Acid dyes, process for the production thereof and their use

Abstract

Dyes of formula (1) ##STR00001##
their preparation and use are described.

Claims

1. A dye of formula (1) ##STR00022## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 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.9, R.sup.10, R.sup.11, R.sup.12 independent of each other is hydrogen, alkyl, substituted alkyl, alkyl chain interrupted by one or two heteroatoms selected from the group consisting of oxygen and sulphur 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.13 and R.sup.18 independent of each other is cyano, carbamoyl, substituted carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl or halogen, R.sup.14 and R.sup.19 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, alkylureido and phenylureido, R.sup.15, R.sup.16, R.sup.17, R.sup.20, R.sup.21 and R.sup.22 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, or 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, 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, 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, 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.15 and R.sup.16, and OR.sup.17, respectively can be positioned ortho or para to R.sup.13, meaning that when the amino rest bearing the substituents R.sup.15 and R.sup.16 is positioned ortho to R.sup.13, the OR.sup.17 is positioned para to R.sup.13, and vice versa; and the same applies to the amino rests bearing the substituents R.sup.20 and R.sup.21, and OR.sup.22, respectively that can be positioned ortho or para to R.sup.18, meaning that when the amino rest bearing, the substituents R.sup.20 and R.sup.21 is positioned ortho to R.sup.18, the OR.sup.22 is positioned para to R.sup.18, and vice versa.

2. The dye according to claim 1, having formula (1a) ##STR00023## wherein R.sup.1a, R.sup.2a, R.sup.3a, R.sup.4a, R.sup.5a, R.sup.6a, R.sup.7a and R.sup.8a 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.9a, R.sup.10a, R.sup.11a and R.sup.12a independent of each other is hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, halogen, trifluoromethyl, SO.sub.3M or (C.sub.1-C.sub.4)-acylamino, R.sup.13a and R.sup.18a independent of each other is cyano, carbamoyl or alkoxycarbonyl, R.sup.14a and R.sup.19a independent of each other is unsubstituted, linear or branched (C.sub.1-C.sub.4)-alkyl, unsubstituted (C.sub.5-C.sub.7)-cycloalkyl or substituted (C.sub.5-C.sub.7)-cycloalkyl with one or more substituents, R.sup.15a, R.sup.16a R.sup.17a, R.sup.20a, R.sup.21a and R.sup.22a independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonyl-alkyl, aminoalkyl, amino-hydroxyalkyl, 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 sulphur, 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 sulphur 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.3a, R.sup.4a, R.sup.5a, R.sup.6a and R.sup.8a independent of each other is SO.sub.3M, hydrogen, alkyl, alkoxy or halogen, whereby at least two of them are SO.sub.3M, R.sup.2a and R.sup.7a is hydrogen, R.sup.9a, R.sup.10a, R.sup.11a and R.sup.12a independent of each other is hydrogen, methyl, methoxy, ethoxy, halogen, SO.sub.3M or acetylamino, R.sup.13a and R.sup.18a independent of each other is cyano or carbamoyl, R.sup.14a and R.sup.19a is methyl, R.sup.15a, R.sup.16a, R.sup.20a and R.sup.21a 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, 2-(2-hydroxyethylsulfanyl)-ethyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxy)propyl, 2-(2-hydroxy ethoxy)ethyl, 3-(4-hydroxybutoxy)propyl, 2-(2-hydroxyethanesulfonyl)-ethyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl, R.sup.17a and R.sup.22a independent of each other is hydrogen, (C.sub.1-C.sub.6) alkyl or (C.sub.1-C.sub.6) alkyl interrupted by O or S, and M is hydrogen, sodium, potassium, lithium or ammonium.

