FR2923827A1 - Use of cationic cyanine derivative as an agent for coloring keratin fibers, preferably human keratin fibers such as hair and/or for brightening of optical fibers - Google Patents

Abstract

Use of cationic cyanine derivative (I) as an agent for coloring keratin fibers, preferably human keratin fibers and/or for brightening of optical fibers, is claimed. Use of cationic cyanine derivative of formula (I) as an agent for coloring keratin fibers, preferably human keratin fibers and/or for brightening of optical fibers, is claimed. A : 5-12 membered aromatic heterocycle comprising at least a cationic charge on nitrogen atom and comprising optionally one or more other heteroatoms of N, O or S, where the heterocycle is optionally substituted and/or condensed with one or more aromatic cycles; B 1alkylene group CH 2or (CH 2) 2; either R 1H, halo, OH, 1-24C alkyl interrupted by one or more heteroatoms and substituted, 1-24C alkoxy interrupted by one or more heteroatoms and substituted, non-substituted amino group (mono- or disubstituted by 1-24C alkyl, interrupted by heteroatoms and substituted); or CR 16-30C (non)aromatic cycle or 5-12 membered heterocycle comprising one or more heteroatoms, where the cylce or heterocycle is optionally substituted and/or condensed; R 21-24C alkoxy, 1-24C alkyl (both interrupted by one or more heteroatoms and/or substituted), H or halo; either R 3H, optionally substituted 1-6C alkyl interrupted by one or more heteroatoms or carbonyl group; and R 4optionally substituted 1-24C alkyl interrupted by one or more heteroatoms or carbonyl group and/or by one or more heterocycles, or optionally substituted aryl; or NR 4, NR 3optionally substituted 5-10 membered heterocycle comprising optionally one or more heteroatoms other then N atom carrying R 4; and X ->inorganic or organic anion. Independent claims are included for: (1) a cosmetic composition comprising one or more direct dyes in a coloring medium; (2) a method for the treatment of keratin fibers, preferably human keratin fibers comprising applying the composition on dry or wet keratin fibers for a sufficient time to obtain the color, then rinsing, washing optionally using shampoo, again rinsing and drying the fibers; (3) a device with several compartments or coloring kit comprising a first compartment comprising the cosmetic composition and a second compartment comprising a composition containing one or more oxidizing agents; and (4) a cationic cyanine derivative of formula (II). R 3H; and R 6, R 71-24C alkyl interrupted by one or more heteroatoms and substituted. [Image] [Image].

Description

PATENT APPLICATION B07-0872FR GD / GL OA07450 SAID OREAL USE OF AT LEAST ONE CYANINE CATIONIC DERIVATIVE FOR HAIR COLORING, COMPOSITION CONTAINING THE SAME, PROCESS FOR TREATING KERATINOUS FIBERS USING THE SAME, DEVICE AND UTILIZATION OF: Alain LAGRANGE 2 Use of at least one cyanine cationic derivative for hair dyeing, composition containing it, process for treating keratin fibers using said composition, device and use The invention relates to the use of one or more particular direct dyes derived from cationic cyanine for hair dyeing. The invention also relates to a cosmetic composition comprising, in a medium suitable for staining, one or more particular direct dyes derived from cationic cyanine. The subject of the invention is also a process for treating keratinous fibers involving this composition, as well as a device comprising it. Finally, it relates to the use of the composition according to the invention as a coloring agent for said fibers. The present invention relates to the field of dyeing keratinous fibers and more particularly to hair dyeing. There are basically two types of coloring. The first type of staining is so-called semi-permanent staining or direct staining, which uses dyes capable of providing more or less marked modification to the natural coloration of the hair. The dyes involved are colored and coloring substances which have a certain affinity with the keratinous fiber. It should be noted that this type of color fades after several washes, which can be a disadvantage. On the other hand, dye homogeneity results with these direct dyes are rarely satisfactory, i.e., the dye has differences between the differently sensitized portions of the hair fibers. It is said that the colorations are selective.

In the case where it is desired to obtain a coloration lighter than the original color of the fibers, it is necessary to use with the direct dyes, at least one oxidizing agent, under conditions of alkaline pH. However, these processing conditions are not without consequences on the properties of the treated fibers. Indeed, in the long run, the fibers are more or less degraded and tend to become rough, dull, brittle and difficult to comb. The second type of staining is permanent staining or oxidation staining. This is carried out with oxidation dye precursors which are colorless or weakly colored compounds, comprising at least one oxidation base possibly associated with one or more couplers. Once mixed with oxidizing products, at the time of use, the precursors can give rise by a process of oxidative condensation to colored compounds and dyes. Given the necessary presence of an oxidizing agent in this type of coloration, the disadvantages mentioned above are also found in this case. It has recently been found that compositions comprising at least one fluorescent direct dye have an interesting alternative to conventional processes employing an oxidizing agent. Thus, for dark hair, more particularly whose pitch is less than or equal to 6 (dark blond), preferably less than or equal to 4 (chestnut), it has been found that there are areas for which the curve reflectance versus wavelength (between 500 and 700 nm) of the hair treated with the composition comprising the fluorescent compound was greater than the curve corresponding to untreated hair. Therefore, the hair

