Acid Dyes, Methods For The Production Thereof and Their Use

The present invention relates to the technical field of dyestuffs for dyeing and printing of hydroxyl- and/or carboxamido-containing material.

Acid dyes with amino pyrazolone couplers are known from prior art and can be used as colorants in different applications, see for example US 5,543,259, JP 60215082 A and WO 2005/018931 A1 .

However, in the context of the dyeing and printing of hydroxyl-, amino and/or carboxamido-containing material the known dyes have a number of technical disadvantages, which require improvement. One such disadvantage is, that many of them are comprising heavy metals such as Cu, Cr or Ni. Such heavy metals are critical from a toxicological as well as an environmental point of view and shall thus be excluded.

Surprisingly, it has now been found that the dyes of the formula (1 ) as described below show highly advantageous properties over the known dyes. These include high tinctorial strength with high brilliancy as well as high fastness properties such as wash, contact and light fastness on the materials mentioned above, on blends containing them as well as on microfibres. Most importantly, dyes of formula (1 ) are substantially heavy metal free and provide dyeings that are levelled. Metals may only be present as counter ions and are selected from the groups of alkali and earth alkali metals, which do not have such effects as heavy metals.

The present invention refers to dyes of formula (1 )

wherein

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ independent of each other is hydrogen, alkyi, alkoxy, halogen, trifluoromethyl or SO3M

- whereby at least two of them are SO3M,

X is oxygen or sulphur, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ independent of each other is hydrogen, alkyi, substituted alkyi, alkyi interrupted by one or two heteroatoms, alkoxy, substituted alkoxy, halogen, trifluoromethyl, cycloalkyl, heterocycloalkyl, cyano, acyloxy, alkylcarbonyl, acylamino, alkylsulfonylamino, amino, monoalkyl-amino, monocycloalkyl-amino, dialkyl-amino, di(cyclo)alkyl-amino, alkylthio, alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, alkylureido or -SO3M,

R ¹³ and R ²⁰ is hydroxyl or amino, R ¹⁴ and R ²¹ independent of each other is hydrogen, alkyl, cycloalkyl, trifluoromethyl, alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino, hydroxyl, monocycloalkyl- amino, monoalkyl-amino, di(cyclo)alkyl-amino, dialkyl-amino, monoaryl-amino, diaryl- amino, monocycloalkylmonoarylamino, monoalkyl monoaryl amino, alkylthio, arylthio, alkylcarbonyl, alkylsulfonyl

or

is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido and phenylureido,

R ¹⁵ and R ²² independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenyl- ureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkyl- aminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl or

alkyl interrupted by one or more heteroatoms, selected from the group consisting of oxygen and sulphur,

or

alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyilureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfannoyl, N- nnonoalkyl-N-nnonoarylsulfannoyl and SO3M

or

alkyl interrupted by one or more heteroatoms, selected from the group consisting of oxygen and sulphur, and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl- amino, Ν,Ν-dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl- amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl- monocycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N- alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N- monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N- monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl- sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO3M, or

aryl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl-N-monoarylsulfamoyl and SO3M, M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal, or a monovalent organic cation, the dyes of formula (1 ) have two to six sulfonic acid groups.

This invention referrs to all tautomeric and geometric isomers of the dyes of formula (1 ) and mixtures thereof.

AlkyI groups appearing in this invention may be straight-chain or branched and are (Ci-Ci2)-alkyl groups, preferably (Ci-C8)-alkyl groups, for example n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, sec-butyl, tert-butyl and methylbutyl.

The same applies to alkoxy groups, which accordingly are preferably (Ci-C8)-alkoxy, for example methoxy and ethoxy, to thioalkoxy groups, which are preferably (Ci-Ce)- thioalkoxy, for example -SCH3 and -SC2H5.

Cycloalkyl groups are preferably (C3-C8)-cycloalkyl and especially preferably cyclopentyl or cyclohexyl. The term cyloalkyl comprises for the purpose of the present invention substituted cycloalklyl groups and unsatured cycloalkyl groups as well. A preferred group of this type is cyclopentenyl. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, acyl, cyano, nitro, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis-(hydroxyalkyl)amino, monoalkyl- mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonyl- amino, alkoxycarbonyl and acyloxy.

Alkenyl groups may be straight-chain or branched and are preferably (C2-C6)-g roups for example vinyl and allyl. The term alkenyl comprises for the purpose of the present invention alkynyl groups as well, for example ethynyl and propargyl. Aryl groups appearing in this invention are preferably phenyl or naphthyl. The terms phenyl and naphthyl comprise unsubstituted as well as substituted phenyl and naphthyl. Preferred substituents are alkyl, cycloalkyl, heterocycloalkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis-(hydroxyalkyl)amino, monoalkyl- mono(hydroxyalkyl)annino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Heteroaryl groups are preferably pyridine, pyrimidine, pyridazine, pyrazine, pyrrole, imidazole, pyrazole, 1 ,2,4-thiadiazole, 1 ,2,4-triazole, tetrazole, thiophene, thiazole, isothiazole, benzothiazole, benzoisothiazole, 1 ,3,4-thiadiazole, furane, oxazole, benzoxazole or isoxazole. The terms heteroayl comprises the above groups in unsubstituted as well as in substituted form. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis-(hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Heterocycloalkyi groups are preferably pyrrolidine, piperidine, morpholine, tetrahydrofuran or piperazine. The term heterocycloalkyi comprises the above groups in unsubstituted as well as in substituted form. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, amino- carbonylamino, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Halogen is preferably chlorine, bromine or fluorine.

M is preferably hydrogen, lithium, sodium, potassium or mono-, di-, tri- or tetra-(Ci- C ₄ )-alkylammonium.

There exist different groups of preferred embodiments. In one preferred embodiment one of R ¹³ and R ²⁰ is hydroxyl and the other is amino. In another preferred embodiment both R ¹³ and R ²⁰ are amino and in still another preferred embodiment both R ¹³ and R ²⁰ are hydrogen. The latter two are described in further detail below.

The present invention refers to dyes of formula (1 ) as shown above

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M

- whereby at least two of them are SO3M, X is oxygen or sulphur,

R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ independent of each other is hydrogen, alkyl, substituted alkyl, alkyl interrupted by one or two heteroatoms, alkoxy, substituted alkoxy, halogen, trifluoromethyl, cycloalkyl, heterocycloalkyl, cyano, acyloxy, alkylcarbonyl, acylamino, alkylsulfonylamino, amino, monoalkyl-amino, monocycloalkyl-amino, dialkyl-amino, di(cyclo)alkyl-amino, alkylthio, alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, alkylureido or -SO3M,

R ¹³ and R ²⁰ is hydroxyl,

R ¹⁴ and R ²¹ independent of each other is hydrogen, alkyl, cycloalkyl, trifluoromethyl, alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino, hydroxyl, monocycloalkyl- amino, monoalkyl-amino, di(cyclo)alkyl-amino, dialkyl-amino, monoaryl-amino, diaryl- amino, monocydoalkylmonoarylamino, monoalkyi monoaryl amino, alkylthio, arylthio, alkylcarbonyl, alkylsulfonyl

or

is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido and phenylureido,

R ¹⁵ and R ²² independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenyl- ureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkyl- aminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl or alkyi interrupted by one or more heteroatoms, selected from the group consisting of oxygen and sulphur,

or

alkyi substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyilureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl-N-monoarylsulfamoyl and SO3M

or

alkyi interrupted by one or more heteroatoms, selected from the group consisting of oxygen and sulphur, and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl- amino, Ν,Ν-dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl- amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl- monocycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N- alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N- monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N- monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl- sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO3M, or aryl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl-N-monoarylsulfamoyl and SO3M,

M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal, or a monovalent organic cation, the dyes of formula (1 ) have two to six sulfonic acid groups.

Particularly preferred embodiments of the present invention are dyes of formula (1 a)

wherein

R ^{1 a} , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a and R ^8a independent of each other is hydrogen, alkyi, alkoxy, halogen, trifluoromethyl or SO3M

- whereby at least two of them are SO3M,

R ^9a , R ^10a , R ^16a and R ^17a independent of each other is hydrogen, alkyi, substituted alkyi, alkyi chain interrupted by one or two heteroatoms, alkoxy, substituted alkoxy, halogen, trifluoromethyl, cycloalkyi, heterocycloalkyi, cyano, acyloxy, alkylcarbonyl, acylamino, alkylsulfonylamino, amino, monoalkyl-amino, monocycloalkyl-amino, dialkyl-amino, di(cyclo)alkyl-amino, alkylthio, alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, alkylureido or -SO3M,

R ^13a and R ^20a is hydroxyl,

R ^14a and R ^{21 a} independent of each other is hydrogen, alkyi, cycloalkyi, trifluoromethyl, alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino, hydroxyl, monocycloalkyl- amino, monoalkyl-amino, di(cyclo)alkyl-amino, dialkyl-amino, monoaryl-amino, diaryl- amino, monocycloalkylmonoarylamino, monoalkyl monoaryl amino, alkylthio, arylthio, alkylcarbonyl, alkylsulfonyl

or

is alkyi substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido and phenylureido, R ^15a and R ^22a independent of each other is hydrogen, alkyi, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl

or

alkyi interrupted by one or more heteroatoms, selected from the group consisting of oxygen and sulfur

or

alkyi substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyilureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl-N-monoarylsulfamoyl and SO3M

or alkyl interrupted by one or more heteroatoms, selected from the group consisting of oxygen and sulphur, and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl- amino, Ν,Ν-dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl- amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl- monocycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N- alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N- monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N- monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl- sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO3M or

aryl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl-N-monoarylsulfamoyl and SO3M

and

M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal, or a monovalent organic cation. In especially preferred dyes of formula (1 a)

R ^{1 a} and R ^6a is SO ₃ M and R ^2a , R ^3a , R ^4a , R ^5a , R ^7a and R ^8a is hydrogen or

R ^2a and R ^5a is SO ₃ M and R ^{1 a} , R ^3a , R ^4a , R ^6a , R ^7a and R ^8a is hydrogen,

R ^9a , R ^10a , R ^16a and R ^17a independent of each other is hydrogen, (Ci-C )-alkyl, (Ci-C )- alkoxy, halogen, trifluoromethyl, (Ci-C ₄ )-acylamino or -SO3M,

R ^13a and R ^20a is hydroxyl,

R ^14a and R ^{21 a} independent of each other is alkyl, cycloalkyl, trifluoromethyl, cyano, carbamoyl, alkoxycarbonyl, COOM, alkylcarbonyl

or

is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, alkoxy, halogen, cyano, COOM, alkoxycarbonyl, acyloxy and carbamoyl,

R ^15a and R ^22a independent of each other is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1 -ethylproyl, 1 ,2-dimethylpropyl, tert-butyl, 3- methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2- hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3- chloropropyl, 2-ethylhexyl, 2-(2-hydroxyethylsulfanyl)-ethyl, 4-(2- hydroxyethansulfonyl)phenyl, 2-(2-hydroxyethoxy)ethyl, 3-(4-hydroxybutoxy)propyl,

