# US 7,611,546 B2 · Composition comprising at least one substituted acetylenic carbocyanin derivative, process for treating keratin fibres using it, and device therefor

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- Number: US 7,611,546 B2
- Document ID: US7611546B2
- Status: Granted
- Kind: B2
- Application number: 12/081,310
- Filed: 2008-04-14
- Published: 2009-03-12
- Granted: 2009-11-03
- Earliest claimed: 2007-04-13
- Assignees: L'oreal
- Inventors: Alain Lagrange
- Web page: https://patentgrep.com/patent/US7611546B2

## CPC

- A61K 8/4926: {having six membered rings}
- A61Q 5/065: {Preparations for temporary colouring the hair, e.g. direct dyes}
- A61Q 5/10: Preparations for permanently dyeing the hair
- A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D)
- A61Q: SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS

## Abstract

The invention relates to a composition for dyeing human keratin fibers, comprising, in a cosmetically acceptable medium, one or more cationic direct dyes comprising at least one carbon-carbon triple bond, for instance dyes of formula (I), (II) or (III) below: in which A1, A2 and A3, independently of each other, correspond to a cationic heterocyclic group and B1, B2 and B3, independently of each other, correspond to a particular aromatic nucleus; n may be equal to 1 or 2.

## Claims

### Claim 1

A composition for dyeing human keratin fibers comprising, in a cosmetically acceptable medium, at least one direct dye chosen from direct dyes of formulae (I), (II) and (III):
wherein:
A1, A2 and A3, independently of each other, are chosen from cationic heterocyclic groups comprising at least one quaternized nitrogen and optionally fused with at least one aromatic nucleus, and wherein A1, A2 and A3 are attached to the at least one C≡C functional group via one of the carbon atoms of the cationic heterocycle or via the at least one aromatic nucleus to which the cationic heterocycle is optionally fused; and wherein said at least one quaternized nitrogen atom optionally bears at least one radical chosen from amino radicals; C2-C20 acyl radicals; and C1-C25 alkyl radicals optionally substituted with at least one radical chosen from phenyl, phenyl-carbonyl, (C1-C4)alkoxycarbonyl, sulfo (—SO3M, wherein M is chosen from a hydrogen atom and alkali metals), ethylenyl (—CH═CH2), acetylenyl (—C≡CH), and phenyl-acetylenyl (—C≡C—C6H5);
A1, A2 and A3 may be optionally substituted, beyond the radicals borne by the quaternized nitrogen atoms, with at least one radical chosen from halogen atoms, C1-C25 alkyl radicals, (C1-C4) alkoxy radicals, (C1-C20)alkylcarbonylamino radicals, and phenyl radicals;
B1, B2 and B3, independently of each other, are aromatic nucleuses chosen from phenyl groups, anthracenyl groups, and naphthyl groups, attached to one or two C≡C functional groups;
B1, B2 and B3 may be optionally substituted with at least one group chosen from:
amino groups optionally bearing one or two radicals, independently of each other, chosen from C1-C18 alkyl, (C1-C20)alkylcarbonyl, (C1-C20)alkylsulfonyl, and phenyl optionally substituted with a C1-C4 alkoxy group;
hydroxyl;
C1-C4 alkoxy;
C1-C10 alkyl optionally bearing an amino group;
phenoxy;
sulfo (—SO3M, wherein M is chosen from a hydrogen atom and alkali metals);
cyano;
trifluoromethyl;
halogen chosen from chlorine, fluorine and bromine; and
acetylthio (CH3—CO—S—);
n is equal to 1 or 2;
the electrical neutrality of the at least one direct dye being optionally assured via at least one cosmetically acceptable anion;
and wherein the composition also comprises at least one surfactant present in an amount ranging from 0.01% to 50% by weight relative to the total weight of the composition, and chosen from anionic, amphoteric, nonionic, zwitterionic and cationic surfactants.

