Acid dyes, process for the production thereof and their use

Abstract

Dyes of formula (1) ##STR00001##
a process for their production and their use are described.

Claims

1. A dye of formula (1) ##STR00011## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO.sub.3Mwhereby at least two of them are SO.sub.3M, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 independent of each other is hydrogen, alkyl, substituted alkyl, alkyl chain 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, SO.sub.3M or alkylureido, R.sup.9 and R.sup.15 independent of each other is cyano, carbamoyl, carbamoyl substituted, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl or halogen, R.sup.10 and R.sup.16 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, or arylthio, 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, alkyl-ureido and phenylureido, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.17, R.sup.18, R.sup.19, R.sup.20 independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyakyl, heteroarylalkyl, or heterocycloalkylalkyl, or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, 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, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo-alkyl-amino, N,N-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-carbamoyl, N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbarnoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalk yl-N-monoarylsulfamo-yl and SO.sub.3M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, and 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, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-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, N,N-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, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO.sub.3M, 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, and whereby the bonds with unfixed attachment points on the pyridine couplers mean that the amino rests bearing the substituents R.sup.11 and R.sup.12, and R.sup.13 and R.sup.14, respectively can be positioned ortho or para to R.sup.9, meaning that when the amino rest bearing the substituents R.sup.11 and R.sup.12 is positioned ortho to R.sup.9, the amino rest bearing the substituents R.sup.13 and R.sup.14 is positioned para to R.sup.9, and vice versa; and the same applies to the amino rests bearing the substituents R.sup.17 and R.sup.18, and R.sup.19 to R.sup.20 , respectively that can be positioned ortho or para to R.sup.15, meaning that when the amino rest bearing the substituents R.sup.17 and R.sup.18 is positioned ortho to R.sup.15, the amino rest bearing the substituents R.sup.19 to R.sup.20 is positioned para to R.sup.15, and vice versa.

2. The dye according to claim 1, having formula (1a) ##STR00012## wherein R.sup.1a, R.sup.2a, R.sup.3a and R.sup.4a independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO.sub.3M, whereby at least two of them are SO.sub.3M, R.sup.5a, R.sup.6a, R.sup.7a and R.sup.8a independent of each other is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, halogen, trifluoromethyl, SO.sub.3M or (C.sub.1-C.sub.4)-acylamino, R.sup.9a and R.sup.15a independent of one another is cyano, carbamoyl, substituted carbamoyl, sulfonylalkyl or alkoxycarbonyl, R.sup.10a and R.sup.16a independent of each other is unsubstituted, linear or branched (C.sub.1-C.sub.4)-alkyl, unsubstiuted (C.sub.5-C.sub.7)-cycloalkyl or substituted (C.sub.5-C.sub.7)-cycloalkyl with one or more substituents, R.sup.11a, R.sup.12a R.sup.13a, R.sup.14a, R.sup.17a, R.sup.18a, R.sup.19a and R.sup.20a independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, or heterocycloalkylalkyl, or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-mono-cycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyl-ureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO.sub.3M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO.sub.3M and M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.

3. The dye according to claim 2, wherein R.sup.1a, R.sup.2a, R.sup.3a and R.sup.4a independent of each other is SO.sub.3M, hydrogen, alkyl, alkoxy or halogenwhereby at least two of them are SO.sub.3M, R.sup.5a, R.sup.6a, R.sup.7a and R.sup.8a independent of each other is hydrogen, methyl, halogen, SO.sub.3M or acetylamino, R.sup.9a and R.sup.15a independent of each other is cyano or carbamoyl, R.sup.10a and R.sup.16a is methyl, R.sup.11a, R.sup.12a R.sup.13a, R.sup.14a, R.sup.17a, R.sup.18a, R.sup.19a and R.sup.20a independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, allyl, 2-methoxyethyl, 3-methoxypropyl, 2-cyanoethyl, 2-(methylthio)ethyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, tetrahydrofurfuryl, 2-furan-2-yl-ethyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxy-ethoxy)ethyl, 3-(4-hydroxyetlaoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl, 3-ethoxybutyl, alkyl substituted by SO.sub.3M or alkyl substituted by COOM and M is hydrogen, sodium, potassium, lithium or ammonium.

4. The dye according to claim 1, having formula (1b) ##STR00013## wherein R.sup.1b, R.sup.2b, R.sup.3b and R.sup.4b independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO.sub.3M, whereby at least two of them are SO.sub.3M, R.sup.5b, R.sup.6b, R.sup.7b and R.sup.8b independent of each other is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, halogen, trifluoromethyl, SO.sub.3M or (C.sub.1-C.sub.4)-acylamino, R.sup.9b and R.sup.15b independent of each other is cyano, carbamoyl, carbamoyl substituted, sulfonylalkyl or alkoxycarbonyl, R.sup.10b and R.sup.16b independent of each other is unsubstituted, linear or branched (C.sub.1-C.sub.4)-alkyl, unsubstiuted (C.sub.5-C.sub.7)-cycloalkyl or substituted (C.sub.5-C.sub.7)-cycloalkyl with one or more substituents, R.sup.11b, R.sup.12b R.sup.13b, R.sup.14b, R.sup.17b, R.sup.18b, R.sup.19b and R.sup.20b independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, or heterocycloalkylalkyl, or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-mono-cycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyl-ureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO.sub.3M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO.sub.3M and M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.

