Granted Patent B2

US 7,374,583 · App. 11/732,214 · Granted May 20, 2008

Abstract

Claims (80)

1. An agent for the oxidative dyeing of fibers, comprising at least one oxidizing agent and at least one cationic azacyanine dye having the general formula (I);

A standing for the 5-or 6-ring group required for the formation of an aromatic carbocyclic or heterocyclic (nitrogen, oxygen or sulfur, up to two additional heteroatoms possibly being contained in addition to the bridge nitrogen);

R1′ being equal to an unbranched or branched (C1-C10) alkyl chain that can be selected from the group consisting of one or more alkoxy groups, hydroxyl groups, carboxylic acid amide groups, dialkylamino groups, alkylamino groups, carboxylic acid ester groups, carboxylic acid groups or sulfonic acid groups, an unsubstituted benzyl group, a benzyl group substituted with one or more alkyl groups, alkoxy groups, alkoxyalkyl groups, hydroxyl groups, hydroxyalkyl groups, carboxylic acid amide groups, dialkylamine groups, carboxylic acid ester groups, alkylcarboxylic acid ester groups, carboxylic acid groups, alkylcarboxylic acid groups, sulfonic acid groups or halogen atoms, or with a six-member or five-member aromatic carbocyclic or heterocyclic (nitrogen, oxygen or sulfur) ring that can be unsubstituted or substituted with one or more alkyl groups, alkoxy groups, alkoxyalkyl groups, hydroxyl groups, hydroxyalkyl groups, carboxylic acid amide groups, dialkylamine groups, carboxylic acid ester groups, alkylcarboxylic acid ester groups, carboxylic acid groups alkylcarboxylic acid groups, sulfonic acid groups and halogen atoms;

R2′ is selected from the group consisting of hydrogen, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxy group, a halogen atom, or a six-member or five-member aromatic carbocyclic or heterocyclic (nitrogen, oxygen or sulfur) ring that can be unsubstituted or substituted with an alkyl group, an alkoxy group, an alkoxyalkyl group, a hydroxyl group, a hydroxyalkyl group, an alkylcarboxylic acid amide group, a dialkylamino group, a carboxylic acid ester group, an alkylcarboxylic acid ester group a carboxylic acid group, an alkylcarboxylic acid group, a sulfonic acid group, an alkylsulfonic acid group, an unsubstituted or substituted benzyl group and a halogen atom; and

B is an aromatic molecule part with tertiary nitrogen.

2. An agent for simultaneous lightening and dyeing of fibers, comprising at least one oxidizing agent comprising at least one cationic azacyanine dye having the general formula (I) according to claim 1 that is stable in relation to oxidizing agents.

3. An oxidative coloring agent for dyeing fibers on the basis of at least one oxidative dye precursor comprising at least one cationic azacyanine dye having the general formula (I) according to claim 1 that is stable in relation to oxidizing agents.

4. An agent according to claim 2 wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide or its additive compounds, urea, melamine, sodium borate, and sodium carbonate.

5. An agent according to claim 3 wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide or its additive compounds, urea, melamine, sodium borate, and sodium carbonate and persulfates.

6. An agent according to claim 1 wherein the compound of formula (I) is selected from the group consisting of compounds having formulas (Ia) to (Ie), the residues R1′, R2′, and B having the meaning cited in claim 1 , and R3′ being equal to hydrogen, an alkyl group, an alkoxy group, an alkoxyalkyl group, a hydroxyl group, a hydroxyalkyl group, an alkylcarboxylic acid amide group, an amino group, an alkylamino group, a dialkylamino group, a carboxylic acid ester group, an alkylcarboxylic acid ester group, a carboxylic acid group, an alkylcarboxylic acid group, a sulfonic acid group, an alkylsulfonic acid group and a halogen atom;

