Reactive azo dyes.

0001The present invention relates to dyes of the formula<chemistry id="chem0001" num="0001"><img file="EP0197418A2_D0001.tif" /></chemistry>wherein<ul id="ul0001" list-style="none"><li>A = NHR, NR R, SR, SOR, SO₂R, CI especially SO₂B,</li><li>B = -CH = CH₂ or -CH₂CH₂-Z where</li><li>Z = alkaline eliminable residue or OH</li><li>K = rest of a coupling component</li><li>R = substituent, especially optionally substituted C₁-C₆Alkyl, aralkyl, aryl, alkenyl or hetaryl, where the two radicals R together can also represent the remaining members of a 5 or 6 ring system which may have further heteroatoms, in particular for<chemistry id="chem0002" num="0002"><img file="EP0197418A2_D0002.tif" /></chemistry>and R can also be or contain a reactive group, in particular for A = NHR or -NRR.</li></ul>

0002Process for their production and their use for dyeing and printing natural and synthetic fiber materials.

0003Suitable coupling components are in particular those of the hydroxybenzene, hydroxynaphthalene, aminobenzene, aminonapthalene, the aromatic-heterocyclic series or the acetoacetic acrylate series, which may have customary substituents, for example arylazo groups and in particular also reactive groups. Substituents in the benzene, naphthalene or aromatic heterocyclic rings of the coupling components are, for example, alkyl, alkoxy, halogen, OH, amino, alkylamino, arylamino, acrylamino such as alkylcarbonylamino, alkylsulfonylamino, acrylcarbonylamino, in particular optionally substituted phenylcarbonylamino, carboxy, sulfoalkyl. Preferred coupling components are in particular those which are free from water-solubilizing residues and how they are^pielswiese are described in DE-OS 2 362 683.

0004Suitable radicals Z are, for example - OSO₃H, -SSO₃H, -OCOCH₃, -OPO₃H₂, -OSO₂CH₃, - S-CN, -NHSO₂CH₃, CI, Br, F, -N (CH₃)₂, -N (C₂H₅)₂, OCOC₆H₅, -OSO₂-C₆H₅-CH₃, -N (CH₃)₃]⁺X- or<chemistry id="chem0003" num="0003"><img file="EP0197418A2_D0003.tif" /></chemistry>

0005Suitable reactive groups, ie groups which react with the OH or NH groups of the fiber under dyeing conditions to form covalent bonds, are in particular those which contain at least one reactive substituent bonded to a 5- or 6-membered aromatic-heterocyclic ring, or to a monoazine, diazine, triazine, for example Pyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxazine or asymmetrical or symmetrical triazine ring, or to such a ring system which has one or more fused aromatic carbocyclic rings, such as a quinoline, phthalazine, cinnoline, quinazoline , Quinoxaline, acridine, phenazine and phenanthridine ring system.

0006Among the reactive substituents on the heterocycle are to be mentioned for example

0007Halogen (CI, Br or F), ammonium including hydrazinium, sulfonium, sulfonyl, azido (-N₃), Rhodanido, thio, thiol ether, oxiether, sulfinic acid and sulfonic acid.

0008The following can be mentioned in detail, for example:<ul id="ul0002" list-style="none"><li>2,4-difluorotriazinyl, 2,4-dichlorotriazinyl-6, monohalogen-sym.-triazinyl radicals, in particular monochloro and monofluorotriazinyl radicals, which are substituted by alkyl, aryl, amino, monoalkylamino, dialkylamino, aralkylamino, arylamino, alkoxy, aryloxy, alkylthio, arylthio are substituted, alkyl preferably being optionally substituted C₁-C₄-Alkyl, Arälkyl preferably optionally substituted phenyl-C₁-C₄alkyl and aryl preferably denotes optionally substituted phenyl or naphthyl and preferred substituents for alkyl being hydroxy, cyano, C.₁-C₄-Alkoxy, carboxy, sulfo or sulfato. are and for phenyl and naphthyl sulfo, C, -C4-alkyl, C, -C.-alkoxy, carboxy, halogen or acylamino.</li></ul>