4 appear lightened, without the need to use an oxidizing agent. It is recalled that the notion of "tone" is based on the classification of natural nuances, a tone separating each nuance from that which immediately follows or precedes it. This definition and the classification of natural shades are well known to professionals in the hair and published in the book Sciences capillary treatments Charles ZVIAK 1988, Ed.Masson, pp.215 and 278. The heights range from 1 (black) to 10 (light light blond), a unit corresponding to a tone; the higher the number, the clearer the nuance. Furthermore, it is important to have compositions which make it possible to obtain staining which is sufficiently stubborn with regard to washes and the action of light, which is rarely the case with the colorations obtained with the direct dyes, which are fluorescent. or not fluorescent. In addition, the storage stability of these compositions can be improved. There is therefore a real need to find compounds which do not have the drawbacks mentioned above. Surprisingly and advantageously, the Applicant has just discovered a new family of particular direct dyes derived from cationic cyanine for the preparation of dyeing compositions of keratinous fibers, in particular human keratinous fibers such as the hair, which made it possible to obtain colorations. with properties of stability, selectivity (color variation between the different parts of a hair or a hair) and satisfactory tenacity. In particular, it has been observed that these particular direct dyes were more stable in an alkaline oxidizing medium. The present invention therefore particularly relates to the use of one or more compounds corresponding to the following formula (I): B (I) X in which: A represents an aromatic heterocycle comprising 5 to 12 ring members, comprising at least a cationic charge on a nitrogen atom and optionally comprising one or more other heteroatoms selected from nitrogen, oxygen and / or sulfur; said aromatic heterocycle being optionally substituted and / or condensed with one or more aromatic rings; B represents an alkylene group CH 2 or (CH 2) 2; R1 represents a hydrogen atom; a halogen atom; a hydroxyl group; a linear, branched or cyclic C1-C24, preferably C1-C4, alkyl radical which may be interrupted by one or more heteroatoms and / or may be substituted; an optionally substituted benzyl or aryl radical; a linear or branched C1-C24, preferably C1-C4, alkoxy group which may be interrupted by one or more heteroatoms and / or may be substituted; an unsubstituted amino group, mono- or disubstituted with one or more C1-C24, preferably C1-C4, linear or branched alkyl groups which may be interrupted by one or more heteroatoms and / or may be substituted, the substituent (s) amino group capable of forming together a saturated or unsaturated heterocycle comprising 5 to 12 members, preferably 5 to 9 members, optionally substituted and / or condensed with one or more optionally aromatic rings;

R 1 may form with a carbon atom of the alkylene group B, a saturated or unsaturated aromatic or non-aromatic C 6 -C 30 or heterocyclic ring comprising from 5 to 12 members and one or more heteroatoms; said ring or heterocycle being optionally substituted and / or fused; R2 represents a hydrogen atom; a halogen atom; a linear or branched C1-C24, preferably C1-C4, alkoxy group which may be interrupted by one or more heteroatoms and / or may be substituted; a linear or branched C1-C24, preferably C1-C4, alkyl radical which may be interrupted by one or more heteroatoms and / or may be substituted; R3 represents a hydrogen atom or a linear or branched, substituted or unsubstituted C1-C6 alkyl radical which may be interrupted by one or more heteroatoms or one or more carbonyl groups; R3 can form with a ring A carbon atom a saturated or unsaturated 5- to 6-membered ring optionally comprising one or more heteroatoms; R4 represents a C1-C24, preferably C1-C4, linear, branched or cyclic, substituted or unsubstituted alkyl radical which may be interrupted by one or more heteroatoms or one or more carbonyl groups and / or by one or more heterocycles; a substituted or unsubstituted aryl radical; R4 can form with the nitrogen atom carrying it and with the substituent R3, a heterocycle comprising 5 to 10 members, saturated or unsaturated, substituted or unsubstituted, and optionally comprising one or more heteroatoms other than the nitrogen atom R4 carrier; X- represents an organic or mineral anion.

As a coloring agent for keratinous fibers, in particular human fibers such as the hair, and / or as an agent for the optical lightening of these fibers. By optical brightening is meant a visible and visual lightening obtained without the use of oxidizing agent. These dyes make it possible to obtain powerful, chromatic, not very selective and tenacious colorings. The direct dye (s) according to the present invention make it possible to obtain lighter dyes than the original color of the keratin fibers, when it is applied to dark fibers, without the presence of an oxidizing agent being necessary. But of course, it is not excluded that the dye or dyes are used in the presence of such an agent. Similarly, the present invention relates to a cosmetic composition which comprises, in a medium suitable for staining, one or more direct dyes of formula (I) as defined above. Another subject of the present invention consists in a process for dyeing keratin fibers, in which the composition based on the particular direct dyes derived from cationic cyanine of formula (I) is applied to said fibers. Another object of the present application relates to a compartment device comprising the composition according to the invention. The present invention also relates to the use of the composition as a coloring agent or as an optical fiber brightener. Another object of the present application relates to direct dyes derived from cationic cyanine of formula (II) which are particular compounds of direct dyes derived from cationic cyanine of formula (I). But other features, aspects, objects and advantages of the present invention will become more apparent upon reading the description and examples which follow. In the context of the definitions of the groups R1, R2, R3, R4, R5, and / or A, by the term substituted, is meant substituted; one or more linear or branched C1-C6 alkyl groups, preferably methyl or ethyl; sulfonic; carboxyl; carboxylate; linear or branched C1-C6 alkoxy, preferably a methoxy group; halogen atoms; aryl radicals optionally substituted with one of the abovementioned substituents; phenylcarbonyl radicals. In the case where R1, R2, R3, R4, R5 and / or A comprise at least one substituted linear or branched alkyl group then this or these alkyl groups can not be substituted by one or more linear or branched alkyl groups. Preferably, A represents a non-condensed aromatic heterocycle such as pyridinium, or optionally substituted imidazolium. More preferably, A represents an optionally substituted pyridinium radical.