3- (2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl, 3-ethoxybutyl, phenyl, 3-methylphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2- methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-chlorophenyl, 3-chlorophenyl,

4- chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl or 3- phenylsulfonamide

and

M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation. Examples of particularly preferred dyes of formula (1 a) are the compounds of the formulae (1 a ¹ to 1 a ³¹² ), mixtures and/or tautomers thereof, wherein R ³ , R ⁴ , R ⁷ and R ⁸ is hydrogen, R ¹³ and R ²⁰ is hydroxyl and the other R ^x are as given in Table 1 :

Table 1

1a ¹⁹ H SOsH SOsH H

Methyl Methyl Methyl 3-Methyl cyclohexyl

1a ²⁰ SOsH H H SOsH

1a ²¹ H SOsH SOsH H

Methyl Methyl Methyl Isopropyl

1a ²² SOsH H H SOsH

1a ²³ H SOsH SOsH H

Methyl Methyl Methyl Sec-butyl

1a ²⁴ SOsH H H SOsH

1a ²⁵ H SOsH SOsH H

Methyl Methyl Methyl 2-Methyl butyl

1a ²⁶ SOsH H H SOsH

1a ²⁷ H SOsH SOsH H

Methyl Methyl Methyl 1-Ethylpropyl

1a ²⁸ SOsH H H SOsH

1a ²⁹ H SOsH SOsH H

Methyl Methyl Methyl 1 ,2-Dimethyl propyl

1a ³⁰ SOsH H H SOsH

1a ³¹ H SOsH SOsH H

Methyl Methyl Methyl Tert-butyl

1a ³² SOsH H H SOsH

1a ³³ H SOsH SOsH H

Methyl Methyl Methyl 3-Methyl butyl

1a ³⁴ SOsH H H SOsH

1a ³⁵ H SOsH SOsH H

Methyl Methyl Methyl Pentan-2-yl

1a ³⁶ SOsH H H SOsH

1a ³⁷ H SOsH SOsH H

1a ³⁸ SOsH H H SOsH Methyl Methyl Methyl 2-Ethylhexyl

1a ³⁹ H SOsH SOsH H

Methyl Methyl Methyl 2,2-Dinnethyl propyl

1a ⁴⁰ SOsH H H SOsH

1a ⁴¹ H SOsH SOsH H

Methyl Methyl Methyl Phenyl

1a ⁴² SOsH H H SOsH

1a ⁴³ H SOsH SOsH H

Methyl Methyl Methyl Benzyl

1a ⁴⁴ SOsH H H SOsH

1a ⁴⁵ H SOsH SOsH H

Methyl F Methyl Methyl

1a ⁴⁶ SOsH H H SOsH

1a ⁴⁷ H SOsH SOsH H

Methyl F Methyl Ethyl

1a ⁴⁸ SOsH H H SOsH

1a ⁴⁹ H SOsH SOsH H

Methyl F Methyl Propyl

1a ⁵⁰ SOsH H H SOsH

1a ⁵¹ H SOsH SOsH H

Methyl F Methyl Butyl

1a ⁵² SOsH H H SOsH

1a ⁵³ H SOsH SOsH H

Methyl F Methyl Pentyl

1a ⁵⁴ SOsH H H SOsH

1a ⁵⁵ H SOsH SOsH H

Methyl F Methyl Cyclobutyl

1a ⁵⁶ SOsH H H SOsH

1a ⁵⁷ H SOsH SOsH H

1a ⁵⁸ SOsH H H SOsH Methyl F Methyl Cyclopentyl

1a ⁵⁹ H SOsH SOsH H

Methyl F Methyl Cyclohexyl

1a ⁶⁰ SOsH H H SOsH

1a ⁶¹ H SOsH SOsH H

Methyl F Methyl 2-Methyl cyclohexyl

1a ⁶² SOsH H H SOsH

1a ⁶³ H SOsH SOsH H

Methyl F Methyl 3-Methyl cyclohexyl

1a ⁶⁴ SOsH H H SOsH

1a ⁶⁵ H SOsH SOsH H

Methyl F Methyl Isopropyl

1a ⁶⁶ SOsH H H SOsH

1a ⁶⁷ H SOsH SOsH H

Methyl F Methyl Sec-butyl

1a ⁶⁸ SOsH H H SOsH

1a ⁶⁹ H SOsH SOsH H

Methyl F Methyl 2-Methyl butyl

1a ⁷⁰ SOsH H H SOsH

1a ⁷¹ H SOsH SOsH H

Methyl F Methyl 1-Ethylpropyl

1a ⁷² SOsH H H SOsH

1a ⁷³ H SOsH SOsH H

Methyl F Methyl 1 ,2-Dimethyl propyl

1a ⁷⁴ SOsH H H SOsH

1a ⁷⁵ H SOsH SOsH H

Methyl F Methyl Tert-butyl

1a ⁷⁶ SOsH H H SOsH

1a ⁷⁷ H SOsH SOsH H

1a ⁷⁸ SOsH H H SOsH Methyl F Methyl 3-methyl butyl

1a ⁷⁹ H SOsH SOsH H

Methyl F Methyl Pentan-2-yl

1a ⁸⁰ SOsH H H SOsH

1a ⁸¹ H SOsH SOsH H

Methyl F Methyl 2-Ethylhexyl

1a ⁸² SOsH H H SOsH

1a ⁸³ H SOsH SOsH H

Methyl F Methyl 2,2-Dinnethyl propyl

1a ⁸⁴ SOsH H H SOsH

1a ⁸⁵ H SOsH SOsH H

Methyl F Methyl Phenyl

1a ⁸⁶ SOsH H H SOsH

1a ⁸⁷ H SOsH SOsH H

Methyl F Methyl Benzyl

1a ⁸⁸ SOsH H H SOsH

1a ⁸⁹ H SOsH SOsH H

NHCOCHs OMe Methyl Methyl

1a ⁹⁰ SOsH H H SOsH

1a ⁹¹ H SOsH SOsH H

NHCOCHs OMe Methyl Ethyl

1a ⁹² SOsH H H SOsH

1a ⁹³ H SOsH SOsH H

NHCOCHs OMe Methyl Propyl

1a ⁹⁴ SOsH H H SOsH

1a ⁹⁵ H SOsH SOsH H

NHCOCHs OMe Methyl Butyl

1a ⁹⁶ SOsH H H SOsH

1a ⁹⁷ H SOsH SOsH H

1a ⁹⁸ SOsH H H SOsH NHCOCHs OMe Methyl Pentyl

1a" H SOsH SOsH H

NHCOCHs OMe Methyl Cyclobutyl

_{1 a} ioo SOsH H H SOsH

_{1 g} 101 H SOsH SOsH H

NHCOCHs OMe Methyl Cyclopentyl

_{1 g} 102 SOsH H H SOsH

_{1 g} 103 H SOsH SOsH H

NHCOCHs OMe Methyl Cyclohexyl

_{1 a} 104 SOsH H H SOsH

_{1 a} 105 H SOsH SOsH H

NHCOCHs OMe Methyl 2-Methyl cyclohexyl

_{1 a} 106 SOsH H H SOsH

_{1 g} 107 H SOsH SOsH H

NHCOCHs OMe Methyl 3-Methyl cyclohexyl

_{1 g} 108 SOsH H H SOsH

_{1 g} 109 H SOsH SOsH H

NHCOCHs OMe Methyl Isopropyl

_{1 g} 110 SOsH H H SOsH

_{1 a} 111 H SOsH SOsH H

NHCOCHs OMe Methyl Sec-butyl

1a ¹¹² SOsH H H SOsH

_{1 a} 113 H SOsH SOsH H

NHCOCHs OMe Methyl 2-Methyl butyl

_{1 a} 114 SOsH H H SOsH

_{1 a} 115 H SOsH SOsH H

NHCOCHs OMe Methyl 1-Ethylpropyl

_{1 a} 116 SOsH H H SOsH

1a ¹¹⁷ H SOsH SOsH H

_{1 g} 118 SOsH H H SOsH NHCOCHs OMe Methyl 1 ,2-Dimethyl propyl

_{1 g} 119 H SOsH SOsH H

NHCOCHs OMe Methyl Tert-butyl

_{1 g} 120 SOsH H H SOsH

1a ¹²¹ H SOsH SOsH H

NHCOCHs OMe Methyl 3-Methyl butyl

1a ¹²² SOsH H H SOsH

_{1 g} 123 H SOsH SOsH H

NHCOCHs OMe Methyl Pentan-2-yl

1a ¹²⁴ SOsH H H SOsH

_{1 a} 125 H SOsH SOsH H

NHCOCHs OMe Methyl 2-Ethylhexyl

_{1 a} 126 SOsH H H SOsH

1a ¹²⁷ H SOsH SOsH H

NHCOCHs OMe Methyl 2,2-Dinnethyl propyl

_{1 g} 128 SOsH H H SOsH

_{1 a} 129 H SOsH SOsH H

NHCOCHs OMe Methyl Phenyl

_{1 a} 130 SOsH H H SOsH

_{1 g} 131 H SOsH SOsH H

NHCOCHs OMe Methyl Benzyl

_{1 g} 132 SOsH H H SOsH

_{1 g} 133 H SOsH SOsH H

Methyl Methyl Methyl 2-Methoxy ethyl

_{1 g} 134 SOsH H H SOsH

_{1 g} 135 H SOsH SOsH H

Methyl Methyl Methyl 3-Methoxy propyl

_{1 g} 136 SOsH H H SOsH

_{1 g} 137 H SOsH SOsH H

_{1 g} 138 SOsH H H SOsH Methyl Methyl Methyl 2-Hydroxyethyl

_{1 g} 139 H SOsH SOsH H 2-Fluoroethyl

Methyl Methyl Methyl

_{1 g} 140 SOsH H H SOsH

_{1 g} 141 H SOsH SOsH H 2-Chloroethyl

Methyl Methyl Methyl

1a ¹⁴² SOsH H H SOsH

_{1 a} 143 H SOsH SOsH H 3-Chloropropyl

Methyl Methyl Methyl

_{1 a} 144 SOsH H H SOsH

_{1 g} 145 H SOsH SOsH H 2-Ethylhexyl

Methyl Methyl Methyl

_{1 g} 146 SOsH H H SOsH

1a ¹⁴⁷ H SOsH SOsH H 2-(2-Hydroxy-ethylsulfanyl)-

Methyl Methyl Methyl

_{1 g} 148 SOsH H H SOsH ethyl

_{1 g} 149 H SOsH SOsH H 2-(2-Hydroxyethoxy)ethyl

Methyl Methyl Methyl

_{1 g} 150 SOsH H H SOsH

_{1 g} 151 H SOsH SOsH H 3-(4-Hydroxybutoxy)propyl

Methyl Methyl Methyl

_{1 g} 152 SOsH H H SOsH

_{1 g} 153 H SOsH SOsH H 4-(2-Hydroxyethane-

Methyl Methyl Methyl

_{1 g} 154 SOsH H H SOsH sulfonyl)phenyl

_{1 g} 155 H SOsH SOsH H

Methyl Methyl Methyl 3-lsopropoxy propyl

_{1 a} 156 SOsH H H SOsH

_{1 g} 157 H SOsH SOsH H

_{1 g} 158 SOsH H H SOsH Methyl Methyl Methyl 3-Ethoxypropyl

_{1 a} 159 H SOsH SOsH H

Methyl Methyl Methyl 3-Ethoxybutyl

_{1 g} 160 SOsH H H SOsH

_{1 g} 161 H SOsH SOsH H

Methyl Methyl Methyl 3-Methyl phenyl

_{1 g} 162 SOsH H H SOsH

_{1 g} 163 H SOsH SOsH H

Methyl Methyl Methyl 2-Methyl phenyl

_{1 g} 164 SOsH H H SOsH

_{1 g} 165 H SOsH SOsH H

Methyl Methyl Methyl 4-Methyl phenyl

_{1 g} 166 SOsH H H SOsH

_{1 g} 167 H SOsH SOsH H

Methyl Methyl Methyl 2-Methoxy phenyl

_{1 g} 168 SOsH H H SOsH

_{1 g} 169 H SOsH SOsH H

Methyl Methyl Methyl 3-Methoxy phenyl

_{1 g} 170 SOsH H H SOsH

1a ¹⁷¹ H SOsH SOsH H

Methyl Methyl Methyl 4-Methoxy phenyl

1a ¹⁷² SOsH H H SOsH

_{1 a} 173 H SOsH SOsH H

Methyl Methyl Methyl 2-Chlorophenyl

1a ¹⁷⁴ SOsH H H SOsH

_{1 g} 175 H SOsH SOsH H

Methyl Methyl Methyl 3-Chlorophenyl

