Dyestuffs of the formula ##STR1## with the substituent meanings mentioned in the description, are suitable for dyeing and printing hydroxyl- and amido-containing textile materials. To prepare these dyestuffs, new intermediates of the formula ##STR2## are used.

The present invention relates to dyestuffs of the formula 
##STR3## 
wherein R.sub.1 -R.sub.4 =H or substituent 
X.sub.4 = 
##STR4## 
O R.sub.5 =H or optionally substituted C.sub.1 -C.sub.6 -alkyl, 
cycloalkyl, aryl or aralkyl, 
Y=bridge member, 
Z.sub.1, Z.sub.2 =H or fibre-reactive radical, 
W=non-fibre-reactive sulphonyl radical, in particular alkyl, aralkyl, 
cycloalkyl or arylsulphonyl radical, preferably a radical --SO.sub.2 Q 
where 
Q=C.sub.2 -alkyl optionally substituted by SO.sub.3 H, COOH, carboxamide, 
sulphonamide, C.sub.1 -C.sub.4 -alkoxy or optionally substituted C.sub.1 - 
or C.sub.3 -C.sub.6 -alkyl, cycloalkyl, aralkyl, aryl, where aryl 
preferably stands for optionally substituted phenyl and aralkyl preferably 
for optionally substituted phenyl-C.sub.1 -C.sub.4 -cycloalkyl. 
Suitable substituents in C.sub.1 - or C.sub.3 -C.sub.6 -alkyl, cycloalkyl, 
aralkyl, aryl are for example SO.sub.3 H, OSO.sub.3 H, S-SO.sub.3 H, COOH, 
optionally substituted carboxamide, --COO--C.sub.1 -C.sub.4 -alkyl, CN, 
--PO.sub.3 H.sub.2, --OPO.sub.3 H.sub.2, --O--CO--C.sub.1 -C.sub.4 -alkyl, 
OH, C.sub.1 -C.sub.4 -alkoxy, --(CH.sub.2 --CH.sub.2 --O).sub.1-4 
--CH.sub.2 --CH.sub.2 OH, --(CH.sub.2 --CH.sub.2 --O).sub.1-4 --CH.sub.2 
--CH.sub.2 --OSO.sub.3 H, halogen. 
Suitable radicals R.sub.1, R.sub.2 are in addition to hydrogen for example 
Cl, Br, C.sub.1 -C.sub.4 -alkyl, aryl, C.sub.1 -C.sub.4 -alkoxy, aryloxy 
in particular optionally substituted phenyl and phenoxy, acylamino, in 
particular acetylamino and benzoylamino, carboxyl, optionally further 
substituted carboxamide. 
Suitable radicals R.sub.3 are in addition to hydrogen for example C.sub.1 
-C.sub.4 -alkyl, Cl, Br, C.sub.1 -C.sub.4 -alkoxy, sulpho, carboxyl. 
Suitable radicals R.sub.4 are for example H, optionally SO.sub.3 H--, 
OSO.sub.3 H--, COOH--, OPO.sub.3 H.sub.2 --, OH-substituted C.sub.1 
-C.sub.4 -alkyl, cyclohexyl, phenyl, sulphophenyl. 
Bridge members Y are for example: 
alkylene radicals such as C.sub.2 -C.sub.6 -alkylene, optionally 
interrupted by O, S or N, optionally substituted, for example ethylene, 
1,2- and 1,3-propylene, 1,2-, 1,3-, 1,4- and 2,3-butylene, 
2-methyl-1,3-propylene, 2,2-dimethylpropylene, 2-methyl-2,4-pentylene, 
1-phenylethylene, 2,5-hexylene, 1,5-pentylene, 1,6-hexylene, 
1,3-cyclohexylene, 1,4-cyclohexylene, 4-methyl-1,3-cyclohexylene, 
2-hydroxy-1,3-propylene, 2-sulphato-1,3-propylene, --CH.sub.2 --CH.sub.2 
--O--CH.sub.2 --CH.sub.2 --, --CH.sub.2 --CH.sub.2 --S--CH.sub.2 
--CH.sub.2, --CH.sub.2 --CH.sub.2 --NH--CH.sub.2 --CH.sub.2 --, 
##STR5## 
aralkylene radicals such as 
##STR6## 
and the radical 
##STR7## 
Suitable bridge members Y are also arylene radicals such as optionally 
substituted phenylene, in particular phenylene and alkyl-, alkoxy-, 
sulpho-, carboxyl- or halogen-substituted phenylene such as 1,2-, 1,3-, 
1,4-phenylene, 3-methyl-1,2-phenylene, 4-methyl-1,2-phenylene, 
2-methyl-1,3-phenylene, 4-methyl-1,3-phenylene, 5-methyl-1,3-phenylene, 
2-methyl-1,4-phenylene, 2,4,6-trimethyl-1,3-phenylene, 
2,3,5,6-tetramethyl-1,4-phenylene, 2,6-dimethyl-1,3-phenylene, 
2-methyl-6-ethyl-1,3-phenylene, 2-methyl-4,6-diethyl-1,3-phenylene, 
2,6-diethyl-4-methyl-1,3-phenylene, 2-methoxy-1,3-phenylene, 
4-methoxy-1,3-phenylene, 6-methoxy-1,3-phenylene, 2-methoxy-1,4-phenylene, 
4-chloro-1,3-phenylene, 2-chloro-1,4-phenylene, such as in particular the 
stated arylene radicals substituted by 1-2 sulpho groups, such as, for 
example, 4-sulpho-1,2-phenylene, 4-sulpho-1,3-phenylene, 
3-sulpho-1,4-phenylene, 2-sulpho-1,4-phenylene, 
4,6-disulpho-1,3-phenylene, 2,5-disulpho-1,4-phenylene, 
2-methyl-5-sulpho-1,3-phenylene, 2-methyl-4-sulpho-1,3-phenylene, 
2,4,6-trimethyl-5-sulpho-1,3-phenylene, 2,6-dimethyl-4- and 
-5-sulpho-1,3-phenylene, 2-methyl-6-sulpho-1,3-phenylene, 
4-methyl-6-sulpho-1,3-phenylene, 6-methyl-4-sulpho-1,3-phenylene, 
3-methyl-6-sulpho-1,4-phenylene, 6-methoxy-4-sulpho-1,3-phenylene, 
4-methoxy-6-sulpho-1,3-phenylene. 
Suitable radicals Q are for example methyl, ethyl, propyl, butyl, pentyl, 
hexyl, allyl and the sulpho-, sulphamoyl-, carboxyl-, carbamoyl-, 
yloxycarbonyl-, cyano-, keto-, C.sub.1 -C.sub.4 -alkoxy-, 
aroxy-substituted C.sub.1 -C.sub.6 -alkyl groups such as CH.sub.2 --COOH, 
--CH.sub.2 --COO-alkyl, --CH.sub.2 --CONH.sub.2, --CH.sub.2 --CN, 
--CH.sub.2 --CO-alkyl, 
##STR8## 
And also sulphato-, thiosulphato-, phosphato-, alkanoyloxy-, halogen-, 
hydroxyl-substituted C.sub.3 -C.sub.6 -alkyl groups such as 
--(CH.sub.2).sub.3-6 --OSO.sub.3 H, --(CH.sub.2).sub.3-6 --OPO.sub.3 
H.sub.2, 
##STR9## 
and also sulpho-, sulphato-, carboxyl-substituted aryl-C.sub.1 -C.sub.4 
-alkyl radicals such as benzyl, o-, m-, p-sulphobenzyl, 
2-phenyl-2-sulphatoethyl, o-, m-, p-carboxybenzyl, 1- or 2-phenylethyl and 
the corresponding phenylsulphonated radicals, 2- and 3-phenyl-1-propyl, 
4-phenyl-2-butyl and the corresponding phenyl-sulphonated radicals, 
naphthylmethyl, 5-, 6-, 7- or 8-sulphonaphthyl-1-methyl, 5-, 6-, 7- or 
8-sulphonaphthyl-1-methyl and also alkyl and aralkyl radicals which are 
interrupted by hetero atoms O, S and N and optionally substituted by 
sulpho, sulphato, carboxyl, hydroxyl, C.sub.1 -C.sub.4 -alkoxy, halogen, 
such as 
##STR10## 
and also aryl radicals in particular optionally substituted phenyl or 
naphthyl radicals such as phenyl, 2-, 3-, 4-sulphophenyl, carboxyphenyl, 
methylphenyl, chlorophenyl, C.sub.1 -C.sub.4 -alkoxyphenyl, 5-, 6-, 7-, 
8-sulpho-1-naphthyl, 5-, 6-, 7-, 8-sulpho-2-naphthyl, 
5,7-disulpho-1-naphthyl, 6,8-disulpho-2-naphthyl. 
Preferably R.sub.1 and R.sub.2 stand for Cl and R.sub.3 stands for H. 
