Monoazo dyes containing a 4-substituted-2-azo-1,1'-diphenylsulfone component

The object of the present invention is to provide novel monoazo dyes which are suitable for dyeing natural and synthetic polyamides from an aqueous bath, which have hues within the yellow to red region, and which also have improved fastness properties, in particular an improved light fastness.
We have found, then, that the monoazo dyes of the formula (1) achieve this object.
The invention thus relates to monoazo dyes of the formula ##STR3## in which K is the radical of a coupling component of the benzene or naphthalene series or of the heterocyclic series, R is a ##STR4## --CO--R.sub.2 or --SO.sub.2 --O--R.sub.2 group in which R.sub.1 is hydrogen or C.sub.1-4 -alkyl and R.sub.2 is a substituted or unsubstituted monosulfo-C.sub.1-12 -alkyl radical, a substituted or unsubstituted monosulfophenyl, disulfophenyl, monosulfonaphthyl or disulfonaphthyl radical, and X and Y, independently of each other, are hydrogen, C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, halogen, C.sub.2-6 -alkanoylamino, C.sub.1-5 -alkylsulfonylamino or a substituted or unsubstituted phenyl or phenoxy radical.
The radical K of a coupling component can contain the substituents customary in the case of azo dyes, for example alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl and tert.-butyl, alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, isobutyloxy, sec.-butyloxy and tert.-butyloxy, phenoxy, alkanoylamino groups having 1 to 6 carbon atoms, such as acetylamino or propionylamino, benzoylamino, amino groups, such as --NH.sub.2, methylamino, ethylamino, dimethylamino, diethylamino, cyanoethylamino, hydroxyethylamino, dihydroxyethylamino, cyclohexylamino, benzylamino and phenylamino, carboxylic acid ester groups, such as methoxycarbonyl and ethoxycarbonyl, trifluoromethyl, nitro, cyano, acetyl, methylsulfonyl, carbamoyl, sulfamoyl, ureido, hydroxyl, carboxyl, sulfo, sulfomethyl and halogen, such as fluorine, chlorine and bromine, as well as fibre-reactive radicals.
K is preferably the radical of an aminobenzene, alkoxybenzene, aminonaphthalene, alkoxynaphthalene, naphthol, aminonaphthol, pyrazolone, aminopyrazole, pyridone, pyrimidine, indole, naphthylimidazole, diphenylamine, pyrazolo[2,3-a]pyrimidine, tetrahydroquinoline or acetoacetamide, which radicals can be further substituted.
C.sub.1-4 -alkyl radicals R.sub.1, X or Y in the formula (1) are independently of one another for example methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, isobutyl or tert.-butyl radicals.
A monosulfo-C.sub.1-12 -alkyl radical R.sub.2 is for example a straight-chain or branched monosulfoalkyl radical, which can be further substituted, for example by halogen, such as fluorine, chlorine or bromine, hydroxyl, cyano, C.sub.1-4 -alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec.-butoxy, tert.-butoxy or isobutoxy, and alkanoyl groups having 1 to 6 carbon atoms, such as the acetyl or propionyl group, and the benzoyl group. Examples of R.sub.2 for use as a monosulfo-C.sub.1-12 -alkyl radical are sulfomethyl, .beta.-sulfoethyl, .gamma.-sulfopropyl and .delta.-sulfobutyl. A monosulfoalkyl radical R.sub.2 is preferably a .beta.-sulfoethyl radical.
A substituted or unsubstituted monosulfophenyl or disulfophenyl radical R.sub.2 is preferably a radical of the formula ##STR5## in which R.sub.3 is hydrogen, C.sub.1-4 -alkyl, for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl and tert.-butyl, C.sub.1-4 -alkoxy, for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec.-butoxy and tert.-butoxy, halogen, for example fluorine, chlorine and bromine, C.sub.2-6 -alkanoylamino, for example acetylamino, propionylamino and butyrylamino, or carboxyl. The following are mentioned by way of example: the 2-, 3- or 4-sulfophenyl, 2,5-disulfophenyl, 4-acetylamino-3-sulfophenyl, 2-chloro-5-sulfophenyl, 2-carboxy-4-sulfophenyl, 2-methyl-4-sulfophenyl, 2-methoxy-5-sulfophenyl, 4-methyl-3-sulfophenyl and 4-chloro-3-sulfophenyl radical.
A substituted or unsubstituted monosulfonaphthyl or disulfonaphthyl radical R.sub.2 is preferably a radical of the formula ##STR6## in which R.sub.3 is as defined under the formula (2). The following are mentioned by way of example: the 1-sulfonaphth-2-yl, 6-sulfonaphth-2-yl and 1,5-disulfonaphth-2-yl radicals.
C.sub.1-4 -alkoxy radicals X and Y are independently of each other for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec.-butoxy or tert.-butoxy radicals.
Halogens X and Y are independently of each other for example fluorine, chlorine or bromine atoms.
C.sub.2-6 -alkanoylamino radicals X and Y are independently of each other for example acetylamino or propionylamino radicals.
Phenyl radicals X and Y can be further substituted, for example by C.sub.1-4 -alkyl groups, such as methyl, C.sub.1-4 -alkoxy groups, such as methoxy and ethoxy, halogen, such as fluorine, chlorine or bromine, alkanoylamino groups having 1 to 6 carbon atoms, such as acetylamino, hydroxyl and carboxyl.
Phenoxy radicals X and X are independently of each other preferably phenoxy radicals which can be further substituted in the phenyl moiety as indicated above.
In preferred monoazo dyes of the formula (1), Y is hydrogen, chlorine or methoxy.
In preferred monoazo dyes of the formula (1), X is bonded to the phenyl ring in p-position relative to the --SO.sub.2 group.
Monoazo dyes of the formula (1) can be substituted in the coupling component K by fibre-reactive groups.
Examples of suitable fibre-reactive groups are those of the aliphatic series, such as acryloyl, mono-, di- or trichloroacryloyl, mono-, di- or tribromoacryloyl, mono-, di- or trichlorometacryloyl, or mono-, di- or tribromometacryloyl, such as --CO--CH.dbd.CH--Cl, --CO--CCl.dbd.CH.sub.2, --CO--CH.dbd.CHBr, --COCBr.dbd.CH.sub.2, --CO--CBr.dbd.CHBr, --CO--CCl.dbd.CH--CH.sub.3, and also --CO--CCl.dbd.CH--COOH, --CO--.dbd.CCl--COOH, 3-chloropropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonylpropionyl, .beta.-sulfatoethylaminosulfonyl, vinylsulfonyl, .beta.-chloroethylsuflonyl, .beta.-sulfatoethylsulfonyl, .beta.-methylsulfonylethylsulfonyl, .beta.-phenylsulfonylethylsulfonyl, 2-fluoro-2-chloro-3,3-difluorocyclobutane-1-carbonyl, 2,2,3,3-tetrafluorocyclobutanecarbon-1-yl, 2,2,3,3-tetrafluorocyclobutane-sulfon-1-yl, .beta.-(2,2,3,3-tetrafluorocyclobut-1-yl)acryloyl, .alpha.- or .beta.-alkylsulfonylacryloyl or -arylsulfonylacryloyl, such as .alpha.- or .beta.-methylsulfonylacryloyl.