5. The dye according to claim 4, wherein R.sup.3b and R.sup.4b is SO.sub.3M, R.sup.1b and R.sup.2b is hydrogen, R.sup.5b, R.sup.6b, R.sup.7b and R.sup.8b independent of each other is hydrogen, methyl, halogen, SO.sub.3M or acetylamino, R.sup.9b and R.sup.15b independent of each other is cyano or carbamoyl, R.sup.10b and R.sup.16b is methyl, R.sub.11b, R.sup.12b R.sub.13b, R.sup.14b, R.sup.17b, R.sup.18b, R.sup.19b and R.sup.20b independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 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, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxyethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl, alkyl substituted by SO.sub.3M or alkyl substituted by COOM and M is hydrogen, sodium, potassium, lithium or ammonium.

6. The dye according to claim 1, having formula (1c) ##STR00014## wherein R.sup.1c, R.sub.2c, R.sup.3c and R.sup.4c independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO.sub.3M, whereby at least two of them are SO.sub.3M, R.sup.5c, R.sup.6c, R.sup.7c and R.sup.8c independent of each other is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, halogen, trifluoromethyl, SO.sub.3M or (C.sub.1-C.sub.4)-acylamino, R.sup.9c and R.sup.15c independent of each other is cyano, carbamoyl, substituted carbamoyl, sulfonylalkyl or alkoxycarbonyl, R.sup.10c and R.sup.16c independent of each other is unsubstituted, linear or branched (C.sub.1-C.sub.4)-alkyl, unsubstiuted (C.sub.5-C.sub.7)-cycloalkyl or substituted (C.sub.5-C.sub.7)-cycloalkyl with one or more substituents, R.sup.11c, R.sup.12c R.sup.13c, R.sup.14c, R.sup.17c, R.sup.18c, R.sup.19c and R.sup.20c independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, amino alkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, or heterocycloalkylalkyl, or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO.sub.3M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO.sub.3M and M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.

7. The dye according to claim 6, wherein R.sup.2c and R.sup.4c is SO.sub.3M, R.sup.1c and R.sup.2c is hydrogen, R.sup.5c, R.sup.6c, R.sup.7c and R.sup.8c independent of each other is hydrogen, methyl, halogen, SO.sub.3M or acetylamino, R.sup.9c and R.sup.15c independent of each other is cyano or carbamoyl, R.sup.10c and R.sup.16c is methyl, R.sup.11c, R.sup.12c R.sup.13c, R.sup.14c, R.sup.17c, R.sup.18c, R.sup.19c and R.sup.20c independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 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, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxyethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl, alkyl substituted by SO.sub.3M or alkyl substituted by COOM and M is hydrogen, sodium, potassium, lithium or ammonium.

8. The dye according to claim 1, having formula (1d) ##STR00015## wherein R.sup.1d, R.sup.2d, R.sup.3d and R.sup.4d independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO.sub.3M whereby at least two of them are SO.sub.3M, R.sup.5d, R.sup.6d, R.sup.7d and R.sup.8d independent of each other is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, halogen, trifluoromethyl, SO.sub.3M or (C.sub.1-C.sub.4)-acylamino, R.sup.9d and R.sup.15d independent of each other is cyano, carbamoyl, carbamoyl substituted, sulfonylalkyl or alkoxycarbonyl, R.sup.10d and R.sup.16d independent of each other is unsubstituted, linear or branched (C.sub.1-C.sub.4)-alkyl, unsubstiuted (C.sub.5-C.sub.7)-cycloalkyl or substituted (C.sub.5-C.sub.7)-cycloalkyl with one or more substituents, R.sup.11d, R.sup.12d R.sup.14d, R.sup.17d, R.sup.18d, R.sup.19d and R.sup.20d independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, or heterocycloalkylalkyl, or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, or alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO.sub.3M or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO.sub.3M and M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.