7. An agent according to claim 1 wherein the group B is selected from the group consisting of substituted indoles, indazoles, indolizines, pyrrolo [1,2-a]pyrazinen, pyrrolo[2,1-b][1,3]thiazoles, pyrrolo[2,1-b][1,3]oxazoles, pyrrolol [1,2-a]imidazoles, pyrazoles, paraphenylenamines, imidazoles, pyrroles and pyrazolin-5-ones having formulas (If) to (Ir);

R1 being equal to an unbranched or branched (C1-C10) alkyl chain that can be substituted with one or more alkoxy groups, hydroxyl groups, carboxylic acid amide groups, dialkylamino groups, alkylamino groups, carboxylic acid ester groups, carboxylic acid groups or sulfonic acid groups, an unsubstituted benzyl group, a benzyl group substituted with alkyl groups, alkoxy groups, alkoxyalkyl groups, hydroxyl groups, hydroxyalkyl groups, carboxylic acid amide groups, dialkylamine groups, carboxylic acid ester groups, alkylcarboxylic acid ester groups, carboxylic acid groups, alkylcarboxylic acid groups, sulfonic acid groups or halogen atoms (F, Cl , Br,I) or with a six-member or five-member aromatic carbocyclic or heterocyclic (nitrogen, oxygen or sulfur) ring that can be unsubstituted or substituted with one or more alkyl groups, alkoxy groups, alkoxyalkyl groups, hydroxyl groups, hydroxyalkyl groups, carboxylic acid amide groups, dialkylamine groups, carboxylic acid ester groups, alkylcarboxylic acid ester groups, carboxylic acid groups, alkylcarboxylic acid groups, sulfonic acid groups or halogen atoms (F, Cl , Br, I): and R2 is hydrogen, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxy group, a halogen atom (F, Cl , Br, I), or a six-member or five-member aromatic carbocyclic or heterocyclic (nitrogen, oxygen or sulfur) ring that can be unsubstituted or substituted with an alkyl group, an alkoxy group, an alkoxy alkyl group, a hydroxyl group, a hydroxyalkyl group, an alkylcarboxylic acid amide group, a dialkylamino group, a carboxylic acid ester group, an alkylcarboxylic acid ester group, a carboxylic acid group, an alkylcarboxylic acid group, a sulfonic acid group, an alkylsulfonic acid group, an unsubstituted or substituted benzyl group or a halogen atom (F, Cl , Br, I);

R3 being equal to hydrogen, an alkyl group, an alkoxy group, an alkoxyalkyl group, a hydroxyl group, a hydroxyalkyl group, an alkylcarboxylic acid amide group, an amino group, an alkylamino group, a dialkylamino group, a carboxylic acid ester group, an alkylcarboxylic acid ester group, a carboxylic acid group, an alkylcarboxylic acid group, a sulfonic acid group, an alkylsulfonic acid group, or a halogen atom; the residues R4, R5, R6, R9, R11, R12, R15, R18, R20 and R21 being, independent of one another, equal to an unbranched or branched (C1-C10) alkyl chain that can be unsubstituted or substituted with an alkoxy group, a hydroxyl group, a carboxylic acid amide group, a dialkylamino group, an alkylamino group, a carboxylic acid ester group, a carboxylic acid group or a sulfonic acid group, an unsubstituted benzyl group, a benzyl group substituted with an alkyl group, an alkoxy group, an alkoxyalkyl group, a hydroxyl group, a hydroxyalkyl group, a carboxylic acid amide group, a dialkylamino group, a carboxylic acid ester group, an alkylcarboxylic acid ester group, a carboxylic acid group, an alkylcarboxylic acid group, a sulfonic acid group or a halogen atom, or with a six-member or five-member aromatic carbocyclic or heterocyclic (nitrogen, oxygen or sulfur) ring that can be unsubstituted or substituted with an alkyl group, an alkoxy group, an alkoxyalkyl group, a hydroxyl group, a hydroxyalkyl group, a carboxylic acid amide group, a dialkylamino group, a carboxylic acid ester group, an alkylcarboxylic acid ester group, a carboxylic acid group, an alkylcarboxylic acid group, a sulfonic acid group or a halogen atom; and R7, R8, R10, R13, R14, R16, R17, R19 and R22 being, independent from one another, equal to hydrogen, an unbranched or branched (C1-C10) alkyl chain that can be unsubstituted or substituted with an alkoxy group, a hydroxyl group, a carboxylic acid amide group, a dialkylamine group, an alkylamine group, a carboxylic acid ester group, a carboxylic acid group or a sulfonic acid group, an unsubstituted benzyl group, a benzyl group substituted with an alkyl group, an alkoxy group, an alkoxyalkyl group, a hydroxyl group, a hydroxyalkyl group, a carboxylic acid amide group, a dialkylamino group, a carboxylic acid ester group, an alkylcarboxylic acid ester group, a carboxylic acid group, an alkylcarboxylic acid group, a sulfonic acid group, or a halogen atom, a hydroxyl group, an amino group, an alkoxy group, a substituted phenyloxy group, a dialkylamino group, a substituted benzylamino group, a substituted phenylamino group, an alkylamino group, or with a six-member or five-member aromatic carbocyclic or heterocyclic (nitrogen, oxygen or sulfur) ring that can be unsubstituted or substituted with an alkyl group, an alkoxy group, an alkoxyalkyl group, a hydroxyl group, a hydroxyalkyl group, a carboxylic acid amide group, a dialkylamine group, a carboxylic acid ester group, an alkylcarboxylic acid ester group, a carboxylic acid group, an alkylcarboxylic acid group, a sulfonic acid group, and a halogen atom.