Reactive radicals which are particularly suitable for synthetic polyamide and for wool are chloroacetyl, bromoacetyl, .alpha.,.beta.-dichloropropionyl, .alpha.,.beta.-dibromopropionyl, .alpha.- chloroacryloyl or .beta.-bromoacryloyl, 2,4-difluoro-5-chloropyrimid-6-yl, 2,4,6-trifluoropyrimid-5-yl, 2,4-dichloro-5-methylsulfonylpyrimidin-6-yl, 2,4-difluoro-5-methylsulfonylpyrimid-6-yl, 2,4-difluorotriazin-6-yl, and fluorotriazinyl radicals of the formula ##STR7## in which R.sub.6 is a substituted or unsubstituted amino group or a free or etherified oxy or thio group, for example the NH.sub.2 group, a C.sub.1 -C.sub.4 -alkyl-monosubstituted or -disubstituted amino group, a C.sub.1 -C.sub.4 -alkoxy group, a C.sub.1 -C.sub.4 -alkylmercapto group, arylamino, in particular phenylamino, or methyl-, methoxy-, chlorine- and, especially, sulfo-substituted phenylamino, phenoxy, mono- or disulfophenoxy and the like, and the corresponding chlorotriazinyl radicals.
Examples of starting materials for introducing such triazine radicals are 2,4-difluoro- or 2,4-dichloro-6-aminotriazine, 2,4-difluoro- or 2,4-dichloro-6-methylaminotriazine, 2,4-difluoro- or 2,4-dichloro-6-ethylaminotriazine, 2,4-difluoro- or 2,4-dichloro-6-phenylaminotriazine, 2,4-difluoro- or 2,4-dichloro-6-(2',3'- or 4'-sulfophenyl)-aminotriazine, 2,4-difluoro- or 2,4-dichloro-6-(2',4' or 3',4'- or 2',5'- or 4',5'-disulfophenyl)-aminotriazine, 2,4-difluoro- or 2,4-dichloro-6-dimethylaminotriazine, 2,4-difluoro or 2,4-dichloro-6-methoxytriazine, 2,4-difluoro- or 2,4-dichloro-6-(.beta.-methoxyethoxy)-triazine, 2,4-difluoro- or 2,4-dichloro-6-methylmercaptotriazine and 2,4-difluoro or 2,4-dichloro-6-phenylmercaptotriazine and 2,4,6-trifluoro or 2,4,6-trichlorotriazine.
In preferred monoazo dyes of the formula (1), K is an N-C.sub.1-4 -alkylaminobenzene or N,N-di-C.sub.1-4 -alkylaminobenzene radical which can be substituted in the benzene ring by methyl, chlorine, acetylamino and benzoylamino and in which the N-alkyl radicals can be substituted independently of each other by hydroxyl, chlorine, cyano, phenyl or sulfophenyl, a methoxybenzene radical, a methoxynaphthalene radical, an aminonaphthalene radical which can be substituted by sulfo, a hydroxynaphthalene radical which can be substituted by sulfo, an aminonaphthol radical which can be substituted in the naphthalene nucleus by sulfo and in which the amino group can be substituted by methyl, .alpha.,.beta.-dibromopropionyl, .alpha.,.beta.-dibromopropionylaminobenzoyl and 2,6-difluoro-5-chloropyrimidylaminobenzoyl, a 1-phenyl-3-methylpyrazolone radical which can be substituted in the phenyl radical by chlorine and methyl, a 1-phenyl-3-methylaminopyrazole radical which can be substituted in the phenyl radical by chlorine and sulfo, a 1-ethyl-4-methyl-6-hydroxypyrid-2-one radical which can be substituted in the 3-position by carbamoyl, a 2,4,6-triaminopyrimidine radical, a 2-methylindole or 1-ethyl-2-methylindole radical, a 1-chlorophenylamino-2-methylnaphthimidazole radical or 2-pentylnaphthimidazole radical, substituted in the naphthalene nucleus by hydroxyl and sulfo, an N-methyl or N-ethyl-1,2,3,4-tetrahydroquinoline radical, or a 2,5-dimethyl-7-aminopyrazolo[2,3-a]pyrimidine radical, and R is a ##STR8## --CO--R.sub.2 or --SO.sub.2 --O--R.sub.2 group in which R.sub.1 is hydrogen or methyl, and R.sub.2 is .beta.-sulfoethyl, 2-, 3- or 4-sulfophenyl in which the phenyl ring can be substituted by methyl, methoxy, chlorine, acetylamino and carboxyl, 2,5-disulfophenyl, monosulfonaphthyl or disulfonaphthyl, X is hydrogen, methyl, chlorine, ethoxy, acetylamino or phenoxy, and Y is hydrogen, chlorine or methoxy.
In particularly preferred monoazo dyes of the formula (1), K is an N,N-di-C.sub.1-4 -alkylaminobenzene radical which can be substituted in the benzene nucleus by methyl, chlorine, acetylamino and benzoylamino and in which the N-alkyl radicals can be substituted independently of each other by hydroxyl, chlorine, cyano, phenyl or sulfophenyl, a 1-phenyl-3-methylaminopyrazole radical which can be substituted in the phenyl radical by chlorine and sulfo, or a 2-methylindole or 1-ethyl-2-methylindole radical, and R, X and Y are as defined above.
In especially preferred monoazo dyes of the formula (1), K is an N,N-diethyl-3-methylaniline radical, an N-ethyl-N-.beta.-hydroxyethyl-3-methylaniline radical, a 1-phenyl-3-methyl-5-aminopyrazole radical or a 2-methylindole radical, R is a .beta.-sulfoethylaminosulfonyl, o-sulfophenylaminosulfonyl, p-sulfophenylaminosulfonyl, p-sulfophenylaminocarbonyl or p-methyl-m-sulfobenzoyl radical, X is methyl or chlorine, and Y is hydrogen.
The invention also relates to a process for preparing monoazo dyes of the formula (1). The process comprises diazotising a diazo component of the formula ##STR9## and coupling it onto a coupling component of the formula
H--K (5),
where K, R, X and Y in the formulae (4) and (5) are as defined under the formula (1).
The diazo component of the formula (4) is generally diazotised through the action of nitrous acid in an aqueous mineral acid solution at a low temperature, and the diazotisation product is coupled onto the coupling component of the formula (5) at acid, neutral to alkaline pH values.
If desired, after the coupling, a free amino group in the radical K can be converted into an acylamino or alkylamino group, by means of an acylating or alkylating agent, and, similarly, a hydroxyl group in the radical K can be alkylated to give an alkoxy group.
Those azo dyes of the formula (1) which contain a fibre-reactive radical are prepared by reacting with one another in any order a diazo component of the formula (4), a formula (5) coupling component which contains an acylatable amino or hydroxyl group, and an acylating agent which contains a fibre-reactive radical.
The coupling components used as containing an acylatable group are preferably of the benzene or naphthalene series.
Preferred versions of the process comprise
(a) using a coupling component of the formula (5) in which K is the radical of an aminobenzene, alkoxybenzene, aminonaphthalene, alkoxynaphthalene, naphthol, aminonaphthol, pyrazolone, aminopyrazole, pyridone, pyrimidine, indole, naphthimidazole, diphenylamine, pyrazolo[2,3-a]pyrimidine, tetrahydroquinoline or acetoacetamide, which radicals can be further substituted,
(b) using a diazo component of the formula (4) in which R.sub.2 is an unsubstituted monosulfo-C.sub.1-12 -alkyl radical, a radical of the formula ##STR10## or a radical of the formula ##STR11## in which R.sub.3 in the formulae (2) and (3) is hydrogen, C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, halogen, C.sub.2-6 -alkanoylamino or carboxyl,
(c) using a diazo component of the formula (4) in which Y is hydrogen, chlorine or methoxy, or
(d) using a diazo component of the formula (4) in which X is bonded to the phenyl ring in p-position relative to the --SO.sub.2 group.