Alternatively, A represents an aromatic heterocycle which is condensed with one or more aromatic rings. In this case, by way of examples, A may be chosen from quinolinium, indolinium, benzothiazolium and optionally substituted benzoxalium. Preferably, A represents an optionally substituted benzothiazolium radical. Preferably, in formula (I), R 2 represents a hydrogen atom, R 3 represents a hydrogen atom or forms with a carbon atom of ring A, a saturated or unsaturated 5-membered ring, R 1 represents a hydrogen atom, hydrogen, a C 1 -C 24 alkoxy radical, preferably a C 1 -C 4 alkoxy radical, an unsubstituted amino radical, an amino radical

9 substituted by one or more C1-C4 alkyl radicals or forms with a carbon atom of the alkylene group B, a C6-C30 aryl radical, R4 represents a C1-C24, preferably C1-C4, alkyl radical, optionally substituted in particular by one or more halogen atoms, a phenylcarbonyl radical and B denotes a methylene or ethylene radical. According to a particular embodiment, B represents (CH 2) 2; A represents a pyridinium radical optionally substituted with one or more C1-C4 alkyl groups, preferably with a methyl group; R2 and R3 represent a hydrogen atom; R1 represents a hydrogen atom or a C1-C6 alkoxy group, preferably a methoxy group, and R4 represents a C1-C4 alkyl group, preferably a methyl group. According to a variant, B represents (CH 2) 2; A represents a benzothiazolium radical optionally substituted with one or more C1-C4 alkyl groups, preferably with a methyl group; R2 and R3 represent a hydrogen atom; R1 represents a hydrogen atom or a C1-C6 alkoxy group, preferably a methoxy group, and R4 represents a C1-C4 alkyl group, preferably an ethyl group. According to another particular embodiment, B represents CH 2; A represents a benzothiazolium radical optionally substituted with one or more C1-C4 alkyl groups, preferably with a methyl group; R2 and R3 represent a hydrogen atom; R1 represents an unsubstituted amino group and R4 represents a C1-C4 alkyl group, preferably a methyl group. According to a variant, B represents CH 2; A represents a pyridinium radical optionally substituted with one or more C1-C4 alkyl groups, preferably with a methyl group, or with one or

Several phenyl radicals; R1 represents a dialkyl (C1-C4) amino group or forms with the carbon atom of the group B an aromatic ring; R2 and R3 represent a hydrogen atom or R3 forms with a ring A carbon atom, a saturated or unsaturated 5-membered ring and R4 represents a C1-C6 alkyl radical optionally substituted with one or more halogen atoms, a phenylcarbonyl radical. It should be noted that X- may be an anion of mineral origin chosen in particular from halides, perhalogenates, sulphates, bisulfates, nitrates, phosphates, hydrogen phosphates, dihydrogen phosphates, boronates, carbonates and bicarbonates. . The anion X- may also be of organic origin, and in this case, more particularly chosen from those originating from salts of mono- or polycarboxylic acids, sulphonic, sulfuric, saturated or unsaturated, aromatic or otherwise, optionally substituted with minus a hydroxyl, amino, or halogen atom. In particular, X- is chosen from chloride, bromide, iodide, perchlorate, sulfate, methosulphate, ethosulphate or toluenesulphonate.

Preferably, the compounds of formula (I) are chosen more particularly from the compounds of formula (II) below: X in which: R2, R3, R4, A, B and X- have the same meanings as in the case of formula (I);

R6 and R7 represent, independently of one another, a hydrogen or halogen atom; a linear or branched C1-C24, preferably C1-C4, alkyl radical which may be interrupted by one or more heteroatoms and / or may be substituted; when R6 and R7 represent a linear C1-C24 alkyl radical which may be interrupted by one or more heteroatoms and / or may be substituted, said alkyl radicals may together form a saturated or unsaturated heterocycle comprising 5 to 12 optionally substituted and / or condensed with one or more optionally aromatic rings. More preferably, in formula (II), A represents a pyridinium radical and B represents CH2. According to a particular embodiment, in the formula (II), when A represents a pyridinium radical, the bicycle may be in the ortho position with respect to the group N + R4. According to another preferred variant, in the formula (II), when A represents a pyridinium radical, the bicycle may be in the para position relative to the N + R 4 group. In formula (II), according to another embodiment, B represents CH 2; A represents a pyridinium radical optionally substituted with one or more C1-C4 alkyl groups, preferably unsubstituted; R2 and R3 represent a hydrogen atom; R6 and R7 represent, independently of one another, a C1-C6 linear alkyl radical, preferably a methyl group, and R4 represents a C1-C4 alkyl radical optionally substituted with a halogen atom, preferably chlorine, or can form with the nitrogen atom carrying it and with the substituent R3, a 5-membered heterocycle, saturated or unsaturated, substituted or unsubstituted, and optionally comprising one or more heteroatoms.

The direct dye entering according to the invention is generally a fluorescent molecule, that is to say which colors by itself, absorbs the light of the visible spectrum and possibly also the ultraviolet (wavelengths from 360 to 760 nanometers) but which, unlike a conventional dye, transforms a portion of the energy absorbed into fluorescent light of longer wavelength than that absorbed, emitted in the visible part of the spectrum. In addition, the fluorescent dye according to the invention is a dye which generates a fluorescence on the support on which it is applied.