_{1 a} 176 SOsH H H SOsH

1a ¹⁷⁷ H SOsH SOsH H

_{1 a} 178 SOsH H H SOsH Methyl Methyl Methyl 4-Chlorophenyl

_{1 a} 179 H SOsH SOsH H

Methyl Methyl Methyl 2-Fluorophenyl

_{1 a} 180 SOsH H H SOsH

_{1 g} 181 H SOsH SOsH H

Methyl Methyl Methyl 3-Fluorophenyl

_{1 g} 182 SOsH H H SOsH

_{1 g} 183 H SOsH SOsH H

Methyl Methyl Methyl 4-Fluorophenyl

_{1 g} 184 SOsH H H SOsH

_{1 g} 185 H SOsH SOsH H

Methyl Methyl Methyl 3-Phenyl sulfonamide

_{1 g} 186 SOsH H H SOsH

_{1 g} 187 H SOsH SOsH H

Methyl Methyl Methyl 2-Aminophenyl

_{1 g} 188 SOsH H H SOsH

_{1 g} 189 H SOsH SOsH H

Methyl Methyl Methyl 3-Aminophenyl

_{1 g} 190 SOsH H H SOsH

_{1 g} 191 H SOsH SOsH H

Methyl Methyl Methyl 4-Aminophenyl

_{1 g} 192 SOsH H H SOsH

_{1 g} 193 H SOsH SOsH H

Methyl F Methyl 2-Methoxy ethyl

_{1 g} 194 SOsH H H SOsH

_{1 g} 195 H SOsH SOsH H

Methyl F Methyl 3-Methoxy propyl

_{1 a} 196 SOsH H H SOsH

_{1 g} 197 H SOsH SOsH H

_{1 g} 198 SOsH H H SOsH Methyl F Methyl 2-Hydroxy ethyl

_{1 g} 199 H SOsH SOsH H

Methyl F Methyl 2-Fluoro ethyl

_{1 a} 200 SOsH H H SOsH

_{1 a} 201 H SOsH SOsH H

Methyl F Methyl 2-Chloro ethyl

_{1 a} 202 SOsH H H SOsH

_{1 a} 203 H SOsH SOsH H

Methyl F Methyl 3-Chloro propyl

_{1 a} 204 SOsH H H SOsH

_{1 a} 205 H SOsH SOsH H

Methyl F Methyl 2-Ethyl hexyl

_{1 a} 206 SOsH H H SOsH

_{1 a} 207 H SOsH SOsH H 2-(2-Hydroxy-ethyl

Methyl F Methyl

_{1 a} 208 SOsH H H SOsH sulfanyl)-ethyl

_{1 a} 209 H SOsH SOsH H

Methyl F Methyl 2-(2-Hydroxyethoxy)ethyl

_{1 a} 210 SOsH H H SOsH

1a ²¹¹ H SOsH SOsH H

Methyl F Methyl 3-(4-Hydroxybutoxy)propyl

1a ²¹² SOsH H H SOsH

_{1 a} 213 H SOsH SOsH H 4-(2-Hydroxyethanesulfonyl)-

Methyl F Methyl

1a ²¹⁴ SOsH H H SOsH phenyl

_{1 a} 215 H SOsH SOsH H

Methyl F Methyl 3-lsopropoxy-propyl

_{1 g} 216 SOsH H H SOsH

1a ²¹⁷ H SOsH SOsH H

_{1 a} 218 SOsH H H SOsH Methyl F Methyl 3-Ethoxy-propyl

_{1 a} 219 H SOsH SOsH H

Methyl F Methyl 3-Ethoxy butyl

_{1 a} 220 SOsH H H SOsH

1a ²²¹ H SOsH SOsH H

Methyl F Methyl 3-Methyl phenyl

_{1 a} 222 SOsH H H SOsH

_{1 a} 223 H SOsH SOsH H

Methyl F Methyl 2-Methyl phenyl

1a ²²⁴ SOsH H H SOsH

_{1 a} 225 H SOsH SOsH H

Methyl F Methyl 4-Methyl phenyl

_{1 g} 226 SOsH H H SOsH

1a ²²⁷ H SOsH SOsH H

Methyl F Methyl 2-Methoxy phenyl

_{1 a} 228 SOsH H H SOsH

_{1 g} 229 H SOsH SOsH H

Methyl F Methyl 3-Methoxy phenyl

_{1 a} 230 SOsH H H SOsH

_{1 a} 231 H SOsH SOsH H

Methyl F Methyl 4-Methoxy phenyl

_{1 a} 232 SOsH H H SOsH

_{1 g} 233 H SOsH SOsH H

Methyl F Methyl 2-Chloro phenyl

_{1 g} 234 SOsH H H SOsH

_{1 a} 235 H SOsH SOsH H

Methyl F Methyl 3-Chloro phenyl

_{1 g} 236 SOsH H H SOsH

_{1 g} 237 H SOsH SOsH H

_{1 a} 238 SOsH H H SOsH Methyl F Methyl 4-Chloro phenyl

_{1 a} 239 H SOsH SOsH H

Methyl F Methyl 2-Fluoro phenyl

_{1 a} 240 SOsH H H SOsH

1a ²⁴¹ H SOsH SOsH H

Methyl F Methyl 3-Fluoro phenyl

1a ²⁴² SOsH H H SOsH

1a ²⁴³ H SOsH SOsH H

Methyl F Methyl 4-Fluoro phenyl

1a ²⁴⁴ SOsH H H SOsH

_{1 a} 245 H SOsH SOsH H

Methyl F Methyl 3-Phenyl sulfonamide

1a ²⁴⁶ SOsH H H SOsH

1a ²⁴⁷ H SOsH SOsH H

Methyl F Methyl 2-Amino phenyl

1a ²⁴⁸ SOsH H H SOsH

1a ²⁴⁹ H SOsH SOsH H

Methyl F Methyl 3-Amino phenyl

1a ²⁵⁰ SOsH H H SOsH

_{1 a} 251 H SOsH SOsH H

Methyl F Methyl 4-Amino phenyl

_{1 a} 252 SOsH H H SOsH

_{1 a} 253 H SOsH SOsH H

NHCOCHs OMe Methyl 2-Methoxy ethyl

_{1 a} 254 SOsH H H SOsH

_{1 a} 255 H SOsH SOsH H

NHCOCHs OMe Methyl 3-Methoxy propyl

_{1 a} 256 SOsH H H SOsH

_{1 a} 257 H SOsH SOsH H

_{1 a} 258 SOsH H H SOsH NHCOCHs OMe Methyl 2-Hydroxy ethyl

_{1 a} 259 H SOsH SOsH H

NHCOCHs OMe Methyl 2-Fluoro ethyl

_{1 a} 260 SOsH H H SOsH

_{1 a} 261 H SOsH SOsH H

NHCOCHs OMe Methyl 2-Chloro ethyl

_{1 a} 262 SOsH H H SOsH

_{1 a} 263 H SOsH SOsH H

NHCOCHs OMe Methyl 3-Chloro propyl

_{1 g} 264 SOsH H H SOsH

_{1 a} 265 H SOsH SOsH H

NHCOCHs OMe Methyl 2-Ethyl hexyl

_{1 g} 266 SOsH H H SOsH

_{1 g} 267 H SOsH SOsH H 2-(2-Hydroxy-ethyl

NHCOCHs OMe Methyl

_{1 a} 268 SOsH H H SOsH sulfanyl)-ethyl

_{1 g} 269 H SOsH SOsH H

NHCOCHs OMe Methyl 2-(2-Hydroxyethoxy)ethyl

_{1 a} 270 SOsH H H SOsH

1a ²⁷¹ H SOsH SOsH H

NHCOCHs OMe Methyl 3-(4-Hydroxybutoxy)propyl

1a ²⁷² SOsH H H SOsH

_{1 a} 273 H SOsH SOsH H 4-(2-Hydroxyethane-

NHCOCHs OMe Methyl

1a ²⁷⁴ SOsH H H SOsH sulfonyl)phenyl

_{1 a} 275 H SOsH SOsH H

NHCOCHs OMe Methyl 3-lsopropoxy-propyl

_{1 g} 276 SOsH H H SOsH

1a ²⁷⁷ H SOsH SOsH H

_{1 a} 278 SOsH H H SOsH NHCOCHs OMe Methyl 3-Ethoxy-propyl

_{1 g} 279 H SOsH SOsH H

NHCOCH3 OMe Methyl 3-Ethoxy butyl

_{1 a} 280 SOsH H H SOsH

_{1 a} 281 H SOsH SOsH H

NHCOCH3 OMe Methyl 3-Methyl phenyl

_{1 a} 282 SOsH H H SOsH

_{1 a} 283 H SOsH SOsH H

NHCOCH3 OMe Methyl 2-Methyl phenyl

_{1 a} 284 SOsH H H SOsH

_{1 a} 285 H SOsH SOsH H

NHCOCH3 OMe Methyl 4-Methyl phenyl

_{1 g} 286 SOsH H H SOsH

_{1 g} 287 H SOsH SOsH H

NHCOCH3 OMe Methyl 2-Methoxy phenyl

_{1 g} 288 SOsH H H SOsH

_{1 g} 289 H SOsH SOsH H

NHCOCH3 OMe Methyl 3-Methoxy phenyl

_{1 a} 290 SOsH H H SOsH

_{1 g} 291 H SOsH SOsH H

NHCOCH3 OMe Methyl 4-Methoxy phenyl

_{1 g} 292 SOsH H H SOsH

_{1 a} 293 H SOsH SOsH H

NHCOCH3 OMe Methyl 2-Chloro phenyl

_{1 g} 294 SOsH H H SOsH

_{1 a} 295 H SOsH SOsH H

NHCOCH3 OMe Methyl 3-Chloro phenyl

_{1 g} 296 SOsH H H SOsH

_{1 g} 297 H SOsH SOsH H

_{1 g} 298 SOsH H H SOsH NHCOCH3 OMe Methyl 4-Chloro phenyl

_{1 a} 299 H SOsH SOsH H

NHCOCHs OMe Methyl 2-Fluoro phenyl

1a ³⁰⁰ SOsH H H SOsH

1a ³⁰¹ H SOsH SOsH H

NHCOCHs OMe Methyl 3-Fluoro phenyl

1a ³⁰² SOsH H H SOsH

1a ³⁰³ H SOsH SOsH H

NHCOCHs OMe Methyl 4-Fluoro phenyl

1a ³⁰⁴ SOsH H H SOsH

1 a ³⁰⁵ H SOsH SOsH H

NHCOCHs OMe Methyl 3-Phenyl sulfonamide

1a ³⁰⁶ SOsH H H SOsH

1a ³⁰⁷ H SOsH SOsH H

NHCOCHs OMe Methyl 2-Amino phenyl

1a ³⁰⁸ SOsH H H SOsH

1a ³⁰⁹ H SOsH SOsH H

NHCOCHs OMe Methyl 3-Amino phenyl

1a ³¹⁰ SOsH H H SOsH

1a ³¹¹ H SOsH SOsH H

NHCOCHs OMe Methyl 4-Amino phenyl

1a ³¹² SOsH H H SOsH

As outlined above another preferred embodiment of the present invention are dyes of formula (1 ) as shown above, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M

- whereby at least two of them are SO3M,

X is oxygen or sulphur,

R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ independent of each other is hydrogen, alkyl, alkyl substituted, alkyl chain interrupted by one or two heteroatoms, alkoxy, alkoxy substituted, halogen, trifluoromethyl, cycloalkyl, heterocycloalkyl, cyano, acyloxy, alkylcarbonyl, acylamino, alkylsulfonylamino, amino, monoalkyl-amino, monocycloalkyl-amino, dialkyl-amino, di(cyclo)alkyl-amino, alkylthio, alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, -SO3M or alkylureido,

R ¹³ and R ²⁰ independent of each other is amino,

R ¹⁴ and R ²¹ independent of each other is hydrogen, alkyl, cycloalkyl, trifluoromethyl, alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino, hydroxyl, monocycloalkyl- amino, monoalkyl-amino, di(cyclo)alkyl-amino, dialkyl-amino, monoaryl-amino, diaryl- amino, monocycloalkylmonoarylamino, monoalkyl monoaryl amino, alkylthio, arylthio, alkylcarbonyl, alkylsulfonyl