0009The following residues are mentioned in detail:<ul id="ul0003" list-style="none"><li>2-amino-4-fluorotriazinyl-6, 2-methylamino-4-fluorotriazinyl-6, 2-ethylamino-4-fluorotriazinyl-6, 2-isopropylamino-4-fluorotriazinyl-6, 2-dimethylamino- 4-fluoro-triazinyl-6, 2-diethylamino-4-fluoro-triazinyl-6, 2-ß-methoxy-ethylamino-4-fluoro-triazinyl-6, 2-ß-hydroxyethylamino-4-fluoro-triazinyl-6, 2-Di- (β-hydroxyethylamino) -4-fluorotriazinyl-6-, 2-β-sulfoethylamino-4-fluorotriazinyl-6, 2-β-sulfoethylmethylamino-4-fluorotriazinyl-6 , 2-carboxymethylamino-4-fluoro-triazinyl-6, 2-ß-cyanoethylamino-4-fluorotriazinyl-6, 2-benzoylamino-4-fluorotriazinyl-6, 2-β-phenylethylamino-4-fluorotriazinyl-6, 2-benzyl-methylamino-4-fluoro- triazinyl-6, 2- (x-sulfobenzy) amino-4-fluoro-triazinyl-6, 2-cyclohexylamino-4-fluoro-triazinyl-6, 2- (o-, m-, p-methylphenyl) -amino- 4-fluoro-triazinyl-6, 2- (o-, m-, p-sulfophenyl) amino-4-fluoro-triazinyl-6, 2- (2 ', 5'-disulfophenyl) amino-4-fluoro triazinyl-6, 2- (o-, m-, p-chlorophenyl) amino-4-fluoro-triazinyl-6, 2- (o-, m-, p-methoxyphenyl) -4-fluorotriazinyl-6, 2- (2'-methyl-4'-sulfophenyl) amino-4-fluorotriazinyl-6, 2- (2'-methyt-5'-sulfophenyl) -amino-4-fluoro-triazinyl-6, 2- (2'-chloro-4'-sulfophenyl) -amino-4-fluoro-triazinyl-6, 2- (2'-chloro-5'-sulfophenyl) amino -4-fluoro-triazinyl-6, 2- (2'-methoxy-4'-sulfophenyl) amino-4-fluoro-triazinyl-6, 2- (o-, m-, p-carboxyphenyl) amino-4 -fluoro-triazinyl-6, 2- (2 ', 4'-disulfophenyl) amino-4-fluoro-triazinyl-6, 2- (3', 5'-disulfophenyl) amino-4-fluoro-triazinyl-6 , 2- (2'-. Carboxy-4-sulfophenyl) amino-4-fluoro-triazinyl-6, 2- (2'-carboxy-4-sulfophenyl) amino-4-fluoro-triazinyl-6, 2- (6'-sulfonaphthyl- (2nd ') -amino-4-fluorotriazinyl-6, 2- (4', 8'-disulfonaphthyl- (2 ')) - amino-4-fluorotriazinyl-6, 2- (6', 8'-disulfonaphthyl - (2 ')) - amino-4-fluorotriazinyl-6, 2- (N-methylphenyl) amino-4-fluorotriazinyl-6, 2- (N-ethylphenyl) amino-4-fluorotriazinyl -6, 2- (N-β-hydroxyethylphenyl) amino-4-fluoro-triazinyl-6, 2- (N-iso-propylphenyl) amino-4-fluoro-triazinyl-6, 2-morpholino-4-fluorotriazinyl-6, 2-piperidino-4-fluorotriazinyl-6, 2- (4 ', 6', 8'-trisulfonaphthyl- (2 ')) - 4-fluorotriazinyl- 6, 2- (3 ', 6', 8'-trisulfonaphthyl- (2 ')) - 4-fluorotriazinyl-6, 2- (3', 6'-disulfonaphthyl- (1 ')) - 4-fluor - triazinyl-6, N-methyl-N- (2,4-dichlorotriazinyl-6) -carbamyl-, N-methyl-N- (2-methylamino-4-chlorotriazinyl-6) -carbamyl-, N-methyl-N - (2-dimethylamino-4-chlorotriazinyl-6) -carbamyl-, N-methyl or. N-ethyl-N- (2,4-dichlorotriazinyl-6) aminoacetyl, 2-methoxy-4-fluorotriazinyl-6, 2-ethoxy-4-fluorotriazinyl-6, 2-phenoxy-4-fluorine triazinyl-6, 2- (o-, m- or p-sulfophenoxy) -4-fluorotriazinyl-6, 2- (o-, m- or p-methyl- or methoxyphenoxy-4-fluoro- triazinyl-6, 2-ß-hydroxyethylmercapto-4-fluoro-triazinyl-6, 2-phenyl-mercapto-4-fluoro-triazinyl-6, 2- (4'-methytphenyl) -mercapto-4-fluorotriazinyl, 2- ( 2 ', 4'-dinitrophenyl) -mercapto-4-fluoro-triazinyl-6, 2-methyl-4-fluorotriazinyl-6, _-2-phenyl-4-fluorotriazinyl-6 and the corresponding 4-chloro or. 4-bromo residues and those from the corresponding halogen atoms with tertiary bases such as trimethylamine, triethylamine, dimethyl-β-hydroxyethylamine, triethanolamine, N, N-dimethylhydrazine, pyridine, a- or y-picoline, nicotinic acid or isonicotinic acid or sulfinates, in particular benzenesulfinic acid available leftovers.</li></ul>

