Cationic naphthyldiazo dyes and keratin fibers-coloring agents containing these dyes
View Patent ↗Cationic naphthyldiazo dyes of general formula (I) and colorants for keratin fibers containing these dyes.
1. An agent for coloring keratin fibers comprising at least one cationic naphthyldiazo dye of general formula (I) and at least one other dye besides the dye of general formula (I),
wherein
R1 stands for a hydrogen atom, halogen atom, straight-chain or branched (C 1 -C 4 )-alkyl group, straight-chain or branched (C 1 -C 4 )-alkoxy group, phenyl group or (C 2 -C 4 )-hydroxyalkyl group;
R2 and R3 can be equal or different and independently of each other stand for a hydrogen atom, hydroxyl group, amino group, acetylamino group, (C 1 -C 6 )-alkoxy group, (C 2 -C 4 )-hydroxyalkoxy group, (C 3 -C 6 )-di- or polyhydroxyalkoxy group, —COOR group, —NRR′ group or —CONRR′ group, wherein R and R′ can be equal or different and stand for a hydrogen atom, a straight-chain or branched (C 1 -C 6 )-alkyl group or a hydroxyethyl group, or R and R′ together with the nitrogen atom to which they are attached form a heterocycle with at least four ring members optionally containing other heteroatoms and R and R′ and the afore-described heterocycle possibly being substituted with an alkyl group, alkoxy group, hydroxyalkyl group or aminoalkyl group;
G stands for a nitrogen atom or a methine group (CH);
Y stands for an oxygen atom, or an N—(C 1 -C 4 )-alkyl group;
L represents a bridging group and stands for a straight-chain or branched (C 1 -C 14 )-alkylene group which optionally can be interrupted by one or more heteroatoms, the bridging group optionally being substituted with one or more hydroxyl groups, monohydroxy-(C 2 -C 6 )-alkyl groups, polyhydroxy-(C 2 -C 6 )-alkyl groups or (C 1 -C 6 )-alkoxy groups;
Q + stands for a saturated cationic group of formula (II) or an unsaturated cationic group of formulas (III) to (V)
wherein
R4 to R6 can be equal or different and independently of each other denote a straight-chain or branched (C 1 -C 6 )-alkyl group, (C 2 -C 4 )-hydroxyalkyl group, (C 3 -C 6 )-dihydroxyalkyl group, (C 3 -C 6 )-polyhydroxyalkyl group or (C 1 -C 6 )-alkoxy-(C 1 -C 4 )-alkyl group, or two of the R4 to R6 groups, together with the nitrogen atom to which they are attached, form a five-membered or six-membered heterocycle optionally interrupted by one or more heteroatoms such as an oxygen atom, sulfur atom or nitrogen atom and optionally bearing other substituents, for example a halogen atom, hydroxyl group, amino group, straight-chain or branched (C 1 -C 6 )-alkyl group, (C 1 -C 6 )-alkoxy group, (C 1 -C 6 )-alkoxy-(C 1 -C 4 )-alkyl group or hydroxyethyl group;
R7 stands for a straight-chain or branched (C 1 -C 8 )-alkyl group, allyl group, vinyl group, hydroxyethyl group or benzyl group;
R8 stands for a hydrogen atom, straight-chain or branched (C 1 -C 9 )-alkyl group, amino group, di-(C 1 -C 6 )-alkylamino group or pyrrolidino group;
R9 stands for a straight-chain or branched (C 1 -C 8 )-alkyl group, allyl group, vinyl group, hydroxyethyl group, dihydroxypropyl group or benzyl group, and
X − stands for an anion.