4. The dye according to claim 1, having formula (1b) ##STR00024## wherein R.sup.1b, R.sup.2b, R.sup.3b, R.sup.4b, R.sup.5b, R.sup.6b, R.sup.7b and R.sup.8b 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.9b, R.sup.10b, R.sup.11b and R.sup.12b independent of each other is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, halogen, trifluoromethyl, (C.sub.1-C.sub.4)-acylamino or SO.sub.3M, R.sup.13b and R.sup.18b independent of each other is cyano, carbamoyl or alkoxycarbonyl, R.sup.14b and R.sup.19b independent of each other is unsubstituted, linear or branched (C.sub.1-C.sub.4)-alkyl, unsubstituted (C.sub.5-C.sub.7)-cycloalkyl or substituted (C.sub.5-C.sub.7)-cycloalkyl with one or more substituents, R.sup.15b, R.sup.16b, R.sup.20b and R.sup.21b 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 sulphur, 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 sulphur 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-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 joined together to form five or six membered ring being unsubstituted or substituted by one or more (C.sub.1-C.sub.4)-alkyl-groups and the ring being uninterrupted or interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur, R.sup.17b and R.sup.22b independent from each other is hydrogen, (C.sub.1-C.sub.6) alkyl, (C.sub.1-C.sub.6) alkoxy, (C.sub.1-C.sub.6) alkyl terminated by halogen or hydroxyl, 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.1b, R.sup.3b, R.sup.4b, R.sup.5b, R.sup.6b and R.sup.8b independent of each other is SO.sub.3M, hydrogen, alkyl, alkoxy or halogen, whereby at least two of them are SO.sub.3M, R.sup.2b and R.sup.7b is hydrogen, R.sup.9b, R.sup.10b, R.sup.11b and R.sup.12b independent of each other is hydrogen, methyl, methoxy, ethoxy, halogen or acetylamino, R.sup.13b and R.sup.18b independent of each other is cyano or carbamoyl, R.sup.14b and R.sup.19b is methyl, R.sup.15b, R.sup.16b, R.sup.20b and R.sup.21b 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, 2-(2-hydroxyethylsulfanyl)-ethyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxy)propyl, 2-(2-hydroxy ethoxy)ethyl, 3-(4-hydroxybutoxy)propyl, 2-(2-hydroxyethanesulfonyl)-ethyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl, 3-ethoxybutyl or (C.sub.2-C.sub.6) alkyl substituted by COOM or SO.sub.3M, or joined together to form five or six membered ring being unsubstituted or substituted by one or more (C.sub.1-C.sub.4)-alkyl-groups and the ring being uninterrupted or interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur, R.sup.17b and .sup.R22b independent from each other is hydrogen or (C.sub.1-C.sub.6) alkyl and M is hydrogen, sodium, potassium, lithium or ammonium.

6. The dye according to claim 1, having formula (1c) ##STR00025## wherein R.sup.1c, R.sup.2c, R.sup.3c, R.sup.4c, R.sup.5c, R.sup.6c, R.sup.7c and R.sup.8c independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO.sub.3M, wherein at least two of them are SO.sub.3M, R.sup.9c, R.sup.10c, R.sup.11c and R.sup.12c independent of each other is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, halogen, trifluoromethyl, (C.sub.1-C.sub.4)-acylamino or SO.sub.3M, R.sup.13c and R.sup.18c independent of each other is cyano, carbamoyl or alkoxycarbonyl, R.sup.14c and R.sup.19c independent of each other is unsubstituted, linear or branched (C.sub.1-C.sub.4)-alkyl, unsubstituted (C.sub.5-C.sub.7)-cycloalkyl or substituted (C.sub.5-C.sub.7)-cycloalkyl with one or more substituents, R.sup.15c, R.sup.16c, R.sup.17c, R.sup.20c, R.sup.21c and R.sup.22c 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, cycloalkyl alkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl or 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, 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 sulphur 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.1c, R.sup.3c, R.sup.4c, R.sup.5c, R.sup.6c and R.sup.8c independent of each other is SO.sub.3M, hydrogen, alkyl, alkoxy or halogen, wherein at least two of them are SO.sub.3M, R.sup.2c and R.sup.7c is hydrogen, R.sup.9c, R.sup.10c, R.sup.11c and R.sup.12c independent of each other is hydrogen, methyl, methoxy, ethoxy, halogen, SO.sub.3M or acetylamino, R.sup.13c and R.sup.18c independent of each other is cyano or carbamoyl, R.sup.14c and R.sup.19c is methyl, R.sup.15c, R.sup.16c, R.sup.17c, R.sup.20c, R.sup.21c and R.sup.22c 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, 2-(2-hydroxyethylsulfanyl)-ethyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxy)propyl, 2-(2-hydroxy ethoxy)ethyl, 3-(4-hydroxybutoxy)propyl, 2-(2-hydroxyethanesulfonyl)-ethyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl, or (C.sub.2-C.sub.6) alkyl substituted by COOM or SO.sub.3M, and M is hydrogen, sodium, potassium, lithium or ammonium.