0010Mono-, di- or trihalopyrimidinyl residues, such as 2,4-dichloropyrimidinyl-6, 2,3,5-trichloropyrimidinyl-6, 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-pyrimidinyl-6, 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 3rd -Monochloroquinoxaline-6-carbonyl-, 2- or 3-monochloroquinoxaline-6-sulfonyl-, 2,3-dichloroquinoxaline-6-carbonyl-, 2,3-dichloroquinoxaline-6-sulfonyl-, 1,4-dichlorophthalazine-6- sulfonyl-or -6-carbonyl-, 2,4-dichloroquinazolin-7-or -6-sulfonyl-or -carbonyl-, 2- or 3- or 4- (4 ', 5'-dichloropyridazon-6'-yl- 1 ') - phenylsulfonyl or carbonyl, β- (4 ', 5'-dichloropyridazon-6'-yl-1') - ethylcarbonyl-, N-methyl-N- (2,3-dichloroquinoxaline-6-sulfonyl) -aminoacetyl-, N-methyl-N- (2,3-dichloroquinoxaline-6-carbonyl) aminoacetyl, and the corresponding bromine and fluorine derivatives of the above-mentioned chlorine-substituted heterocyclic radicals, among them, 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-4-pyrimidinyl, 2-fluoro-5-nitro-6-chloro-4-pyrimidinyl, 5-bromo-2-fluoro-4-pyrimidinyl, 2-fluoro -5-cyan-4-pyrimidinyl-, 2-fluoro-5-methyl-4-pyrimidinyl-, 2,5,6-trifluoro-4-pyrimidinyl-, 5-chloro-6-chloromethyl-2-fluoro-4- pyrimidinyl-, 2,6-di-fluoro-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-4-pyrimidinyl-, 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-cyan-4-pyrimidinyl, 2-fluoro-4-dichloromethyl-5-chloropyrimidine -6-yl, 2-fluoro-5-chloropyrimidin-4-yl; 2-methyl-4-fluoro-5-methylsulfonylpyrimidinyl-6; 2,6-difluoro-5-methylsulfonyl-4-pyrimidinyl, 2,6-dichloro-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; triazine residues containing sulfonyl groups, such as 2,4-bis (phenylsulfonyl) triazinyl-6-, 2- (3'-carboxyphenyl) sulfonyl-4-chlorotriazinyl-6-, 2- (3'-sulfophenyl) sulfonyl-4- chlorotriazinyl-6, 2,4-bis (3'-carboxyphenylsulfonyl -) - triazinyl-6; pyrimidine rings containing sulfonyl groups, such as 2-carboxymethylsulfonyl-pyrimidinyl-4-, 2-methylsulfonyl-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-6-ethyl-pyrimidinyl-4-, 2-phenylsulfonyl-5-chloro-6-methyl-pyrimidinyl -4-, 2,6-bis-methylsulfonyl-pyrimidinyl-4-, 2,6-bismethylsulfonyl-5-chloro-pyrimidinyl-4-, 2,4-bis-methylsulfonyl-pyrimidine-5-sulfonyl-, 2-methylsulfonyl -pyrimidinyl-4, 2-phenylsulfonyl-pyrimidinyl-4-, 2-trichloromethylsulfonyl-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-bromo-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-chloro-6-ethyl-pyrimidinyl-4- , 2-methylsulfonyl-5-chloro-6-chloromethyl-pyrimidinyl-4-, 2-methylsulfonyl-4-chloro-6-methylpyrimidine-5-sulfonyl-, 2-methylsulfonyl-5-nitro-6-methylpyrimidinyl-4-, 2,5,6-tris-methylsulfonyl-pyrimidinyl-4-, 2-methylsulfonyl-5,6-dimethyl-pyrimidinyl-4-, 2-ethylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl -6-chloro-pyrimidinyl-4-, 2,6-bis-methylsulfonyl-5-chloro-pyrimidinyl-4-, 2-methylsulfonyl-6-carboxypyrimidinyl-4-, 2-methylsulfonyl-5-sulfo-pyrimidinyl-4-, 2-methylsulfonyl-6-carbomethoxy-pyrimidinyl -4-, 2-methylsulfonyl-5-carboxypyrimidinyl-4-, 2-methylsulfonyl-5-cyano-6-methoxypyrimidinyl-4-, 2-methylsulfonyl-5-chloropyrimidinyl-4-, 2-sulfoethylsulfonyl -6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-bromopyrimidinyl-4-, 2-phenylsulfonyl-5-chloro-pyrimidinyl-4-, 2-carboxymethylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4- , 2-methylsulfonyl-6-chloropyrimidine-4-and -5-carbonyl-, 2,6-bis- (methylsulfonyl) -pyrimidine-4-or -5-carbonyl-, 2-ethylsulfonyl-6-chloropyrimidine-5-carbonyl- , 2,4-bis (methylsulfonyl) pyrimidine-5-sulfonyl-, 2-methylsulfonyl-4-chloro-6-methylpyrimidine-5-sulfonyl-or -carbonyl-; 2-chlorobenzthiazole-5-or -6-carbonyl- or -5-or - 6-sulfonyl-, 2-arylsulfonyl- or alkylsulfonylbenzthiazole-5-or -6-carbonyl-or -5-or -6-sulfonyl-, such as 2-Methylsulfonyl- or 2-ethylsulfonylbenzthiazole-5-or -6-sulfonyl- or - carbonyl-, 2-phenylsulfonylbenzthiazole-5-or -6-sulfonyl- or carbonyl- and the corresponding 2-sulfonylbenzthiazole-5 containing sulfo groups in the condensed benzene ring or 6-carbonyl or sulfonyl derivatives, 2-chlorobenzoxazole-5-or-6-carbonyl-or -sulfonyl-, 2-chlorobenzimidazole-5-or -6-carbonyl-or -sulfonyl-, 2-chloro-1-methylbenzimidazole-5-or -6-carbonyl- or sulfonyl-, 2-chloro-4-methylthiazole- (1,3) -5-carbonyl- or -4-or -5-sulfonyl-, N-oxide of 4-chloro or 4-nitroquinoline-5-carbonyl.