2. The agent as defined in claim 1 , wherein the dye of formula (I) is selected from dyes wherein
R1stands for a hydrogen atom, a chlorine atom or a methyl group,
R2 and R3 are equal or different and independently of each other stand for hydrogen, a hydroxyl group, methoxy group, —NRR′ group or —CONRR′ group wherein R and R′ can be equal or different and stand for a hydrogen atom, a methyl group or a hydroxyethyl group, or R and R′ together with the nitrogen atom to which they are attached form a heterocycle with five or six ring members;
G stands for a nitrogen atom or a methine group (CH);
Y stands for oxygen or an N-methyl group;
L stands for a straight-chain (C 2 -C 4 )-bridging group;
Q + stands for a saturated cationic group of formula (II) or an unsaturated cationic group of formulas (III) to (V), the R4 to R6 groups possibly being equal or different and independently of each other denote a straight-chain (C 1 -C 3 )-alkyl group, a hydroxyethyl group or a methoxyethyl group, or two of the R4 to R6 groups together with the nitrogen atom to which they are attached form a five-membered or six-membered heterocycle;
R7 stands for a methyl group or hydroxyethyl group;
R8 stands for a hydrogen atom, methyl group, dimethylamino group or pyrrolidino group;
R9 stands for a methyl group, ethyl group or hydroxyethyl group, and
X − stands for a chloride anion, bromide anion or methylsulfate anion.
3. The agent as defined in claim 1 , wherein the dye of general formula (I) is selected from among 2-{2-[(2-hydroxy-1-naphthyl)diazenyl]phenoxy}-N,N,N-trimethylethanaminium methylsulfate, 2-{2-[(4-hydroxy-1-naphthyl)diazenyl]phenoxy}-N,N,N-trimethylethanaminium chloride, 2-(2-{2-[(2-hydroxy-1-naphthyl)diazenyl]-phenoxy}ethyl)-1-methylpyridinium methylsulfate, 2-{2-[(2,7-dihydroxy-1-naphthyl)-diazenyl]phenoxy}-N,N,N-trimethylethanaminium chloride, 4-(2-{2-[(2-hydroxy-1-naphthyl)-diazenyl]phenoxy}ethyl)-4-methylmorpholin-4-ium chloride, 2-[(2-{[2-hydroxy-7-(methyloxy)-1-nanhthalenyl]diazenyl}phenyl)oxy]-N,N,N-trimethylethanaminium chloride, 2-[{4-[(2-hydroxy-1-naphthalenyl)diazenyl]phenyl}(methyl)amino]-N,N,N-trimethylethanaminium methylsulfate, 2-[{2-[(2-hydroxy-1-naphthalen-yl)diazenyl]phenyl}(methyl)amino-N,N,N-trimethylethanaminium methylsulfate, 2-[{2-(4-hydroxy-1-naphthalenyl)diazenyl]phenyl}(methyl)amino]-N, N, N-trimethylethanaminium methylsulfate, 2-({5-[(2-hydroxy-1-naphthyl)diazenyl-2-pyridinyl}-oxy)-N,N,N-trimethylethanaminium chloride, 2-({3-[(2-hydroxy-1-naphthyl)diazenyl]-2-pyridinyl}oxy)-N,N,N-trimethylethanaminium chloride, 2-({3-[(4-hydroxy-1-naphthyl)diazenyl]-2-pyridinyl}oxy)-N,N,N-trimethylethanaminium chloride, 2-{3-[(2-hydroxy-1-naphthyl)diazenyl]phenoxy}-N,N,N-trimethylethanaminium chloride, 3-(2-{2-[(2-hydroxy-1-naphthyl)diazenyl]phenoxy}ethyl)-1-methyl-1H-imidazol-3-ium chloride, 2-({2-[(2,4-dihydroxy-1-naphthalenyl)diazenyl]phenyl}oxy)-N,N,N-trimethylethanaminium chloride and 2-{[2-({2-hydroxy-3-[(phenylamino)carbonyl]-1-naphthalenyl}diazenyl)phenyl]oxy}-N,N,N-trimethylethanaminium chloride.
4. The agent as defined in claim 1 , wherein the agent contains the dye of formula (I) in a total amount from 0.01 to 10 weight percent.
5. The agent as defined in claim 1 , wherein the other dye is selected from among 3-[(4,5-dihydro-3-methyl-5-keto-1-phenyl-1H-pyrazol-4-yl)-azo]-N,N,N-trimethylbenzenaminium chloride, 3[(3-methyl-5-hydroxy-1-phenyl-1H-pyrazol-4-yl)azo]trimethylammoniobenzene chloride, 8[(4-aminophenyl)azo]-7-hydroxy-N,N,N-trimethyl-2-naphthalenaminium chloride, 8-[(4-amino-3-nitrophenyl)-azo]-7-hydroxy-N,N,N-trimethyl-2-naphthalenaminium chloride, 8-[(4-amino-2-nitrophenyl)azo]-7-hydroxy-N,N,N-trimethyl-2-naphthalenaminium chloride, 7-hydroxy-N,N,N-trimethyl-8-{[2-(methyloxy)phenyl]azo}-2-naphthalenaminium chloride, 3-[(4-amino-6-bromo-5,8-dihydro-1-hydroxy-8-imino-5-keto-2-naphthalenyl)-amino]-N,N,N-trimethylbenzenammonium chloride and N,N-dimethyl-3-{[4-(methyl-amino)-9,10-diketo-9,10-dihydro-1-anthracenyl]amino}-N-propyl-1-propanaminium bromide.