According to the present invention, the direct dye is preferably soluble in the medium of a composition at least 1 gram per liter and preferably at least 5 grams per liter at a temperature of 25 ° C. According to a particularly advantageous embodiment of the invention, the compound of formula (I) corresponds to one of the following compounds: ## STR1 ## 3,4-Dihydro-1 (2H) - 3 - [(3,4-dihydro-6-methoxy-1 (2H) -naphthalenylidene) methyl] -3-naphthalenylidene) methyl] -1,4-ethyl-3 benzothiazolium dimethyl-, pyridinium (Z) Me Me N + + Me Me X_ 1 OMe X Salt of 3 - [(3,4-dihydro-1 (2H) - salt of 3 - [(3,4-dihydro-6 methoxy-1 (2H) -naphthalenylidene) methyl] -1,4-naphthalenylidene) methyl] -1,4-dimethylpyridinium (Z) dimethylpyridinium (E) Me Me + I + Me E ~ / X-E 3 - [(3,4-dihydro-6-methoxy-naphthalenylidene) methyl] -1,4-i (3 - [(3,4-dihydro-1 (2H)] - iodide salt ( 2H) -naphthalenylidene) methyl] -1,4-dimethylpyridinium (E) dimethylpyridinium (E) Me Me + + Z e E + O I - iodide of 3 - [(3, 3 - [(3,4-Dihydro-1 (2H) -methoxy-1 (2H) -naphthalenylidene) methyl] -1,4-naphthalene 4-dihydro-6-iodide lidene) methyl] -1,4-dimethyl- (E) -pyridinium dimethyl- (Z) -pyridinium Me Et / + 1H 3 - [(3,4-dihydro-1) 3-iodide 2H) - 2 - [(3,4-Dihydro-1 (2H) -naphthalenylidene) methyl] -1,4-naphthylidene) methyl] -3-dimethyl- (Z) -pyridinium ethylbenzothiazolium iodide PE Met Ph + 00 N * to X C104 2 - [[5- (4 - [[5- (Dimethylamino) -2,3-dihydro- (dimethylamino) -2,3-dihydro-1H-inden-1-ylidene] salt methyl] -1-methyl-1H-inden- 1 -ylidene] methyl] -3-2,6-diphenylpyridinium methyl-benzothiazolium CH ph N N, N Ph - X l v + \ CH2-IPh 4- (1 (2H) br- Bromide - 5- [5- (Dimethylamino) -2,3-dihydro-1H-acenaphthylenylidenemethyl) -1- (2-oxo-2-inden-1-ylidene) salt 6,7-dihydro-2-methyl-1,3-phenylethyl) pyridinium diphenyl-5H-cyclopenta [c] pyridinium o 0 N / .SO 2 / N + 0 O • o I / / N Toluene-4-sulphonate 2- (5-Dimethylamino-indan-1- (4- (5-dimethylaminoindan-1-ylidenemethyl) -1-ylidenemethyl) -1-ethyl-pyridiniumethyl toluene-4-sulfonate 1-pyridinium Cl Cl + Os / ~ N + / I / / N 0- 0 // 1- (5-Dimethylamino) 1- (2-Chloro-ethyl) -4- (5-toluene-4-sulfonate) chloride indan-dimethylamino-indan-1-ylidenemethyl) -1-ylidene) -2,3-dihydro-1H-pyridinium indolizinylium The anions mentioned in this table above are given by way of example only. The nature of the anion is not critical in terms of the dyeing result. The synthesis of these dyes is known. By way of example, mention may be made of the articles Sczepan Phys.chem.Chem.Phys. 2001,3,3555-3561 and Photochem. Photobiolo.Sci 2003, pages 1264-3561.

The invention further relates to a cosmetic composition comprising the direct dye (s) of formulas (I) in a medium suitable for dyeing. The direct dye (s) of formula (I) may be present in a content by weight ranging from 0.001 to 10% by weight, preferably in a content by weight ranging from 0.01 to 8% by weight, and more preferably in a weight content ranging from 0.1 to 5% by weight, relative to the total weight of the composition. The appropriate medium for the coloration also called staining medium is a cosmetic medium generally consisting of water or a mixture of water and one or more organic solvents to solubilize compounds that are not sufficiently soluble in the water. water. By way of organic solvent, mention may be made, for example, of linear or branched C 1 -C 4 alkanols, such as ethanol and isopropanol; glycerol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethano, and mixtures thereof. The solvent or solvents may be present in proportions ranging preferably from 1 to 40% by weight relative to the total weight of the dyeing composition, and even more preferably from 5 to 30% by weight approximately.

The pH of the composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in the field.

Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids. Among the alkalinizing agents that may be mentioned, by way of example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula (III): wherein R is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 6 alkyl radical; Rx, Ry, Rz and Rt, which may be identical or different, represent a hydrogen atom, a C1-C6 alkyl radical or a C1-C6 hydroxyalkyl radical.