Examples of suitable fibre-reactive radicals Z, that is to say those which 
react with materials containing hydroxyl groups or amide groups under 
dyeing conditions and form a covalent bond, are those which contain at 
least one detachable substituent bonded to a heterocyclic or aliphatic 
radical, in particular those which contain at least one reactive 
substituent bonded to a 5-membered or 6-membered heterocyclic ring, such 
as to a monoazine, diazine or triazine ring, for example a pyridine, 
pyrimidine, pyridazine, pyrazine, thiazine, oxazine or asymmetric or 
symmetric triazine ring, or to a ring system of this type which contains 
one or more fused-on aromatic rings, such as a quinoline, phthalazine, 
quinazoline, quinoxaline, acridine, phenazine or phenanthridine ring 
system; the 5-membered or 6-membered heterocyclic rings, which contain at 
least one reactive substituent, are accordingly preferably those which 
contain one or more nitrogen atoms and can contain 5-membered or, 
preferably, 6-membered fused-on carbocyclic rings. 
Examples which may be mentioned of the reactive substituents on the 
heterocycle are: halogen (Cl, Br or F), ammonium, including hydrazinium, 
sulphonium, sulphonyl, azido (--N.sub.3), thiocyanato, thio, thiolether, 
oxyether, sulphinic acid and sulphonic acid. Specific examples which may 
be mentioned are: mono- or dihalogeno-symmetric-triazinyl radicals, for 
example 2,4-dichlorotriazin-6-yl, 2-amino-4-chlorotriazin-6-yl, 
2-alkylamino-4-chlorotriazin-6-yl, such as 
2-methylamino-4-chlorotriazin-6-yl, 2-ethylamino- or 
2-propylamino-4-chlorotriazin-6-yl, 
2-.beta.-hydroxyethylamino-4-chlorotriazin-6-yl, 
2-di-.beta.-hydroxyethylamino-4-chlorotriazin-6-yl and the corresponding 
sulphuric acid half-esters, 2-diethylamino-4-chlorotriazin-6-yl, 
2-morpholino- or 2-piperidino-4-chlorotriazin-6-yl, 
2-cyclohexylamino-4-chlorotriazin-6-yl, 2-arylamino- and substituted 
arylamino-4-chlorotriazin-6-yl, such as 
2-phenylamino-4-chlorotriazin-6-yl, 2-(o-, m- or p-carboxy- or 
-sulphophenyl)-amino-4-chlorotriazin-6-yl and 2-(2',4'-2',5'- or 
3',4'-disulphophenyl)-amino-4-chlorotriazin-6-yl, 
2-alkoxy-4-chlorotriazin-6-yl, such as 2-methoxy- or 
-ethoxy-4-chlorotriazin-6-yl, 
2-(phenyl-sulphonylmethoxy)-4-chlorotriazin-6-yl, 2-aryloxy- and 
substituted aryloxy-4-chlorotriazin-6-yl, such as 
2-phenoxy-4-chlorotriazin-6-yl, 
2-(p-sulphophenyl)-hydroxy-4-chlorotriazin-6-yl, 2-(o-, m- or p-methyl- or 
-methoxyphenyl)-hydroxy-4-chlorotriazin-6-yl, 2-alkylmercapto- or 
2-arylmercapto- or 2-(substituted aryl)-mercapto-4-chlorotriazin-6-yl, 
such as 2-.beta.-hydroxyethylmercapto-4-chlorotriazin-6-yl, 
2-phenylmercapto-4-chlorotriazin-6-yl, 
3-(4'-methylphenyl)-mercapto-4-chlorotriazin-6-yl, 
2-(2',4'-dinitro)-phenyl-mercapto-4-chlorotriazin-6-yl, 
2-methyl-4-chlorotriazin-6-yl, 2-phenyl-4-chlorotriazin-6-yl, 
2,4-difluorotriazin-6-yl, monofluorotriazinyl radicals which are 
substituted by amino, alkylamino, aralkylamino or arylamino groups, alkyl 
denoting, in particular, optionally substituted C.sub.1 -C.sub.4 -alkyl, 
aralkyl denoting, in particular, optionally substituted phenyl-C.sub.1 
-C.sub.4 -alkyl and aryl denoting, in particular, phenyl or naphthyl which 
is optionally substituted by sulpho, alkyl, in particular C.sub.1 -C.sub.4 
-alkyl, alkoxy, in particular C.sub.1 -C.sub.4 -alkoxy, carboxylic acid or 
acylamino groups and halogen atoms, such as fluorine, chlorine or bromine, 
for example 2-amino-4-fluorotriazin-6-yl, 
2-methylamino-4-fluorotriazin-6-yl, 2-ethylamino-4-fluorotriazin-6-yl, 
2-isopropylamino-4-fluorotriazin-6-yl, 
2-dimethylamino-4-fluorotriazin-6-yl, 2-diethylamino-4-fluorotriazin-6-yl, 
2-.beta.-methoxy-ethylamino-4-fluorotriazin-6-yl, 
2-.beta.-hydroxyethylamino-4-fluorotriazin-6-yl, 
2-di-(.beta.-hydroxyethylamino)-4-fluorotriazin-6-yl, 
2-.beta.-sulphoethylamino-4-fluorotriazin-6-yl, 
2-.beta.-sulphoethyl-methylamino-4-fluorotriazin-6-yl, 
2-carboxymethylamino-4-fluorotriazin-6-yl, 
2-.beta.-cyanoethylamino-4-fluorotriazin-6-yl, 
2-benzylamino-4-fluorotriazin-6-yl, 
2-.beta.-phenylethylamino-4-fluorotriazin-6-yl, 
2-benzyl-methylamino-4-fluorotriazin-6-yl, 
2-(x-sulphobenzyl)-amino-4-fluorotriazin-6-yl, 
2-cyclohexylamino-4-fluorotriazin-6-yl, 2-(o-, m- or 
p-methylphenyl)-amino-4-fluorotriazin-6-yl, 2-(o-, m- or 
p-sulphophenyl)-amino-4-fluorotriazin-6-yl, 
2-(2',5'-disulphophenyl)-amino-4-fluorotriazin-6-yl, 2-(o-, m- or 
p-chlorophenyl)-amino-4-fluorotriazin-6-yl, 2-(o-, m- or 
p-methoxyphenyl)-4-fluorotriazin-6-yl, 
2-(2'-methyl-4'-sulphophenyl)-amino-4-fluorotriazin-6-yl, 
2-(2'-methyl-5'-sulphophenyl)-amino-4-fluorotriazin-6-yl, 
2-(2'-chloro-4'-sulphophenyl)-amino-4-triazin-6-yl, 
2-(2'-chloro-5'-sulphophenyl)-amino-4-triazin-6-yl, 
2-(2'-methoxy-4'-sulphophenyl)-amino-4-fluorotriazin-6-yl, 2-(o-, m- or 
p-carboxyphenyl)-amino-4-fluorotriazin-6-yl, 
2-(2',4'-disulphophenyl)-amino-4-fluorotriazin-6-yl, 2-( 
3',5'-disulphophenyl)-amino-4-fluorotriazin-6-yl, 
2-(2'-carboxy-4-sulphophenyl)-amino-4-fluorotriazin-6-yl, 
2-(6'-sulphonaphth-2'-yl)-amino-4-fluorotriazin-6-yl, 
2-(4',8'-disulphonaphth-2'-yl)-amino-4-fluorotriazin-6-yl, 
2-(6',8'-disulphonaphth-2'-yl)-amino-4-fluorotriazin-6-yl, 
2-(N-methylphenyl)-amino-4-fluorotriazin-6-yl, 
2-(N-ethylphenyl)-amino-4-fluorotriazin-6-yl, 
2-(N-.beta.-hydroxyethylphenyl)-amino-4-fluorotriazin-6-yl, 
2-(N-isopropylphenyl)-amino-4-fluorotriazin-6-yl, 
2-morpholino-4-fluorotriazin-6-yl, 2-piperidino-4-fluorotriazin-6-yl, 
2-(4',6',8'-trisulphonaphth-2'-yl)-4-fluorotriazin-6-yl, 
2-(3',6',8'-trisulphonaphth-2'-yl)-4-fluorotriazin-6-yl, 
2-(3',6'-disulphonaphth-1'-yl)-4-fluorotriazin-6-yl, 2-chloro- or 
2-fluoro-4-(4'-.beta.-sulphatoethylsulphonylphenylamino)-6-triazinyl, 
2-chloro- or 
2-fluoro-4-(3'-.beta.-sulphatoethylsulphonylphenylamino)-6-triazinyl, 
2-chloro- and 
2-fluoro-4-(.beta.-(.beta.'-sulphatoethylsulphonyl)-ethylamino)-6-triaziny 
l and 
2-fluoro-4-bis-(.beta.-(.beta.'-chloroethylsulphonyl)-ethyl)-amino-6-triaz 
inyl. 