or

is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido and phenylureido,

R ¹⁵ and R ²² independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkyl- aminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl, or

alkyi interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur

or

alkyi substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo- alkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N- monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkyl- ureido, phenyilureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbo- nyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl- carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamo- yl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N- monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamo- yl and SO ₃ M

or

alkyi interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl- amino, Ν,Ν-dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl- amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl- monocycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycar- bonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N- monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, Ν,Ν-dicycloalkyl-sulfamoyl, N,N-dialkyl- sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N- monoarylsulfannoyl, N-monoalkyl-N-nnonoarylsulfannoyl and SO3M

or

aryl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo- alkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-mono- aryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamo- yl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N- diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl- carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N- dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamo-

M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation,

and

the dyes of formula (1 ) have two to six sulfonic acid groups. Preferred are dyes of formula (1 b)

wherein R ^{1 b} , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b and R ^8b independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M

- whereby at least two of them are SO3M,

X is oxygen,

R ^9b , R ^10b , R ^16b and R ^17b independent of each other is hydrogen, alkyl, alkyl substituted, alkyl chain interrupted by one or two heteroatoms, alkoxy, alkoxy substituted, halogen, trifluoromethyl, cycloalkyi, heterocycloalkyi, cyano, acyloxy, alkylcarbonyl, acylamino, alkylsulfonylamino, amino, monoalkyl-annino, monocyclo- alkyl-amino, dialkyl-amino, di(cyclo)alkyl-amino, alkylthio, alkylsulfonyl, alkoxycarbo- nyl, carbamoyl, sulfamoyl, ureido, -SO3M or alkylureido,

R ^13b and R ^20b independent of each other is amino, R ^14b and R ^{21 b} independent of each other is hydrogen, alkyl, cycloalkyi, trifluoromethyl, alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino, hydroxyl, monocycloalkyl- amino, monoalkyl-annino, di(cyclo)alkyl-amino, dialkyl-amino, monoaryl-amino, diaryl- amino, monocycloalkylmonoarylamino, monoalkyl monoaryl amino, alkylthio, arylthio, alkylcarbonyl, alkylsulfonyl

or

is alkyi substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido and phenylureido, R ^15b and R ^22b independent of each other is hydrogen, alkyi, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkyl- aminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl, or

alkyi interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur

or

alkyi substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo- alkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-mono- aryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyilureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamo- yl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N- diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl- carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N- dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamo- yl and SO ₃ M

or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl- amino, Ν,Ν-dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl- amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl- monocycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N- alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N- monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocyclo- alkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N- monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, Ν,Ν-dicycloalkyl-sulfamoyl, N,N- dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N- monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO3M

or

aryl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo- alkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-mono- aryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamo- yl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N- diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl- carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N- dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamo- yl and SO ₃ M and M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.

Especially preferred are dyes of formula (1 b), wherein:

R ^{1 b} and R ^6b is SO ₃ M and R ^2b and R ^5b is hydrogen,

or R ^{1 b} and R ^6b is hydrogen and R ^2b and R ^5b is SO ₃ M,

R ^3b , R ^4b , R ^7b and R ^8b is hydrogen,

R ^9b , R ^10b , R ^16b and R ^17b independent of each other is hydrogen, (Ci-C )-alkyl, (Ci-C )- alkoxy, halogen, trifluoromethyl, -SO3M or (Ci-C ₄ )-acylamino,

R ^13b and R ^20b independent from each other is amino,

R ^14b and R ^{21 b} independent of each other is alkyl, cycloalkyl, trifluoromethyl, cyano, carbamoyl, alkoxycarbonyl, COOM, alkylcarbonyl

or

is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, alkoxy, halogen, cyano, COOM, alkoxycarbonyl, acyloxy and carbamoyl,

R ^15b and R ^22b independent of each other is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1 -ethylproyl, 1 ,2-dimethylpropyl, tert-butyl, 3- methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2- hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3- chloropropyl, 2-ethylhexyl, 2-(2-hydroxyethylsulfanyl)-ethyl, 4-(2-hydroxyethane- sulfonyl)phenyl, 2-(2-hydroxyethoxy)ethyl, 3-(4-hydroxybutoxy)propyl, 3-(2-phenoxy- ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl, 3-ethoxybutyl, phenyl, 3- methylphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-methoxyphenyl, 3- methoxyphenyl, 4-methoxyphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2- fluorophenyl, 3-fluorophenyl, 4-fluorophenyl or 3-phenylsulfonamide and M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation. Examples of particularly preferred dyes of formula (1 b) are the compounds of the formulae (1 b ¹ to 1 b ³¹² ) mixtures and/or tautomers thereof, wherein R ³ , R ⁴ , R ⁷ and R ⁸ is hydrogen, R ¹³ and R ²⁰ is amino and the other R ^x are as given in Table 2:

Table 2:

_{1 b} 19 H SOsH SOsH H

Methyl Methyl Methyl 3-Methylcyclohexyl

_{1 b} 20 SOsH H H SOsH

1b ²¹ H SOsH SOsH H

Methyl Methyl Methyl Isopropyl

1b ²² SOsH H H SOsH

1b ²³ H SOsH SOsH H

Methyl Methyl Methyl Sec-butyl

1b ²⁴ SOsH H H SOsH

1b ²⁵ H SOsH SOsH H

Methyl Methyl Methyl 2-Methyl butyl

_{1 b} 26 SOsH H H SOsH

1b ²⁷ H SOsH SOsH H

Methyl Methyl Methyl 1 -Ethyl propyl

_{1 b} 28 SOsH H H SOsH

_{1 b} 29 H SOsH SOsH H

Methyl Methyl Methyl 1 ,2-Dimethyl propyl

_{1 b} 30 SOsH H H SOsH

1b ³¹ H SOsH SOsH H

Methyl Methyl Methyl Tert-butyl

1b ³² SOsH H H SOsH

_{1 b} 33 H SOsH SOsH H

Methyl Methyl Methyl 3-Methyl butyl

1b ³⁴ SOsH H H SOsH

_{1 b} 35 H SOsH SOsH H

Methyl Methyl Methyl Pentan-2-yl

_{1 b} 36 SOsH H H SOsH

1b ³⁷ H SOsH SOsH H

_{1 b} 38 SOsH H H SOsH Methyl Methyl Methyl 2-Ethylhexyl

_{1 b} 39 H SOsH SOsH H

Methyl Methyl Methyl 2,2-Dinnethyl propyl

_{1 b} 40 SOsH H H SOsH

1b ⁴¹ H SOsH SOsH H

Methyl Methyl Methyl Phenyl

1b ⁴² SOsH H H SOsH

1b ⁴³ H SOsH SOsH H

Methyl Methyl Methyl Benzyl

_{1 b} 44 SOsH H H SOsH

1b ⁴⁵ H SOsH SOsH H

Methyl F Methyl Methyl

_{1 b} 46 SOsH H H SOsH

1b ⁴⁷ H SOsH SOsH H

Methyl F Methyl Ethyl

_{1 b} 48 SOsH H H SOsH

_{1 b} 49 H SOsH SOsH H

Methyl F Methyl Propyl

_{1 b} 50 SOsH H H SOsH

1b ⁵¹ H SOsH SOsH H

Methyl F Methyl Butyl

1b ⁵² SOsH H H SOsH

_{1 b} 53 H SOsH SOsH H

Methyl F Methyl Pentyl

1b ⁵⁴ SOsH H H SOsH

_{1 b} 55 H SOsH SOsH H

Methyl F Methyl Cyclobutyl

_{1 b} 56 SOsH H H SOsH

1b ⁵⁷ H SOsH SOsH H

_{1 b} 58 SOsH H H SOsH Methyl F Methyl Cyclopentyl

_{1 b} 59 H SOsH SOsH H

Methyl F Methyl Cyclohexyl

_{1 b} 60 SOsH H H SOsH

_{1 b} 61 H SOsH SOsH H

Methyl F Methyl 2-Methyl cyclohexyl

_{1 b} 62 SOsH H H SOsH

_{1 b} 63 H SOsH SOsH H

Methyl F Methyl 3-Methyl cyclohexyl

_{1 b} 64 SOsH H H SOsH

_{1 b} 65 H SOsH SOsH H

Methyl F Methyl Isopropyl

_{1 b} 66 SOsH H H SOsH

_{1 b} 67 H SOsH SOsH H

Methyl F Methyl Sec-butyl

_{1 b} 68 SOsH H H SOsH

_{1 b} 69 H SOsH SOsH H

Methyl F Methyl 2-Methyl butyl

_{1 b} 70 SOsH H H SOsH

1b ⁷¹ H SOsH SOsH H

Methyl F Methyl 1 -Ethylpropyl

1b ⁷² SOsH H H SOsH

1b ⁷³ H SOsH SOsH H

Methyl F Methyl 1 ,2-Dimethyl propyl

1b ⁷⁴ SOsH H H SOsH

1b ⁷⁵ H SOsH SOsH H

Methyl F Methyl Tert-butyl

_{1 b} 76 SOsH H H SOsH

1b ⁷⁷ H SOsH SOsH H

_{1 b} 78 SOsH H H SOsH Methyl F Methyl 3-Methyl butyl

_{1 b} 79 H SOsH SOsH H

Methyl F Methyl Pentan-2-yl

_{1 b} 80 SOsH H H SOsH

_{1 b} 81 H SOsH SOsH H

Methyl F Methyl 2-Ethylhexyl

_{1 b} 82 SOsH H H SOsH

_{1 b} 83 H SOsH SOsH H

Methyl F Methyl 2,2-Dinnethyl propyl

_{1 b} 84 SOsH H H SOsH

_{1 b} 85 H SOsH SOsH H

Methyl F Methyl Phenyl

_{1 b} 86 SOsH H H SOsH

_{1 b} 87 H SOsH SOsH H

Methyl F Methyl Benzyl

_{1 b} 88 SOsH H H SOsH

_{1 b} 89 H SOsH SOsH H

NHCOCH3 OMe Methyl Methyl

_{1 b} 90 SOsH H H SOsH

_{1 b} 91 H SOsH SOsH H

NHCOCH3 OMe Methyl Ethyl

_{1 b} 92 SOsH H H SOsH

_{1 b} 93 H SOsH SOsH H

NHCOCH3 OMe Methyl Propyl

_{1 b} 94 SOsH H H SOsH

_{1 b} 95 H SOsH SOsH H

NHCOCH3 OMe Methyl Butyl

_{1 b} 96 SOsH H H SOsH

_{1 b} 97 H SOsH SOsH H

_{1 b} 98 SOsH H H SOsH NHCOCH3 OMe Methyl Pentyl

1b" H SOsH SOsH H

NHCOCH3 OMe Methyl Cyclobutyl

_{1 b} 100 SOsH H H SOsH

_{1 b} 101 H SOsH SOsH H

NHCOCH3 OMe Methyl Cyclopentyl

_{1 b} 102 SOsH H H SOsH

_{1 b} 103 H SOsH SOsH H

NHCOCH3 OMe Methyl Cyclohexyl

_{1 b} 104 SOsH H H SOsH

_{1 b} 105 H SOsH SOsH H

NHCOCH3 OMe Methyl 2-Methyl cyclohexyl

_{1 b} 106 SOsH H H SOsH

_{1 b} 107 H SOsH SOsH H

NHCOCH3 OMe Methyl 3-Methyl cyclohexyl

_{1 b} 108 SOsH H H SOsH

_{1 b} 109 H SOsH SOsH H

NHCOCH3 OMe Methyl Isopropyl

_{1 b} 110 SOsH H H SOsH

_{1 b} 111 H SOsH SOsH H

NHCOCH3 OMe Methyl Sec-butyl

_{1 b} 112 SOsH H H SOsH

_{1 b} 113 H SOsH SOsH H

NHCOCH3 OMe Methyl 2-Methyl butyl

_{1 b} 114 SOsH H H SOsH

_{1 b} 115 H SOsH SOsH H

NHCOCH3 OMe Methyl 1 -Ethylpropyl

_{1 b} 116 SOsH H H SOsH

_{1 b} 117 H SOsH SOsH H

_{1 b} 118 SOsH H H SOsH NHCOCH3 OMe Methyl 1 ,2-Dimethyl propyl

_{1 b} 119 H SOsH SOsH H

NHCOCH3 OMe Methyl Tert-butyl

_{1 b} 120 SOsH H H SOsH

_{1 b} 121 H SOsH SOsH H

NHCOCH3 OMe Methyl 3-Methyl butyl

_{1 b} 122 SOsH H H SOsH

_{1 b} 123 H SOsH SOsH H

NHCOCH3 OMe Methyl Pentan-2-yl

_{1 b} 124 SOsH H H SOsH

_{1 b} 125 H SOsH SOsH H

NHCOCH3 OMe Methyl 2-Ethylhexyl

_{1 b} 126 SOsH H H SOsH

_{1 b} 127 H SOsH SOsH H

NHCOCH3 OMe Methyl 2,2-Dinnethyl propyl

_{1 b} 128 SOsH H H SOsH

_{1 b} 129 H SOsH SOsH H

NHCOCH3 OMe Methyl Phenyl

_{1 b} 130 SOsH H H SOsH

_{1 b} 131 H SOsH SOsH H

NHCOCH3 OMe Methyl Benzyl

_{1 b} 132 SOsH H H SOsH

_{1 b} 133 H SOsH SOsH H

Methyl Methyl Methyl 2-Methoxy ethyl

_{1 b} 134 SOsH H H SOsH

_{1 b} 135 H SOsH SOsH H

Methyl Methyl Methyl 3-Methoxy propyl

_{1 b} 136 SOsH H H SOsH

_{1 b} 137 H SOsH SOsH H

_{1 b} 138 SOsH H H SOsH Methyl Methyl Methyl 2-Hydroxy ethyl

_{1 b} 139 H SOsH SOsH H

Methyl Methyl Methyl 2-Fluoroethyl

_{1 b} 140 SOsH H H SOsH

_{1 b} 141 H SOsH SOsH H

Methyl Methyl Methyl 2-Chloroethyl

_{1 b} 142 SOsH H H SOsH

_{1 b} 143 H SOsH SOsH H

Methyl Methyl Methyl 3-Chloropropyl

_{1 b} 144 SOsH H H SOsH

_{1 b} 145 H SOsH SOsH H

Methyl Methyl Methyl 2-Ethylhexyl

_{1 b} 146 SOsH H H SOsH

_{1 b} 147 H SOsH SOsH H 2-(2-Hydroxy ethyl sulfanyl)-

Methyl Methyl Methyl

_{1 b} 148 SOsH H H SOsH ethyl

_{1 b} 149 H SOsH SOsH H

Methyl Methyl Methyl 2-(2-Hydroxyethoxy)ethyl

_{1 b} 150 SOsH H H SOsH

_{1 b} 151 H SOsH SOsH H

Methyl Methyl Methyl 3-(4-Hydroxybutoxy)propyl

_{1 b} 152 SOsH H H SOsH

_{1 b} 153 H SOsH SOsH H 4-(2-Hydroxyethanesulfonyl)-

Methyl Methyl Methyl

_{1 b} 154 SOsH H H SOsH phenyl

_{1 b} 155 H SOsH SOsH H

Methyl Methyl Methyl 3-lsopropoxypropyl

_{1 b} 156 SOsH H H SOsH

_{1 b} 157 H SOsH SOsH H

_{1 b} 158 SOsH H H SOsH Methyl Methyl Methyl 3-Ethoxypropyl

_{1 b} 159 H SOsH SOsH H

Methyl Methyl Methyl 4-Ethoxybutyl

_{1 b} 160 SOsH H H SOsH

_{1 b} 161 H SOsH SOsH H

Methyl Methyl Methyl 3-Methyl phenyl

_{1 b} 162 SOsH H H SOsH

_{1 b} 163 H SOsH SOsH H

Methyl Methyl Methyl 2-Methyl phenyl

_{1 b} 164 SOsH H H SOsH

_{1 b} 165 H SOsH SOsH H

Methyl Methyl Methyl 4-Methyl phenyl

_{1 b} 166 SOsH H H SOsH

_{1 b} 167 H SOsH SOsH H

Methyl Methyl Methyl 2-Methoxy phenyl

_{1 b} 168 SOsH H H SOsH

_{1 b} 169 H SOsH SOsH H

Methyl Methyl Methyl 3-Methoxy phenyl

_{1 b} 170 SOsH H H SOsH

_{1 b} 171 H SOsH SOsH H

Methyl Methyl Methyl 4-Methoxy phenyl

_{1 b} 172 SOsH H H SOsH

_{1 b} 173 H SOsH SOsH H

Methyl Methyl Methyl 2-Chloro phenyl

_{1 b} 174 SOsH H H SOsH

_{1 b} 175 H SOsH SOsH H

Methyl Methyl Methyl 3-Chloro phenyl

_{1 b} 176 SOsH H H SOsH

_{1 b} 177 H SOsH SOsH H

_{1 b} 178 SOsH H H SOsH Methyl Methyl Methyl 4-Chloro phenyl

_{1 b} 179 H SOsH SOsH H

Methyl Methyl Methyl 2-Fluoro phenyl

_{1 b} 180 SOsH H H SOsH

_{1 b} 181 H SOsH SOsH H

Methyl Methyl Methyl 3-Fluoro phenyl

_{1 b} 182 SOsH H H SOsH

_{1 b} 183 H SOsH SOsH H

Methyl Methyl Methyl 4-Fluoro phenyl

_{1 b} 184 SOsH H H SOsH

_{1 b} 185 H SOsH SOsH H

Methyl Methyl Methyl 3-Phenyl sulfonamide

_{1 b} 186 SOsH H H SOsH

_{1 b} 187 H SOsH SOsH H

Methyl Methyl Methyl 2-Amino phenyl