The particularly preferred monoazo dyes of the formula (1) are prepared by diazotising a diazo component of the formula (4) in which R is a ##STR12## --CO--R.sub.2 or --SO.sub.2 --O--R.sub.2 group in which R.sub.1 is hydrogen or methyl, and R.sub.2 is .beta.-sulfoethyl, 2-, 3- or 4-sulfophenyl in which the phenyl ring can be substituted by methyl, methoxy, chlorine, acetylamino and carboxyl, 2,5-disulfophenyl or monosulfonaphthyl or disulfonaphthyl, and in which X is hydrogen, methyl, chlorine, ethoxy, acetylamino or phenoxy, and Y is hydrogen, chlorine or methoxy, and coupling the diazotisation product onto a coupling component of the formula (5) in which K is an N-C.sub.1-4 -alkylaminobenzene or N,N-di-C.sub.1-4 -alkylaminobenzene radical which can be substituted in the benzene ring by methyl, chlorine, acetylamino and benzoylamino and in which the N-alkyl radicals can be substituted independently of each other by hydroxyl, chlorine, cyano, phenyl or sulfophenyl, a methoxybenzene radical, a methoxynaphthalene radical, an aminonaphthalene radical which can be substituted by sulfo, a hydroxynaphthalene radical which can be substituted by sulfo, an aminonaphthol radical which can be substituted in the naphthalene nucleus by sulfo, and in which the amino group can be substituted by methyl, .alpha.,.beta.-dibromopropionyl, .alpha.,.beta.-dibromopropionylaminobenzoyl and 2,6-difluoro-5-chloropyrimidylaminobenzoyl, a 1-phenyl-3-methylpyrazolone radical which can be substituted in the phenyl radical by chlorine and methyl, a 1-phenyl-3-methylaminopyrazole radical which can be substituted in the phenyl radical by chlorine and sulfo, a 1-ethyl-4-methyl-6-hydroxypyrid-2-one radical which can be substituted in the 3-position by carbamoyl, a 2,4,6-triaminopyrimidine radical, a 2-methylindole of 1-ethyl-2-methylindole radical, a 1-chlorophenylamino-2-methylnaphthimidazole or 2-pentylnaphthimidazole radical which can be substituted in the naphthalene nucleus by hydroxyl and sulfo, an N-methyl or N-ethyl-1,2,3,4-tetrahydroquinoline radical, or a 2,5-dimethyl-7-aminopyrazolo[2,3-a]pyrimidine radical.
Use is made in particular of a coupling component of the formula (5) in which K is an N,N-di-C.sub.1-4 -alkylaminobenzene radical which can be substituted in the benzene nucleus by methyl, chlorine, acetylamino and benzoylamino and in which the N-alkyl radicals can be substituted independently of one another by hydroxyl, chlorine, cyano, phenyl or sulfophenyl, a 1-phenyl-3-methylaminopyrazole radical which can be substituted in the phenyl radical by chlorine and sulfo, or a 2-methylindole or 1-ethyl-2-methylindole radical.
The especially preferred monoazo dyes of the formula (1) are prepared by diazotising a diazo component of the formula (4) in which R is a .beta.-sulfoethylaminosulfonyl, o-sulfophenylaminosulfonyl, p-sulfophenylaminosulfonyl, p-sulfophenylaminocarbonyl or p-methyl-m-sulfobenzoyl radical, X is methyl or chlorine, and Y is hydrogen, and coupling the diazotisation product onto a coupling component of the formula (5) in which K is an N,N-diethyl-3-methylaniline radical, an N-methyl-N-.beta.-hydroxyethyl-3-methylaniline radical, a 1-phenyl-3-methyl-5-aminopyrazole radical or a 2-methylindole radical.
The following are mentioned as examples from the large number of possible coupling components: aniline, dimethylaniline, diethylaniline, 3-methyldimethylaniline, 3-methyldibutylaniline, 3-methyldiethylaniline, 3-acetylaminodimethylaniline, 3-methoxycarbonylaminodimethylaniline, 3-ureidodimethylaniline, 3-methyl-6-methoxydiethylaniline, 3-methyl-N-ethyl-N-butylaniline, 2,5-dimethoxydiethylaniline, N-ethyl-N-benzylaniline, N-ethyl-N-(.beta.-cyanoethyl)-aniline, N-ethyl-N-(.beta.-hydroxyethyl)-aniline, N-ethyl-N-(.beta.-acetoxyethyl)-aniline, N,N-dibutylaniline, 3-acetylamino-N,N-diethylaniline, N-methyl-N-(.beta.-cyanoethyl)-aniline, 3-methyl-N,N-di-(.beta.-cyanoethyl)-aniline, 3-chloro-N,N-dimethylaniline, 3-methyl-N-ethyl-N-benzylaniline, N,N-di-n-propylaniline, 3-acetylamino-N,N-di-(.beta.-hydroxyethyl)-aniline, 3-methyl-N,N-di-(.beta.-acetoxyethyl)-aniline, 3-methyl-N-ethyl-N-(3'-sulfobenzyl)-aniline, N-ethyl-N-(.beta.-chloroethyl)-aniline, 2-methoxy-5-acetylamino-N-benzylaniline, 2-methoxy-5-acetylamino-N-(.beta.-acetoxyethyl)-N-benzylaniline, 3-methyl-N,N-dibutylaniline, 3-methyl-N-ethyl-N-(.beta.-cyanoethyl)-aniline, 2-methyl-5-acetylamino-N,N-dimethylaniline, 2-chloro-5-acetylamino-N,N-dimethylaniline, 2-chloro-5-acetylamino-N-(.gamma.-phenoxy-.beta.-hydroxy-n-propyl)-aniline, 3-ureidoaniline, N-ethyl-N-(.beta.-hydroxyethyl)-aniline, N-ethyl-N-(3'-sulfobenzyl)-aniline, 3-methyl-N-ethyl-(.beta.-sulfoethyl)-aniline, 3-benzoylamino-N,N-diethylaniline, 3-(p-tolylsulfamoyl)-N,N-diethylaniline, 3-(p-chlorobenzoylamino)-N,N-diethylaniline, 3-methoxy-N,N-diethylaniline, 3-methyl-N,N-di-(.beta.-hydroxyethyl)-aniline, 3-methyl-6-methoxy-N,N-di(.beta.-hydroxyethyl)-aniline, 3-acetylaminoaniline, 3-methyl-N-ethyl-N-phenethylaniline, N,N-di-(.beta.-cyano- or hydroxyethyl)-aniline, 3-acetylamino-N,N-di-(.beta.-cyanoethyl)-aniline, 3-methyl-N-ethyl-N-(.beta.-hydroxyethyl)-aniline, 3-methyl-N-ethyl-N-(.beta.-hydroxyethyl)-aniline, N-(.beta.-cyanoethyl)-aniline, N-methyl-N-benzylaniline, phenol, 3-methylphenol, methoxybenzene, 3-ethoxytoluene, 1-hydroxy-4-methoxybenzene, 1-hydroxy-4-tert.-butylbenzene, 1-hydroxy-7-amino-3-sulfonaphthalene, 1-hydroxy-7-methylaminosulfonaphthaline, 7-phenylamino-3-sulfonaphthalene, 2-aminonaphthalene, 2-amino-6-sulfonaphthalene, 2-amino-5-acetylaminomethylnaphthalene, .beta.-naphthol, 2-amino-5-methylaminosulfonylnaphthalene, 1-hydroxy-8-amino-3,6-disulfonaphthalene, 1-hydroxy-8-amino-3,5-disulfonaphthalene, 1-hydroxy-8-benzoylamino-3,6-disulfonaphthalene, 1-hydroxy-8-benzoylamino-3,5-disulfonaphthalene, 1-hydroxy-8-ureido-3,6-disulfonaphthalene, 1-hydroxy-8-ureido-3,5-disulfonaphthalene, 1-hydroxy-8-acetylamino-3,6-disulfonaphthalene, 1-hydroxy-8-ureido-3,5-disulfonaphthalene, 1-(3'-chlorophenyl)-3-methylpyrazol-5-one, 1-(2'-chloro-6'-methylphenyl)-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 1-(2',3'- or 4'-sulfophenyl)-3-methylpyrazol-5-one, 1-(2'-chloro-4'- or 5',-sulfophenyl)-3-methylpyrazol-5-one, 1-(3'- or 4'-dibromopropionylamino)-benzoylamino-8-hydroxy-3,6-disulfonaphthalene, 1-(3'- or 4'-dibromopropionylamino)-benzoylamino-8-hydroxy-4,6-disulfonaphthalene, 2-.alpha.,.beta.