The cosmetic composition may further comprise one or more additional direct dyes of nonionic, cationic or anionic, and preferably cationic or nonionic nature, or combinations thereof. Generally, these direct dyes are chosen from nitric, neutral, acidic or cationic benzene dyes, neutral acidic or cationic neutral dyes, azomethine, methine, quinonic direct, acidic or cationic neutral anthraquinone, naphthoquinone, benzoquinone, direct azine dyes, phenotiazinic indigoids, xanthenics, phenanthridines, phthalocyanines, those derived from triarylmethane, triarylmethane direct dyes, indoamine direct dyes, natural direct dyes, alone or in mixtures. It may for example be chosen from the following benzene dyes: 1-hydroxy-3-nitro-4-N- (γ-hydroxypropyl) amino benzene, N - ((3-hydroxyethyl) amino-3-nitro- 4-amino benzene, 1-amino-3-methyl-4-N - ((3-hydroxyethyl) amino-6-nitro benzene, 1-hydroxy-3-nitro-4-N - ((3- hydroxyethyl) amino benzene, 1,4-diamino-2-nitrobenzene, 1-amino-2-nitro-4-methylamino benzene, N - ((3-hydroxyethyl) -2-nitro-para-phenylenediamine, - 1-amino-2-nitro-4 - ((3-hydroxyethyl) amino-5-chloro benzene, 2-nitro-4-amino-diphenylamine, -1α-amino-3-nitro-6-hydroxybenzene. 1- (3-aminoethyl) amino-2-nitro-4- (3-hydroxyethyloxy) benzene, 1- (R, y-dihydroxypropyl) oxy-3-nitro-4- (3-hydroxyethyl) amino benzene, 1-hydroxy-3-nitro-4-aminobenzene, 1-hydroxy-2-amino-4,6-dinitrobenzene, 1-methoxy-3-nitro-4- (3-hydroxyethyl) amino benzene, 2-nitro-4'-hydroxydiphenylamine, 1-amino-2-nitro-4-hydroxy-5-methylbenzene, 1- (3-hydroxyethyl) thyloxy-3-methylamino-4-nitrobenzene, 1-methylamino-2-nitro-5- (3, y-dihydroxypropyl) oxybenzene, 1 - ((3-hydroxyethyl) amino-2-methoxy-4- nitrobenzene, 1 - ((3-aminoethyl) amino-2-nitro-5-methoxy-benzene, 1,3-di ((3-hydroxyethyl) amino-4-nitro-6-chlorobenzene, amino-2-nitro-6-methyl-benzene, 1 - ((3-hydroxyethyl) amino-2-hydroxy-4-nitrobenzene, N - ((3-hydroxyethyl) -2-nitro-4- trifluoromethylaniline, 4 - ((3-hydroxyethyl) amino-3-nitro-benzenesulfonic acid,

4-ethylamino-3-nitro-benzoic acid, 4 - ((3-hydroxyethyl) amino-3-nitro-chlorobenzene, 4 - ((3-hydroxyethyl) amino-3-nitro-methylbenzene 4- (3,5-dihydroxypropyl) amino-3-nitro-trifluoromethylbenzene, 1 - ((3-ureidoethyl) amino-4-nitrobenzene, 1,3-diamino-4-nitrobenzene, - 1-hydroxy-2-amino-5-nitrobenzene, 1-amino-2- [tris (hydroxymethyl) methyl] amino-5-nitrobenzene, 1 - ((3-hydroxyethyl) amino-2- nitrobenzene, 4- (3-hydroxyethyl) amino-3-nitrobenzamide, Among the additional blue or violet nitro-benzene direct dye additives, mention may be made, for example, of the compounds chosen from: 1- (3-hydroxyethyl) amino-4 N, N-bis- (3-hydroxyethyl) amino-2-nitrobenzene, 1- (y-hydroxypropyl) amino 4-N, N-bis - ((3-hydroxyethyl) amino-2-nitrobenzene, - ((3-hydroxyethyl) amino-4- (N-methyl, N- (3-hydroxyethyl) amino-2-nitrobenzene, 1 - ((3-hydroxyethyl) amino 4- (N-ethyl, N- (3- hydroxy ethyl) amino 2-nitrobenzene, 1- (3, yd) hydroxypropyl) amino-4- (N-ethyl, N- (3-hydroxyethyl) amino-2-nitrobenzene, 2-nitroparaphenylenediamines of the following formula NHRa NRbRc in which: Rb represents a C1-C4 alkyl radical, a radical; hydroxyethyl or (3-hydroxypropyl or γ-hydroxypropyl; Ra and Rc, which are identical or different, represent a 13-hydroxyethyl, - (3-hydroxypropyl, γ-hydroxypropyl, or (3, γ-dihydroxypropyl) radical, at least one of Rb, Rc or Ra radicals representing a radical y hydroxypropyl and Rb and Rc can not simultaneously designate a radical (3-hydroxyethyl when Rb is a γ-hydroxypropyl radical, such as those described in French Patent FR 2,692,572. The composition implemented in the context of this first variant may also comprise, in addition to or in substitution for these nitrated benzene dyes, azo dyes, anthraquinone, naphthoquinone or benzoquinone dyes, indigo dyes, or dyes derived from triarylmethane, which direct dyes may in particular be basic dyes, among which mention may be made more particularly of the colorants known in the Color Index, 3rd edition, under the names "Basic Brown 16", "Basic Brown 17", "Basi c Yellow 57 "," Basic Red 76 "," Basic Violet 10 "," Basic Blue 26 "and" Basic Blue 99 ", or acid direct dyes, among which we can more particularly mention the dyes known in the Color Index, 3rd edition, under the names "Acid Orange 7", "Orange Acid 24", "Acid Yellow 36", Acid Red 33 "," Acid Red 184 "," Acid Black 2 "," Acid Violet 43 ", and" Acid Blue 62 ", or cationic direct dyes such as NO2

Those described in patent applications WO 95/01772, WO 95/15144 and EP 714954 and the content of which forms an integral part of the present invention, and in particular the following cationic direct dyes: Basic Red 51, Basic Orange 31, Basic Yellow 87.