### Claim 2 (depends on 1)

The composition according to claim 1, wherein, A1, A2 and A3, independently of each other, are cationic heterocyclic groups comprising at least one quaternized nitrogen, optionally fused with at least one aromatic nucleus, chosen from pyridinium, (benz)imidazolium, (benzo)thiazolium, benzoxazolium, (iso)quinolinium, (benz)indolium, acridinium, quinolizinium, phenazinium, and pyrrolopyridinium groups.

### Claim 3 (depends on 1)

The composition according to claim 1, wherein the at least one direct dye is chosen from direct dyes of formula (I) and further wherein said A1 is chosen from phenazinium groups.

### Claim 4 (depends on 1)

The composition according to claim 1, wherein B1 is an anthracenyl group.

### Claim 5 (depends on 1)

The composition according to claim 1, wherein the at least one direct dye is chosen from direct dyes of formula (II), and further wherein:
n is 1; and
A2 is chosen from optionally substituted pyridinium, benzimidazolium, (benzo)thiazolium, benzoxazolium, (iso)quinolinium, (benz)indolium, acridinium, thioxanthilium, quinolizinium and pyrrolopyridinium groups.

### Claim 6 (depends on 1)

The composition according to claim 1, wherein the at least one direct dye is of chosen from direct dyes of formula (II), and further wherein:
n is 2; and
A2 is chosen from pyridinium groups.

### Claim 7 (depends on 1)

The composition according to claim 1, wherein B2, independently of each other, is chosen from optionally substituted phenyl groups and naphthyl groups.

### Claim 8 (depends on 1)

The composition according claim 1, wherein the at least one direct dye is of chosen from direct dyes of formula (III), and further wherein A3 is chosen from pyridinium groups.

### Claim 9 (depends on 1)

The composition according to claim 1, wherein B3 is chosen from phenyl groups.