-dibromopropionylamino-1-hydroxy-6-sulfonaphthalene, 3-.alpha.,.beta.-dibromopropionyl-N-methylamino-8-hydroxy-6-sulfonaphthalene, 1-[3'-(2",4"-difluoro-5'-chloropyrimidylamino)-benzoylamino]-8-hydroxy-4,6-disulfonaphthalene, 1-(2'-methyl-4'-sulfophenyl)-3-methylpyrazol-5-one, 1-[4',8'-disulfonaphth-2-yl]-3-methylpyrazol-5-one, 1-[5',7'-disulfonaphthal-2-ene]-3-methylpyrazol-5-one, 1-(2'-chloro-5'-sulfophenyl)-3-methyl-5-aminopyrazole, 1-(2'-chloro-4'-sulfophenyl)-3-methyl-5-aminopyrazole, 1-(3'- or 4'-sulfophenyl)-3-methyl-5-aminopyrazole, 1-ethyl-3-cyano-4-methyl-6-hydroxypyrid-2-one, 1-ethyl-3-carbamoyl-4-methyl-6-hydroxypyrid-2-one, 1-ethyl-4-methyl-6-hydroxypyrid-2-one, 1-ethyl-4-methyl-3-methylsulfonyl-6-hydroxypyrid-2-one, 2-methylindole, 2-phenylindole, 1-methyl-2-phenylindole, 1-octyl-2-methylindole, 2,4,6-triaminopyrimidine, N-methyl-N,N-diphenylamine, acetoacetanilide, 1-(4'-methylphenyl)-3-methylpyrazol-5-one, 1-ethyl-2-methylindole, 1-phenyl-3-methyl-5-aminopyrazole, 7-amino-2,5-dimethylpyrazol[2,3-a]pyrimidine, 1-methoxynaphthalene, 1-hydroxy-4-sulfonaphthalene, 1-(2'-chlorophenylamino)-9-hydroxy-2-methyl-1H-naphtho(1,2-d)imidazole-7-sulfonic acid, 1-(2'-chlorophenylamino)-9-hydroxy-2-pentyl-1H-naphtho(1,2-d)imidazole-7-sulfonic acid, N-methyl-1,2,3,4-tetrahydroquinoline, N-ethyl-1,2,3,4-tetrahydroquinoline, 3-methyl-N-ethyl-N-propylaniline.
The present invention also relates to compounds which are used as diazo components and have the formula ##STR13## in which R, X and Y are as defined under the formula (1).
In preferred compounds of the formula (4), R is a ##STR14## --CO--R.sub.2 or --SO.sub.2 --O--R.sub.2 group in which R.sub.1 is hydrogen or C.sub.1-4 -alkyl and R.sub.2 is an unsubstituted monosulfo-C.sub.1-12 -alkyl radical, a radical of the formula ##STR15## or a radical of the formula ##STR16## in which R.sub.3 in the formulae (2) and (3) is hydrogen, C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, halogen, C.sub.2-6 -alkanoylamino or carboxyl, and X and Y are as defined under formula (1).
In likewise preferred compounds of the formula (4),
(a) Y is hydrogen, chlorine or methoxy, and
(b) X is bonded to the phenyl ring in p-position relative to the --SO.sub.2 group.
In particular preferred compounds of the formula (4), R is a ##STR17## --CO--R.sub.2 or --SO.sub.2 O--R.sub.2 group in which R.sub.1 is hydrogen or methyl, R.sub.2 is .beta.-sulfoethyl, 2-, 3- or 4-sulfophenyl in which the phenyl ring can be substituted by methyl, methoxy, chlorine, acetylamino and carboxyl, 2,5-disulfophenyl, monosulfonaphthyl or disulfonaphthyl, X is hydrogen, methyl, chlorine, ethoxy, acetylamino or phenoxy, and Y is hydrogen, chlorine or methoxy.
In especially preferred compounds of the formula (4), R is a .beta.-sulfoethylaminosulfonyl, o-sulfophenylaminosulfonyl, p-sulfophenylaminosulfonyl, p-sulfophenylaminocarbonyl or p-methyl-m-sulfobenzoyl radical, X is methyl or chlorine, and Y is hydrogen.
Compounds of the formula (4) are prepared by reacting compounds of the formula ##STR18## in which Z is a --SO.sub.2 --Hal or --CO--Hal group and Hal is halogen, with a compound of the formula
[H(R.sub.1)N, HO, H--R.sub.2 ( 7)
in which R.sub.1 and R.sub.2 are as defined under the formula (4), to give a compound of the formula ##STR19## in which R is as defined under the formula (4) and Hal is halogen, condensing the compound of the formula (8) with a compound of the formula ##STR20## in which X and Y are as defined under the formula (4), and then reducing the NO.sub.2 group.
A version of the process for preparing compounds of the formula ##STR21## in which R' is an ##STR22## group, and R.sub.1, R.sub.2, X and Y are as defined under the formula (4), comprises reacting a compound of the formula ##STR23## in which Z is an --SO.sub.2 --Hal or --CO--Hal group and Hal is halogen, with an amine of the formula ##STR24## and then reducing the nitro group, while R.sub.1, R.sub.2, X and Y in the formulae (11) and (12) are as defined under the formula (10).
The ways of preparing compounds of the formula (4) are known per se. The reactions are carried out at temperatures between 0.degree. and 150.degree. C., if desired under pressure in an aqueous solution or mixtures of organic solvents, for example acetone and water, and at pH values between 7 and 10. The nitro group is likewise reduced by methods known per se, for example in glacial acetic acid in the presence of iron powder.
Examples which may be mentioned of starting compounds of the formula (6) are 4-chloro-3-nitrobenzoyl chloride and 4-chloro-3-nitrobenzene-1-sulfonyl chloride.
Examples which may be mentioned of starting compounds of the formula (7) are 2-, 3- or 4-sulfophenylaniline, taurine, N-methyltaurine, 2-aminonaphthalene-6-sulfonic acid, 2-aminonaphthalene-1-sulfonic acid, 2-aminonaphthalene-1,5-disulfonic acid, 2,5-disulfoaniline, 4-acetylamino-3-sulfoaniline, 2-chloro-5-sulfoaniline, 2-carboxy-4-sulfoaniline, 2-methyl-4-sulfoaniline, 2-methoxy-5-sulfoaniline, 4-methyl-3-sulfoaniline, 4-sulfophenol, 2-sulfotoluene and 2-chlorobenzenesulfonic acid.
Examples which may be mentioned of starting compounds of the formula (9) are 4-chlorobenzenesulfinic acid, benzenesulfinic acid, 4-ethoxybenzenesulfinic acid, 4-acetylaminobenzenesulfinic acid, 4-phenoxybenzenesulfinic acid, 4-bromobenzenesulfinic acid, 4-iodobenzenesulfinic acid, 2-methylbenzenesulfinic acid, 3-methylbenzenesulfinic acid, 4-methylbenzenesulfinic acid, 2,3-dimethylbenzenesulfinic acid, 3,4-dimethylbenzenesulfinic acid, 2,4-dimethylbenzenesulfinic acid, 2,5-dimethylbenzenesulfinic acid, 3,5-dimethylbenzenesulfinic acid, 2-methyl-5-isopropylbenzenesulfinic acid, 2-methoxybenzenesulfinic acid, 2-ethoxybenzenesulfinic acid, 4-methoxybenzenesulfinic acid, 2-methoxy-5-methylbenzenesulfinic acid, 2-bromo-5-methoxybenzenesulfinic acid and 2-methyl-4-chlorobenzenesulfinic acid.