8. An agent according to claim 1 wherein the azacyanine dye having formula (I) is selected from the group consisting of

(1E)-1-({4-[bis(2-hydroxyethyl)amino]phenyl}imino)-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-{[4-(dimethylamino)phenyl]imino}-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-{[4-(diethylamino)phenyl]imino}-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-[(5-amino-1-methyl-1H-pyrazol-4-yl)imino]-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-{[5-amino-1-(4-methylbenzyl)-1H-pyrazol-4-yl]imino}-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-{[5-amino-1-(3-methylbenzyl)-1H-pyrazol-4-yl]imino}-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-{[5-amino-1-(4-methylbenzyl)-1H-pyrazol-4-yl]imino}-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-{[5-amino-1-(2-hydroxymethyl)-1H-pyrazol-4-yl]imino}-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium -acetate,

(1E)-1-[(5-amino-1-benzyl-1H-pyrazol-4-yl)imino]-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-[(5-amino-1-ethyl-1H-pyrazol-4-yl)imino]-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-[(5-amino-1-isopropyl-1H-pyrazol-4-yl)imino]-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-[(5-amino-1-pentyl-1H-pyrazol-4-yl)imino]-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-{[5-amino-1-(4-methoxybenzyl)-1H-pyrazol-4-yl]imino}-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-{[(5-amino-1-(3-methoxybenzyl)-1H-pyrazol-4-yl]imino}-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-{[5-amino-1-(2-methoxybenzyl)-1H-pyrazol-4-yl]imino}-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-{[5-amino-1-(4-chlorbenzyl)-1H-pyrazol-4-yl]imino}-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-{[5-amino-1-(3-chlorbenzyl)-1H-pyrazol-4-yl]imino}-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-{[5-amino-1-(2-chlorbenzyl)-1H-pyrazol-4-yl]imino}-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-{[1-(4-methoxybenzyl)-5-(methylamino)-1H-pyrazol-4-yl]imino}-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-{[5-[(2-hydroxyethyl)amino]-1-(4-methoxybenzyl)-1H-pyrazol-4-yl]imino}-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-{[1-(2-hydroxyethyl)-5-methylamino)-1H-pyrazol-4-yl]imino}-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-[(1-ethyl-5-hydroxy-1H-pyrazol-4-yl)imino]-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-3-(4-methoxyphenyl)-2-methyl-1-[(1-methyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)imino]-1H-indolizinium-acetate,