_{1 b} 188 SOsH H H SOsH

_{1 b} 189 H SOsH SOsH H

Methyl Methyl Methyl 3-Amino phenyl

_{1 b} 190 SOsH H H SOsH

_{1 b} 191 H SOsH SOsH H

Methyl Methyl Methyl 4-Amino phenyl

_{1 b} 192 SOsH H H SOsH

_{1 b} 193 H SOsH SOsH H

Methyl F Methyl 2-Methoxy ethyl

_{1 b} 194 SOsH H H SOsH

_{1 b} 195 H SOsH SOsH H

Methyl F Methyl 3-Methoxy propyl

_{1 b} 196 SOsH H H SOsH

_{1 b} 197 H SOsH SOsH H

_{1 b} 198 SOsH H H SOsH Methyl F Methyl 2-Hydroxy ethyl

_{1 b} 199 H SOsH SOsH H

Methyl F Methyl 2-Fluoro ethyl

_{1 b} 200 SOsH H H SOsH

_{1 b} 201 H SOsH SOsH H

Methyl F Methyl 2-Chloro ethyl

_{1 b} 202 SOsH H H SOsH

_{1 b} 203 H SOsH SOsH H

Methyl F Methyl 3-Chloro propyl

_{1 b} 204 SOsH H H SOsH

_{1 b} 205 H SOsH SOsH H

Methyl F Methyl 2-Ethyl hexyl

_{1 b} 206 SOsH H H SOsH

_{1 b} 207 H SOsH SOsH H 2-(2-Hydroxy-ethyl sulfanyl)-

Methyl F Methyl

_{1 b} 208 SOsH H H SOsH ethyl

_{1 b} 209 H SOsH SOsH H

Methyl F Methyl 2-(2-Hydroxyethoxy)ethyl

_{1 b} 210 SOsH H H SOsH

_{1 b} 211 H SOsH SOsH H

Methyl F Methyl 3-(4-Hydroxybutoxy)propyl

_{1 b} 212 SOsH H H SOsH

_{1 b} 213 H SOsH SOsH H 4-(2-Hydroxyethanesulfonyl)-

Methyl F Methyl

_{1 b} 214 SOsH H H SOsH phenyl

_{1 b} 215 H SOsH SOsH H

Methyl F Methyl 3-lsopropoxy-propyl

_{1 b} 216 SOsH H H SOsH

_{1 b} 217 H SOsH SOsH H

_{1 b} 218 SOsH H H SOsH Methyl F Methyl 3-Ethoxy-propyl

_{1 b} 219 H SOsH SOsH H

Methyl F Methyl 4-Ethoxy butyl

_{1 b} 220 SOsH H H SOsH

_{1 b} 221 H SOsH SOsH H

Methyl F Methyl 3-Methyl phenyl

_{1 b} 222 SOsH H H SOsH

_{1 b} 223 H SOsH SOsH H

Methyl F Methyl 2-Methyl phenyl

_{1 b} 224 SOsH H H SOsH

_{1 b} 225 H SOsH SOsH H

Methyl F Methyl 4-Methyl phenyl

_{1 b} 226 SOsH H H SOsH

_{1 b} 227 H SOsH SOsH H

Methyl F Methyl 2-Methoxy phenyl

_{1 b} 228 SOsH H H SOsH

_{1 b} 229 H SOsH SOsH H

Methyl F Methyl 3-Methoxy phenyl

_{1 b} 230 SOsH H H SOsH

_{1 b} 231 H SOsH SOsH H

Methyl F Methyl 4-Methoxy phenyl

_{1 b} 232 SOsH H H SOsH

_{1 b} 233 H SOsH SOsH H

Methyl F Methyl 2-Chloro phenyl

_{1 b} 234 SOsH H H SOsH

_{1 b} 235 H SOsH SOsH H

Methyl F Methyl 3-Chloro phenyl

_{1 b} 236 SOsH H H SOsH

_{1 b} 237 H SOsH SOsH H

_{1 b} 238 SOsH H H SOsH Methyl F Methyl 4-Chloro phenyl

_{1 b} 239 H SOsH SOsH H

Methyl F Methyl 2-Fluoro phenyl

_{1 b} 240 SOsH H H SOsH

_{1 b} 241 H SOsH SOsH H

Methyl F Methyl 3-Fluoro phenyl

_{1 b} 242 SOsH H H SOsH

_{1 b} 243 H SOsH SOsH H

Methyl F Methyl 4-Fluoro phenyl

_{1 b} 244 SOsH H H SOsH

_{1 b} 245 H SOsH SOsH H

Methyl F Methyl 3-Phenyl sulfonamide

_{1 b} 246 SOsH H H SOsH

_{1 b} 247 H SOsH SOsH H

Methyl F Methyl 2-Amino phenyl

_{1 b} 248 SOsH H H SOsH

_{1 b} 249 H SOsH SOsH H

Methyl F Methyl 3-Amino phenyl

_{1 b} 250 SOsH H H SOsH

_{1 b} 251 H SOsH SOsH H

Methyl F Methyl 4-Amino phenyl

_{1 b} 252 SOsH H H SOsH

_{1 b} 253 H SOsH SOsH H

NHCOCH3 OMe Methyl 2-Methoxy ethyl

_{1 b} 254 SOsH H H SOsH

_{1 b} 255 H SOsH SOsH H

NHCOCH3 OMe Methyl 3-Methoxy propyl

_{1 b} 256 SOsH H H SOsH

_{1 b} 257 H SOsH SOsH H

_{1 b} 258 SOsH H H SOsH NHCOCH3 OMe Methyl 2-Hydroxy ethyl

_{1 b} 259 H SOsH SOsH H

NHCOCH3 OMe Methyl 2-Fluoro ethyl

_{1 b} 260 SOsH H H SOsH

_{1 b} 261 H SOsH SOsH H

NHCOCH3 OMe Methyl 2-Chloro ethyl

_{1 b} 262 SOsH H H SOsH

_{1 b} 263 H SOsH SOsH H

NHCOCH3 OMe Methyl 3-Chloro propyl

_{1 b} 264 SOsH H H SOsH

_{1 b} 265 H SOsH SOsH H

NHCOCH3 OMe Methyl 2-Ethyl hexyl

_{1 b} 266 SOsH H H SOsH

_{1 b} 267 H SOsH SOsH H 2-(2-Hydroxy-ethyl sulfanyl)-

NHCOCH3 OMe Methyl

_{1 b} 268 SOsH H H SOsH ethyl

_{1 b} 269 H SOsH SOsH H

NHCOCH3 OMe Methyl 2-(2-Hydroxyethoxy)ethyl

_{1 b} 270 SOsH H H SOsH

_{1 b} 271 H SOsH SOsH H

NHCOCH3 OMe Methyl 3-(4-Hydroxybutoxy)propyl

_{1 b} 272 SOsH H H SOsH

_{1 b} 273 H SOsH SOsH H 4-(2-Hydroxyethanesulfonyl)-

NHCOCH3 OMe Methyl

_{1 b} 274 SOsH H H SOsH phenyl

_{1 b} 275 H SOsH SOsH H

NHCOCH3 OMe Methyl 3-lsopropoxy-propyl

_{1 b} 276 SOsH H H SOsH

_{1 b} 277 H SOsH SOsH H

_{1 b} 278 SOsH H H SOsH NHCOCH3 OMe Methyl 3-Ethoxy-propyl

_{1 b} 279 H SOsH SOsH H

NHCOCH3 OMe Methyl 4-Ethoxy butyl

_{1 b} 280 SOsH H H SOsH

_{1 b} 281 H SOsH SOsH H

NHCOCH3 OMe Methyl 3-Methyl phenyl

_{1 b} 282 SOsH H H SOsH

_{1 b} 283 H SOsH SOsH H

NHCOCH3 OMe Methyl 2-Methyl phenyl

_{1 b} 284 SOsH H H SOsH

_{1 b} 285 H SOsH SOsH H

NHCOCH3 OMe Methyl 4-Methyl phenyl

_{1 b} 286 SOsH H H SOsH

_{1 b} 287 H SOsH SOsH H

NHCOCH3 OMe Methyl 2-Methoxy phenyl

_{1 b} 288 SOsH H H SOsH

_{1 b} 289 H SOsH SOsH H

NHCOCH3 OMe Methyl 3-Methoxy phenyl

_{1 b} 290 SOsH H H SOsH

_{1 b} 291 H SOsH SOsH H

NHCOCH3 OMe Methyl 4-Methoxy phenyl

_{1 b} 292 SOsH H H SOsH

_{1 b} 293 H SOsH SOsH H

NHCOCH3 OMe Methyl 2-Chloro phenyl

_{1 b} 294 SOsH H H SOsH

_{1 b} 295 H SOsH SOsH H

NHCOCH3 OMe Methyl 3-Chloro phenyl

_{1 b} 296 SOsH H H SOsH

_{1 b} 297 H SOsH SOsH H

_{1 b} 298 SOsH H H SOsH NHCOCH3 OMe Methyl 4-Chloro phenyl

_{1 b} 299 H SOsH SOsH H

NHCOCHs OMe Methyl 2-Fluoro phenyl

1 b ³⁰⁰ SOsH H H SOsH

_{1 b} 301 H SOsH SOsH H

NHCOCHs OMe Methyl 3-Fluoro phenyl

_{1 b} 302 SOsH H H SOsH

1 b ³⁰³ H SOsH SOsH H

NHCOCHs OMe Methyl 4-Fluoro phenyl

_{1 b} 304 SOsH H H SOsH

1 b ³⁰⁵ H SOsH SOsH H

NHCOCHs OMe Methyl 3-Phenyl sulfonamide

1 b ³⁰⁶ SOsH H H SOsH

_{1 b} 307 H SOsH SOsH H

NHCOCHs OMe Methyl 2-Amino phenyl

1 b ³⁰⁸ SOsH H H SOsH

1 b ³⁰⁹ H SOsH SOsH H

NHCOCHs OMe Methyl 3-Amino phenyl

_{1 b} 310 SOsH H H SOsH

_{1 b} 31 1 H SOsH SOsH H

NHCOCHs OMe Methyl 4-Amino phenyl

_{1 b} 312 SOsH H H SOsH

The present invention also provides a process for the production of dyes of formula (1 ) and mixtures thereof comprising

a) diazotization of a compound of formula (2)

wherein R ¹ to R ⁸ are defined as above,

b) reacting the diazonium salt obtained in a) with compounds of formula (3) and (4)

wherein R ⁹ to R ¹² and R ¹⁶ to R ¹⁹ are defined as above, to give an intermediate formula (5)

c) diazotizing the intermediate of formula (5) and

d) reacting the diazonium salt(s) obtained in c) with compounds of formula (6) and (7) or mixtures thereof wherein R ¹³ to R ¹⁵ and R ²⁰ to R ²² are defined as above.

The diazotization of the compounds of formula (2) and (5), respectively can be performed by means of diazotization methods that are known to a person skilled in the art, preferably by using sodium nitrite or nitrosylsulfuric acid in acidic medium using inorganic acids such as hydrochloric acid, sulfuric acid or phosphoric acid or mixtures thereof or organic acids such as acetic acid or propionic acid or mixtures thereof. Also mixtures of inorganic acid with organic acids can be advantageously used.

The coupling reaction of the diazonium salts obtained by diazotization of the compound of the formula (2) onto the compounds of formulae (3) and (4) as well as the coupling reaction of the the diazonium salts obtained by diazotization of the compound of the formula (5) onto the compounds of formulae (6) and (7) can likewise be performed by known methods. These reactions can be performed using stoichiometric amounts of the diazocompound, but may also advantageously be performed using a surplus of 5 to 10 % of the diazocompound.