Examples which may be mentioned of starting compounds of the formula (11) are 4'-chloro-, 4'-methyl-, 4'-ethoxy-, 4'-acetylamino-, 4'-H- or 4'-phenoxy-2-nitro-1,1'-diphenylsulfone-4-sulfonyl or 1-4-carbonyl chloride.
The amines mentioned for the formula (7) are examples of starting compounds of the formula (12).
Examples which may be mentioned of compounds of the formula (4) are 4'-chloro-, 4'-methyl-, 4'-ethoxy-, 4'-acetylamino- or 4'-phenoxy-2-amino-N-(.beta.-sulfoethyl)-1,1'-diphenylsulfone-4-sulfonamide or -carboxamide, 4'-chloro-, 4'-methyl-, 4'-ethoxy, 4'-acetylamino or 4'-phenoxy-2-amino-N-(2"-, 3"- or 4"-sulfophenyl)-1,1'-diphenylsulfone-4-sulfonamide or -carboxamide, 4'-chloro-, 4'-methyl-, 4'-ethoxy-, 4'-acetylamino- or 4'-phenoxy-2-amino-N-(1"-sulfonaphth-2-yl, 6"-sulfonaphth-2-yl or 1",5"-disulfonaphth-2-yl)-1,1'-diphenylsulfone-4-sulfonamide or carboxamide, 2-amino-N-methyl-N-(.beta.-sulfoethyl)-1,1'-diphenylsulfone-4-sulfonamide or -carboxamide, 2-amino-N-(2"-, 3"- or 4"-sulfophenyl)-1,1'-diphenylsulfone-4-sulfonamide or carboxamide, 2-amino-N-(.beta.-sulfoethyl)-1,1-diphenylsulfone-4-sulfonamide or -carboxamide, 2-amino-N-(1"-sulfonapth-2-yl, 6"-sulfonaphth-2-yl or 1",5"-disulfonaphth-2-yl)-1,1'-diphenylsulfone-4-sulfonamide or -carboxamide, 2-amino-N-(4"-acetylamino-3"-sulfophenyl)-1,1'-diphenylsulfone-4-sulfonamide, 4'-methyl-2-amino-N-(2"-chloro-5"-sulfophenyl)-1,1'-diphenylsulfone-4-sulfonamide, 2-amino-N-(2"-chloro-5"-sulfophenyl)-1,1'-diphenylsulfone-4-sulfonamide, 2-amino-N-(2"-carboxy-4"-sulfophenyl)-1,1'-diphenylsulfone-4-sulfonamide, 4'-chloro-2-amino-N-(2",5"-disulfophenyl)-1,1-diphenylsulfone-4-sulfonamide, 4'-methyl-2-amino-N-(2"-carboxy-4"-sulfophenyl)-1,1'-diphenylsulfone-4-sulfonamide, 4'-methyl-2-amino-N-(2"-methyl-4"-sulfophenyl)-1,1'-diphenylsulfone-4-sulfonamide, 2-amino-N-(2"-methyl-4"-sulfophenyl)-1,1'-diphenylsulfone-4-sulfonamide, 4'-methyl-2-amino-N-(2"-methoxy-5"-sulfophenyl)-1,1'-diphenylsulfone-4-sulfonamide, 2-amino-N-(2"-methoxy-5"-sulfophenyl)-1,1-diphenylsulfone-4-sulfonamide, 4'-methyl-2'-methoxy-2-amino-N-(3"-sulfophenyl)-1,1'-diphenylsulfone-4-sulfonamide, 2'-methoxy-2-amino-N-(3"-sulfophenyl)-1,1' -diphenylsulfone-4-sulfonamide, 4'-chloro- or 4'-methyl-2-amino-N-(2"-chloro-5"-, 2"-methyl-4"-, 2"-methoxy-5"- or 4"-acetylamino-3"-sulfophenyl)-1,1'-diphenylsulfone-4-carboxamide, 2-amino-N-(2"-chloro-5"-, 2"-methyl-4"-, 2"-methoxy-5"- or 4"-acetylamino-3"-sulfophenyl)-1,1'-diphenylsulfone-4-carboxamide, 4'-methyl-2-amino-N-(4"-sulfophenyl)-1,1'-diphenylsulfone-4-sulfonamide, 4'-acetylamino-2-amino-N-(4"-sulfophenyl)-1,1'-diphenylsulfone-4-sulfonamide, 4'-chloro- or 4'-methyl-2-amino-N-(4"-methyl-3"- or 4"-chloro-3"-sulfophenyl)-1,1'-diphenylsulfone-4-phenylcarbonyl, 2-amino-N-(4"-methyl-3"- or 4"-chloro-3"-sulfophenyl)-1,1'-diphenylsulfone-4-phenylcarbonyl, 4'-bromo-, 4'-iodo-, 2'-methyl-, 3'-methyl-, 2',3'-dimethyl-, 3',4-dimethyl-, 2',4'-dimethyl, 2',5'-dimethyl- or 3',5'-dimethyl-2-amino-N-(.beta.-sulfoethyl or 2"-, 3"- or 4"-sulfophenyl)-1,1'-diphenylsulfone-4-sulfonamide or -carboxamide, 2'-methoxy-, 2'-ethoxy, 4'-methoxy-, 2'-methoxy-5'-methyl-, 2'-bromo-5'-methoxy or 2'-methyl-4'-chloro-2-amino-N-(2"-chloro-5"-, 2"-methyl-4"-, 2"-methoxy-5"- or 4"-acetylamino-3"-sulfophenyl)-1,1-diphenylsulfone-4-sulfonamide or -carboxamide.
The dyes used in the invention are either in the form of their free sulfonic acid or, preferably, in the form of its salts.
Examples of possible salts are the alkali metal, alkaline earth metal or ammonium salts or of the salts of an organic amine. Examples which may be mentioned are the sodium, lithium, potassium or ammonium salts or the salt of triethanolamine.
Dyes of the formula (1) are suitable for dyeing and printing materials containing amide groups, such as textile fibres and textile yarns and fabrics made of wool, silk and polyurethane fibres, but in particular for dyeing and printing synthetic polyamide, for which the customary dyeing methods are used.
They are distinguished by brilliance and tinctorial strength, and good affinity and build-up and they produce dyeings of generally good fastness properties, such as fastness to rubbing, acids and alkalis, and wet fastness properties, in particular fastness to washing, water, hot water and perspiration, and they produce level dyeings. It is particularly noteworthy that the light fastness is very good and that the resistance to formaldehyde is very good.
In the following examples the parts are parts by weight. The temperatures are in degree centrigrade. Parts by weight relate to parts by volume as the gramme relates to the cubic centimeter.

EXAMPLE 1 ##STR25##
81.6 g of aniline-2-sulfonic acid (84.9% pure) are dissolved at room temperature in 400 ml of water and brought to pH 9 by adding 10N sodium hydroxide solution. 123.4 g of 4-chloro-3-nitrobenzene-1-sulfonyl chloride (82.9% pure) are added, and the reaction mixture is stirred at room temperature for 28 hours while pH 9 is maintained by means of 10N sodium hydroxide solution. After a further 2 hours, at 45.degree.-50.degree., the turbid solution at pH 9 is clarified with active charcoal and is then brought to pH 7 by means of concentrated hydrochloric acid, and the precipitated product is filtered off at 30.degree., is washed with 250 ml of water and is dried in a vacuum cabinet at 60.degree.-70.degree.. The yield is 134.9 g.