(1E)-1-[(2-hydroxy-4,5-dimethyl-1-phenyl-1H-pyrrol-3-yl)imino]-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-[(5-hydroxy-2-methyl-1-phenyl-1H-imidazol-4-yl)imino]-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-[(2-hydroxy-1-methyl-1H-indol-3-yl)imino]-2-methyl-3-phenyl-1H-indolizinium-acetate,

(1E)-1-[(2-hydroxy-1-ethyl-1H-indol-3-yl)imino]-2-methyl-3-phenyl-1H-indolizinium-acetate,

(1E)-1-{[2-hydroxy-1-(2-hydroxyethyl)-1H-indol-3-yl]imino}-2-methyl-3-phenyl-1H-indolizinium-acetate,

(1E)-3-(4-methoxyphenyl)-1-{[3-(4-methoxyphenyl)-1-indolizinyl]imino}-1H-indolizinium-chloride,

(1E)-3-(4-methoxyphenyl)-1-{[3-(4-methoxyphenyl)-1-indolizinyl]imino}-1H-indolizinium-bromide,

(8E)-6-(4-methoxyphenyl)-8-{[6-(4-methoxyphenyl)pyrrolo[1,2-a]pyrazin-8-yl]imino}-8H-pyrrolo[1,2-a]pyrazin-5-ium-bromide,

(7E)-5-(4-methoxyphenyl)-7-{[5-(4-methoxyphenyl)pyrrolo[2,1-b][1,3]thiazol-7-yl]imino}-7H-pyrrolo[2,1-b][1,3]thiazol-4-ium-chloride,

(1E)-3-(4-methoxyphenyl)-1-{[3-(4-methoxyphenyl)-2-methyl-1-indolizinyl]imino}-2-methyl-1H-indolizinium-acetate,

(1E)-3-(4-methoxyphenyl)-1-{[3-(4-methoxyphenyl)-2-phenyl-1-indolizinyl]imino}-2-phenyl-1H-indolizinium-acetate,

(1E)-1-{[5-amino-1-(2-hydroxyethyl)-1H-pyrazol-4-yl]imino}-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-{[5-amino-1-(2-hydroxyethyl)-1H-pyrazol-4-yl]imino}-2-methyl-3-phenyl-1H-indolizinium-acetate,

(1E)-1-{[5-amino-1-(2-hydroxyethyl)-1H-pyrazol-4-yl]imino}-2,3-diphenyl-1H-indolizinium-acetate,

(1E)-1-{[-5-(dimethylamino)-1,3-dimethyl-1H-pyrazol-4-yl]imino}-3-(4-methoxyphenyl)-1H-indolizinium-acetate,

(1E)-1-{[5-(dimethylamino)-1-(2-hydroxyethyl)-1H-pyrazol-4-yl]imino}-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(1E)-1-{[5-(dimethylamino)-1-(2-hydroxyethyl)-1H-pyrazol-4-yl]imino}-3-(4-methoxyphenyl)-2-phenyl-1H-indolizinium-acetate,

(8E)-8-{[5-(dimethylamino)-1-(2-hydroxyethyl)-1H-pyrazol-4-yl]imino}-6-(4-methoxyphenyl)-8H-pyrrolo[1,2-a]pyrazin-5-ium-acetate,

(7E)-7-{[5-(dimethylamino)-1-(2-hydroxyethyl)-1H-pyrazol-4-yl]imino}-5-(4-methoxyphenyl)-7H-pyrrolo[2,1-b][1,3]thiazol-4-ium-acetate,

(1E)-1-[(1-ethyl-5-hydroxy-1H-pyrazol-4-yl)imino]-2-methyl-3-phenyl-1H-indolizinium-chloride,

(1E)-1-[(1-ethyl-5-hydroxy-1H-pyrazol-4-yl)imino]-3-(4-methoxyphenyl)-2-phenyl-1H-indolizinium-chloride,

(1E)-1-[(5-hydroxy-1-phenyl-1H-pyrazol-4-yl)imino]-3-(4-methoxyphenyl)-2-phenyl-1H-indolizinium-bromide,