Among the natural direct dyes include henna, chamomile, indigo, among others. When they are present, the additional direct dye (s) preferably represent from 0.001 to 10% by weight, and even more preferably from 0.01 to 8% by weight relative to the total weight of the composition. When it is intended for the oxidation dyeing, the cosmetic composition in accordance with the invention also comprises one or more oxidation bases chosen from oxidation bases conventionally used for oxidation dyeing and among which one mention may in particular be made of paraphenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases and their addition salts with an acid or with an alkaline agent. Among the para-phenylenediamines, para-phenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine and 2,6-diethyl-para-phenylenediamine may be mentioned by way of example; 2,5-dimethyl paraphenylene diamine, N, N-dimethyl para-phenylenediamine, N, N-diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl 3-methyl aniline, N, N-bis - ((3-hydroxyethyl) para-phenylenediamine, 4-N, N-bis - ((3-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- ( (3-hydroxyethyl) amino 2-chloroaniline, 2-13-hydroxyethyl paraphenylenediamine, 2-fluoro-para-phenylenediamine,

2-isopropyl paraphenylenediamine, N- (P-hydroxypropyl) paraphenylenediamine, 2-hydroxy-methyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, (3-hydroxyethyl) paraphenylene diamine, N- (3'-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-P-hydroxyethyloxy para-phenylenediamine, 2-P-acetylaminoethyloxy para-phenylene diamine, N- (β-methoxyethyl) paraphenylenediamine and 4'-aminophenyl-1- (3-hydroxy) pyrrolidine, and their addition salts with an acid or with an alkaline agent. Among the para-phenylenediamines mentioned above, it is particularly preferred paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-P-hydroxyethyl paraphenylenediamine, 2-P-hydroxyethyloxy para-phenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylene diamine, 2,3-dimethyl paraphenylenediamine, N, N-bis - ((3-hydroxyethyl) paraphenylenediamine, 2-chloro-para-phenylene diamine, 2- (3-acetylaminoethyloxy) paraphenylene diamine, and their addition salts with an acid or with an alkaline agent.

Among the bis-phenylalkylenediamines, N, N'-bis- (13-hydroxyethyl) N, N'-bis- (4'-aminophenyl) -1,3-diaminopropanol may be mentioned by way of example, N, N'-bis - ((3-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'- bis- (β-hydroxyethyl) N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylene diamine, N, N'-bis (ethyl) N, N'-bis- (4'-amino, 3'-methylphenyl) ethylene-diamine, 1,8-bis- (2,5-diamino phenoxy) -3,5-dioxaoctane, and their addition salts with a acid or with an alkaline agent.

Among the para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro-phenol, 4-amino-3-hydroxymethyl-phenol may be mentioned by way of example, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (3-hydroxyethylaminomethyl) phenol, 4-amino-2-fluoro phenol, and their addition salts with an acid or with an alkaline agent. Among the ortho-aminophenols, 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-amino phenol may be mentioned by way of example, and their addition salts with an acid or with an alkaline agent. Among the heterocyclic bases, there may be mentioned more particularly by way of example, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives and their addition salts with an acid or with an alkaline agent. In particular, the heterocyclic oxidation bases are chosen from 2,4,5,6-tetraaminopyrrimidine, 1-13-hydroxyethyl-4,5-diaminopyrazole, 2,3-diamino-6,7-dihydro-1H- 5H-pyrazolo [1,2-A] pyrazol-1-one and their salts.

When used, the oxidation base (s) preferably represent from 0.001 to 10% by weight, and even more preferably from 0.01 to 8% by weight, relative to the total weight of the composition. When it is intended for the oxidation dyeing, the composition according to the invention may also comprise one or more couplers so as to modify or enrich in glints the shades obtained by using the direct dyes and the dye base (s). 'oxidation. The couplers that may be used may be chosen from the couplers conventionally used in oxidation dyeing and among which may be mentioned in particular meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers and heterocyclic couplers and their addition salts with an acid. or with an alkaline agent.

These couplers are more particularly chosen from 2-methyl-5-amino phenol, 5-N - ((3-hydroxyethyl) amino 2-methyl phenol, 3-amino phenol, 1,3-dihydroxy benzene, 1, 3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1 - ((3-hydroxyethyloxy) benzene, 2-amino-4 - ((3-hydroxyethylamino) -methoxy benzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol, 1-B-hydroxyethylamino -3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy N-methylindole, 2-amino-3-hydroxy pyridine, 6-hydroxybenzomorpholine 3,5-diamino-2,6-dimethoxypyridine, 1-N- (B-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- (13-hydroxyethylamino) toluene, 2,6-dihydroxy-4-methyl pyridine, 1-H 3 -methyl pyrazole-5-one, 1-phenyl-3-methyl-pyrazole-5-one, 2,6-dimethyl pyrazolo [1,5-b] -1,2,4-triazole, 2,6-dimethyl [3,2-c] -1,2,4-triazole, 6-methyl pyrazolo [1,5-b] a] -benzimidazole, and their addition salts with an acid or with an alkaline agent. When present, the coupler or couplers preferably represent from 0.001 to 10% by weight, and even more preferably from 0.01 to 8% by weight relative to the total weight of the composition.

In general, the addition salts with an acid that can be used in the context of the compositions of the invention (oxidation bases and couplers) are chosen especially from hydrochlorides, hydrobromides, sulphates, citrates and succinates. , tartrates, tosylates, benzenesulfonates, lactates and acetates. The addition salts with an alkaline agent that can be used in the context of the compositions of the invention (oxidation bases and couplers) are chosen in particular from the addition salts with the alkaline or alkaline-earth metals, with ammonia, with organic amines including alkanolamines and compounds of formula (III). The composition according to the invention can make it possible to obtain lighter dyes than the original color of the keratin fibers, when it is applied to dark fibers, without the presence of an oxidizing agent being necessary. But of course, it is not excluded that the composition according to the invention comprises such an oxidizing agent. The cosmetic composition according to the invention may also comprise one or more cosmetic adjuvants.