0011Furthermore, reactive groups of the aliphatic series are to be mentioned, such as acryloyl, mono-, di- or trichloracryloyl, such as -CO-CH = CH-Cl, -CO-CCI = C_H2, -CO-CCI = CH-CH₃, further -CO-CCI = CH-COOH, -CO-CH = CCI-COOH, β-chloropropionyl-, 3-phenyisulfonylpropionyl-, 3-methylsulfonylpropionyl-, 2-fluoro-2-chloro-3,3-difluorocyclobutane-1 -carbonyl-, 2,2,3,3-tetrafluorocyclobutane-carbonyl1-or -sulfonyl-1-, β- (2,2,3,3-tetrafluorocyclobutyl-2) -aryloxy-, or or β-bromoacryloyl-, - or β-alkyl or arylsulfoacrylolyl group, such as - or β-methylsulfonylacryloyl, chloroacetyl, vinylsulfonyl, -SO₂CH₂CH₂Z where Z = alkali-releasable group, especially -OSO₃H, -OCOCH₃, - OPO₃H₂, -OCOC₆H₅, Di-C₁-C₄-Alkylamino, quaternary ammonium, especially -R (C₁-C₄-Alkyl) X^Θ<chemistry id="chem0004" num="0004"><img file="EP0197418A2_D0004.tif" /></chemistry>or<chemistry id="chem0005" num="0005"><img file="EP0197418A2_D0005.tif" /></chemistry>With<ul id="ul0004" list-style="none"><li>X⁹ = Anion, in particular halogen or sulfate anion, -S₂O₃H, -CI, -Br, -F, -SCN, -NHSO₂CH₃, - OSO₂C.₆H₅.</li></ul>

0012Reactive dyes of the formula are particularly preferred<chemistry id="chem0006" num="0006"><img file="EP0197418A2_D0006.tif" /></chemistry>and those of the formula<chemistry id="chem0007" num="0007"><img file="EP0197418A2_D0007.tif" /></chemistry>wherein<ul id="ul0005" list-style="none"><li>R '= (CH₂)_nNHY.</li><li>n = 2 or 3 and</li><li>Y = fiber reactive residue.</li></ul>

0013Further preferred dyes are those of the formulas<chemistry id="chem0008" num="0008"><img file="EP0197418A2_D0008.tif" /></chemistry><chemistry id="chem0009" num="0009"><img file="EP0197418A2_D0009.tif" /></chemistry><chemistry id="chem0010" num="0010"><img file="EP0197418A2_D0010.tif" /></chemistry>

0014The dyes are prepared by diazotization of amines of the formula<chemistry id="chem0011" num="0011"><img file="EP0197418A2_D0011.tif" /></chemistry>and clutch with clutch components<chemistry id="chem0012" num="0012"><img file="EP0197418A2_D0012.tif" /></chemistry>in a manner known per se.

0015Suitable coupling components (7) are, for example, those of the hydroxybenzene, hydroxynaphthalene, aminobenzene, aminonaphthalene, amino-hydroxynaphthalene, amino-hydroxybenzene, pyrazolone, pyridine, aminopyridine or acetoacetic arylide series, in particular also those which have sulfo groups. In particular phenol, 1-hydroxy-3-or -4-methylbenzene, 1-hydroxy-benzene-4-sulfonic acid, 1-hydroxy-naphthalene, 2-hydroxy-naphthalene, 2-hydroxynaphthalene-6-or -7-sulfonic acid, 2 -Hydroxynaphthalene-3,6-or -6,8-disulfonic acid, 1-hydroxynapthalene-4-sulfonic acid, 1-hydroxynaphthalene-4,6-or -4,7-disulfonic acid, 1-amino-3-methylbenzene, 1-amino -2-methoxy-5-methylbenzene, 1-amino-2,5-dimethylbenzene, 3-aminophenylurea, 1-amino-3-acetylaminobenzene, 1-amino-3-hydroxyacetylaminobenzene, 1,3-diaminobenzene-4-sulfonic acid, 1-amino-naphthalene-6-or -8-sulfonic acid, 1-amino-2-methoxynaphthalene-6-sulfonic acid, 2-amino-naphthalene-5,7-disulfonic acid, 1-amino-8- hydroxynaphthalene-6-sulfonic acid, 1-amino-8-hydroxynaphthalene-2,4-disulfonic acid, 2-hydroxy-3-aminonaphthalene-5,7-disulfonic acid, 1-amino-8-hydroxynaphthalene-2,4,6-trisulfonic acid, 1-hydroxy-8-acetylaminonaphthalene-3-sulfonic acid, 1-benzoylamino-8-hydroxynaphthalene-3,6-or -4,6-disulfonic acid, 2-benzoylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-methyl or. 2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid, 2- (N-acetyl-N-methylamino) -5-hydroxynaphthalene-7-sulfonic acid, 2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5- hydroxynaphthalene-1,7-disulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfonic acid, 2-methyl or. -ethylamino-8-hydroxynaphthalene-6-sulfonic acid, 2- (N-acetyl-N-methylamino) -8-hydroxynaphthalene-6-sulfonic acid, 2-acetyl-amino-8-hydroxynaphthalene-6-sulfonic acid, 2-amino-8 -hydroxynaphthalene-3,6-disulfonic acid, 2-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid, 1-amino-5-hydroxynaphthalene-7-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-resp. -4,6-disulfonic acid, 1-acetylamino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1- (3'-nitrobenzoyl-amino) -8-hydroxynaphthalene-3,6-or. -4,6-disulfonic acid, 1- (3'-nitrobenzoylamino) -8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 2- (4'-amino-3'-sulfophenylamino) -5-hydroxynaphthalene-7-sulfonic acid, 3-methylpyrazolone- (5), 1-phenyl-3-methyl-5-pyrazo -Ion, 1- (4'-sulfophenyl) -3-methyl-5-pyrazolone, 1- (4'-sulfophenyl) -pyrazolone (5) -3-carboxylic acid, 1- (3'-aminophenyl) -3-methyl -5-pyrazolone, 1- (2 ', 5'-disulfophenyl) -3-methyl-5-pyrazolone, 1- (2'-methyl-4'-sulfophenyl) -5-pyrazolone-3-carboxylic acid, 1- ( 4 ', 8'-disulfonaphthyl- [2']) - 3-methyl-5-pyrazolone, 1- (5 ', 7'-disulfonapthyl- [2']) - me-3-thyl-5-pyrazolone, 1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-5-pyrazolone, 3-sulfo-4-methyl-6-hydroxypyridone- (2), 1-ethyl-3-cyano or -3-chloro-4-methyl-6-hydroxypyridone- (2), 1-ethyl-3-sulfomethyl-4-methyl-6-hydroxypyridone- (2), 2,4,6-triamino-3-cyanopyridine, 2nd - (3'-Sulfophenylamino) -4,6-diamino-3-cyanopyridine, 2- (2'-hydroxyethylamino) -3-cyan-4-methyl-6-aminopyridine, 2,6-bis- ( 2'-hydroxyethylamino) -3-cyan-4-methylpyridine, 1-ethyl-3-car bamoyl-4-methyl-6-hydroxypyridone- (2), 1-ethyl-3-sulfomethyl-4-methyl-5-carbamoyl-6-hydroxypyridone- (2), N-acetoacetylaminobenzene, 1- (N-acetoacetylamino) -2-methoxybenzene-5-sulfonic acid, 4-hydroxyquinolone- (2nd ).