### Claim 10

A composition for dyeing human keratin fibers comprising, in a cosmetically acceptable medium, at least one direct dye chosen from:
Pyridinium salt, 4-[(4-
Pyridinium salt, 4-[(4-
aminophenyl)ethynyl]-1 -methyl
hydroxyphenyl)ethynyl]-1 -methyl
Pyridinium salt, 4-[(4-
Pyridinium salt, 1-methyl-4-[(4-
ethylphenyl)ethynyl]-1 -methyl-
methylphenyl)ethynyl]
Pyridinium salt, 4-[(4-
Salt of 4-methylbenzenesulfonic acid
cyanophenyl)ethynyl]-1-methyl
(1:1) and of pyridinium, 4-[[4-
(dimethylamino)phenyl]ethynyl]-1-
methyl-, monohydrate
Quinolizinium salt, 4-[[4-
(trifluoromethyl)phenyl]ethynyl]-
Pyridinium trichloride, 4,4′,4″-[nitrilotris(4,1-phenylene-2,1-ethynediyl)]tris[1 -
methyl-, trichloride
Quinolizinium salt, 1-[[4-
Quinolizinium salt, 3-[(3-
(trifluoromethyl)phenyl]ethynyl]-
bromophenyl)ethynyl]-
Quinolizinium salt, 3-[[4-
Quinolizinium salt, 3-[(4-
(trifluoromethyl)phenyl]ethynyl]-
methoxyphenyl)ethynyl]-
Quinolizinium salt, 3-[(4-
Quinolizinium salt, 2-[(3-
methylphenyl)ethynyl]-
bromophenyl)ethynyl]-
Quinolizinium salt, 2-[[4-
Quinolizinium salt, 2-[(4-
(trifluoromethyl)phenyl]ethynyl]
methoxyphenyl)ethynyl]
Quinolizinium salt, 2-[(4-
Quinolizinium salt, 4-[(4-
methylphenyl)ethynyl]-
methoxyphenyl)ethynyl]-
Quinolizinium salt, 1-[(4-
Pyridinium iodide, 5-[[4-
methoxyphenyl)ethynyl]-
(acetylthio)phenyl]ethynyl]-1-methyl-2-
(phenylethynyl)
Pyridinium salt, 2-methyl-1-(2-oxo-2-
Pyridinium salt, 4-[(4-
phenylethyl)-6-(phenylethynyl)-
methoxyphenyl)ethynyl]-1-octadecyl-
Pyridinium salt, 1-docosyl-4-[(4-
Isoquinolinium salt, 6-[(4-
methoxyphenyl)ethynyl]-
methoxyphenyl)ethynyl]-2-methyl
Pyridinium salt, 1-decyl-4-[(4-
Isoquinolinium salt, 6-[[4-
methoxyphenyl)ethynyl]-
(dimethylamino)phenyl]ethynyl]-2-methyl
Pyridinium salt, 3-[[4-(1-amino-1-
Pyridinium salt, 1-(2-oxo-2-phenylethyl)-
methylethyl)phenyl]ethynyl]-1-methyl
2-(phenylethynyl)-
Isoquinolinium salt, 2-methyl-6-
Pyridinium salt, 1-octadecyl-4-
(phenylethynyl)-
(phenylethynyl)-
Pyridinium salt, 1-docosyl-4-
Salt of trifluoromethanesulfonic acid
(phenylethynyl)-
(1:1) and of pyridinium, 3,5-bis[(4-
hydroxy-3-methoxyphenyl)ethynyl]-1-
methyl
Salt of trifluoromethanesulfonic acid
Pyridinium salt, 4-[(4-
(1:1) and of pyridinium, 2,6-bis[(4-
bromophenyl)ethynyl]-1-dodecyl
hydroxy-3-methoxyphenyl)ethynyl]-1-
methyl
Pyridinium salt, 1-methyl-3,5-
Pyridinium salt, 1-methyl-4-(1-
bis(phenylethynyl)-
naphthalenylethynyl)
Thioxanthylium perchlorate, 4-chloro-
Pyridinium salt, 1-methyl-3-
9-[[4-(dimethylamino)phenyl]ethynyl]
(phenylethynyl)-
3H-Pyrrolo[2,3-b]pyridinium salt, 7-(6-
Pyridinium inner salt, 4-[[4-
ethoxy-6-oxohexyl)-2,3,3-trimethyl-5-