6. The agent as defined in claim 1 , wherein the agent is a hair colorant.
7. An agent for coloring keratin fibers that is in the form of a tinting fixative or dye fixative, comprising at least one cationic naphthyldiazo dye of general formula (I) and at least one polymer selected from the group consisting of natural polymers, synthetic polymers, and modified polymers of natural origin,
wherein
R1 stands for a hydrogen atom, halogen atom, straight-chain or branched (C 1 -C 4 )-alkyl group, straight-chain or branched (C 1 -C 4 )-alkoxy group, phenyl group or (C 2 -C 4 )-hydroxyalkyl group;
R2 and R3 can be equal or different and independently of each other stand for a hydrogen atom, hydroxyl group, amino group, acetylamino group, (C 1 -C 6 )-alkoxy group, (C 2 -C 4 )-hydroxyalkoxy group, (C 3 -C 6 )-di- or polyhydroxyalkoxy group, —COOR group, —NRR′ group or —CONRR′ group, wherein R and R′ can be equal or different and stand for a hydrogen atom, a straight-chain or branched (C 1 -C 6 )-alkyl group or a hydroxyethyl group, or R and R′ together with the nitrogen atom to which they are attached form a heterocycle with at least four ring members optionally containing other heteroatoms and R and R′ and the afore-described heterocycle possibly being substituted with an alkyl group, alkoxy group, hydroxyalkyl group or aminoalkyl group;
G stands for a nitrogen atom or a methine group (CH);
Y stands for an oxygen atom, or an N—(C 1 -C 4 )-alkyl group;
L represents a bridging group and stands for a straight-chain or branched (C 1 -C 14 )-alkylene group which optionally can be interrupted by one or more heteroatoms, the bridging group optionally being substituted with one or more hydroxyl groups, monohydroxy-(C 2 -C 6 )-alkyl groups, polyhydroxy-(C 2 -C 6 )-alkyl groups or (C 1 -C 6 )-alkoxy groups;
Q + stands for a saturated cationic group of formula (II) or an unsaturated cationic group of formulas (III) to (V)
wherein
R4 to R6 can be equal or different and independently of each other denote a straight-chain or branched (C 1 -C 6 )-alkyl group, (C 2 -C 4 )-hydroxyalkyl group, (C 3 -C 6 )-dihydroxyalkyl group, (C 3 -C 6 )-polyhydroxyalkyl group or (C 1 -C 6 )-alkoxy-(C 1 -C 4 )-alkyl group, or two of the R4 to R6 groups, together with the nitrogen atom to which they are attached, form a five-membered or six-membered heterocycle optionally interrupted by one or more heteroatoms such as an oxygen atom, sulfur atom or nitrogen atom and optionally bearing other substituents, for example a halogen atom, hydroxyl group, amino group, straight-chain or branched (C 1 -C 6 )-alkyl group, (C 1 -C 6 )-alkoxy group, (C 1 -C 6 )-alkoxy-(C 1 -C 4 )-alkyl group or hydroxyethyl group;
R7 stands for a straight-chain or branched (C 1 -C 6 )-alkyl group, allyl group, vinyl group, hydroxyethyl group or benzyl group;
R8 stands for a hydrogen atom, straight-chain or branched (C 1 -C 9 )-alkyl group, amino group, di-(C 1 -C 6 )-alkylamino group or pyrrolidino group;
R9 stands for a straight-chain or branched (C 1 -C 8 )-alkyl group, allyl group, vinyl group, hydroxyethyl group, dihydroxypropyl group or benzyl group, and
X − stands for an anion.