The halogenotriazinyl radicals can also be attached to a second 
halogenotriazinyl radical. Examples of radicals of this type are the 
following: 
##STR11## 
The reactive halogen atoms in the abovementioned 
2-halogeno-4-substituted-triazinyl radicals can also be replaced by 
tertiary bases, such as trimethylamine, triethylamine, 
dimethyl-.beta.-hydroxyethylamine, triethanolamine, N,N-dimethylhydrazine, 
pyridine, .alpha.- or .psi.-picoline, nicotinic acid or isonicotinic acid, 
to form quaternary salts. 
Mono-, di- or tri-halogenopyrimidinyl radicals, such as 
2,4-dichloropyrimidin-6-yl, 2,4,5-trichloropyrimidin-6-yl, 
2,4-dichloro-5-nitro-, -5-methyl-, -5-carboxymethyl-, -5-carboxy-, 
-5-cyano-, -5-vinyl-, -5-sulpho-, -5-mono-, -di- or -tri-chloromethyl- or 
-5-carboalkoxy-pyrimidin-6-yl, 2,6-dichloropyrimidine-4-carbonyl, 
2,4-dichloropyrimidin-6-yl, 2,6-dichloropyrimidine-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-sulphonyl, 
2-chloro-quinoxaline-3-carbonyl, 2- or 3-monochloroquinoxaline-6-carbonyl, 
2- or 3-monochloroquinoxaline-6-sulphonyl, 
2,3-dichloroquinoxaline-6-carbonyl, 2,3-dichloroquinoxaline-6-sulphonyl, 
1,4-dichlorophthalazine-6-sulphonyl or -6-carbonyl, 
2,4-dichloroquinazoline-7- or -6-sulphonyl or -carbonyl, 2- or 3- or 
4-(4',5'-dichloro-6'-pyridazon-1'-yl)-phenylsulphonyl or -carbonyl, 
.beta.-(4',5'-dichloro-6'-pyridazon-1'-yl)-ethylcarbonyl, 
N-methyl-N-(2,4-dichloro-triazin-6-yl)-carbamyl, 
N-methyl-N-(2-methylamino-4-chlorotriazin-6-yl)-carbamyl, 
N-methyl-N-(2-dimethylamino-4-chlorotriazin-6-yl)-carbamyl, N-methyl- or 
N-ethyl-N-(2,4-dichlorotriazin-6-yl)-aminoacetyl, 
N-methyl-N-(2,3-dichloroquinoxaline-6-sulphonyl)-aminoacetyl, 
N-methyl-N-(2,3-dichloroquinoxaline-6-carbonyl)-aminoacetyl, and the 
corresponding bromine and fluorine derivatives of the abovementioned 
chlorine-substituted radicals, and of these, for example, 
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-fluoro-5-methyl-6-chloro-4pyrimidinyl, 
2-fluoro-5nitro-6-chloro-4-pyrimidinyl, 5-bromo-2-fluoro-4-pyrimidinyl, 
2-fluoro-5cyano-4pyrimidinyl, 2-fluoro-5-methyl-4-pyrimidinyl, 
2,5,6-trifluoro-4-pyrimidinyl, 
5-chloro-6chloromethyl-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-5chloromethyl- 
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-methylsulphonyl-4pyrimidinyl, 2-fluoro-5-carboxamido-4-pyrimidinyl, 
2-fluoro-5-carbomethoxy-4-pyrimidinyl, 
2-fluoro-5-bromo-6-trifluoromethyl-4-pyrimi-dinyl, 
2-fluoro-6-carboxamido-4-pyrimidinyl, 
2-fluoro-6-carbomethoxy-4-pyrimidinyl, 2-fluoro-6-phenyl-4-pyrimi-dinyl, 
2-fluoro-6-cyano-4-pyrimidinyl, 
2-fluoro-4di-chloromethyl-5-chloropyrimidin-6-yl, 
2-fluoro-5-chloro-pyrimidin-4-yl, 
2-methyl-4-fluoro-5-methylsulphonylpyrimidin-6-yl, 
2,6-difluoro-5-methylsulphonyl-4-pyrimidinyl, 
2,6-dichloro-5-methylsulphonyl-4-pyrimidinyl, 
2-fluoro-5-sulphonamido-4-pyrimidinyl, 
2-fluoro-5-chloro-6-carbo-methoxy-4pyrimidinyl and 
2,6-difluoro-5-trifluormethyl-4-pyrimidinyl; triazine radicals containing 
sulphonyl groups, such as 2,4-bis-(phenylsulphonyl)-triazin-6-yl, 
2-(3'-carboxyphenyl)-sulphonyl-4-chlorotriazin-6-yl, 
2-(3'-sulphophenyl)-sulphonyl-4-chlorotriazin-6-yl and 
2,4-bis-(3'-carboxyphenylsulphonyl)-triazin-6-yl; pyrimidine rings 
containing sulphonyl groups, such as 
2-carboxy-methylsulphonyl-pyrimidin-4-yl, 
2-methylsulphonyl-6-methyl-pyrimidin-4-yl, 
2-methylsulphonyl-6-ethyl-pyrimidin-4-yl, 
2-phenylsulphonyl-5-chloro-6methyl-pyrimidin-4-yl, 
2,6-bis-methylsulphonyl-pyrimidin-4-yl, 
2,6-bis-methylsulphonyl-5-chloro-pyrimidin-4-yl, 
2,4-bis-methylsulphonyl-pyrimidine-5-sulphonyl, 
2-methylsulphonyl-pyrimidin-4-yl, 2-phenylsulphonyl-pyrimidin-4-yl, 
2-trichloro-methylsulphonyl-6-methyl-pyrimidin-4-yl, 
2-methylsulphonyl-5-chloro-6-methyl-pyrimidin-4-yl, 
2-methylsulphonyl-5-bromo-6-methyl-pyrimidin-4-yl, 
2-methylsulphonyl-5chloro-6-methyl-pyrimidin-4-yl, 
2-methylsulphonyl-5-bromo-6-methyl-pyrimidin-4-yl, 
2-methylsulphonyl-5-chloro-6-ethyl-pyrimidin-4-yl, 
2-methylsulphonyl-5-chloro- 6-chloromethyl-pyrimidin-4-yl, 
2-methylsulphonyl-4-chloro-6-methylpyrimidine-5-sulphonyl, 
2-methylsulphonyl-5-nitro-6-methyl-pyrimidin-4-yl, 
2,5,6-tris-methylsulphonyl-pyrimidin-4-yl, 
2-methylsulphonyl-5,6-dimethyl-pyrimidin-4-yl, 
2-ethysulphonyl-5-chloro-6-methyl-pyrimidin-4-yl, 
2-methylsulphonyl-6-chloro-pyrimidin-4-yl, 
2,6-bis-methylsulphonyl-5-chloro-pyrimidin-4-yl, 
2-methylsulphonyl-6-carboxy-pyrimidin-4-yl, 
2-methylsulphonyl-5-sulpho-pyrimidin-4-yl, 
2-methylsulphonyl-5-cyano-6-methoxy-pyrimidin-4-yl, 
2-methylsulphonyl-5-chloro-pyrimidin-4-yl, 
2-sulphoethylsulphonyl-6-methyl-pyrimidin-4-yl, 
2-methylsulphonyl-5-bromo-pyrimidin-4-yl, 
2-phenylsulphonyl-5-chloro-pyrimidin-4-yl, 2-carboxy 
methylsulphonyl-5-chloro-6-methyl-pyrimidin-4-yl, 
2-methylsulphonyl-6-chloropyrimidine-4- and -5-carbonyl, 
2,6-bis-(methyl-sulphonyl)-pyrimidine-4- or -5-carbonyl, 
2-ethylsulphon-yl-6-chloropyrimidine-5-carbonyl, 
2,4-bis-(methylsulphon-yl)-pyrimidine-5-sulphonyl and 
2-methylsulphonyl-4-chloro-6-methylpyrimidine-5-sulphonyl or -carbonyl; 
triazine rings containing ammonium groups, such as 
2-tri-methylammonium-4-phenyl-amino- or -4-(o-, m- or 
p-sulpho-phenyl)-amino-triazin-6-yl, 
2-(1,1-dimethylhydrazinium)-4-phenyl-amino- or -4-(o-, m- or 
p-sulphophenyl)-amino-triazin-6-yl, 
2-(2-isopropylidene-1,1-dimethyl)-hydrazinium-4-phenyl-amino- or -4-(o-, 
m- or p-sulphophenyl)-amino-trazin-6-yl and 2-N-aminopyrrolidinium- or 
2-N-aminopiperidinium-4-phenyl-amino- or -4-(o-, m- or 
p-sulphophenyl)-amino-triazin-6-yl, and furthermore, 4-phenylamino- or 
4-(sulphophenylamino)-triazin-6-yl radicals which contain 
1,4-bisazabicyclo-[2,2,2]-octane or 1,2-bisazabicyclo-[0,3,3]-octane 
bonded in quaternary form in the 2-position via a nitrogen bond, and 
2-pyridinium-4-phenyl-amino- or -4-(o-, m- or 
p-sulphophenyl)-amino-triazin-6-yl and the corresponding 
2-onium-triazin-6-yl radicals which are substituted in the 4-position by 
alkylamino, such as methylamino, ethylamino or .beta.-hydroxyethylamino or 
alkoxy, such as phenoxy, or sulphophenoxy groups; 
2-chlorobenzo-thiazole-5- or -6-carbonyl or -5- or -6-sulphonyl, 
2-arylsulphonyl- or -alkylsulphonyl-benzothiazole-5- or -6-carbonyl or -5- 
or -6-sulphonyl, such as 2-methylsulphonyl- or 
2-ethylsulphonyl-benzothiazole-5- or -6-sulphonyl or -carbonyl, 
2-phenylsulphonylbenzothiazole-5- or -6-sulphonyl or -carbonyl and the 
corresponding 2-sulphonyl-benzothiazole-5- or -6-carbonyl or -sulphonyl 
derivatives containing sulpho groups in the fused-on benzene ring, 
2-chlorobenzoxazole-5- or -6-carbonyl or -sulphonyl, 
2-chlorobenzimidazole-5- or -6-carbonyl or -sulphonyl, 
2-chloro-1-methylbenzimidazole-5- or -6-carbonyl or -sulphonyl, 
2-chloro-4-methylthiazole-(1,3)-5-carbonyl or -4- or -5-sulphonyl, and the 
N-oxide of 4-chloro- or 4-nitro-quinoline-5-carbonyl. 