The compounds of the formula (2) are known and commercially available or can be synthesised by means of common chemical reactions known to a person skilled in the art such as the methods disclosed in DE140613C.

The pyrazoles of formula (6) and (7) in which R ¹³ and R ¹⁶ denote hydroxy are commercially available or such pyrazolones can be synthesized via methods dis- closed in the literature such as WO 2010/076553. Pyrazoles of formula (6) and (7) in which R ¹³ and R ¹⁶ are amino groups are commercially available or such aminopyrazoles can be synthesized via methods disclosed in the literature such as US 6,338,741 .

Through analogy, all the pyrazoles that are used in this invention can be synthesized as described.

The dyes of the present invention can be used alone or as a mixture with other dyes according to the present invention and/or other substances.

Thus a chemical composition comprising one or more dye(s) as described above is also an aspect of the present invention.

A chemical composition consisting of two or more dyes as described above forms another preferred aspect of the present invention.

Also an aqueous solution for dying comprising one or more dye(s) as described above forms an aspect of the present invention. The dyes of the present invention are suitable for dyeing and printing of natural, manufactured regenerated, modified or synthetic hydroxyl- amino-, and/or carboxamido-containing fiber materials and their blends by the application methods numerously described in the art for acid dyes. Therefore, the present invention also is directed to a Process for dyeing or printing carboxamido- and/or hydroxyl-containing material, comprising contacting the carboxamido- and/or hydroxyl-containing material with a dye as described above.

The use of a dye as described above, a chemical composition as described above or of an aqueous solution as described above for dying fibers, as well as blends of such fibres selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers and Lyocell fibers forms another aspect of the present invention.

Still another aspect of the present invention is/are: Fiber and blends containing such fiber selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers, and Lyocell fibers comprising one or more dye(s) of the present invention either in chemically and/or physically bound form.

The above-mentioned substrates to be dyed can be present in various forms such as but not limited to yarn, woven fabric, loop-formingly knitted fabric or carpet. For instance in the form of sheetlike structures, such as paper and leather, in the form of films, such as nylon films, or in the form of a bulk mass, for example composed of polyamide and polyurethane, in particular in the form of fibers, for example cellulose fibers. The fibers are preferably textile fibers, for example in the form of woven fabrics or yarns or in the form of hanks or wound packages. The dyes of the present invention and their salts and/or mixtures can be used as a single dyeing colorant in dyeing or printing processes or can be part of a di-, tri- or multi-component combination colorant in dyeing or in printing compositions. The di-, tri- or multi-component shade dyeings show similar fastness level as compared to dyeing performed with a single colorant component.

Dyes of the present invention and their salts or mixtures are highly compatible with other known and/or commercially available acid dyes and they can be used together with such dyes of related chromophores and similar technical performance to obtain specific hues. Similar technical performance includes: comparable build-up, compa- rable fastness properties and comparable exhaustion rates during dyeings.

The dyes according to the invention can be applied to the materials mentioned, especially the fiber materials mentioned, by the application techniques known for water-soluble dyes. This applies to both, dyeing and printing processes.

It applies in particular to the production of dyeings on fiber materials composed of wool or other natural polyamides or of synthetic polyamides and their mixtures with other fiber material. In general, the material to be dyed is introduced into the bath at a temperature of about 40 °C, agitated therein for some time, the dyebath is then adjusted to the desired weakly acidic, preferably weakly acetic acid, pH and the actual dyeing is carried out at a temperature between 60 and 98 °C. However, the dyeings can also be carried out at the boil or in a sealed dyeing apparatus at temperatures of up to 106 °C.

Since the water solubility of the dyes according to the invention is very good, they can also be used with advantage in customary continuous dyeing processes.

The dyes of the present invention can also be used in digital printing processes, in particular in digital textile printing. For this the dyes of the present invention need to be formulated in aqueous inks.

An Ink for digital textile printing, comprising a dye of the present invention is another aspect of the present invention.

The inks of the present invention comprise the dye of the present invention in amounts which preferably range from 0.1 to 50 % by weight, more preferably from 0.5 to 30 % by weight and most preferably from 1 to 15 % by weight, based on the total weight of the ink.

If desired the inks may contain further dyes used in digital printing in addition to the one or more dyes of the present invention.

For the inks of the present invention to be used in the continuous flow process, a conductivity of 0.5 to 25 mS/m can be set by adding an electrolyte. Useful electrolytes include for example lithium nitrate and potassium nitrate. The inks of the present invention may include organic solvents at a total level of 1 to 50 % by weight and preferably 5 to 30 % by weight. Suitable organic solvents are for example alcohols, for example methanol, ethanol, 1 -propanol, isopropanol, 1 -butanol, tert-butanol, pentyl alcohol, polyhydric alcohols for example: 1 ,2-ethanediol, 1 ,2,3-propanetriol, butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,2-propanediol, 2,3-propanediol, pentanediol, 1 ,4-pentanediol, 1 ,5-pentanediol, hexanediol, D,L-1 ,2-hexanediol, 1 ,6- hexanediol, 1 ,2,6-hexanetriol, 1 ,2-octanediol, polyalkylene glycols, for example: polyethylene glycol, polypropylene glycol, alkylene glycols having 1 to 8 alkylene groups, for example: monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, thioglycol, thiodiglycol, butyltriglycol, hexylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, low alkyl ethers of polyhydric alcohols, for example: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, tripropylene glycol isopropyl ether, polyalkylene glycol ethers, such as for example: polyethylene glycol monomethyl ether, polypropylene glycol glycerol ether, polyethylene glycol tridecyl ether, polyethylene glycol nonylphenyl ether, amines, such as for example: methylamine, ethylamine, triethylamine, diethylamine, dimethylamine, trimethylamine, dibutylamine, diethanolamine, triethanolamine, N-acetylethanolamine, N-formylethanolamine, ethylenediamine, urea derivatives, such as for example: urea, thiourea, N-methylurea, Ν,Ν'-epsilon dimethylurea, ethyleneurea, 1 ,1 ,3,3-tetramethylurea, amides, such as for example: dimethylformamide, dimethylacetamide, acetamide, ketones or keto alcohols, such as for example: acetone, diacetone alcohol, cyclic ethers, such as for example: tetrahydrofuran, trimethylolethane, trimethylolpropane, 2-butoxyethanol, benzyl alcohol, 2-butoxyethanol, gamma butyrolactone, epsilon-caprolactam, further sulfolane, dimethylsulfolane, methylsulfolane, 2,4-dimethylsulfolane, dimethyl sulfone, butadiene sulfone, dimethyl sulfoxide, dibutyl sulfoxide, N-cyclohexylpyrrolidone, N-methyl-2-pyrrolidone, N-ethylpyrrolidone, 2-pyrrolidone, 1 -(2-hydroxyethyl)- 2-pyrrolidone, 1 -(3-hydroxypropyl)-2-pyrrolidone, 1 ,3-dimethyl-2-imidazolidinone, 1 ,3-dimethyl-2-innidazolinone, 1 ,3-bismethoxynnethylinnidazolidine, 2-(2- methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol, 2-(2- propoxyethoxy)ethanol, pyridine, piperidine, butyrolactone, trimethyl propane, 1 ,2-dimethoxypropane, dioxane ethyl acetate, ethylenediaminetetraacetate ethyl pentyl ether, 1 ,2-dimethoxypropane and trimethylpropane.

The inks of the present invention may further include customary additives, for example viscosity moderators to set viscosities in the range from 1 .5 to 40.0 mPas in a temperature range from 20 to 50 °C. Preferred inks have a viscosity of 1 .5 to 20 mPas and particularly preferred inks have a viscosity of 1 .5 to 15 mPas.

Useful viscosity moderators include rheological additives, for example:

polyvinylcaprolactam, polyvinylpyrrolidone and their copolymers polyetherpolyol, associative thickeners, polyurea, polyurethane, sodium alginates, modified galactomannans, polyetherurea, polyurethane, nonionic cellulose ethers.

As further additives the inks of the invention may include surface-active substances to set surface tensions of 20 to 65 mlM/m, which are adapted if necessary as a function of the process used (thermal or piezo technology). Useful surface-active substances include for example: all surfactants, preferably nonionic surfactants, butyldiglycol, 1 ,2-hexanediol. The inks of the present invention may further comprise customary additives, for example substances to inhibit fungal and bacterial growth in amounts from 0.01 to 1 % by weight based on the total weight of the ink.

The inks may be prepared in a conventional manner by mixing the components in water.

The inks of the invention are particularly useful in inkjet printing processes for printing a wide variety of pretreated materials, such as silk, leather, wool, polyamide fibers and polyurethanes, and cellulosic fiber materials of any kind. Blend fabrics, for example blends of cotton, silk, wool with polyester fibers or polyamide fibers can similarly be printed.

In contrast to conventional textile printing, where the printing ink already contains all necessary chemicals, in digital or inkjet printing the auxiliaries have to be applied to the textile substrate in a separate pretreatment step.

The pretreatment of the textile substrate, for example cellulose and regenerated cellulose fibers and also silk and wool, is effected with an aqueous alkaline liquor prior to printing. In addition there is a need for thickeners to prevent flowing of the motives when the printing ink is applied, for example sodium alginates, modified polyacrylates or highly etherified galactomannans.

These pretreatment reagents are uniformly applied to the textile substrate in a defined amount using suitable applicators, for example using a 2- or 3-roll pad, contactless spraying technologies, by means of foam application or using appropriately adapted inkjet technologies, and subsequently dried.

The examples below serve to illustrate the invention. Parts and percentages are by weigh unless noted otherwise. The relationship between parts by weight and parts by volume is that of the kilogram to the liter.

Example 1

10.06 g of 5,5'-Diamino-2,2'-ureylene-bis-benzenesulfonic acid were first dissolved in water at slightly acidic pH to give a complete solution. Ice was added to the solution and when the temperature reached 10 to 15 °C, 10.6 ml of 5N of sodium nitrite solution were added dropwise. The reaction mixture was further cooled down to 0 to 8 °C when the mixture was added dropwise into 12.38 g of concentrated HCI with 12 g of ice. A yellow suspension was formed and the reaction mixture was completed within an hour. 6.30 g of 2,5-Dimethyl-phenylamine were added directly into the diazo suspension and stirred. A violet precipitate was observed upon addition. The intermediate precipitate, 4,4'-Bis-(4-amino-2,5-dimethyl-phenylazo)-biphenyl-2,2'-disu lfonic acid obtained was filtered off with suction and washed with organic solvent and dried.

15.22 g of the dried intermediate, 5,5'-Bis-(4-amino-2,5-dimethyl-phenylazo)-2,2'- ureylene-bis-benzenesulfonic acid, were then dissolved in water at slightly acidic pH to give a complete reddish orange solution. Ice was added to the solution and when the temperature reached 10 to 15 °C, 10.1 ml of 5N of sodium nitrite solution were added dropwise. The reaction mixture was further cooled down to 0 to 8 °C when the mixture was added dropwise into concentrated HCI with ice. A violet suspension was formed and the reaction mixture was completed in 90 mins.