0016Preferred amino compounds of the formula (6) are, for example:<chemistry id="chem0013" num="0013"><img file="EP0197418A2_D0013.tif" /></chemistry><chemistry id="chem0014" num="0014"><img file="EP0197418A2_D0014.tif" /></chemistry><chemistry id="chem0015" num="0015"><img file="EP0197418A2_D0015.tif" /></chemistry><chemistry id="chem0016" num="0016"><img file="EP0197418A2_D0016.tif" /></chemistry><chemistry id="chem0017" num="0017"><img file="EP0197418A2_D0017.tif" /></chemistry><chemistry id="chem0018" num="0018"><img file="EP0197418A2_D0018.tif" /></chemistry><chemistry id="chem0019" num="0019"><img file="EP0197418A2_D0019.tif" /></chemistry><chemistry id="chem0020" num="0020"><img file="EP0197418A2_D0020.tif" /></chemistry><chemistry id="chem0021" num="0021"><img file="EP0197418A2_D0021.tif" /></chemistry><chemistry id="chem0022" num="0022"><img file="EP0197418A2_D0022.tif" /></chemistry>

0017Dyes of the formula (1) with B = CH₂CH₂OSO₃H can also be produced. by using dyes of the formula (7)<chemistry id="chem0023" num="0023"><img file="EP0197418A2_D0023.tif" /></chemistry>sulfated with oleum or sulfuric acid monohydrate on the hydroxyethyl grouping.

0018In general, other hydroxyalkyl radicals in A or K can also be converted into sulfatoalkyl radicals by this process.

0019The amino compounds (6) can be prepared, for example, by adding (2-chloro-5-nitrophenyl) (2-hydroxyethyl) sulfone of the formula (8) by neutralizing ethoxylation of 2-chloro-5-nitrobenzenesulfinic acid aqueous conditions is accessible, with compounds of the formula HA or corresponding salts NaA, if A = SO₂R or SR, with elimination of HCl, the resulting nitrosulfones (9) then reduced and finally the group -SO₂CH₂CH₂OH converted to the -SOZB group:<chemistry id="chem0024" num="0024"><img file="EP0197418A2_D0024.tif" /></chemistry>

0020The condensation with the compounds HA or NaA is carried out above 70 ° C., most advantageously between 80-120 ° C., if appropriate under pressure. Water, an organic solvent, such as an alcohol or dimethylformamide, or a mixture of these can serve as the reaction medium. An auxiliary base, such as triethylamine, sodium hydrogen carbonate or soda, can be added to trap the hydrogen chloride liberated, or, in the case where HA is an amine, the nucleophile is used in about twice the equimolar amount. The reduction of (9) can be carried out catalytically with hydrogen, with metal acid (for example iron / acetic acid) or with other reducing agents customary for aromatic nitro compounds.

0021Another display variant for the nitro compounds (9) consists in condensing the alkali salts of 2-chloro-5-nitrobenzenesulfinic acid with compounds HA or NaA, if A = SOZR or SR, above 70 ° C. in an aqueous medium, if appropriate under pressure and the condensation products of the formula<chemistry id="chem0025" num="0025"><img file="EP0197418A2_D0025.tif" /></chemistry>alkylated with ethylene oxide under heat and under pressure and neutral conditions.

0022Nitro compounds of the formula (9) with A = SOR can be obtained by treating compounds of the formula (9) with A = SR under mild conditions with H₂O₂ oxidized.

0023Under more drastic conditions (> 50 ° C) or by choosing a different oxidizing agent - (e.g. chlorine solution, potassium permanganate) this results in nitro compounds of formula (9) with A = SO₂R, such as the disulfone of the formula<chemistry id="chem0026" num="0026"><img file="EP0197418A2_D0026.tif" /></chemistry>After catalytic reduction of the nitro group with hydrogen / Raney nickel, (12) is sulfated with oleum, or is reacted using the process described in EP-A 107 614.