8. A process for the production of the dye according to claim 1, comprising the steps a) diazotization of a compound of formula (2) ##STR00026## wherein R.sup.1 to R.sup.8 are defined as in claim 1, b) reacting diazonium salt obtained in step a) with the compounds of formula (3) and (4) in stoichiometric amounts ##STR00027## wherein R.sup.9 to R.sup.12 are defined as in claim 1, to yield an intermediate of formula (5) ##STR00028## c) diazotization of the compound of formula (5), d) reacting the diazonium salts obtained in step c) with the compounds of the formula (6), (7), (8) and (9) or mixtures thereof ##STR00029## wherein R.sup.11 to R.sup.24 are defined as in claim 1.

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

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

11. An aqueous solution for dyeing comprising one or more chemical compounds according to claim 9.

12. 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.

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

14. A process for dying fibers which comprises contacting the fiber with the dye according to claim 1, wherein the fiber is selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres, vegetable fibers, seed fibers, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibers, sisal, henequen, banana; stalk fibers, bamboo; fibers from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fiber, fur, leather materials; manufactured, regenerated and recycled fibers, cellulosic fibers; paper fibers, cellulosic regenerated fibers, viscose rayon fibers, acetate and triacetate fibers and Lyocell fibers.

15. A fiber and blends containing a fiber selected from the group consisting on synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres, vegetable fibers, seed fibers, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibers, sisal, henequen, banana; stalk fibers, bamboo; fibers from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fiber, fur, leather materials; manufactured, regenerated and recycled fibers, cellulosic fibers; paper fibers, cellulosic regenerated fibers, viscose rayon fibers, 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 on the fiber.

Description

EXAMPLE 1

(1) 8.62 g of 4,4-Diamino-biphenyl-2,2-disulfonic acid was first dissolved in water at slightly acidic pH to give a complete solution. Ice was added to the solution and when temperature reached 10 to 15 C., 10.6 ml of 5 N 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 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 obtained intermediate precipitate, 4,4-Bis-(4-amino-2,5-dimethyl-phenylazo)-biphenyl-2,2-disulfonic acid, was filtered off with suction and washed with organic solvent and dried.

(3) 15.22 g of the dried intermediate, 4,4-Bis-(4-amino-2,5-dimethyl-phenylazo)-biphenyl-2,2e-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 5 N 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 reaction mixture was completed in 90 mins.

(4) The obtained reaction mixture was used in the next step as described below: 11.63 g of 6-Hydroxy-2-(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. Precipitate obtained was filtered off with suction and washed with brine giving product of the formula 1a.sup.190. The analytic data are consistent with the assigned structure for product 1a.sup.190. The product dyes the targeted fibre materials in brilliant scarlet to red shades.

(5) Through analogy, all the dyes of formulae (1a.sup.1-1a.sup.404)(1b.sup.1-1b.sup.24) and (1c.sup.1-1c.sup.184) can be synthesized according to the method described above.

DYEING EXAMPLE 1

(6) 1 part of the dye 1a.sup.190 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 dyeing obtained gave 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.190 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 dyeing obtained gave red shade and has very good light and wet fastness and also good levelness in the fibre.

DYEING EXAMPLE 3

(8) 100 parts of polyamide-6 material were padded with a 1000 parts 50 C. liquor solution that consisted of 40 parts of the dye 1a.sup.190, 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 dyeing obtained gave red shade and has very good light and wet fastness and also good levelness in the fibre.

DYEING EXAMPLE 4

(9) 1 part of the dye 1a.sup.190 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 are 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. The dyeing obtained gave red shade and has very good light and wet fastness and also good levelness in the fibre.

DYEING EXAMPLE 5

(10) 1 part of the dye 1a.sup.190 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) were 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 red shade and has very good light and wet fastness and also good levelness in the fibre.

EXAMPLE 6

Preparation of an Ink

(11) 3 parts of the dye 1a.sup.190 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, a red printing ink was obtained. The red printing ink can be used for ink jet printing on paper, polyamide or wool textiles.

DYEING EXAMPLE 7

(12) 4 parts of chemically bleached (pine wood) sulphite pulp was mixed up with 100 parts of 55 C. water. 1 part of the dye 1a.sup.190 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 red paper produced from the mixture has good wet fastnesses.