The obtained reaction mixture was used in the next step as described below:

5-Methyl-2-phenyl-2H-pyrazol-3-ol was stirred in methanol and adjusted to slightly acidic. The obtained violet suspension was added dropwise into the methanol solution and stirred. Brilliant orange precipitate was observed upon addition. Precipitate obtained was filtered off with suction and washed with brine giving product of the formula 1 a ⁴¹ . The analytic data are consistent with the assigned structure for product 1 a ⁴¹ .

The product dyes the targeted fibre materials in brilliant orange shades.

Through analogy, all the dyes of formulae (1 a ¹ -1 a ³¹² ) can be synthesized according to the method described above.

Dyeing example 1 -1

1 part of the dye 1 a ⁴¹ of this invention was dissolved in 2000 parts of water and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 6 parts of sodium acetate were added. The pH was then adjusted to 5 using acetic acid (80 %ic). The dyebath was heated to 50 °C for 10 minutes and then entered with 100 parts of a woven polyamide-6 fabric. The temperature was raised to 98 °C over the course of 50 minutes and then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 60 °C and removal of the dyed material. The polyamide-6 fabric was washed with hot and cold water, soaped and then spun and dried. The orange dyeings obtained have very good light and wet fastness and also good levelness in the fibre.

Dyeing example 1 -2 1 part of the dye 1 a ⁴¹ of this invention was dissolved in 2000 parts of water and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 6 parts of sodium acetate were added. The pH was then adjusted to 5.5 using acetic acid (80 %ic). The dyebath was heated to 50 °C for 10 minutes and then entered with 100 parts of a woven polyamide-6,6 fabric. The temperature was raised to 120 °C over the course of 50 minutes and then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 60 °C and removal of the dyed material. The polyamide-6,6 fabric was washed with hot and cold water, soaped and then spun and dried. The orange dyeings obtained have very good light and wet fastness and also good levelness in the fibre.

Dyeing example 1 -3 100 parts of polyamide-6 material were padded with a 1000 parts 50 °C liquor solution that consists of 40 parts of the dye 1 a ⁴¹ , 100 parts of urea, 20 parts of a non ionic solubilizer based on butyldiglycol, 20 parts of acetic acid to adjust the pH to 4.0, 10 parts of levelling assistant (based on ethoxylated aminopropyl fatty acid amide) and 810 parts of water. The material was rolled up and placed into a steaming chamber at 85 to 98 °C for 3 to 6 hours. After fixation, the fabric was washed with hot and cold water, soaped and then spun and dried.

The orange dyeings obtained have very good light and wet fastness and also good levelness in the fibre. Dyeing example 1 -4

1 part of the dye 1 a ⁴¹ of this invention was dissolved in 2000 parts of water and 5 parts of sodium sulphate, and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 5 parts of sodium acetate were added. The pH was then adjusted to 4.5 using acetic acid (80 %ic). The dyebath was heated to 50 °C for 10 minutes and then entered with 100 parts of a woven wool fabric. The temperature was raised to 100 °C over the course of 50 minutes and then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 90 °C and removal of the dyed material. The wool fabric was washed with hot and cold water, soaped and then spun and dried.

The orange dyeings obtained have very good light and wet fastness and also good levelness in the fibre.

Dyeing example 1 -5

1 part of the dye 1 a ⁴¹ of this invention was dissolved in 1000 parts of soft water and 7.5 parts of sodium sulphate, and 1 part of a wetting agent (anionic) was added. 100 parts of bleached cotton knitted fabric were added to this solution. The dye bath was then heated up to 98 °C with a gradient of 2 °C/min then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling down to 80 °C. At 80 °C the dyeing was continued for another 20 minutes. The dyed material was then removed and was washed with hot and cold water, soaped and then spun and dried.

The orange dyeings obtained have very good light and wet fastness and also good levelness in the fibre. Dyeing example 1 -6

3 parts of the dye 1 a ⁴¹ of this invention dissolved in 82 parts of deionized water were added into the dyebath with 15 parts of diethylene glycol at 60 °C. On cooling, a yellow printing ink was obtained. The orange printing ink can be used for ink jet printing on paper, polyamide or wool textiles. Dyeing example 1 -7

4 parts of chemically bleached (pine wood) sulphite pulp were mixed up with 100 parts of 55 °C water. 1 part of the dye 1 a ⁴¹ of this invention was dissolved in 100 parts of hot water. 80 parts of this solution were given to the mixed-up pulp and mixed for 2 minutes. After that the mixture was sized with resin size in a conventional manner and mixed for another 2 minutes. 55 parts of this solution were then diluted with 2000 parts of cold water and the paper was produced out of this solution.

The orange paper produced from the mixture has good wet fastnesses.

Example 2

10.06 g of 5,5'-diamino-2,2'-ureylene-bis-benzenesulfonic acid was first dissolved in water at slightly acidic pH to give a complete solution. Ice is added to the solution and when temperature reaches 10 to 15 °C, 10.6 ml of 5 N of sodium nitrite solution was added dropwise. The reaction mixture was further cooled down to 0 to 8 °C when the mixture was added dropwise into 12.38 g of concentrated HCI with 12 g of ice. Yellow suspension was formed and reaction mixture was completed within an hour.

6.30 g of 2,5-dimethyl-phenylamine was added directly into the diazo suspension and stirred. A violet precipitate was observed upon addition. The intermediate precipitate, 4,4'-bis-(4-amino-2,5-dimethyl-phenylazo)-biphenyl-2,2'-disu lfonic acid obtained was filtered off with suction and washed with organic solvent and dried.

15.22 g of the dried intermediate, 5,5'-bis-(4-amino-2,5-dimethyl-phenylazo)-2,2'- ureylene-bis-benzenesulfonic acid, was then dissolved in water at slightly acidic pH to give a complete reddish orange solution. Ice was added to the solution and when temperature reached 10 to 15 °C, 10.1 ml of 5 N sodium nitrite solution was added dropwise. The reaction mixture was further cooled down to 0 to 8 °C when the mixture was added dropwise into concentrated HCI with ice. Violet suspension was formed and reaction mixture was completed in 90 mins. 5-methyl-2-m-tolyl-3,4-dihydro-2H-pyrazol-3-ylamine was stirred in methanol and adjusted to slightly acidic. The diazo was added dropwise into the methanol solution and stir. Brilliant orange precipitate was observed upon addition. Precipitate obtained was filtered off with suction and washed with brine giving product of the formula 1 b ¹⁶¹ . The analytic data are consistent with the assigned structure for product 1 b ¹⁶¹ . The product dyes the targeted fibre materials in brilliant orange shade.

Through analogy, all the dyes of formulae (1 b ¹ -1 b ³¹² ) can be synthesized according to the method described above. Dyeing example 2-1

1 part of the dye 1 b ¹⁶¹ of this invention was dissolved in 2000 parts of water and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 6 parts of sodium acetate were added. The pH was then adjusted to 5 using acetic acid (80 %). The dyebath was heated to 50 °C for 10 minutes and then entered with 100 parts of a woven polyamide-6 fabric. The temperature was raised to 98 °C over the course of 50 minutes and then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 60 °C and removal of the dyed material. The polyamide-6 fabric was washed with hot and cold water, soaped and then spun and dried. The orange dyeings obtained have very good light and wet fastness and also good levelness in the fibre.

Dyeing example 2-2 1 part of the dye 1 b ¹⁶¹ of this invention was dissolved in 2000 parts of water and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 6 parts of sodium acetate were added. The pH was then adjusted to 5.5 using acetic acid (80 %). The dyebath was heated to 50 °C for 10 minutes and then entered with 100 parts of a woven polyamide-6,6 fabric. The temperature was raised to 120 °C over the course of 50 minutes and then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 60 °C and removal of the dyed material. The polyamide-6,6 fabric was washed with hot and cold water, soaped and then spun and dried. The orange dyeings obtained have very good light and wet fastness and also good levelness in the fibre.

Dyeing example 2-3

100 parts of polyamide-6 material were padded with a 1000 parts 50 °C liquor solution that consisted of 40 parts of the dye 1 b ¹⁶¹ , 100 parts of urea, 20 parts of a non ionic solubilizer based on butyldiglycol, 20 parts of acetic acid to adjust the pH to 4.0, 10 parts of levelling assistant (based on ethoxylated aminopropyl fatty acid amide) and 815 parts of water. The material was rolled up and placed into a steaming chamber at 85 to 98 °C for 3 to 6 hours. After fixation, the fabric was washed with hot and cold water, soaped and then spun and dried. The orange dyeings obtained have very good light and wet fastness and also good levelness in the fibre.

Dyeing example 2-4 1 part of the dye 1 b ¹⁶¹ of this invention was dissolved in 2000 parts of water and 5 parts of sodium sulphate, and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 5 parts of sodium acetate were added. The pH was then adjusted to 4.5 using acetic acid (80 %). The dyebath was heated to 50 °C for 10 minutes and then entered with 100 parts of a woven wool fabric. The temperature was raised to 100 °C over the course of 50 minutes and then dyeing is carried out at this temperature for 60 minutes. This was followed by cooling to 90 °C and removal of the dyed material. The wool fabric was washed with hot and cold water, soaped and then spun and dried. The orange dyeings obtained have very good light and wet fastness and also good levelness in the fibre.

Dyeing example 2-5

1 part of the dye 1 b ¹⁶¹ of this invention was dissolved in 1000 parts of soft water and 7.5 parts of sodium sulphate, and 1 parts of a wetting agent (anionic) were added. 100 part of bleached cotton knitted fabric was added to this solution. The dye bath was then heated up to 98 °C with a gradient of 2 °C/min then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling down to 80 °C. At 80 °C the dyeing was continued for another 20 minutes. The dyed material was then removed and was washed with hot and cold water, soaped and then spun and dried. The orange dyeings obtained have very good light and wet fastness and also good levelness in the fibre.

Dyeing example 2-6

3 parts of the dye 1 b ¹⁶¹ of this invention dissolved in 82 parts of deionized water was added into the dyebath with 15 parts of diethylene glycol at 60 °C. On cooling, an orange printing ink is obtained. The orange printing ink can be used for ink jet printing on paper, polyamide or wool textiles.

Dyeing example 2-7

4 parts of chemically bleached (pine wood) sulphite pulp was mixed up with 100 parts of 55 °C water. 1 part of the dye 1 b ¹⁶¹ of this invention was dissolved in 100 parts of hot water. 80 parts of this solution was given to the mixed-up pulp and mixed for 2 minutes. After that the mixture was sized with resin size in a conventional manner and mixed for another 2 minutes. 55 parts of this solution was then diluted with 2000 parts of cold water and the paper was produced out of this solution. The orange paper produced from the mixture has good wet fastnesses.