0024Diazo components of the formula (6) which are substituted in the radical R by an additional fiber-reactive group Y are prepared by a slightly modified process, such as the diazo component for dyes of the structure (3). Thereafter, the aminoalkyl-substituted diamino sulfone of the formula<chemistry id="chem0027" num="0027"><img file="EP0197418A2_D0027.tif" /></chemistry>condensed at pH 7-8 with a heterocyclic reactive component Hal-Y (Hal = F, CI, Br), such as 5-chloro-2,4,6-trifluoropyrimidine. However, it is also possible to diazotize (13) and couple to HK and only then carry out the condensation with Hal-Y.

0025The reactive dyes of the formula (1) are suitable for dyeing and printing a wide variety of materials, such as silk, leather, wool, polyamide fibers and polyester fibers, but in particular cellulosic materials, such as linen, cellulose, regenerated cellulose and especially cotton. They are suitable both in the exhaust process and for the pad dyeing process, according to which the goods are impregnated with aqueous and, if appropriate, also salt-containing dye solutions, and the dyes are fixed after an alkali treatment or in the presence of alkali, possibly in the heat.

0026The reactive dyes of the formula (1) are particularly suitable for dyeing cotton by the exhaust process and the cold residence process, the difference between the degree of exhaustion and the degree of fixation being remarkably small, ie the hydrolysis fraction being very low.

0027The reactive dyes of the formula (1) are notable for high reactivity and good fixing power. With the pad-steam process, they only require short steaming times. The dyes are extremely soluble and give dyeings with a good fastness level.

0028Dyes of the formula (1) in which the radicals K and R do not have a water-solubilizing substituent are particularly suitable for single-bath dyeing of polyester-cotton blended fabrics, with the polyester content being sufficiently dyeable in addition to the cotton at elevated temperature. Dyeing processes of this type are described in detail in DE-OS 2 362 683.

example 1

002930.7 g of [5-nitro-2- (2-hydroxyethyl) mercaptophenyi] (2-hydroxyethyi) sttfon and 2 g of sodium tungstate are heated to 80 ° C. in 100 ml of water / 100 ml of glacial acetic acid. To do this, slowly drop 20 g of a 35% hydrogen peroxide solution, then increase to 90 ° C. and allow 20 g of hydrogen peroxide to run in again. The mixture is stirred for one hour at 90-95 ° C, clarified, cooled to room temperature and the precipitated crystalline nitrodisulfone of the formula is isolated

0030<chemistry id="chem0028" num="0028"><img file="EP0197418A2_D0028.tif" /></chemistry>After drying, 31.4 g are obtained as colorless needles with a melting point of 192 ° C.

003127.1 g of nitrodisulfone (12) are dissolved in 200 ml of isopropanol at 50 ° C., 3 g of Raney nickel are added and the mixture is hydrogenated at 65 ° C. and 5-10 bar in an autoclave until complete hydrogen absorption. The catalyst is separated from the cooled reaction solution by filtration and the solution is concentrated. The residue is recrystallized from 200 ml of water. 22.9 g of aminodisulfone of the formula (14) are obtained.<chemistry id="chem0029" num="0029"><img file="EP0197418A2_D0029.tif" /></chemistry>

0032At 0 ° C., 21.6 g of aminodisulfone (14) are introduced in portions into 50 g of sulfuric acid monohydrate. After the addition, the mixture is warmed slowly to room temperature and stirred for two hours. The temperature is then raised to 40 ° C. within 30 minutes and stirring is continued at this temperature for a further three hours. The reaction solution is poured onto 200 g of ice / 100 ml of water, and the resulting solution is adjusted to pH 6 with the addition of ice with sodium hydrogen carbonate. The solution is evaporated to dryness in vacuo at 40-50 ° C. and the water-soluble diaminosulfone of the formula (15) is obtained.<chemistry id="chem0030" num="0030"><img file="EP0197418A2_D0030.tif" /></chemistry>which contains plenty of sodium sulfate

0033The solution of the aminodisulfone (15) obtained by discharge on ice can also be directly diazotized without intermediate isolation and reacted with the coupling components.

Example 2

003427 g (2-chloro-5-nitrophenyl) (2-hydroxyethyl) sulfone and 15 g morpholine are refluxed in 50 ml isopropanol for one hour. The reaction mixture, cooled to 60 ° C., is diluted with 200 ml of water, adjusted to pH 7.0 and suctioned off after stirring for one hour. After drying at 70 ° C., 31 g of nitrosulfone of the formula (16) are obtained. (Any primary and secondary alkylamines and donor-substituted anilines can be converted analogously)

0035<chemistry id="chem0031" num="0031"><img file="EP0197418A2_D0031.tif" /></chemistry>

003631 g of nitrosulfone of the formula (16) are suspended in 200 ml of methanol, 3 g of activated Raney nickel are added and the mixture is hydrogenated at 50 ° C. using hydrogen under pressure. After complete absorption of hydrogen, the cooled suspension is diluted with 200 ml of acetone, the catalyst is separated off by filtration and the filtrate is concentrated. There remain 26.5 g of uniform aminosulfone of the formula (17). (Melting point: 188 ° C)<chemistry id="chem0032" num="0032"><img file="EP0197418A2_D0032.tif" /></chemistry>

0037These 26.5 g of aminosulfone are introduced at 20 ° C. in 50 ml of 20% oleum. After stirring for 2 hours at 30 ° C., the solution is poured onto a mixture of 100 g of ice / 50 ml of water. With solid soda, the solution is dulled to pH 2.5 to 3.0 and salted out with 40 g of potassium chloride. After suction and drying, 75 g of salt-containing sulfatoethylsulfonyl diazo component of the formula (18)<chemistry id="chem0033" num="0033"><img file="EP0197418A2_D0033.tif" /></chemistry>