Also to be mentioned are reactive groups of the aliphatic series, such as 
acryloyl, mono, di- or tri-chloroacryloyl, such as --CO--CH.dbd.CH--Cl, 
--CO--CCl.dbd.CH.sub.2 and --CO--CCl.dbd.CH--CH.sub.3, and furthermore 
--CO--CCl.dbd.CH--COOH, and --CO--CCl.dbd.CH--CH.sub.3, 
.beta.-chloropropionyl, 3-phenylsulphonylpropionyl, 
3-methylsulphonylpropionyl, .beta.-sulphatoethylaminosulphonyl, 
vinylsulphonyl, .beta.-chloroethylsulphonyl, 
.beta.-sulphatoethylsulphonyl, .beta.-phosphatoethylsulphonyl, 
.beta.-thiosulphatoethylsulphonyl, .beta.-methylsulphonylethylsulphonyl, 
.beta.-phenylsulphonylethylsulphonyl, 
2-fluoro-2-chloro-3,3-difluorocyclobutane-1-carbonyl, 
2,2,3,3-tetrafluorocyclobutane-1-carbonyl or -1-sulphonyl, 
.beta.-(2,2,3,3-tetrafluoro-1-cyclobutyl)-acryloyl and .alpha.- or 
.beta.-bromoacryloyl, or .alpha.- or .beta.-alkyl- or 
-aryl-sulphonylacryloy groups, such as .alpha.- or 
.beta.-methylsulphonylacryloyl and .alpha.,.beta.-dichloro- or 
dibromo-propionyl. 
However, preferred fibre-reactive radicals are those which contain at least 
one reactive substituent bonded to a 5- or 6-membered heterocyclic ring, 
in particular to a so-called triazine ring or pyrimidine ring. 
Preferred dyestuffs of the formula (I) are those of the formula 
##STR12## 
wherein Z.sub.3, Z.sub.4 =heterocyclic fibre-reactive radical or H, 
R'.sub.1, R'.sub.2 =Cl, Br, CH.sub.3, H, 
Q.sub.1 =sulpho-C.sub.1 -C.sub.6 -alkyl, 3- to 6-sulphato-C.sub.3 -C.sub.6 
-alkyl, sulphophenyl-C.sub.1 -C.sub.4 -alkyl, carbonyl-C.sub.1 -C.sub.6 
-alkyl and 
Y, R.sub.4 have the abovementioned meaning, 
and also those of the formula 
##STR13## 
wherein Y.sub.1 =C.sub.2 -C.sub.6 -alkylene, cyclohexylene and 
Z.sub.3, Z.sub.4, R.sub.4 and Q.sub.1 have the abovementioned meaning. 
Particular preference is given to dyestuffs of the formula 
##STR14## 
wherein R'.sub.4 =H, CH.sub.2 --CH.sub.2 --OSO.sub.3 H, 
Z.sub.5, Z.sub.6 =halogenotriazinyl or halogenopyrimidinyl radical and 
Q.sub.1 has the abovementioned meaning. 
The preparation of compounds of the formula I where Z.sub.1 and/or Z.sub.2 
=fibre-reactive radical is effected in a manner known per se by reaction 
of compounds of the formula 
##STR15## 
wherein R.sub.4, X, Y have the abovementioned meaning, with reactive 
components 
EQU Z-halogen (VI) 
wherein 
Z=fibre-reactive radical 
halogen=F, Cl, Br. 
The condensation of the dioxazine compounds of the formula (V) and the 
reactive components (VI) is carried out either in an aqueous or 
aqueous-organic medium, depending on the reactive component employed, at 
temperatures of 0.degree.-80.degree. C. and pH 3-9 in the presence of 
alkaline condensing agents such as aqueous alkali metal hydrogencarbonate, 
alkali metal carbonate, alkali metal hydroxide, alkali metal 
hydrogenphosphate, dialkali metal phosphate or trialkali metal phosphate 
solution, or in aprotic organic solvents such as toluene, halogenobenzene, 
nitrobenzene, dimethylformamide, N-methylpyrrolidone, tetramethylene 
sulphone, dimethyl sulphoxide, acetone, methyl ethyl ketone in the 
presence or absence of aprotic organic bases such as trialkylamine, 
N,N-dialkylaniline, pyridine or alkylpyridines at temperatures of 
0.degree.-80.degree. C. 
The preparation of compounds of the formula (V) is effected by methods 
known per se by condensing 1,4-benzoquinones of the formula 
##STR16## 
wherein R.sub.1 and R.sub.2 have the abovementioned meaning and 
T.sub.1 and T.sub.2 denote hydrogen, Cl, Br, Oalkyl or Oaryl, 
with the likewise claimed aminosulphone compounds of the formula 
##STR17## 
wherein R.sub.4, X, Y and Q have the abovementioned meaning, to give anil 
compounds of the formula 
##STR18## 
wherein R.sub.1, R.sub.3, R.sub.4, X, Y have the abovementioned meaning 
and ring closure of the anil compounds (IX) to give the dioxazine dyestuff 
bases (V). 
Depending on the reaction conditions used for the ring closure, the 
sulphonyl group W with the dioxazines (V) can appear in the benzo rings of 
the dioxazine system either in the o- or in the p-positions relative to 
the ring oxygen atoms of the dioxazine system. 
Aminosulphone compounds of the formula (VIII) are prepared from 
nitrosulphones of the formula 
##STR19## 
wherein R.sub.4, X, Y have the abovementioned meaning, by reduction with 
catalytic hydrogen or with metals and acid such as, for example, with iron 
or zinc in the presence of acetic acid or hydrochloric acid or with other 
reagents suitable for the reduction of aromatic nitro compounds. 
Compounds of the formula (X) can be prepared for example by condensation of 
2-chloro-5-nitrobenzenesulphones of the formula 
##STR20## 
wherein halogen=F, Cl, Br and W has the abovementioned meaning, with amino 
compounds of the formula 
##STR21## 
wherein R.sub.4, R.sub.5, Y have the abovementioned meaning, or with 
compounds of the formula 
EQU HX--Y--G (XIII) 
wherein G=NO.sub.2, acylamino such as formylamino, acetylamino, 
oxalylamino, benzoylamino, tosylamino and X, Y have the abovementioned 
meaning, and subsequent conversion of the group G into 
##STR22## 
by reduction or hydrolysis. 
Compounds of the formula (XI) can be obtained by reaction of 
2-halogeno-5-nitrobenzenesulphinic acids with halogen compounds 
EQU Hal--Q (XIV) 
wherein halogen=F, Cl, Br, I and Q has the abovementioned meaning, or by 
addition of 2-halogeno-5-nitrobenzenesulphinic acids onto alkylated 
ethylene oxides of the formula 
##STR23## 
wherein R.sub.8 =H or C.sub.1 -C.sub.4 -alkyl, 
R.sub.9 =H or C.sub.1 -C.sub.4 -alkyl, 
R.sub.10 =C.sub.1 -C.sub.4 -alkyl, aryl 
or by addition of 2-halogeno-5-nitrobenzenesulphinic acids onto compounds 
which contain activated double bonds and have the formula 
##STR24## 
wherein A.sub.1 =H or activating substituent such as COOH, CN, COOC.sub.1 
-C.sub.4 -alkyl, 
A.sub.2 =activating substituent such as COOH, CN, CH.dbd.O, COOC.sub.1 
-C.sub.4 -alkyl, CONH.sub.2, SO.sub.3 H, C.sub.6 H.sub.5, 
R.sub.6, R.sub.7 =H, C.sub.1 -C.sub.4 -alkyl or wherein A.sub.1, A.sub.2 
can also be attached to the activated double bond to give 
##STR25## 
and if desired subsequent conversion of the primary sulphone product of 
the formula 
##STR26## 
wherein halogen, A.sub.1, A.sub.2, R.sub.6 and R.sub.7 have the 
above-mentioned meaning, into the compounds of the formula (XI). 