(dihexylamino)phenyl]ethynyl]-1-(4-
[[4-[(methylsulfonyl)amino]-
sulfobutyl)
phenyl]ethynyl
Pyridinium methanesulfonate, 1-
Acridinium salt, 9-[(2-
amino-2-(phenylethynyl)
bromophenyl)ethynyl]-10-methyl
Pyridinium salt, 4-[[4-(dimethylamino)-
Pyridinium salt, 4-[[4-(dimethylamino)-
2,3,5,6-tetrafluorophenyl]ethynyl]-
2,3,5,6-tetrafluorophenyl]ethynyl]-1-
2,3,5,6-tetrafluoro-1-methyl
methyl-
Pyridinium salt, 4-[[4-
Pyridinium salt, 4-[[4-
(dimethylamino)phenyl]ethynyl]-
(dimethylamino)phenyl]ethynyl]-1-
2,3,5,6-tetrafluoro-1-methyl-
methyl
Pyridinium iodide, 1-methyl-3,5-
Pyridinium iodide, 1-methyl-3-
bis(phenylethynyl)
(phenylethynyl)
Phenazinium salt, 2,2′-(9,10-
Salt of trifluoromethanesulfonic acid and
anthracenediyldi-2,1-
of pyridinium, 1-methyl-2-
ethynediyl)bis[5,10-dimethyl
(phenylethynyl)
Salt of trifluoromethanesulfonic acid
Salt of trifluoromethanesulfonic acid
(1:1) and of pyridinium, 1-(2-propynyl)-
(1:1) and of thiazolium, 3-methyl-2-
2-[(3,4,5-trimethoxyphenyl)ethynyl]
(phenylethynyl)
Salt of trifluoromethanesulfonic acid
Salt of trifluoroacetic acid(1:1) and of
(1:1) and of benzothiazolium, 3-
pyridinium, 1-methyl-2-(phenylethynyl)
methyl-2-(phenylethynyl)
Salt of trifluoroacetic acid (1:1) and of
Pyridinium salt, 4-[[4-[bis(4-
1H-Benzimidazolium, 1-methyl-2-
methoxyphenyl)amino]phenyl]ethynyl]-1-
(phenylethynyl)-3-(3-phenyl-2-
butyl
propynyl)
Salt of trifluoroacetic acid (:1) and of
Pyridinium salt, 2-(phenylethynyl)-1-(2-
thiazolium, 3-methyl-2-(phenylethynyl)
propenyl)-
Pyridinium inner salt, 4-[[4-
3H-Pyrrolo[2,3-b]pyridinium inner salt,
(dibutylamino)phenyl]ethynyl]-1-(3-
2,3,3-trimethyl-5-[[4-
sulfopropyl)
[(methylsulfonyl)amino]phenyl]ethynyl]-
7-(3-sulfobutyl)
3H-Pyrrolo[2,3-b]pyridinium, 7-(6-
3H-Pyrrolo[2,3-b]pyridinium inner salt,
ethoxy-6-oxohexyl)-2,3,3-trimethyl-5-
2,3,3-trimethyl-7-(3-sulfobutyl)-5-[(4-
[[4-[(methylsulfonyl)amino]-
sulfophenyl)ethynyl]
phenyl]ethynyl]-bromide
3H-Pyrrolo[2,3-b]pyridinium inner salt,
Benzothiazolium salt, 3-methyl-2-[(4-
7-(6-ethoxy-6-oxohexyl)-2,3,3-
phenoxyphenyl)ethynyl]-
trimethyl-5-[(4-sulfophenyl)ethynyl]
3H-Pyrrolo[2,3-b]pyridinium inner salt,
Benzothiazolium salt, 2-[(4-
2,3,3,7-tetramethyl-5-[(4-
methoxyphenyl)ethynyl]-3-methyl
sulfophenyl)ethynyl]
Benzothiazolium salt, 3-methyl-2-[[4-
Salt of trifluoromethanesulfonic acid
(1-methylethyl)phenyl]ethynyl]-
(1:1) and of
1H-Benzimidazolium, 1,3-dimethyl-2-
(phenylethynyl)
Benzothiazolium salt, 3-methyl-2-
Salt of 2,4,6-trinitrophenol (1:1) and of
(phenylethynyl)-
quinolizinium, 2-(phenylethynyl)
Salt of trifluoromethanesulfonic acid
Isoquinolinium iodide, 6-[(4-
(1:1) 1H-Benzimidazolium, 1-methyl-2-
methoxyphenyl)ethynyl]-2-methyl