The cosmetic adjuvant (s), which are conventionally used in cosmetic compositions, in particular for dyeing human keratin fibers, may be chosen from anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof; inorganic or organic or polymeric thickeners; antioxidants; penetrants; sequestering agents; perfumes ; buffers; dispersants; conditioning agents such as, for example, cations, cationic or amphoteric polymers, chitosans, volatile or non-volatile silicones, modified or unmodified; film-forming agents; ceramides and pseudo-ceramides; vitamins and provitamins, sunscreens; solid compounds such as pigments, pearlescent agents; plasticizing agents, solubilizing agents, acidifying agents, basifying agents, neutralizing agents, hydroxy acids, solvents, penetrating agents, preserving agents; stabilizing agents; opacifying agents. Of course, one skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the composition according to the invention are not, or not substantially, impaired by the addition or additions considered. The composition according to the invention may be in various forms, such as in the form of liquids, shampoos, creams, gels, or in any other suitable form.

A particularly preferred form according to the present invention is a composition comprising in a cosmetically acceptable aqueous medium, one or more direct dyes as defined above, and one or more surfactants. These surfactants may be nonionic, anionic, cationic or zwitterionic. The anionic surfactants that can be used in the compositions of the invention are chosen in particular from salts, in particular alkali metal salts such as sodium salts, ammonium salts, amine salts, sodium salts and the like. aminoalcohols or alkaline earth metal salts, for example, magnesium, of the following types alkylsulfates, alkylethersulfates, alkylamidoethersulfates, alkylarylpolyethersulfates, monoglyceride-sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, α-olefins, sulfonates, paraffinsulfonates, alkylsulfosuccinates, alkylethersulfosuccinates, alkylamidesulfosuccinates, alkylsulfoacetates, acylsarcosinates and acylglutamates, the alkyl and acyl groups of all these compounds having from 6 to 24 carbon atoms and the aryl group denoting preferably a phenyl or benzyl group.

It is also possible to use C 6-24 alkyl monoesters and polyglycoside dicarboxylic acids such as alkyl glucoside citrates, alkyl polyglycoside tartrates and alkyl polyglycoside sulfosuccinates, alkylsulfosuccinamates, acylisethionates and N acetyltaurates, the alkyl or acyl group of all these compounds containing from 12 to 20 carbon atoms. Another group of anionic surfactants that can be used in the compositions of the present invention is that of acyl lactylates, the acyl group of which contains from 8 to 20 carbon atoms.

In addition, mention may also be made of alkyl-D-galactosideuronic acids and their salts as well as polyoxyalkylenated (C 6-24) alkyl ether carboxylic acids, (C 6-24) alkyl (C 6-24) aryl ether polyoxyalkylenated carboxylic acids, polyoxyalkylenated amidoether carboxylic acids and their salts, in particular those containing from 2 to 50 ethylene oxide units, and mixtures thereof. Alkyl sulphates, alkyl ether sulphates and mixtures thereof are preferably used, in particular in the form of alkali metal or alkaline earth metal salts, ammonium, amine or aminoalcohol. Examples of additional nonionic surfactants useful in the compositions of the present invention are described for example in "Handbook of Surfactants" by M. R. PORTER, Blackie & Son editions (Glasgow and London), 1991, pp. 116-178. They are chosen in particular from alcohols, alpha-diols and alkyl (C1-20) phenols having a fatty chain comprising, for example, from 8 to 18 carbon atoms, the number of ethylene oxide or propylene oxide groups being go in particular from 2 to 50 and the number of glycerol groups that can range from 2 to 30.

It is also possible to mention the condensates of ethylene oxide and of propylene oxide on fatty alcohols; the polyethoxylated fatty amides preferably having from 2 to 30 ethylene oxide units, the polyglycerolated fatty amides comprising on average from 1 to 5 glycerol groups and in particular from 1.5 to 4, the fatty acid esters of sorbitan ethoxylates having from 2 to 30 ethylene oxide units, sucrose fatty acid esters, polyethylene glycol fatty acid esters, (C6-24) alkyl polyglycosides, N- (C6-24) alkyl derivatives glucamine, amine oxides such as oxides

C 1 -C 14 alkyl) amines or N- (C 10-14) -aminopropylmorpholine oxides. The more particularly preferred nonionic surfactants are chosen from alkylpolyglucosides.