It is also possible to functionalise phenyl or hydroxyl groups in the 
radicals Q and/or Y and/or R.sub.4, R.sub.5 in compounds of the formula 
(IX) in the subsequent ring closure reaction to give compounds of the 
formula (V) in sulphuric acid or oleum subsequently with SO.sub.3 H or 
OSO.sub.3 H substituents. 
The condensation of the benzoquinones of the formula (VII) with the 
aminosulphone compounds of the formula (VIII) is best carried out in an 
aqueous or aqueous-organic medium in the presence of alkaline condensing 
agents at pH 3-11, preferably pH 4-8, and at temperatures of 
20.degree.-90.degree. C., preferably 40.degree.-70.degree. C., or in 
buffered solutions which contain above alkaline condensing agents. It is 
also possible to carry out the reaction in a purely organic medium in the 
presence of acid-binding agents. 
Alkaline condensing agents are for example sodium hydrogencarbonate, sodium 
carbonate, sodium acetate, potassium acetate, sodium hydroxide, potassium 
hydroxide, sodium phosphates, sodium borate. 
In general the condensation products of the formula (IX) are obtained as 
sparingly soluble brown products. 
A variant for preparing compounds of the formula (IX) consists in the 
addition of aminosulphone compounds of the formula (VIII) onto 
1,4-benzoquinones of the formula 
##STR27## 
wherein R.sub.1 and R.sub.2 have the abovementioned meaning, and the 
oxidation of the adduct intermediates. 
The cyclisation of the quinone condensation products (IX) can be carried 
out by methods which are known per se, such as those mentioned in German 
Offenlegungsschriften 2,122,262, 2,124,080, 2,302,382, 2,344,781, 
2,503,611 and 2,823,828, and in British Patent Specification 2,019,872, in 
particular in concentrated sulphuric acid and, in particular, in oleum 
with SO.sub.3 contents of 1-50%, at temperatures of 10.degree.-80.degree. 
C., if appropriate with the addition of oxidising agents, such as 
potassium peroxodisulphate or ammonium peroxodisulphate or organic 
peroxides. 
The new dyestuffs are useful products which are distinguished by high 
tinctorial strengths. They are suitable for a very wide range of uses in 
dispersed or dissolved form. 
In the form of water-soluble compounds, they are preferably of interest for 
dyeing textile materials containing hydroxyl of amide groups, in 
particular materials of natural or regenerated cellulose and nylon and 
polyurethane fibres, wool and silk. 
If the dyestuffs are water-soluble reactive dyestuffs, the materials 
mentioned are dyed or printed by the generally known processes which are 
customary for reactive dyestuffs. Blue dyeings and prints which have good 
light and wet fastness are then obtained. 
The temperatures in the examples are in .degree.C. The formulae of the 
water-soluble dyestuffs in the description and in the examples are those 
of the free acids. If the dyestuffs are reactive dyestuffs, these are as a 
rule isolated and used in the form of their alkali metal salts, in 
particular the lithium, sodium or potassium salts.

EXAMPLE 1 
3-(2-chloro-5-nitrophenylsulphonyl)-propionic acid 
36 g of sodium 2-chloro-5-nitrobenzenesulphinate, 12.6 g of solid sodium 
hydrogen carbonate and 22.5 g of maleic anhydride are heated at 
100.degree. C. in 250 ml of water for 3 hours. After cooling down, a 
further 12.6 g of sodium hydrogencarbonate and 22.5 g of maleic anhydride 
are then added. After a further 5 hours of stirring at 100.degree. C., the 
cooled, weakly acid reaction mixture is filtered with suction. The filter 
is cake at 50.degree. C. in 300 ml of water, and the suspension is cooled 
down to 20.degree. C. and is filtered again with suction. Drying gives 
35.1 g of 3-(2-chloro-5-nitrophenylsulphonyl)-propionic acid. 
______________________________________ 
.sup.1 HNMR (d.sub.6 -DMSO): .tau. = -2 to -1.5 (broad COOH), 
______________________________________ 
1.41 
##STR28## (d, 1H), 1.53 (dd, 1H), 2.02 (d, 1H) 6.19 (t, 
CH.sub.2), 7.36 (t, CH.sub.2) 
______________________________________ 
EXAMPLE 2 
3-[2-(2(2-N-.beta.-hydroxyethyl)aminoethyl)amino-5-nitrophenylsulphonyl]-pr 
opionic acid 
29.5 g of 3-(2-chloro-5-nitrophenylsulphonyl)propionic acid and 30 g of 
2-(2-aminoethylamino)ethanol are refluxed in 200 ml of isopropanol for 
three hours. The reaction mixture is cooled down and filtered with 
suction, and the precipitate is washed twice with 100 ml of water and is 
dried. This give 30.5 g of pale yellow 
3-[2-(2-.beta.-hydroxyethyl)aminoethyl)-amino-5-nitrophenylsulphonyl]-prop 
ionic acid. 
______________________________________ 
.sup.1 HNMR (d.sub.6 -DMSO/CF.sub.3 CO.sub.2 H): 
.tau. = 1.38 (broad 
##STR29## NH.sub.2.sup.+) 1.61 (d, 1H), 1.75 (dd, 1H), 2.65 
(t, NH), 2.88 (d, 1H), 6.2- 6.4 (m, 6H), 6.80 (m, 
2H), 6.90 (m, 2H), 7.35 (t, CH.sub.2) 
______________________________________ 
EXAMPLE 3 
3-[2-(2-(N-.beta.-hydroxyethyl)-aminoethyl)-amino-5-aminophenylsulphonyl]-p 
ropionic acid 
28.9 g of 
3-[2-(2-(N-.beta.-hydroxyethyl)-aminoethyl)-amino-5-nitrophenylsulphonyl]- 
propionic acid are suspended in 200 ml of ethanol and 200 ml of water. In 
an autoclave 1 g of Raney nickel is added, 7-10 bar of hydrogen are 
injected, and the temperature is raised to 60.degree.-65.degree. C. until 
there is no further consumption on injection of further hydrogen. After 
the reduction has ended, the resultant solution is clarified hot from 
Raney nickel, the nickel residue is washed with 30 ml of hot water, and 
the resultant solution is reacted as per Example 4. 
______________________________________ 
##STR30## .tau. = 2.25 (d, 1H), 2.35 (dd, 1H), 2.90 (d, 
1H), 6.05 (t, 2H), 6.16 (m, 4H), 6.55 (6, 2H), 
6.65 (t, 2H), 7.15 (t, 2H). 
______________________________________ 
EXAMPLE 4 
A solution, obtained as per Example 3, of 24.8 g of 
3-[2-(2-(N-.beta.-hydroxyethyl)-aminoethyl)-amino-5-aminoophenylsulphonyl] 
-propionic acid in 200 ml of ethanol and 230 ml of water is brought to pH 
5.5 with concentrated hydrochloric acid. After addition of 9.2 g of 
2,3,5,6-tetrachloroquinone the reaction mixture is warmed to 40.degree. C. 
and the pH is maintained with 2N sodium carbonate solution. After 2 hours 
the temperature is raised to 50.degree. C. and after a further 2 hours to 
60.degree. C. The reaction product crystallises out in fine brown needles. 
When the condensation has ended and there is no further consumption of 
sodium carbonate, the reaction product is filtered off with suction while 
still hot, is washed with 100 ml of 50% strength ethanol and then with 
water and finally with acetone and is dried at 60.degree. C. The product 
corresponds to the formula 
##STR31## 
EXAMPLE 5 
15 g of the condensation product obtained in Example 4 are gradually added 
at 0.degree.-5.degree. C. to 80 g of 90% strength sulphuric acid, and the 
mixture is stirred for 1 hour until solution is complete. The olive-green 
solution then has gradually added to it 3.4 g of pyrolusite having an 
active content of 88% MnO.sub.2. The reaction mixture is stirred at 
0.degree.-5.degree. C. for one hour and at 20.degree.-25.degree. C. for a 
further hour. The colour of the reaction mixture has changed from 
olive-green to violet. The violet solution is added to 800 g of ice-water, 
the precipitated reaction product is filtered off with suction, the filter 
cake is washed with water until it gives a weakly acid (pH 3-3.5) and 
sulphate-free reaction and is then dried at 60.degree. C. in a circulation 
air cabinet. 
