, crock fastness and in 
particular chlorine fastness. 
The Examples which follow illustrate the invention. The temperatures are 
given in degrees Celsius and parts and percentages are by weight, unless 
otherwise stated. Parts by weight relate to parts by volume as the 
kilogram to the liter. 
The most important process variants are described in the illustrative 
embodiments. 
Preparation of the intermediates of the formula (8)

EXAMPLE 1 
44.8 parts of 2-naphthylamino-1-sulfonic acid are dissolved in 400 parts of 
water under neutral conditions, and the solution is cooled down to 
0.degree.-5.degree. C. At this temperature, 28.3 parts of 
2,4,6-trifluoro-1,3,5-triazine are added dropwise over 20 minutes while 
the pH of the reaction solution is kept at 7 by the simultaneous addition 
of sodium hydroxide solution. Following addition of a neutral mixture of 
37.9 parts of 1,3-phenylenediamine-4-sulfonic acid in 300 parts of water, 
the reaction mixture is left at 0.degree.-2.degree. C. and pH 7-8 for 1 
hour for the condensation reaction to proceed. The temperature is then 
raised to 20.degree.-25.degree. C. over about 2 hours. After the reaction 
has ended, 56.2 parts of diazotized 
1-amino-4-(2-sulfatoethylsulfonyl)benzene are added, and the coupling 
reaction is carried out at 0.degree.-10.degree. C. and pH 4-5. Stirring at 
5.degree.-20.degree. C. and pH 7 for 1 hour gives the dye of the formula: 
##STR17## 
It dyes cotton in yellow shades. 
Examples 2-30q 
The method of Example 1 can be used to prepare the following compounds 
which each dye cotton in a yellow shade: 
__________________________________________________________________________ 
Ex.: 
Compound of the formula 
__________________________________________________________________________ 
##STR18## 
3 
##STR19## 
4 
##STR20## 
5 
##STR21## 
6 
##STR22## 
7 
##STR23## 
8 
##STR24## 
9 
##STR25## 
10 
##STR26## 
11 
##STR27## 
12 
##STR28## 
13 
##STR29## 
14 
##STR30## 
15 
##STR31## 
16 
##STR32## 
17 
##STR33## 
18 
##STR34## 
19 
##STR35## 
20 
##STR36## 
21 
##STR37## 
22 
##STR38## 
23 
##STR39## 
24 
##STR40## 
25 
##STR41## 
26 
##STR42## 
27 
##STR43## 
28 
##STR44## 
29 
##STR45## 
30 
##STR46## 
30a 
##STR47## 
30b 
##STR48## 
30c 
##STR49## 
30d 
##STR50## 
30e 
##STR51## 
30f 
##STR52## 
30g 
##STR53## 
30h 
##STR54## 
30i 
##STR55## 
30j 
##STR56## 
30k 
##STR57## 
30l 
##STR58## 
30m 
##STR59## 
30n 
##STR60## 
30o 
##STR61## 
30p 
##STR62## 
30q 
##STR63## 
__________________________________________________________________________ 
Preparation of the dyes of the formula (1) 
Example 31 
8.6 parts of the compound of Example 1 are diazotized in a conventional 
manner using sodium nitride and hydrochloric acid and coupled onto 2.1 
parts of m-sulfonylmethylpyrazolidine under neutral conditions. After the 
coupling reaction has ended, the reaction solution is subjected to reverse 
osmosis and freeze-dried, leaving the dye of the formula: 
##STR64## 
It dyes cotton in scarlet shades having good allround fastness properties. 
Examples 32-80 
Similar dyes are obtained on reacting the diazo components and coupling 
components mentioned in the table with each other as described in Example 
31. The dyes obtained dye cotton in the stated shade with good allround 
fastness properties. 
__________________________________________________________________________ 
Diazo- 
Ex. 
component 
No. 
of Example 
Coupling component Shade 
__________________________________________________________________________ 
32 1 
##STR65## Orange 
33 1 
##STR66## Orange 
34 1 
##STR67## Orange 
35 1 
##STR68## Navy 
36 6 
##STR69## Scarlet 
37 6 
##STR70## Orange 
38 6 
##STR71## Orange 
39 6 
##STR72## Red 
40 6 
##STR73## Navy 
41 6 
##STR74## Greenish blue 
42 7 
##STR75## Orange 
43 7 
##STR76## Orange 
44 7 
##STR77## Red 
45 7 
##STR78## Scarlet 
46 7 
##STR79## Navy 
47 7 
##STR80## Greenish blue 
48 7 
##STR81## Bordeaux 
49 7 
##STR82## Olive 
50 7 
##STR83## Red 
51 7 
##STR84## Violet 
52 21 
##STR85## Orange 
53 28 
##STR86## Scarlet 
54 28 
##STR87## Orange 
55 28 
##STR88## Red 
56 28 
##STR89## Navy 
57 28 
##STR90## Greenish blue 
58 28 
##STR91## Bordeaux 
59 6 
##STR92## Red 
60 1 
##STR93## Bordeaux 
61 1 
##STR94## Red 
62 6 
##STR95## Bordeaux 
63 6 
##STR96## Olive 
64 7 
##STR97## Olive 
65 30n 
##STR98## Navy 
66 30l 
##STR99## Black 
67 6 
##STR100## Navy 
68 6 
##STR101## Violet 
69 6 
##STR102## Red 
70 6 
##STR103## Brown 
71 6 
##STR104## Violet 
72 6 
##STR105## Navy 
73 30b 
##STR106## Red 
74 30b 
##STR107## Olive 
75 30b 
##STR108## Navy 
76 30b 
##STR109## Navy 
77 6 
##STR110## Blue 
78 6 
##STR111## Blue 
79 30m 
##STR112## Green 
80 6 
##STR113## Blue 
__________________________________________________________________________ 
Dyeing Method I 
2 parts of the dye of Example 31 are dissolved in 400 parts of water; 1500 
parts of a solution containing 53 g of sodium chloride per liter are 
added. This dyebath is entered at 40.degree. C. with 100 parts of a cotton 
fabric. After 45 minutes 100 parts of a solution containing 16 g of sodium 
hydroxide and 20 g of anhydrous sodium carbonate per liter are added. The 
temperature of the dyebath is held at 40.degree. C. for a further 45 
minutes. Then the dyed fabric is rinsed, soaped off at the boil for a 
quarter of an hour with a nonionic detergent, rinsed once more and dried. 