Example 3

003893 g (2-chloro-5-nitrophenyl) (2-hydroxyethyl) sulfone are refluxed in 200 ml isopropanol with 50 g solid soda and 70 g mercaptoethanol for 6 hours. The mixture is separated from the precipitated salts at 50 ° C. The solution is concentrated on a rotary evaporator, the residue is treated with 300 ml of water and the crystalline precipitate is separated off. After drying, 91 g of [2- (2-hydroxyethyl) mercapto-5-nitrophenyl] - (2-hydroxyethyl) sulfone, mp. 109 ° C., are obtained.<chemistry id="chem0034" num="0034"><img file="EP0197418A2_D0034.tif" /></chemistry>

003991 g of the mercaptonitrosulfone are dissolved in 200 ml of isopropanol, and 5 g of Raney nickel are added to the solution. It is catalytically hydrogenated and worked up as described in Example 2. 94 g [5-amino-2- (2-hydroxyethyl) mercaptophenyl] (2-hydroxyethyl) sulfone are isolated as a viscous, somewhat dark-colored oil<chemistry id="chem0035" num="0035"><img file="EP0197418A2_D0035.tif" /></chemistry>

0040This oil is sulfated analogously to the aminodisulfone in Example 1 with 20% oleum. The resulting aqueous solution can be used directly for further diazotization. The new diazo component has the structure<chemistry id="chem0036" num="0036"><img file="EP0197418A2_D0036.tif" /></chemistry>

Example 4

004170 g (2-chloro-5-nitrophenyl) (2-hydroxyethyl) sulfone and 62 g sodium p-toluenesulfinate are reacted in 400 ml of water at 110 ° C. in an autoclave under pressure (1.5 bar). The response time is 4-5 hours. The reaction mixture is diluted with 250 ml of water and suction filtered at 60 ° C; the precipitate is washed several times with 100 ml of water and dried. 90 g of disulfone of the formula of melting point 184 ° C. result.<chemistry id="chem0037" num="0037"><img file="EP0197418A2_D0037.tif" /></chemistry>

004277 g of the above disulfone are catalytically hydrogenated in analogy to Example 1 in isopropanol at 50 ° C. Concentration of the reaction solution provides 61 g of crystalline aminodisulfone (melting point 169 ° C.) of the formula<chemistry id="chem0038" num="0038"><img file="EP0197418A2_D0038.tif" /></chemistry>

004360 g of this aminodisulfone are sulfated in the procedure described in Example 1 in 100 ml of 20% oleum. Discharge on ice provides a fine crystalline substance of the structure<chemistry id="chem0039" num="0039"><img file="EP0197418A2_D0039.tif" /></chemistry>

Example 5

0044145 g of the monosodium salt of the aminodisulfone of the formula (15) (see Example 1) are stirred in 200 ml of water, 200 g of ice and 100 ml and 71 ml of a 30% sodium nitrite solution are added dropwise below 5 ° C. The mixture is stirred for 30 minutes and then the excess nitrite is removed with a few ml of amidosulfonic acid solution. A neutral solution of 50 g of H-acid (monosodium salt) in 250 ml of water is added dropwise to this suspension in the course of 30 minutes, and the pH of this mixture is then adjusted to 2.0 by slowly adding a 20% potassium hydrogen carbonate solution over the course of an hour. After a further hour, the pH is slowly increased to 6.0 to 6.5, 10 g of sodium phosphate and 15 g of disodium phosphate are added, and spray drying is carried out after one hour of stirring. A dark, salt-containing dye powder is obtained, which dyes cotton in black tones with high fixation yields both in the exhaust process and in the block-cold residence process (λ_Max = 590 nm (H₂0)).

0045The dye has the structure<chemistry id="chem0040" num="0040"><img file="EP0197418A2_D0040.tif" /></chemistry>

0046The following dyes are obtained by the same process using the corresponding diazo compounds:

Example 6

0047<chemistry id="chem0041" num="0041"><img file="EP0197418A2_D0041.tif" /></chemistry>

Example 7

0048<chemistry id="chem0042" num="0042"><img file="EP0197418A2_D0042.tif" /></chemistry>

Example 8

0049<chemistry id="chem0043" num="0043"><img file="EP0197418A2_D0043.tif" /></chemistry>

Example 9

005072.5 g of monosodium salt of the aminodisulfone of the formula (15) are diazotized analogously to Example 5 and coupled to 50 g of H-acid (monosodium salt). 450 ml of an aqueous solution containing 48 g of diazotized 2-amino-1,5-naphthalenedisulfonic acid are added to the red neutral dye solution and the pH is kept between 5.5-6.5 by adding dilute sodium hydroxide solution.

0051After no further change in pH can be observed, spray drying. The dye of the structure isolated as a dark powder<chemistry id="chem0044" num="0044"><img file="EP0197418A2_D0044.tif" /></chemistry>dyes cotton in navy blue to black tones (λ_Max = 623 nm (H₂O)).