This gives 15.76 g of a substance of the formula 
##STR32## 
which, at pH 7, gives a clear blue solution in water. 
EXAMPLE 6 
10.0 g of triphendioxazine compound of Example 5 are dissolved in 200 ml 
of water by adjusting the pH to 7, and the solution is cooled down to 
0.degree.-5.degree. C. 4.5 g of 2,4,6-trifluoro-5-chloropyrimidine are 
added dropwise, and the pH of the reaction mixture is maintained at 
8.5-9.0 with sodium carbonate solution. After the condensation has ended, 
the reaction mixture is brought to 6.0, and the dyestuff is salted out at 
20.degree. C. with 20 g of sodium chloride. The precipitate is filtered 
off with suction, is washed with 5% strength sodium chloride solution and 
is dried at 50.degree. C. in a circulating air cabinet. The resultant 
dyestuff conforms to the formula 
##STR33## 
It dyes cotton from a long liquor in deep bright blue shades. C.I. 
indicator number 13. 
.lambda..sub.max =614 nm in water. 
EXAMPLE 7 
A solution of 5.7 g of 2-aminobenzenesulphonic acid in 110 ml of water has 
added to it at 0.degree.-5.degree. C. and dropwise 4.9 g of cyanuric 
fluoride in the course of 5 minutes, and the pH is maintained at 3.5-4.0 
with 2N sodium carbonate solution. After the condensation has ended, the 
suspension of the reactive component is carefully brought to pH 6, and a 
solution, adjusted to pH 7, of 10.0 g of the triphendioxazine component of 
Example 5 in 200 ml of water is then added. During the addition, the 
reaction mixture is maintained with sodium carbonate solution at pH 9 and 
the temperature is maintained at 5.degree.-10.degree. C. If after some 
hours the consumption of sodium carbonate has ceased and the starting 
triphendioxazine is no longer detectable by chromatography, the resultant 
solution is brought to pH 6 and warmed to 20.degree. C. The reactive 
dyestuff is salted out with 50 g of sodium chloride, and the precipitate 
is filtered off with suction and washed with 10% strength sodium chloride 
solution. After pasting with pH 6 phosphate buffer the dyestuff is dried 
at 50.degree. C. in a circulating air cabinet. It conforms to the formula 
##STR34## 
and dyes cotton from a long liquor in bright blue shades. C.I. indicator 
number 13. .lambda..sub.max =627 nm in water. 
EXAMPLE 8 
3-[2-(2-aminoethyl)amino-5-nitrophenylsulphonyl]-propionic acid 
29.5 g of 3-(2-chloro-5-nitro-5-nitrophenylsulphonyl)propionic acid and 15 
g of 1,2-diaminoethane are refluxed in 150 ml of isopropanol for two 
hours. The reaction mixture is cooled down to 0.degree. C. and filtered 
with suction. The isolation is suspended in 100 ml of water, the 
suspension is brought to pH 3.5, and 15 g of sodium chloride are added for 
salting out. The precipitated betaine is filtered off with suction and 
dried. The yield of 
3-[2-(-aminoethyl)amino-5-nitrophenylsulphonyl]-propionic acid is 28.5 g. 
______________________________________ 
.sup.1 HNMR (d.sub.6 -DMSO/CF.sub.3 CO.sub.2 H): 
##STR35## .tau. = 1.31 (d, 1H), 1.60 (dd, 1H), 2.80 (broad NH), 
2.95 (d, 1H), 5.95 (m, 2H), 6.20 (m, 2H), 6.32 (m, 
2H), 6.90 (m, 2H). 
______________________________________ 
EXAMPLE 9 
3-[5-amino-2-(2-aminoethyl)-aminophenylsulphonyl]-propionic acid 
27.0 g of 3-[2-(2-aminoethyl)-amino-5-nitrophenylsulphonyl]-propionic acid 
are suspended in 150 ml of water and 150 ml of ethanol. In an autoclave 1 
g of nickel is added to the suspension, 60-70 bar of hydrogen are 
injected, and the temperature is raised to 60.degree. C. Stirring is 
continued for some time until no further hydrogen is absorbed. After 
letting down, the resultant solution is clarified at 70.degree. C. with 1 
g of activated charcoal, the clarification residue is washed with 20 ml of 
hot water, and the combined filtrates are reacted as per Example 10. 
______________________________________ 
.sup.1 HNMR (DCl) 
##STR36## = 2.25(d,1H),2.35(dd,1H), 2.90(d,1H),6.20(m,4H), 
6.60(t,2H)7.15(t,2H). 
______________________________________ 
EXAMPLE 10 
The solution, obtained in Example 9, of 23.2 g of 
3-[5-amino-2-(2-aminoethyl)-aminophenylsulphonyl]-propionic acid in 150 ml 
of ethanol and 170 ml of water is adjusted with concentrated hydrochloric 
acid from pH 7 to 5.5. 9.9 g of 2,3,5,6-tetrachloroquinone are added, the 
temperature is raised to 40.degree. C. and the pH is maintained at 5.5 
with sodium carbonate solution. After 2 hours the temperature is raised to 
50.degree. C. and after a further 2 hours to 60.degree. C. When the 
absorption of sodium carbonate has ceased, the reaction product, which has 
crystallised out in brown needles, is filtered off with suction while 
still hot, and is washed with 100 ml of 50% strength ethanol, then with 
water and finally with acetone. Drying at 60.degree. C. gives a substance 
which gives olive-green solutions in concentrated sulphuric acid and has 
the formula 
##STR37## 
EXAMPLE 11 
15 g of the condensation product obtained in Example 10 are gradually added 
at 0.degree.-5.degree. C. to 70 g of 90% strength sulphuric acid. The 
mixture is stirred for an hour until solution is complete. The above 
olive-green soluton has gradually added to it 4.0 g of pyrolusite having 
an active content of 88% MnO.sub.2, while the temperature is further 
maintained at 0.degree.-5.degree. C. The colour of the reaction mixture 
gradually changes from olive-green to bluish violet. Stirring is continued 
at 0.degree.-5.degree. C. for a further hour and then at 
20.degree.-25.degree. C. for an hour, and the solution is then added to 
700 g of ice-water. The precipitated product is filtered off with suction, 
is washed with water until free of sulphuric acid and is dried at 
60.degree. C. in a circulating air cabinet. This gives a substance of the 
formula 
##STR38## 
which gives a bright blue solution in water on addition of sodium 
hydroxide solution. 
EXAMPLE 12 
9.5 g of 2-aminobenzene-1,4-disulphonic acid are dissolved in 90 ml of 
water by addition of sodium carbonate solution up to pH 4. To the solution 
is added dropwise at 0.degree.-5.degree. C. at a uniform rate 5.1 g of 
cyanuric fluoride in the cource of 10 minutes, the pH is maintained at 
4.0-4.5 by addition of further sodium carbonate solution, the mixture is 
subsequently stirred for a further 30 minutes and is then brought to pH 
5.5. 
8.9 g of triphendioxazine compound of Example 11 are dissolved in 180 ml of 
water, 18 ml of caprolactam and 6.5 g of 15% strengh sodium hydroxide 
solution. 
This solution and the solution of the reactive component prepared above are 
added dropwise at 0.degree.-5.degree. C. in equal amounts to 50 ml of 
ice-water in such a way that the pH in the reaction mixture is maintained 
at 9.0. If necessary, this is achieved by metered addition of 2N sodium 
hydroxide solution. After the two solutions have been combined, the pH is 
further maintained at 9.0, and the batch is stirred at 0.degree.-5.degree. 
C. for some further hours until the condensation has ended. The 
temperature is raised to 20.degree. C., and the dyestuff is salted out of 
the solution with sodium chloride, is filtered off with suction and is 
washed with sodium chloride solution. The filter cake is mixed with a 
little phosphate buffer (pH =6) and is dried at 50.degree. C. in vacuo. 
This gives a dyestuff in the formula 
##STR39## 
which dyes cellulose fibres from a long liquor in bright blue shades. C.I. 
indicator number 13. .lambda..sub.max =614 nm in water. 
EXAMPLE 13 
benzyl 2-chloro-5-nitrophenyl sulphone 
24.4 g of the sodium salt of 2-chloro-5-nitrobenzenesulphinic acid are 
dissolved in 150 ml of ethanol under reflux conditions, and 35 g of benzyl 
chloride are gradually added. After 10 to 12 hours under reflux conditions 
the solution is cooled down to 60.degree. C., and the precipitated salt is 
separated off by filtration. The solution, on cooling down to 0.degree. 
C., yields 24.1 g of colourless crystals of benzyl 2-chloro-5-nitrophenyl 
sulphone. 