8. The agent as defined in claim 7 , wherein the agent contains the dye of formula (I) in a total amount from 0.01 to 10 weight percent.
9. The agent as defined in claim 7 , wherein the dye of formula (I) is selected from dyes wherein
R1 stands for a hydrogen atom, a chlorine atom or a methyl group,
R2 and R3 are equal or different and independently of each other stand for hydrogen, a hydroxyl group, methoxy group, —NRR′ group or —CONRR′ group wherein R and R′ can be equal or different and stand for a hydrogen atom, a methyl group or a hydroxyethyl group, or R and R′ together with the nitrogen atom to which they are attached form a heterocycle with five or six ring members;
G stands for a nitrogen atom or a methine group (CH);
Y stands for oxygen or an N-methyl group;
L stands for a straight-chain (C 2 -C 4 )-bridging group;
Q + stands for a saturated cationic group of formula (II) or an unsaturated cationic group of formulas (III) to (V), the R4 to R6 groups possibly being equal or different and independently of each other denote a straight-chain (C 1 -C 3 )-alkyl group, a hydroxyethyl group or a methoxyethyl group, or two of the R4 to R6 groups together with the nitrogen atom to which they are attached form a five-membered or six-membered heterocycle;
R7 stands for a methyl group or hydroxyethyl group;
R8 stands for a hydrogen atom, methyl group, dimethylamino group or pyrrolidino group;
R9 stands for a methyl group, ethyl group or hydroxyethyl group, and
X − stands for a chloride anion, bromide anion or methylsulfate anion.
10. The agent as defined in claim 7 , wherein the dye of general formula (I) is selected from among 2-{2-[(2-hydroxy-1-naphthyl)diazenyl]phenoxy}-N,N,N-trimethylethanaminium methylsulfate, 2-{2-[(4-hydroxy-1-naphthyl)diazenyl]phenoxy}-N,N,N-trimethylethanaminium chloride, 2-(2-{2-[(2-hydroxy-1-naphthyl)diazenyl]-phenoxy}ethyl)-1-methylpyridinium methylsulfate, 2-{2-[(2,7-dihydroxy-1-naphthyl)-diazenyl]phenoxy}-N,N,N-trimethylethanaminium chloride, 4-(2-{2-[(2-hydroxy-1-naphthyl)-diazenyl]phenoxy}ethyl)-4-methylmorpholin-4-ium chloride, 2-[(2-{[2-hydroxy-7-(methyloxy)-1-naphthalenyl]diazenyl}phenyl)oxy]-N,N,N-trimethylethanaminium chloride, 2-[{4-[(2-hydroxy-1-naphthalenyl)diazenyl]phenyl}(methyl)amino]-N,N,N-trimethylethanaminium methylsulfate, 2-[{2-[(2-hydroxy-1-naphthalen-yl)diazenyl]phenyl}(methyl)amino-N,N,N-trimethylethanaminium methylsulfate, 2-[{2-(4-hydroxy-1-naphthalenyl)diazenyl]phenyl}(methyl)amino]-N,N,N-trimethylethanaminium methylsulfate, 2-({5-[(2-hydroxy-1-naphthyl)diazenyl-2-pyridinyl}-oxy)-N,N,N-trimethylethanaminium chloride, 2-({3-[(2-hydroxy-1-naphthyl)diazenyl]-2-pyridinyl}oxy)-N,N,N-trimethylethanaminium chloride, 2-({3-[(4-hydroxy-1-naphthyl)diazenyl]-2-pyridinyl}oxy)-N,N,N-trimethylethanaminium chloride, 2-{3-[(2-hydroxy-1-naphthyl)diazenyl]phenoxy}-N,N,N-trimethylethanaminium chloride, 3-(2-{2-[(2-hydroxy-1-naphthyl)diazenyl]phenoxy}ethyl)-1-methyl-1H-imidazol-3-ium chloride, 2-({2-[(2,4-dihydroxy-1-naphthalenyl)diazenyl]phenyl}oxy)-N,N,N-trimethylethanaminium chloride and 2-{[2-({2-hydroxy-3-[(phenylamino)carbonyl]-1-naphthalenyl}diazenyl)phenyl]oxy}-N,N,N-trimethylethanaminium chloride.
11. The agent as defined in claim 7 , wherein the agent is a hair colorant.