0052Analogously to Example 9, the following dyes are obtained when using the corresponding diazo components

Example 10

0053<chemistry id="chem0045" num="0045"><img file="EP0197418A2_D0045.tif" /></chemistry>

Example 11

0054<chemistry id="chem0046" num="0046"><img file="EP0197418A2_D0046.tif" /></chemistry>

Example 12

0055If in Example 9 the second diazo component is replaced by diazotized 2-amino-4- [4 '- (2', 6'-difluoro-5'-chloro) pyrimidyl] amino-benzenesulfonic acid, the following bifunctional reactive dye results, based on cotton intense black coloring with high fixation yield (616 nm)<chemistry id="chem0047" num="0047"><img file="EP0197418A2_D0047.tif" /></chemistry>

0056Further valuable reactive dyes are obtained if the corresponding 2-substituted (5-aminophenyl) (2-sulfatoethyl) sulfones are diazotized according to the information in Example 5 and coupled to the corresponding sulfo-containing coupling components in a conventional manner

Example 13

0057<chemistry id="chem0048" num="0048"><img file="EP0197418A2_D0048.tif" /></chemistry>

Example 14

0058<chemistry id="chem0049" num="0049"><img file="EP0197418A2_D0049.tif" /></chemistry>

Example 15

0059<chemistry id="chem0050" num="0050"><img file="EP0197418A2_D0050.tif" /></chemistry>

Example 16

0060<chemistry id="chem0051" num="0051"><img file="EP0197418A2_D0051.tif" /></chemistry>

Example 17

0061<chemistry id="chem0052" num="0052"><img file="EP0197418A2_D0052.tif" /></chemistry>

Example 18

0062<chemistry id="chem0053" num="0053"><img file="EP0197418A2_D0053.tif" /></chemistry>

Example 19

0063<chemistry id="chem0054" num="0054"><img file="EP0197418A2_D0054.tif" /></chemistry>

Example 20

0064<chemistry id="chem0055" num="0055"><img file="EP0197418A2_D0055.tif" /></chemistry>

Example 21

0065<chemistry id="chem0056" num="0056"><img file="EP0197418A2_D0056.tif" /></chemistry>

Example 22

0066<chemistry id="chem0057" num="0057"><img file="EP0197418A2_D0057.tif" /></chemistry>

Example 23

0067<chemistry id="chem0058" num="0058"><img file="EP0197418A2_D0058.tif" /></chemistry>

Example 24

0068<chemistry id="chem0059" num="0059"><img file="EP0197418A2_D0059.tif" /></chemistry>

Example 25

0069<chemistry id="chem0060" num="0060"><img file="EP0197418A2_D0060.tif" /></chemistry>

Example 26

0070<chemistry id="chem0061" num="0061"><img file="EP0197418A2_D0061.tif" /></chemistry>

Example 27

0071<chemistry id="chem0062" num="0062"><img file="EP0197418A2_D0062.tif" /></chemistry>

Example 28

0072<chemistry id="chem0063" num="0063"><img file="EP0197418A2_D0063.tif" /></chemistry>

Example 29

0073<chemistry id="chem0064" num="0064"><img file="EP0197418A2_D0064.tif" /></chemistry>

Example 30

0074<chemistry id="chem0065" num="0065"><img file="EP0197418A2_D0065.tif" /></chemistry>

Example 31

0075<chemistry id="chem0066" num="0066"><img file="EP0197418A2_D0066.tif" /></chemistry>

Example 32

Example 32

0076<chemistry id="chem0067" num="0067"><img file="EP0197418A2_D0067.tif" /></chemistry>

Example 33

007764 g of the diazo component of the formula<chemistry id="chem0068" num="0068"><img file="EP0197418A2_D0068.tif" /></chemistry>

0078Are concentrated in 200 ml of water / 100 g of ice and 150 ml. Hydrochloric acid stirred at 0-5 ° C and 35 ml of a 30% sodium nitrite solution were added dropwise. After stirring for 2 hours at 5-10 ° C, the excess nitrite is removed with amidosulfonic acid solution. Then a solution of 27.3 g of N-ethyl-N- (β-cyanoethyl) -3-methylaniline in 50 ml of water / 10 ml of conc. Hydrochloric acid and stir the coupling mixture at 10 ° C for 2 hours. After adding 200 g of ice, the pH of the mixture is slowly adjusted to pH 2.5 to 3 with dilute sodium hydroxide solution and kept constant for a further 2 hours. The precipitated dye is filtered off with suction at pH 3.5, washed twice with 250 ml of water and dried. This results in approx. 90 g of a dark red dye, which is particularly suitable for single-bath dyeing or printing of polyester / cotton blended fabrics in reddish-orange shades. For example the fabric with a dye liquor. padded, which contains about 6 g / l of the above dye, 2 g / l of sodium hydrogen carbonate and conventional dyeing aids; the fabric is squeezed to 75% liquor absorption and possibly thermosolated after intermediate drying at 120 ° C. After soaping, rinsing and drying, a uniformly colored blended fabric is obtained.

0079The following dyes are suitable for the same area of ​​application and provide uniform colors in the specified shades:

Example 34

0080<chemistry id="chem0069" num="0069"><img file="EP0197418A2_D0069.tif" /></chemistry>

Example 35

0081<chemistry id="chem0070" num="0070"><img file="EP0197418A2_D0070.tif" /></chemistry>

Example 36

0082<chemistry id="chem0071" num="0071"><img file="EP0197418A2_D0071.tif" /></chemistry>

Example 37

0083<chemistry id="chem0072" num="0072"><img file="EP0197418A2_D0072.tif" /></chemistry>

Example 38

0084<chemistry id="chem0073" num="0073"><img file="EP0197418A2_D0073.tif" /></chemistry>

Example 39

0085<chemistry id="chem0074" num="0074"><img file="EP0197418A2_D0074.tif" /></chemistry>

Example 40

0086<chemistry id="chem0075" num="0075"><img file="EP0197418A2_D0075.tif" /></chemistry>