______________________________________ 
.sup.1 HNMR (d.sub.6 -DMSO): 
##STR40## .tau. = 1.59 (dd, 1H), 1.70 (d, 1H), 2.05 (d, 1H), 2.80 
(m, 5H), 5.12 (s, CH.sub.2). 
______________________________________ 
EXAMPLE 14 
[2-(2-aminoethyl)amino-5-nitrophenyl]-benzyl sulphone 
16.0 g of benzyl 2-chloro-5-nitrophenyl sulphone and 12.0 g of 
1,2-diaminoethane are refluxed in 100 ml of isopropanol for one hour. The 
reaction mixture is cooled down, and the solids are filtered off with 
suction, are washed with 50 ml of water and are dried. This gives 19.2 g 
of pale yellow [2-(2-aminoethyl)-amino-5-nitrophenyl]-benzyl sulphone. 
______________________________________ 
.sup.1 HNMR (d.sub.6 -DMSO): 
##STR41## .tau. = 1.87 (dd, 1H), 1.96 (d, 1H), 2.75-2.90 (m, 5H + 
NH), 3.13 (d, 1H) 5.45 (s, CH.sub.2), 6.84 (t, 
CH.sub.2), 6.5-6.9 (broad NH.sub.2), 7.27 (t, 
______________________________________ 
CH.sub.2). 
EXAMPLE 15 
5-amino-2-(2-aminoethyl)-aminophenyl benzyl sulphone 
20.0 g of 2-(2-aminoethyl)-amino-5-nitrophenyl benzyl sulphone are 
suspended in 100 ml of ethanol and 100 ml of water. In an autoclave 1 g of 
Raney nickel is added, 40 bar of hydrogen are injected, and the 
temperature is raised to 60.degree. C. until after a further injection of 
hydrogen there is no further consumption. After the reduction has ended 
the resultant solution is clarified hot from Raney nickel, the nickel 
residue is washed with 40 ml of hot water, and the resulting solution is 
reacted as per Example 16. 
EXAMPLE 16 
The solution obtained in Example 15, of 17.4 g of 
5-amino-2-(aminoethyl)-aminophenyl benzyl sulphone in 100 ml of ethanol 
and 140 ml of water is brought to pH 6 with hydrochloric acid. 7.0 g of 
2,3,5,6-tetrachlorquinone are added, the temperature is raised to 
45.degree. C. and the pH is constantly maintained at 5.5-6.0 with 2N 
sodium carbonate solution. After 2 hours the temperature is raised to 
55.degree. C. and after a further hour to 65.degree. C. After the reaction 
has ended, the crystalline product is filtered off with suction at 
20.degree. C., is washed with a mixture of ethanol and water and then with 
water and is dried at 60.degree. C. in a circulating air cabinet. The 
brown product conforms to the formula 
##STR42## 
EXAMPLE 17 
15.2 g of the condensation product obtained in Example 16 are gradually 
added at 0.degree.-5.degree. C. to 45 ml of 20% strength oleum. The 
temperature is allowed to rise to 20.degree. C., and at 20.degree. C. 10.5 
g of potassium peroxodisulphate are added in the course of 1 hour. After 
the addition, stirring is continued for one hour, and the blue solution is 
then added to 450 g of ice-water. The precipitated product is filtered off 
with suction and washed with water. The filter cake is suspended in 200 ml 
of water, the suspension is brought to pH 8 with sodium hydroxide 
solution, 15 g of sodium chloride are added for salting out, and the 
precipitate is filtered off with suction and washed with 5% strength 
sodium chloride solution. The product dried at 60.degree. C. conforms to 
the formula 
##STR43## 
EXAMPLE 18 
6.1 g of 2-aminobenzene-1,4-disulphonic acid are dissolved at pH 6 in 50 ml 
of water. To this solution are added 4.7 g of cyanuric chloride and 10 ml 
of acetone and at 20.degree. C. the pH is maintained at 5.5 with sodium 
carbonate solution until a clear solution is formed and the condensation 
has ended. 
To the reactive component is added a solution at pH 9 of 11.0 g of 
triphendioxaxine component from Example 17 in 100 ml of water, and the pH 
is maintained at 9 with dilute sodium hydroxide solution. When the 
reaction has ended after several hours, the pH of the solution is adjusted 
to 7, the resultant dyestuff is salted out with 80 g of sodium chloride, 
is filtered off with sucton, is washed with 25% strength sodium chloride 
solution and is dried at 60.degree. C. in a circulating air cabinet. 
The dyestuff conforms to the formula 
##STR44## 
It can be used to dye and print cellulose fibres in deep bright blue 
shades. C.I. indicator number 13. .lambda..sub.max =614 nm in water. 
EXAMPLE 19 
If a solution of 11.0 g of triphendioxazine component from Example 17 in 
110 ml of water (pH 9) is reacted with a solution of a reactive component 
which has been prepared at 0.degree.-5.degree. C. and pH 4.0 from 8.1 g of 
2-aminobenzene-1,4-disulphonic acid and 4.8 g of cyanuric fluoride in 80 
ml of water analogously to Example 12 at pH 9.0, this after salting out, 
isolation and drying gives a dyestuff of the formula 
##STR45## 
which dyes cotton in bright blue shades. C.I. indicator number 13. 
.lambda..sub.max =614 nm in water. 
EXAMPLE 20 
If a solution of 10.0 g of triphendioxazine component of Example 17 in 200 
ml of water (pH 9) is reacted with the suspension of the reactive 
component prepared from 5.1 g of 2-aminobenzenesulphonic acid and 4.2 g of 
cyanuric fluoride analogously to Example 12 by gradually adding dyestuff 
solution and reactive component simultaneously to 50 ml of water and 
maintaining in the reaction mixture the pH at 9.0 and the temperature at 
0.degree.-5.degree. C., then this gives after isolation and drying a 
dyestuff of the formula 
##STR46## 
which likewise dyes cellulose fibres in bright blue shades. C.I. indicator 
number 13. .lambda..sub.max =624 nm in water. 
Further reactive dyestuffs which dye cellulose fibres in bright blue shades 
(C.I. indicator number 13) are obtained when, analogously to the preceding 
examples, the aminosulphones listed in column 1 of the table below are 
condensed with the quinones of column 2 in a molar ratio of 2:1, the 
resultant condensation products are converted in 90-100% strength 
sulphuric acid or oleum in the presence of oxidising agents such as 
MnO.sub.2 or peroxodisulphates into the triphendioxazines of column 3, and 
these are condensed with the reactive components of the last column. 