(phenylethynyl)-3-(3-phenyl-2-
propynyl)
Salt of 2,4,6-trinitrophenol (1:1) and of
Benzoxazolium inner salt, 2-methyl-5-
quinolizinium, 1-(phenylethynyl)
(phenylethynyl)-3-(4-sulfobutyl)
Isoquinolinium iodide, 6-[[4-
Salt of trifluoromethanesulfonic acid
(dimethylamino)phenyl]ethynyl]-2-
(1:1) and of quinolinium, 1-methyl-2-
methyl
(phenylethynyl)
Isoquinolinium iodide, 2-methyl-6-
Salt of trifluoromethanesulfonic acid
(phenylethynyl)
(1:1) and of
3H-Indolium, 1,3,3-trimethyl-2-
(phenylethynyl)
Benzothiazolium inner salt, 2-methyl-5-
Pyridinium methyl sulfate, 4-[(4-
(phenylethynyl)-3-(4-sulfobutyl)
chlorophenyl)ethynyl]-1-methyl-, methyl
sulfate
Salt of trifluoromethanesulfonic acid
Pyridinium bromide, 4-[(4-
(1:1) and of b
bromophenyl)ethynyl]-1-docosyl
Benzothiazolium, 2-[(4-
chlorophenyl)ethynyl]-3-methyl-,
Pyridinium methyl sulfate, 4-[(4-
Pyridinium perchlorate, 1-butyl-3,5-
bromophenyl)ethynyl]-1-methyl-
dimethyl-2,6-diphenyl-4-(phenylethynyl)
Pyridinium bromide, 4-[(4-
Pyridinium bromide, 4-[(4-
bromophenyl)ethynl]-1-dodecyl
methoxyphenyl)ethynyl]-1-octadecyl
Pyridinium perchlorate, 3,5-dimethyl-
Pyridinium bromide, 1-docosyl-4-[(4-
2,6-diphenyl-4-(phenylethynyl)-1-
methoxyphenyl)ethynyl]
(phenylmethyl)
Pyridinium perchlorate, 1,3,5-trimethyl-
Pyridinium bromide, 1-docosyl-4-
2,6-diphenyl-4-(phenylethynyl)
(phenylethynyl)
Pyridinium bromide, 1-decyl-4-[(4-
1-Methyl-4-phenylethynylpyridinium
methoxyphenyl)ethynyl]
perchlorate
Pyridinium bromide, 1-octadecyl-4-
1-Methyl-2,6-
(phenylethynyl)
bis(phenylethynyl)pyridinium perchlorate
1-Methyl-2-phenylethynylquinolinium
1-Ethyl-2-phenylethynylquinolinium
para-toluenesulfonate
perchlorate
1-Methyl-2-phenylethynylpyridinium
Salt of 1-Methyl-4-
perchlorate
phenylethynylpyridinium methyl
1-Methyl-2-phenylethynylquinolinium
Pyridinium bromide, 2-methyl-1-(2-oxo-
perchlorate
2-phenylethyl)-6-(phenylethynyl)
Methyl-2-phenylethynylpyridinium
1H-Benzimidazolium 1,3-dimethyl-2-(1-
methyl sulfate
naphthalenylethynyl) methyl sulfate
Pyridinium methyl sulfate, 4-[[4-
Benzimidazolium iodide, 1,3-dimethyl-2-
(dimethylamino)-2-[(1-
(phenylethynyl)-,
oxooctadecyl)amino]phenyl]ethynyl]-
1-methyl-3-[(1-oxooctadecyl)amino]
Benz[cd]indolium perchlorate, 1-acetyl-
Pyridinium iodide, 1-methyl-4-(1-
5-ethoxy-2-(phenylethynyl)
naphthalenylethynyl)-,
Phenazinium salt, 2,2′-(1,4-phenylenedi-2,1-ethynediyl)bis[5,10-dimethyl-
and wherein the composition also comprises at least one surfactant present in an amount ranging from 0.01% to 50% by weight relative to the total weight of the composition, and chosen from anionic, amphoteric, nonionic, zwitterionic and cationic surfactants.