131.5 g of this compound are stirred together with 96.0 g of sodium 4-chlorobenzenesulfinate (68.8% pure) into 1,000 ml of water, and the suspension is brought to pH 7.5 by means of dilute sodium hydroxide solution. After a dwell time of 15 hours at 112.degree.-115.degree. in a tantalum autoclave, the slurry is diluted at 80.degree. with 300 ml of water and filtered. The solids content of the well-pressed filter cake is 188 g.
187 g of this material, which is nitrodiphenyl sulfone, are introduced at 94.degree.-97.degree. in the course of 25 minutes into 600 ml of water which contains 64 g of iron powder and 4.5 ml of glacial acetic acid. The mixture is stirred at the reflux temperature for 20 minutes and is then carefully admixed, at 90.degree.-80.degree., with 5.6 g of sodium carbonate, and the iron residue is filtered off. The filtrate is brought to pH 11.8 by means of 10N sodium hydroxide solution and is clarified with active charcoal. Sodium chloride is added, the mixture is stirred for 1 hour, and the precipitate is filtered off, is washed with sodium chloride solution and is dried at 60.degree.-70.degree. in vacuo.
This gives, in virtually pure form, 178 g of the compound with the formula shown above.
EXAMPLE 2 ##STR26##
75 g of taurine are stirred into 600 ml of water, and pH 9.5 is established by means of concentrated sodium hydroxide solution. The solution is cooled down to 0.degree., and a solution of 203.5 g of 4-chloro-3-nitrobenzene-1-sulfonyl chloride (75.6% pure) in 200 ml of acetone is added dropwise. The pH established above is held at a constant value by means of sodium hydroxide solution, and the product precipitated on adding salt is separated off. The washed and dried product is obtained in a yield of 131.7 g.
131 g of this compound are stirred together with 57.6 g of Na toluene-4-sulfinate into 450 ml of water, and the suspension is adjusted to pH 7.5 by means of sodium carbonate. After a dwell time of 20 hours at 105.degree.-107.degree. in a tantalum autoclave, the slurry is turned into a solution by means of hot water. The product is salted out, is filtered, is washed and is dried at 60.degree.-70.degree. in vacuo. This gives 135.8 g of powder.
135 g of the nitrodiphenyl sulfone are reduced at the boil in 700 ml of water which contains 58 g of iron powder and 8 ml of glacial acetic acid. 9.8 g of sodium carbonate are carefully added, and the iron residue is filtered off. Sodium chloride is added to the filtrate, and the precipitated product is filtered off, is washed and is dried at 60.degree.-70.degree. in vacuo.
This gives, in a chromatographically pure form, 151.2 g of the compound with the formula shown above.
EXAMPLE 3 ##STR27##
Sodium hydroxide solution is used to bring 46 g of phenol-4-sulfonic acid (75.6% pure) into solution in 300 ml of water at room temperature and bring the solution to pH 8.5. 67.2 g of 4-chloro-3-nitrobenzene-1-sulfonyl chloride (74% pure) dissolved in 100 ml of acetone are then added dropwise while the pH is maintained at a value of 8.5 by means of 10N sodium hydroxide solution. 15 hours later the precipitate is filtered off with suction and washed.
The filter cake is stirred together with 31.6 g of Na toluene-4-sulfinate (95.6% pure) into 300 ml of water, and pH 8 is established by means of sodium carbonate. After a dwell time of 20 hours at 104.degree.-107.degree. in a steel autoclave, the product is filtered off and washed. The moist filter cake is introduced into 250 ml of water which contains 34 g of iron powder and 3 ml of glacial acetic acid, and is reduced at the boil. 7 g of sodium carbonate are carefully added, the iron residue is filtered off, and the filtrate is evaporated to dryness. The yield is 76 g.
EXAMPLE 4 ##STR28##
87.5 g of sulfanilic acid (99% pure) are stirred into 500 ml of water brought to pH 7-8 by means of concentrated sodium hydroxide solution, and the solution is cooled down to 5.degree., when 106.2 g of 4-chloro-3-nitrobenzoyl chloride dissolved in 100 ml of acetone are added dropwise. The mixture is stirred for a while at pH 7 and the carboxamide is then precipitated by adding sodium chloride. After drying in vacuo at 60.degree.-70.degree., the filter from the washed product weighs 163 g. 61.2 g of this compound are left together with 30.7 g of Na toluene-4-sulfinate (95.6% pure) for some hours in 300 ml of water at reflux temperature. The filtered and washed sulfone derivative is dried at 60.degree.-70.degree. in vacuo to give 66.8 g of a chromatographically pure substance.
66 g of the nitrodiphenyl sulfone are reduced at the boil in 250 ml of water which contains 30 g of iron powder and 2 ml of glacial acetic acid. 3.1 g of sodium carbonate are carefully added, the iron residue is filtered off, and the pure product in the filtrate is precipitated by adding sodium chloride. It is then filtered off, washed, and dried at 60.degree.-70.degree. in vacuo. The yield is 62 g of the compound of the formula shown above.
EXAMPLE 5 ##STR29##
138 g of 1-chloro-2-nitro-4'-methylbenzophenone are sulfonated at 20.degree.-48.degree. in 450 ml of 25% oleum. The mixture is poured onto ice, and the product is precipitated with sodium chloride, is filtered off, is dissolved again in water and is salted out with potassium chloride. The precipitate is filtered off with suction, is washed and is dried at 60.degree.-70.degree. in vacuo. The yield is 221.4 g.
59.8 g of this compound, together with 20.46 g of Na toluene-4-sulfinate (95.6% pure), are brought to pH 8 in 300 ml of water, and are heated at the boil for some time. The sulfone derivative is filtered off cold, is washed, is added, as a moist material, to 300 ml of water which contains 20 g of iron powder and 2 ml of glacial acetic acid, and is reduced therein at the boil to give an amine. 3.1 g of sodium carbonate is carefully added, the iron residue is filtered off with suction, and the product is precipitated in the filtrate by means of sodium chloride. It is then filtered off, washed, and dried at 60.degree.-70.degree. in vacuo to give 49.7 g of the compound with the formula shown above.
EXAMPLE 6 ##STR30##
12.53 g of the compound of Example 1 (80.2% pure) are stirred into 100 ml of neutral ice-water and then admixed with 5 ml of 4N sodium nitrite. 6 ml of concentrated hydrochloric acid are added, and the suspension is left to stir for some time, and any excess nitrite is then destroyed by means of sulfamic acid.
3.26 g of N,N-diethyl-m-toluidine are emulsified in 40 ml of water which contains 2.12 g of sodium carbonate. The diazonium salt suspension prepared above is added dropwise at pH 8.5, maintained by means of sodium hydroxide solution, and the coupling product is acidified after some time with hydrochloric acid. The dye is filtered off, washed, and dried at 60.degree.-70.degree. in vacuo.
This gives 10.41 g of a water-soluble dye which contains sodium carbonate as a diluent and which dyes polyamide from a weakly acid bath in brilliant red shades. The dye builds up well and has superb light fastness, very good resistance to formaldehyde and good wet fastness properties.
EXAMPLE 7 ##STR31##
8.87 g of 2-amino-4'-methyldiphenylsulfone-4-sulfanilido-2"-sulfonic acid (81.5% pure) are suspended in 75 ml of neutral ice-water and are then admixed first with 3.75 ml of 4N sodium nitrite and then with 4.5 ml of concentrated hydrochloric acid. The suspension is stirred some more, and any slight excess of nitrite is destroyed with sulfamic acid. A solution of 2.7 g of 3-methyl-1phenyl-5-pyrazolimine (96.3% pure) in 20 ml of water and 2 ml of hydrochloric acid is then added, and the coupling reaction is allowed to go to completion at room temperature. The dye is filtered off, is dissolved in water brought to pH 8 by means of sodium hydroxide solution, and is precipitated with sodium chloride. The dye is filtered off again, is washed, and is dried at 60.degree.-70.degree. in vacuo.