__________________________________________________________________________ 
Triphendioxazine 
__________________________________________________________________________ 
##STR47## 
2 
##STR48## 
3 
##STR49## 
4 
" 
5 
##STR50## 
6 
##STR51## 
7 
" 
8 
" 
9 
##STR52## 
10 
##STR53## 
11 
##STR54## 
12 
##STR55## 
13 
##STR56## 
14 
" 
15 
##STR57## 
16 
##STR58## 
17 
##STR59## 
18 
" 
19 
##STR60## 
20 
##STR61## 
21 
" 
22 
" 
23 
##STR62## 
24 
" 
25 
##STR63## 
26 
" 
27 
##STR64## 
28 
##STR65## 
29 
" 
30 
##STR66## 
31 
##STR67## 
32 
" 
33 
##STR68## 
34 
" 
35 
##STR69## 
36 
" 
37 
" 
38 
##STR70## 
39 
" 
40 
##STR71## 
41 
##STR72## 
42 
##STR73## 
43 
##STR74## 
44 
##STR75## 
45 
##STR76## 
46 
##STR77## 
47 
##STR78## 
48 
##STR79## 
49 
##STR80## 
50 
##STR81## 
51 
##STR82## 
52 
##STR83## 
53 
##STR84## 
54 
##STR85## 
55 
##STR86## 
56 
" 
57 
##STR87## 
58 
##STR88## 
59 
##STR89## 
60 
##STR90## 
61 
##STR91## 
62 
##STR92## 
63 
##STR93## 
64 
##STR94## 
__________________________________________________________________________ 
Aminosulphone Quinone Reactive component 
__________________________________________________________________________ 
##STR95## 
##STR96## 
##STR97## 
2 
##STR98## " 
##STR99## 
3 
##STR100## " 
##STR101## 
4 
" " 
##STR102## 
5 
##STR103## " 
##STR104## 
6 
##STR105## 
##STR106## 
##STR107## 
7 
" " 
##STR108## 
8 
" " 
##STR109## 
9 
##STR110## " 
##STR111## 
10 
##STR112## " 
##STR113## 
11 
##STR114## 
##STR115## 
##STR116## 
12 
##STR117## " 
##STR118## 
13 
##STR119## " 
##STR120## 
14 
" " 
##STR121## 
15 
##STR122## " 
##STR123## 
16 
##STR124## 
##STR125## 
##STR126## 
17 
##STR127## " 
##STR128## 
18 
" " 
##STR129## 
19 
##STR130## " 
##STR131## 
20 
##STR132## 
##STR133## 
##STR134## 
21 
" " 
##STR135## 
22 
" " 
##STR136## 
23 
##STR137## " 
##STR138## 
24 
" " 
##STR139## 
25 
##STR140## 
##STR141## 
##STR142## 
26 
" " 
##STR143## 
27 
##STR144## " 
##STR145## 
28 
##STR146## " 
##STR147## 
29 
" " 
##STR148## 
30 
##STR149## 
##STR150## 
##STR151## 
31 
##STR152## " 
##STR153## 
32 
" " 
##STR154## 
33 
##STR155## " 
##STR156## 
34 
" " 
##STR157## 
35 
##STR158## 
##STR159## 
##STR160## 
36 
" " 
##STR161## 
37 
" " 
##STR162## 
38 
##STR163## 
##STR164## 
##STR165## 
39 
" " 
##STR166## 
40 
##STR167## " 
##STR168## 
41 
##STR169## 
##STR170## 
##STR171## 
42 
##STR172## 
##STR173## 
##STR174## 
43 
##STR175## 
##STR176## 
##STR177## 
44 
##STR178## " " 
45 
##STR179## " 
##STR180## 
46 
##STR181## " 
##STR182## 
47 
##STR183## 
##STR184## 
##STR185## 
48 
##STR186## 
##STR187## 
##STR188## 
49 
" 
##STR189## 
##STR190## 
50 
##STR191## 
##STR192## 
##STR193## 
51 
##STR194## 
##STR195## 
##STR196## 
52 
##STR197## " 
##STR198## 
53 
##STR199## " 
##STR200## 
54 
##STR201## " 
##STR202## 
55 
##STR203## 
##STR204## 
##STR205## 
56 
" 
##STR206## 
##STR207## 
57 
##STR208## " 
##STR209## 
58 
##STR210## " 
##STR211## 
59 
##STR212## " 
##STR213## 
60 
##STR214## 
##STR215## 
##STR216## 
61 
##STR217## " " 
62 
##STR218## " 
##STR219## 
63 
##STR220## " " 
64 
##STR221## " 
##STR222## 
__________________________________________________________________________ 
EXAMPLE 21 
2-chloro-5-nitrophenyl 2-hydroxypropyl sulphone 
150 g (0.5 mol) of 81% pure sodium 2-chloro-5-nitrobenzenesulphinate are 
presented in 300 ml of water at pH 8-8.5 and 60.degree. C. To this are 
added dropwise in the couse of about 8 hours 200 ml of propylene oxide 
while the pH of the reaction mixture is constantly maintained between 7.5 
and 9.5 with 20% strength sulphuric acid. After cooling down, the solids 
are filtered off with suction and washed twice with 200 ml of water. 
Drying at 70.degree. C. in vacuo gives 118 g of colourless 
2-chloro-5-nitrophenyl 2-hydroxypropyl sulphone. 
______________________________________ 
##STR223## .sup.1NMR (d.sub.6 -DMSO): .tau. = 1.39 (d, 1H), 1.56 
(dd, 1H), 2.06 (d, 1H), 5.15 (d, OH), 5.90 (m, CH), 
6.20-6.40 (m, CH.sub.2), 8.85 (d, CH.sub.3). 
______________________________________ 
EXAMPLE 22 
2-(2-aminoethylamino)-5-nitrophenyl 2-hydroxypropyl sulphone 
28 g (0.1 mol) of 2-chloro-5-nitrophenyl 2-hydroxypropyl sulphone are 
refluxed in 100 ml of isopropanol. To this are added gradually 15 ml of 
ethylenediamine, and heating is continued with stirring for a further 
hour. The cold reaction solution is diluted with 300 ml of water and 
stirred at 20.degree. C. for two hours. The precipitated yellowish 
crystals are filtered off with suction, washed with 100 ml of water and 
dried. This gives 28 g of uniform 2-(2-aminoethylamino)-5-nitrophenyl 
2-hydroxypropyl sulphone. 
______________________________________ 
##STR224## .sup.1NMR (d.sub.6 -DMSO/CF.sub.3 COOH): .tau. = 1.62 
(d, 1H), 1.80 (dd, 1H), 2.10 (broad NH.sub.3.sup.+), 
2.70 (t, NH), 2.95 (d, 1H), 5.90 (m, CH), 6.31 (t, 
CH.sub.2), 6.40-6.65 (m, CH.sub.2), 6.95 (m, 
CH.sub.2), 8.81 (d, CH.sub.3). 
______________________________________ 
EXAMPLE 23 
[5-amino-2-(2-aminoethylamino)-phenyl]2-hydroxypropyl sulphone 
26.4 g of 2-(2-aminoethylamino)-5-nitrophenyl 2-hydroxy-1-propyl sulfone 
are suspended in 200 ml of isopropanol. In an autoclave 1 g of Raney 
nickel is added to the suspension, 60-70 bar of hydrogen are injected and 
the temperature is raised to 60.degree. C. 
The batch is stirred some more until no further hydrogen is absorbed. After 
letting down the reaction mixture is diluted with 200 ml of water, the 
resultant solution is clarified at 60.degree. C. from nickel, and the 
residue is washed with 40 ml of water. The combined filtrates are reacted 
as per Example 24. 
An evaporated aliquot of the solution leaves a slowly crystallising viscous 
mass of the amine. 
______________________________________ 
##STR225## .sup.1 HNMR(DCl): = 2.17 (d, 1H9, 2.32-2.37, (dd, 
1H), 2.87 (d, 1H), 5.63 (m, CH), 6.23 (t, CH.sub.2), 
6.38 (m, CH.sub.2), 6.63 (m, CH.sub.2), 8.68 (d, 
CH.sub.3). 
______________________________________ 
EXAMPLE 24 
A solution, obtained in Example 23, of 20.5 g of 
5-amino-2-(2-aminoethylamino)-phenyl 2-hydroxy-1-propyl sulphone in 215 ml 
of water and 180 ml of isopropanol is brought to pH 6.0 with concentrated 
hydrochloric acid. To this are added 9.2 g of 2,3,5,6-tetrachloroquinone, 
the temperature is raised to 40.degree. C., and the pH is maintained at 
5.5-5.8 with 2N sodium carbonate solution. After 2 hours the temperature 
is raised to 50.degree. C. and the pH is maintained some more until the 
consumption of sodium carbonate has ceased. To the brown solution obtained 
are added dropwise 550 ml of 25% strength sodium chloride solution in the 
course of 2 hours, the thrown precipitate is filtered off with suction, 
and the filter cake is washed with dilute sodium chloride solution and 
with acetone. This gives a brown product of the formula 
##STR226## 
EXAMPLE 25 
11.9 g of the condensation product obtained in Example 24 are gradually 
added at -5.degree. to 0.degree. C. to 50 ml of 20% strength oleum. After 
the addition, the temperature of the solution is allowed to rise to 
15.degree. C., and 7.7 g of potassium peroxodisulphate are added in the 
course of 45 minutes with cooling at such a rate that the temperature is 
maintained at 20.degree. C. The reaction mixture is stirred at 20.degree. 
C. for about 2 hours. It is then carefully added to 270 g of ice, the 
precipitated product is filtered off with suction at 0.degree.-10.degree. 
C., and the filter cake is washed with 300 ml of water until 
sulphate-free. The product obtained conforms to the formula 
##STR227## 
and after neutralisation gives a clear blue solution in water. The product 
can be dried at 50.degree. C. in a circulating air cabinet. 
EXAMPLE 26 
11.2 g of the triphendioxazine component of Example 25 in the form of a 
moist filter cake are dissolved in 200 ml of water by setting a pH of 8.0. 
The bluish violet solution is immediately cooled down to 0.degree. C. and 
a solution of 2-(2,4-difluorotriazinyl)-aminobenzene-1,4-disulphonic acid 
or of the partial sodium salt, which is prepared from 9.1 g of 
2-aminobenzene-1,4-disulphonic acid and 4.9 g of cyanuric fluoride by the 
method of Example 12, is then added in the course of 5 minutes. 
In the reaction mixture the pH is maintained at 8.0 with 2N sodium 
hydroxide solution and the temperature at 0.degree.-5.degree. C. After the 
reaction has ended, the solution has turned a pure blue colour. The 
temperature is then allowed to rise to 20.degree. C., and the dyestuff is 
salted out of the solution with potassium chloride. The precipitate is 
filtered off with suction, and the filter cake is washed with 20% strength 
potassium chloride solution and after addition of a little phosphate 
buffer solution is dried at 45.degree. C. in vacuo. This gives a dyestuff 
of the formula 
##STR228## 
which dyes cellulose fibres from a long liquor in bright blue shades. C.I. 
indicator number 13. .rho..sub.max =616 nm in water.