9. The dye according to claim 8, wherein R.sup.1d and R.sup.3d is SO.sub.3M, R.sup.2d and R.sup.4d is hydrogen, R.sup.5d, R.sup.6d, R.sup.7d R.sup.8d independent of each other is hydrogen, methyl, halogen, SO.sub.3M or acetylamino, R.sup.9d and R.sup.15d independent of each other is cyano or carbamoyl, R.sup.10d R.sup.16d is methyl, R.sup.11d, R.sup.12d R.sup.13d, R.sup.14d, R.sup.17d, R.sup.18d, R.sup.19d and R.sup.20d independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 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, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxyethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl, alkyl substituted by SO.sub.3M or alkyl substituted by COOM and M is hydrogen, sodium, potassium, lithium or ammonium.

10. A process for the preparation of the dye according to claim 1 and mixtures thereof comprising the steps a) diazotization of a compound of formula (2) ##STR00016## wherein R.sup.1 to R.sup.4 are defined as in claim 1, b) reacting the diazonium salt obtained in step a) with stoichiometric amounts of compounds of formula (3) and (4) ##STR00017## wherein R.sup.5 to R.sup.8 are defined as in claim 1, to yield an intermediate of formula (5) ##STR00018## c) diazotization of the compound of formula (5), d) reacting the diazonium salt obtained in step c) with the compounds of formula (6), (7), (8) and (9) or mixtures thereof ##STR00019## wherein R.sup.11 to R.sup.20 are defined as in claim 1.

11. A chemical composition comprising one or more dye(s) according to claim 1.

12. A chemical composition consisting essentially of two or more dyes according to claim 1.

13. An aqueous solution for dying comprising one or more dyes according to claim 1.

14. A process for dyeing or printing carboxamido- and/or hydroxyl-containing material, comprising contacting the carboxamido- and/or hydroxyl-containing material with the dye according to claim 1.

15. An ink for digital textile printing comprising the dye according to claim 1.

16. A fiber and blend containing the 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) according to claim 1 either in chemically and/or physically bound form.

Description

EXAMPLE 1

(1) 7.96 g of 3,7-Diamino-naphthalene-1,5-disulfonic 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 HCl with 12 g of ice. Yellow suspension was formed and the reaction mixture was completed within an hour.

(2) 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, 3,7-Bis-(4-amino-2,5-dimethyl-phenylazo)-naphthalene-1,5-disulfonic acid obtained was filtered off with suction, washed with organic solvent and dried.

(3) 15.22 g of the dried intermediate, 3,7-Bis-(4-amino-2,5-dimethyl-phenylazo)-naphthalene-1,5-disulfonic 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 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 HCl with ice. Violet suspension was formed and the reaction mixture was completed in 90 mins.

(4) The obtained reaction mixture was used in the next step as described below: 14.62 g of 2,6-Bis-(3-methoxy-propylamino)-4-methyl-nicotinonitrile were stirred in methanol and adjusted to slightly acidic. The reaction mixture was added dropwise into the methanol solution and stirred. Brilliant orange precipitate was observed upon addition. The precipitate obtained was filtered off with suction and washed with brine giving the product of the formula 1a.sup.52. The analytic data are consistent with the assigned structure for product 1a.sup.52. The product dyes the targeted fibre materials in brilliant red to reddish violet shades.

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

DYEING EXAMPLE 1

(6) 1 part of the dye 1a.sup.52 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 than 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 dyeing obtained gave dark red shade and has very good light and wet fastness and also good levelness in the fibre.

DYEING EXAMPLE 2

(7) 1 part of the dye 1a.sup.52 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.

(8) The dyeing obtained gave dark red shade and has very good light and wet fastness and also good levelness in the fibre.

DYEING EXAMPLE 3

(9) 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 m.sup.52, 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.

(10) The dyeing obtained gave dark red shade and has very good light and wet fastness and also good levelness in the fibre.

DYEING EXAMPLE 4

(11) 1 part of the dye 1a.sup.52 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 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.

(12) The dyeing obtained gave dark red shade and has very good light and wet fastness and also good levelness in the fibre.

DYEING EXAMPLE 5

(13) 1 part of the dye 1a.sup.52 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 dyeings obtained gave dark red shade and has very good light and wet fastness and also good levelness in the fibre.

DYEING EXAMPLE 6

(14) 3 parts of the dye 1a.sup.52 of this invention dissolved in 82 parts of deionized water is added into the dyebath with 15 parts of diethylene glycol at 60 C. On cooling, a red printing ink is obtained. The red printing ink can be used for ink jet printing on paper, polyamide or wool textiles.

DYEING EXAMPLE 7

(15) 4 parts of chemically bleached (pine wood) sulphite pulp is mixed up with 100 parts of 55 C. water. 1 part of the dye 1a.sup.52 of this invention is dissolved in 100 parts of hot water. 80 parts of this solution is given to the mixed-up pulp and mixed for 2 minutes. After that the mixture is sized with resin size in a conventional manner and mixed for another 2 minutes. 55 parts of this solution is then diluted with 2000 parts of cold water and the paper is produced out of this solution. The red paper produced from the mixture has good wet fastnesses.