This gives 7.51 g of a dye which dyes polyamide from a weakly acid bath in brilliant yellow shades. The dye builds up well and has good all-round fastness properties.
Example 8 ##STR32##
8.87 g of 2-amino-4'-methyldiphenylsulfone-4-sulfanilido-2"-sulfonic acid (81.5% pure) are diazotised as in Example 7. A solution of 1.97 g of 2-methylindole in 6 ml of concentrated hydrochloric acid is then added dropwise, and the coupling is completed at room temperature. The dye is filtered off, is dissolved in water containing sodium hydroxide solution under alkaline conditions, and is precipitated with sodium chloride. It is filtered off, washed, and dried at 60.degree.-70.degree. in vacuo to give 5.53 g of a dye which dyes polyamide material from a weakly acid bath in brilliant reddish yellow shades. The build-up, the light fastness and the resistance of formaldehyde and acid are very good.
Example 9 ##STR33##
8.87 g of 2-amino-4'-methyldiphenylsulfone-4-sulfanilido-2"-sulfonic acid (81.5% pure) are diazotised as in Example 7. 6.38 g of 1-(2'-chloro-6'-methylphenyl)-3-methylpyrazol-5-one (52.4% pure) are heated to 70.degree. in 50 ml of water containing 8 ml of 2N sodium hydroxide solution, and the mixture is clarified. The filtrate is cooled down to 2.degree., and the diazonium salt suspension prepared above is added dropwise while, at the same time, the pH is kept at a constant value of approximately 9 by means of 2N sodium hydroxide solution. The dye is precipitated with potassium chloride, is filtered off, is washed and is dried at 60.degree.-70.degree. in vacuo.
This gives 8.5 g of a dye which dyes polyamide material from a weakly acid bath in brilliant reddish yellow shades and has good all-round fastness properties.
Example 10 ##STR34##
8.87 g of 2-amino-4'-methyldiphenylsulfone-4-sulfanilido-2"-sulfonic acid (81.5% pure) are diazotised as in Example 7. 17.84 g of 3-.alpha.,.beta.-dibromopropionylaminoenzoyl-K-acid (55.1% pure) are dissolved in 80 ml of water at pH 7, and the solution is cooled down to 2.degree.. The diazo suspension is added dropwise while the pH is kept at a constant value of 7 by means of sodium hydroxide solution. The dye is salted out with potassium chloride, is filtered off with suction and is dried at 60.degree.-70.degree. in vacuo. The yield is 14.3 g.
The method of Examples 1 to 10 is repeated, except that a compound of the formula ##STR35## is used as diazo component and the compounds listed in the table below are used as coupling component, affording likewise valuable dyes which have similar, good properties and which dye polyamide or wool in the indicated shade.
TABLE Diazo component Example Y X R Coupling component Shade on polyamide 1 H CH.sub.3 SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR36## greenish yellow 2 H CH.sub.3 SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR37## red 3 H CH.sub.3 SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR38## yellowish red 4 H CH.sub.3 SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR39## yellowish red 5 H CH.sub.3 SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR40## reddish orange 6 H CH.sub.3 SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR41## red 7 H CH.sub.3 SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR42## yellowish red 8 H CH.sub.3 SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR43## reddish orange 9 H CH.sub.3 SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR44## reddish orange 10 H CH.sub.3 SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR45## red 11 H CH.sub.3 SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR46## red 12 H CH.sub.3 SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR47## reddish yellow 13 H CH.sub.3 SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR48## reddish yellow 14 H CH.sub.3 ##STR49## ##STR50## red 15 H CH.sub.3 ##STR51## ##STR52## reddish yellow 16 H H SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR53## red 17 H Cl SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H " red 18 H C.sub.2 H.sub.5 O SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H " red 19 H NHCOCH.sub.3 SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H " red 20 H CH.sub.3 ##STR54## ##STR55## red 21 H CH.sub.3 " ##STR56## yellowish red 22 H CH.sub.3 " ##STR57## reddish yellow 23 H CH.sub.3 " ##STR58## greenish yellow 24 H NHCOCH.sub.3 " ##STR59## red 25 H NHCOCH.sub.3 ##STR60## " red 26 H H " " red 27 H CH.sub.3 " " red 28 H Cl ##STR61## " red 29 H H " " red 30 H CH.sub.3 " " red 31 H Cl ##STR62## " red 32 H H " " red 33 H CH.sub.3 " " red 34 H CH.sub.3 " " red 35 H C H.sub.3 " ##STR63## reddish yellow 36 H CH.sub.3 " ##STR64## reddish yellow 37 H NHCOCH.sub.3 ##STR65## " reddish yellow 38 H CH.sub.3 " ##STR66## reddish yellow 39 H NHCOCH.sub.3 " ##STR67## yellow 40 H CH.sub.3 " ##STR68## yellow 41 H CH.sub.3 " ##STR69## yellowish red 42 H Cl ##STR70## ##STR71## reddish yellow 43 H Cl " ##STR72## yellow 44 H Cl " ##STR73## yellowish red 45 H Cl " ##STR74## red 46 H Cl " ##STR75## red 47 H Cl ##STR76## ##STR77## reddish yellow 48 H Cl ##STR78## " reddish yellow 49 H H " " reddish yellow 50 H H ##STR79## " reddish yellow 51 H H ##STR80## " reddish yellow 52 H CH.sub.3 ##STR81## " reddish yellow 53 H CH.sub.3 ##STR82## ##STR83## yellow 54 H Cl ##STR84## ##STR85## yellowish red 55 H Cl " ##STR86## yellowish orange 56 H Cl " ##STR87## orange 57 H Cl " ##STR88## reddish orange 58 H Cl " ##STR89## yellowish red 59 H ##STR90## ##STR91## " yellowish red 60 H Cl " ##STR92## red 61 H Cl " ##STR93## violet 62 H Cl " ##STR94## brown 63 H CH.sub.3 " ##STR95## yellowish red 64 H CH.sub.3 " ##STR96## greenish yellow 65 H CH.sub.3 " ##STR97## reddish yellow 66 H CH.sub.3 " ##STR98## reddish orange 67 H CH.sub.3 ##STR99## ##STR100## red 68 H CH.sub.3 " ##STR101## yellow 69 H CH.sub.3 " ##STR102## yellow 70 H CH.sub.3 " ##STR103## reddish yellow 71 H H " ##STR104## red 72 H Cl " " red 73 H Cl " ##STR105## yellow 74 H H " " yellow 75 H H " ##STR106## yellow 76 H CH.sub.3 " ##STR107## yellowish red 77 H CH.sub.3 ##STR108## ##STR109## red 78 H CH.sub.3 " ##STR110## red 79 H CH.sub.3 " ##STR111## red 80 H H " " red 81 H CH.sub.3 ##STR112## ##STR113## red 82 H CH.sub.3 " ##STR114## red 83 H CH.sub.3 " ##STR115## bluish red 84 H CH.sub.3 " ##STR116## red 85 H CH.sub.3 " ##STR117## yellow 86 H CH.sub.3 " ##STR118## reddish yellow 87 H CH.sub.3 " ##STR119## yellowish red 88 H Cl " ##STR120## red 89 H H " " red 90 H H " ##STR121## red 91 H Cl " " red 92 H Cl ##STR122## " red 93 H Cl " ##STR123## red 94 H H " " red 95 H Cl " ##STR124## red 96 H Cl ##STR125## " red 97 H CH.sub.3 " " red 98 H CH.sub.3 ##STR126## " red 99 H Cl " " red 100 H Cl ##STR127## " red 101 H CH.sub.3 ##STR128## " red 102 H CH.sub.3 ##STR129## " red 103 H H " " red 104 H H ##STR130## " red 105 H CH.sub.3 " " red 106 H Cl ##STR131## ##STR132## red 107 H Cl " ##STR133## yellowish red 108 H CH.sub.3 ##STR134## ##STR135## red 109 H CH.sub.3 SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR136## red 110 H CH.sub.3 SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR137## red 111 H CH.sub.3 ##STR138## " red 112 OCH.sub.3 CH.sub.3 ##STR139## ##STR140## red 113 OCH.sub.3 H " " red 114 H CH.sub.3 ##STR141## ##STR142## yellowish red 115 H CH.sub.3 " ##STR143## yellowish red 116 H CH.sub.3 " ##STR144## yellow 117 H CH.sub.3 " ##STR145## reddish yellow 118 H CH.sub.3 " ##STR146## reddish orange 119 H CH.sub.3 ##STR147## ##STR148## yellowish red 120 H H " " yellowish red 121 H Cl " " yellowish red 122 H CH.sub.3 " ##STR149## yellow 123 H H " " yellow 124 H Cl " " yellow 125 H CH.sub.3 " ##STR150## reddish yellow 126 H H " " reddish yellow 127 H Cl " " reddish yellow 128 H CH.sub.3 ##STR151## ##STR152## yellowish red 129 H H " " yellowish red 130 H Cl " " yellowish red 131 H CH.sub.3 " ##STR153## yellow 132 H H " " yellow 133 H Cl " " yellow 134 H CH.sub.3 " ##STR154## reddish yellow 135 H H " " reddish yellow 136 H Cl " " reddish yellow 137 H CH.sub.3 CONHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR155## yellowish red 138 H CH.sub.3 CONHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR156## yellow 139 H CH.sub.3 CONHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR157## reddish yellow 140 H CH.sub.3 CONHCH.sub.2 CH.sub.2 SO.sub.3 H ##STR158## red 141 H CH.sub.3 ##STR159## ##STR160## yellowish red 142 H CH.sub.3 " ##STR161## yellow 143 H CH.sub.3 " ##STR162## reddish yellow 144 H CH.sub.3 ##STR163## " reddish yellow 145 H CH.sub.3 " ##STR164## yellowish red 146 H CH.sub.3 " ##STR165## yellow 147 H H " " yellow 148 H Cl " " yellow 149 H Cl " ##STR166## yellowish red 150 H H " " yellowish red 151 H CH.sub.3 ##STR167## " yellowish red 152 H CH.sub.3 ##STR168## " yellowish red 153 H CH.sub.3 ##STR169## " yellowish red 154 H CH.sub.3 ##STR170## ##STR171## yellowish red 155 H CH.sub.3 " ##STR172## reddish yellow 156 H CH.sub.3 " ##STR173## yellow 157 H H " ##STR174## yellowish red 158 H Cl " " yellowish red 159 H H " ##STR175## reddish yellow 160 H Cl " " reddish yellow 161 H H " ##STR176## yellow 162 H Cl " " yellow 163 H CH.sub.3 ##STR177## ##STR178## yellowish red 164 H H " " yellowish red 165 H Cl " " yellowish red Shade on wool 166 H CH.sub.3 ##STR179## ##STR180## red 167 H Cl " " red 168 H CH.sub.3 ##STR181## " red 169 H CH.sub.3 SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H " " 170 H CH.sub.3 ##STR182## " red 171 H CH.sub.3 ##STR183## ##STR184## red 172 H CH.sub.3 " ##STR185## yellowish red 173 H CH.sub.3 " ##STR186## reddish orange 174 H CH.sub.3 " ##STR187## red 175 H CH.sub.3 ##STR188## ##STR189## red 176 H H " " red 177 H Cl " " red 178 H CH.sub.3 ##STR190## " red 179 H H " " red 180 H Cl " " red 181 H CH.sub.3 ##STR191## " red 182 H H " " red 183 H Cl " " red 184 H Cl ##STR192## " red 185 H Cl SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H " red 186 H Cl ##STR193## ##STR194## red 187 H H " " red 188 H CH.sub.3 ##STR195## " red 189 H H " " red 190 H Cl " " red 191 H Cl SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H " red 192 H Cl ##STR196## ##STR197## red 193 H CH.sub.3 " " red 194 H H " " red 195 H Cl ##STR198## " red 196 H Cl " ##STR199## red 197 H CH.sub.3 " " red 198 H H " " red 199 H CH.sub.3 ##STR200## " red 200 H H " " red 201 H Cl " " red 202 H H SO.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.3 H " red 203 H CH.sub.3 ##STR201## ##STR202## red 204 Cl Cl ##STR203## ##STR204## red 205 Cl Cl ##STR205## " red 206 Cl Cl ##STR206## " red 207 Cl Cl ##STR207## ##STR208## red 208 Cl Cl ##STR209## " red 209 Cl Cl ##STR210## " red 210 Cl Cl ##STR211## " red 211 Cl Cl ##STR212## " red 212 Cl Cl ##STR213## " red 213 Cl Cl ##STR214## ##STR215## red 214 Cl Cl ##STR216## " red 215 Cl Cl ##STR217## " red 216 Cl Cl ##STR218## ##STR219## red 217 Cl Cl ##STR220## ##STR221## red 218 Cl Cl ##STR222## " red 219 Cl Cl ##STR223## ##STR224## red 220 Cl Cl ##STR225## " red 221 Cl Cl ##STR226## " red *In these cases (Examples 55 and 56), the coupling components used in the coupling were not those indicated in the table but the corresponding free hydroxy compounds, i.e. phenol and naphthol respectively, and the hydroxy groups were akylated after the coupling. The reason the table shows for Examples 55 and 56 the already etherified hydroxy compounds as coupling components is merely to clarify the structure of the end products.
Dyeing method I
10 parts of Helanca jersey are dyed in 500 parts of an aqueous liquor which contains per liter 1 g of monosodium phosphate and which has been brought to pH 6 by means of disodium phosphate. The amount of the dye of Example 6 is 1.4% on weight of fibre. The dyeing time at a temperature of 98% is 30-90 minutes. The dyed Helanca fabric is then taken out of the bath and conventionally washed and dried.
This gives a deep red Helanca fabric which has a bright shade and very good overall fastness properties and which is in particular very resistant to formuladehyde.
Dyeing method II
10 parts of wool fabric are dyed in 500 parts of an aqueous liquor which contains, on weight of fibre, 4% by weight of ammonium sulfate, 1.5% by weight of 80% acetic acid, 1% by weight of a substituted alkylaminopolyglycol ether and 3% by weight of the dye of Example 10, at a temperature of 98.degree. for 30 to 90 minutes. The bath is then cooled down to 80.degree. and is neutralised by adding 2.5% by weight of 25% aqueous ammonia, and the dyeing is completed at this temperature in the course of 15 minutes. The dyed wool fabric is then taken out of the bath and conventionally washed and dried.
This gives a wool fabric which has a bright shade and good overall fastness properties.

Number	Name	Date
2449130	Krebser et al.	Sep 1948
2551887	Kuster	May 1951
3417076	Sartori	Dec 1968
3692769	Weaver et al.	Sep 1972
3951944	Fuchs	Apr 1976
4042580	Groebke	Aug 1977
4046757	Meybeck et al.	Sep 1977
4052444	Laubert et al.	Oct 1977
4119624	Boyd et al.	Oct 1978
4193916	Back et al.	Mar 1980
4267104	Giles et al.	May 1981

Number	Date	Country
0039306	Mar 1981	EPX
0042357	Jun 1981	EPX
2021615	Dec 1979	GBX

Monoazo dyes containing a 4-substituted-2-azo-1,1'-diphenylsulfone component

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