(1E)-1-{[5-hydroxy-1-(4-methoxyphenyl)-1H-pyrazol-4-yl]imino}-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium-acetate,

(8E)-8-[(1-ethyl-5-hydroxy-1H-pyrazol-4-yl)imino]-6-phenyl-8H-pyrrolo[1,2-a]pyrazin-5-ium-acetate,

(7E)-7-[(1-ethyl-5-hydroxy-1H-pyrazol-4-yl)imino]-6-methyl-5-phenyl-7H-pyrrolo[2,1-b][1,3]thiazol-4-ium-chloride,

(1E)-1-{[5-(benzylamino)-1-isopropyl-1H-pyrazol-4-yl]imino}-3-phenyl-1H-indolizinium-acetate,

(1E)-1-{[5-(benzylamino)-1-isopropyl-1H-pyrazol-4-yl]imino}-2-methyl-3-phenyl-1H-indolizinium-acetate,

(7E)-7-{[5-(benzylamino)-1-isopropyl-1H-pyrazol-4-yl]imino}-5-phenyl-7H-pyrrolo[2,1-b][1,3]thiazol-4-ium-acetate,

(1E)-1-{[5-(benzylamino)-1-isopropyl-1H-pyrazol-4-yl]imino}-3-(4-hydroxyphenyl)-1H-indolizinium-acetate,

(1E)-1-{[5-amino-1-(4-methylbenzyl)-1H-pyrazol-4-yl]imino}-2-methyl-3-phenyl-1H-indolizinium-acetate,

(1E)-1-{[5-amino-1-(4-methylbenzyl)-1H-pyrazol-4-yl]imino}-2,7-dimethyl-3-phenyl-1H-indolizinium-acetate,

(1E)-1-[(2-hydroxy-1-methyl-1H-indol-3-yl)imino]-2,7-dimethyl-3-phenyl-1H-indolizinium-acetate,

(1E)-1-[(1-Ethyl-5-hydroxy-1H-pyrazol-4-yl)imino]-3-[4-(methyloxy)-phenyl]-1H-indolizinium-acetate,

(1E)-1-({5-amino-1-[(4-methylphenyl)methyl]-1H-pyrazol-4-yl}imino)-3-[4-(methyloxy)phenyl]-1H-indolizinium-acetate,

(1E)-1-({1-(1-methylethyl)-5-[(phenylmethyl)amino]-1H-pyrazol-4-yl}imino)-3-[4-(methyloxy)phenyl]-1H-indolizinium-acetate,

(1E)-1-{[5-amino-1-(2-hydroxyethyl)-1H-pyrazol-4-yl]imino}-3-[4-(methyloxy)phenyl]-1H-indolizinium-acetate,

(1E)-1-[(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)imino]-3-[4-(methyloxy)phenyl]-1H-indolizinium-acetate,

(1E)-3-[4-(methyloxy)phenyl[-1-({3-[4-(methyloxy)phenyl]-1-indolizinyl}imino)-1H-indolizinium-acetate and

(1E)-1-{[3,5-bis(dimethylamino)-1-methyl-1H-pyrazol-4-yl]imino}-3-(4-methoxyphenyl)-2-methyl-1H-indolizinium acetate.

9. An agent according to claim 1 wherein the azacyanine dye of formula (I) is contained in a total quantity of 0.01wt% to 15wt%.

10. An agent according to claim 1 wherein it additionally comprises natural or synthetic direct-penetrating dyes selected from the group consisting of vegetable dyes, azo dyes, triphenylmethane dyes, quinone dyes, cationic dyes, anionic dyes and nitro dyes.

11. An agent according to claim 1 wherein said agent is a hair dye.

12. A method for dyeing hair having differing degrees of damage, the color vehicle comprising the azacyanine dye having formula (I) according to claim 1 being applied to the previously damaged hair parts without an oxidizing agent in pure form or mixed with an acidic, neutral or basic aqueous thinning agent while the color vehicle mixed with the oxidizing agent is applied to the hair parts that were previously damaged only slightly or not at all.

Assignments (8)