Dyeing Method II 
2 parts of the reactive dye of Example 31 are dissolved in 400 parts of 
water, 1500 parts of a solution containing 53 g of sodium chloride per 
liter are added. This dyebath is entered at 35.degree. C. with 100 parts 
of a cotton fabric. After 20 minutes 100 parts of a solution containing 16 
g of sodium hydroxide and 20 g of anhydrous sodium carbonate per liter are 
added. The temperature of the dyebath is held at 35.degree. C. for a 
further 15 minutes. The temperature is then raised over 20 minutes to 
60.degree. C. The temperature is held at 60.degree. C. for a further 35 
minutes. Thereafter the dyed fabric is rinsed, soaped off at the boil for 
a quarter of an hour with a nonionic detergent, rinsed once more and 
dried. 
Dyeing Method III 
8 parts of the reactive dye of Example 31 are dissolved in 400 parts of 
water; 1400 parts of a solution containing 100 g of sodium sulfate per 
liter are added. This dyebath is entered at 25.degree. C. with 100 parts 
of a cotton fabric. After 10 minutes 200 parts of a solution containing 
150 g of trisodium phosphate per liter are added. Then the temperature of 
the dyebath is raised to 60.degree. C. over 10 minutes. The temperature is 
held at 60.degree. C. for a further 90 minutes. Thereafter the dyed fabric 
is rinsed, soaped off at the boil for a quarter of an hour with a nonionic 
detergent, rinsed once more and dried. 
Dyeing Method IV 
4 parts of the reactive dye of Example 31 are dissolved in 50 parts of 
water. 50 parts of a solution containing 5 g of sodium hydroxide and 20 g 
of anhydrous sodium carbonate per liter are added. The solution obtained 
is used for padding a cotton fabric to a wet pick-up of 70 % of its weight 
and the fabric is then wound onto a batching roller. It is stored in that 
state at room temperature for 3 hours. Thereafter the dyed fabric is 
rinsed, soaped off at the boil for a quarter of an hour with a nonionic 
detergent, rinsed once more and dried. 
Dyeing Method V 
6 parts of the reactive dye of Example 31 are dissolved in 50 parts of 
water. 50 parts of a solution containing 16 g of sodium hydroxide and 0.04 
l of 38.degree. B e waterglass per liter are added. The solution obtained 
is used for padding a cotton fabric to a wet pick-up of 70% of its weight 
and the fabric is then wound onto a batching roller. It is stored in that 
state at room temperature for 10 hours. Thereafter the dyed fabric is 
rinsed, soaped off at the boil for a quarter of an hour with a nonionic 
detergent, rinsed once more and dried. 
Dyeing Method VI 
2 parts of the reactive dye of Example 31 are dissolved in 100 parts of 
water with 0.5 parts of sodium m-nitrobenzenesulfonate. The solution 
obtained is used for impregnating a cotton fabric to a wet pick-up of 75% 
of its weight and the fabric is then dried. The fabric is then impregnated 
with a 20.degree. C. solution containing 4 g of sodium hydroxide and 300 g 
of sodium chloride per liter, squeezed off to a weight increase of 75%, 
the dyeing is steamed at 100.degree.-102.degree. C. for 30 seconds, 
rinsed, soaped off at the boil for a quarter of an hour in a 0.3% solution 
of a nonionic detergent, rinsed and dried. 
Printing Method I 
3 parts of the reactive dye of Example 31 are sprinkled with rapid stirring 
into 100 parts of a stock thickening containing 50 parts of 5% sodium 
alginate thickening, 27.8 parts of water, 20 parts of urea, 1 part of 
sodium m-nitrobenzenesulfonate and 1.2 parts of sodium bicarbonate. The 
resulting print paste is used for printing a cotton fabric, which is then 
dried and steamed at 102.degree. C. in saturated steam for 2 minutes. The 
fabric bearing the print is then rinsed, if desired soaped off at the boil 
and rinsed once more, and subsequently dried. 
Printing Method II 
5 parts of the reactive dye of Example 31 are sprinkled with rapid stirring 
into 100 parts of a stock thickening containing 50 parts of 5 % sodium 
alginate thickening, 36.5 parts of water, 10 parts of urea, 1 part of 
sodium m-nitrobenzenesulfonate and 2.5 parts of sodium bicarbonate. The 
resulting print paste, the stability of which corresponds to the 
industrial requirements, is used for printing a cotton fabric, which is 
then dried and steamed at 102.degree. C. in saturated steam for 8 minutes. 
The fabric bearing the print is then rinsed, if desired soaped off at the 
boil and rinsed once more, and subsequently dried.