### Claim 11 (depends on 1)

The composition according to claim 1, wherein the at least one direct dye is present in an amount ranging from 0.01% to 20% by weight relative to the total weight of the composition.

### Claim 12 (depends on 1)

The composition according to claim 1, further comprising at least one oxidizing agent.

### Claim 13

A process for treating keratin fibers, comprising:
applying to the keratin fibers a cosmetic composition comprising, in a cosmetically acceptable medium, at least one direct dye chosen from direct dyes of formulae (I), (II) and (III):
wherein:
A1, A2 and A3, independently of each other, are chosen from cationic heterocyclic groups comprising at least one quaternized nitrogen and optionally fused with at least one aromatic nucleus, and wherein A1, A2 and A3 are attached to the at least one C≡C functional group via one of the carbon atoms of the cationic heterocycle or via the at least one aromatic nucleus to which the cationic heterocycle is optionally fused; and wherein said at least one quaternized nitrogen atom optionally bears at least one radical chosen from amino radicals; C2-C20 acyl radicals; and C1-C25 alkyl radicals optionally substituted with at least one radical chosen from phenyl, phenyl-carbonyl, (C1-C4)alkoxycarbonyl, sulfo (—SO3M, wherein M is chosen from a hydrogen atom and alkali metals), ethylenyl (—CH═CH2), acetylenyl (—C≡CH), and phenyl-acetylenyl (—C≡C—C6H5);
A1, A2 and A3 may be optionally substituted, beyond the radicals borne by the quaternized nitrogen atoms, with at least one radical chosen from halogen atoms, C1-C25 alkyl radicals, (C1-C4) alkoxy radicals, (C1-C20)alkylcarbonylamino radicals, and phenyl radicals;
B1, B2 and B3, independently of each other, are aromatic nucleuses chosen from phenyl groups, anthracenyl groups, and naphthyl groups, attached to one or two C≡C functional groups;
B1, B2 and B3 may be optionally substituted with at least one group chosen from:
amino groups optionally bearing one or two radicals, independently of each other, chosen from C1-C18 alkyl, (C1-C20)alkylcarbonyl, (C1-C20)alkylsulfonyl, and phenyl optionally substituted with a C1-C4 alkoxy group;
hydroxyl;
C1-C4 alkoxy;
C1-C10 alkyl optionally bearing an amino group;
phenoxy;
sulfo (—SO3M, wherein M is chosen from a hydrogen atom and alkali metals);
cyano;
trifluoromethyl;
halogen chosen from chlorine, fluorine and bromine; and
acetylthio (CH3—CO—S—);
n is equal to 1 or 2;
the electrical neutrality of the at least one direct dye being optionally assured via at least one cosmetically acceptable anion.

### Claim 14 (depends on 13)

The process according to claim 13, wherein the keratin fibers are chosen from human keratin fibers.

### Claim 15

A multi-compartment device for dyeing and lightening the hair, comprising:
at least one first compartment containing a composition comprising, in a cosmetically acceptable medium, at least one direct dye chosen from direct dyes of formulae (I), (II) and (III):
wherein:
A1, A2 and A3, independently of each other, are chosen from cationic heterocyclic groups comprising at least one quaternized nitrogen and optionally fused with at least one aromatic nucleus, and wherein A1, A2 and A3 are attached to the at least one C≡C functional group via one of the carbon atoms of the cationic heterocycle or via the at least one aromatic nucleus to which the cationic heterocycle is optionally fused; and wherein said at least one quaternized nitrogen atom optionally bears at least one radical chosen from amino radicals; C2-C20 acyl radicals; and C1-C25 alkyl radicals optionally substituted with at least one radical chosen from phenyl, phenyl-carbonyl, (C1-C4)alkoxycarbonyl, sulfo (—SO3M, wherein M is chosen from a hydrogen atom and alkali metals), ethylenyl (—CH═CH2), acetylenyl (—C≡CH), and phenyl-acetylenyl (—C≡C—C6H5);
A1, A2 and A3 may be optionally substituted, beyond the radicals borne by the quaternized nitrogen atoms, with at least one radical chosen from halogen atoms, C1-C25 alkyl radicals, (C1-C4) alkoxy radicals, (C1-C20)alkylcarbonylamino radicals, and phenyl radicals;
B1, B2 and B3, independently of each other, are aromatic nucleuses chosen from phenyl groups, anthracenyl groups, and naphthyl groups, attached to one or two C≡C functional groups;
B1, B2 and B3 may be optionally substituted with at least one group chosen from:
amino groups optionally bearing one or two radicals, independently of each other, chosen from C1-C18 alkyl, (C1-C20)alkylcarbonyl, (C1-C20)alkylsulfonyl, and phenyl optionally substituted with a C1-C4 alkoxy group;
hydroxyl;
C1-C4 alkoxy;
C1-C10 alkyl optionally bearing an amino group;
phenoxy;
sulfo (—SO3M, wherein M is chosen from a hydrogen atom and alkali metals);
cyano;
trifluoromethyl;
halogen chosen from chlorine, fluorine and bromine; and
acetylthio (CH3—CO—S—);
n is equal to 1 or 2;
the electrical neutrality of the at least one direct dye being optionally assured via at least one cosmetically acceptable anion; and
at least one second compartment containing a composition comprising at least one oxidizing agent.