The amphoteric or zwitterionic surfactants that may be used in the present invention may be in particular derivatives of secondary or tertiary aliphatic amines, in which the aliphatic group is a linear or branched chain containing from 8 to 22 carbon atoms and containing at least one anionic group such as, for example, a carboxylate, sulfonate, sulfate, phosphate or phosphonate group. Mention may in particular be made of (C 8-20) alkyl betaines, sulphobetaines, (C 8-20) alkylamido (C 6-18) alkylbetaines or (C 8-20) alkylamido (C 6-18 alkyl) sulphobetaines. Among the amine derivatives, mention may be made of the products sold under the name MIRANOL, as described in US Pat. Nos. 2,528,378 and 2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982, under the names Amphocarboxy. glycinate and Amphocarboxypropionate of respective structures (A) and (B): Ra-CONHCH2CH2-N (Rb) (Re) (CH2O0-) (A) in which: Ra represents an alkyl group derived from an acid Ra-O00H present in hydrolyzed coconut oil, a heptyl, nonyl or undecyl group, Rb represents a beta-hydroxyethyl group, and Re represents a carboxymethyl group; and Ra'-CONHCH2CH2-N (B) (B ') (B) wherein B is -CH2CH2OX', B 'is - (CH2) z-Y', with z = 1 or 2, X 'is the group -CH2CH2-COOH or a hydrogen atom, Y 'represents -COOH or the group -CH2-CHOH-SO3H, Ra' represents an alkyl group of an acid Ra'-COOH present in coconut oil or in the hydrolysed linseed oil, an alkyl group, especially C 17 and its iso form, an unsaturated C 17 group. These compounds are classified in the CTFA dictionary, 5th edition, lauroamphodiacetate disodium, capryloamphodiacetate caprylamphodipropionate 1993, under the names cocoamphodiacetate disodium, disodium, disodium caprylamphodiacetate, disodium, cocoamphodipropionate disodium lauroamphodipropionate, disodium, disodium capryloamphodipropionate, cocoamphodipropionique . marketed lauroamphodipropionique acid, commercial acid By way of example, mention may be made of cocoamphodiacetate by Rhodia under the name MIRANOL C2M concentrate. The amphoteric or zwitterionic surfactants mentioned hereinabove are preferably C 8-20 alkylbetaines, C 8-20 alkylamido (C 6-18 alkyl) betaines and mixtures thereof. the invention one or more anionic surfactants and one or more amphoteric or zwitterionic surfactants Examples of cationic surfactants that may be mentioned include salts of primary, secondary or tertiary fatty amines, optionally polyoxyalkylenated; such as chlorides or bromides of tetraalkylammonium,

Alkylamidoalkyltrialkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium or alkylpyridinium; imidazoline derivatives; or oxides of amines with a cationic character. The surfactant (s) used in the composition according to the invention may be present in an amount ranging from 0.01% to 40% by weight, preferably ranging from 0.5% to 30%, relative to to the total weight of the composition. It is not excluded, even if this does not correspond to a preferred embodiment of the invention, that the composition contains one or more oxidizing agents chosen, for example, from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and enzymes such as peroxidases and two- or four-electron oxidoreductases. The use of hydrogen peroxide is particularly preferred.

Another subject of the invention is constituted by a process for treating keratinous fibers, in particular human keratinous fibers such as the hair. According to a first variant, a composition as defined is applied to said fibers, dry or wet, for a sufficient time, after which it is rinsed, optionally washed with shampoo, rinsed again and the fibers are dried or allowed to dry. resulting. According to a second variant of the process, a composition as defined is applied to said fibers, dry or wet, without final rinsing.

The first variant is usable for any type of compositions, whether or not these comprise an oxidizing agent and / or a direct dye and / or an oxidation base possibly associated with a coupler.

The second variant is suitable for compositions which do not comprise an oxidation dye (oxidation base and optionally coupler) or an oxidizing agent. In the case of the first variant of the method, the application time is usually sufficient to develop the desired coloration and / or lightening (s). As an indication, the duration of application of the composition is about 5 to 60 minutes and more particularly about 15 to 60 minutes.

Furthermore, the temperature at which the process according to the invention is carried out is generally between room temperature (15 to 25 ° C.) and 60 ° C. and more particularly between 15 and 45 ° C. In the case where the composition comprises an oxidizing agent, the method according to the invention comprises a preliminary step consisting in storing, in separate form, on the one hand, a composition comprising, in a medium suitable for coloring, one or more corresponding direct dyes. in the formula (I), optionally one or more additional direct dyes and / or optionally one or more oxidation bases optionally associated with one or more couplers, and secondly, a composition comprising, in a cosmetically medium acceptable, one or more oxidizing agents, then to proceed to their mixing at the time of use. Once this is done, the process according to the invention is carried out in accordance with what has been mentioned before. Another subject of the invention is a multi-compartment device, comprising at least one compartment containing a composition comprising one or more direct dyes corresponding to the formula (I) according to the invention, and at least one other compartment

31 comprising a composition comprising one or more oxidizing agents. This device may be equipped with means for delivering the desired mixture onto the hair, such as the devices described in patent FR 2586913.

Note that in the case where the composition contains one or more additional direct dyes and / or one or more oxidation bases optionally associated with one or more couplers, according to a first variant, this or these compounds are in the first compartment of the previously described device. According to a second variant, the additional direct dye (s) and / or the oxidation base (s) / coupler (s) are stored in a third compartment. It is specified that it would not be excluded to have a third variant combining the two previous ones, in which the additional direct dye (s) and / or the oxidation base (s) and possibly the coupler (s) would be partly in the first compartment, with the direct dye (s) corresponding to one of the formulas and partly in a third compartment. The subject of the present invention is also compounds of the following formula (II): embedded image in which: R 2, R 4, A, B and X have the same meanings as in the case of formula (I) ) previously defined; R3 denotes a hydrogen atom; R6 and R7 represent independently one or the other a C1-C24 alkyl radical, preferably C1-C4, linear or branched,

32 can be interrupted by one or more heteroatoms and / or can be substituted. Preferably, A denotes a pyridinium ring optionally substituted with one or more C 1 -C 4 alkyl and / or C 6 -C 30 aryl groups. The following examples are intended to illustrate the invention without limiting its scope. EXAMPLES 1. EXAMPLE 1: Synthesis of 2 (5-dimethylaminoindan -ylidenemethyl) -1-ethyl-pyridinium N BuLi toluene sulfonate AT)

Step 1: Synthesis of 5-dimethylamino-1-indanone (A)

This synthesis was carried out from commercial 5-fluoro-1-indanone treated with dimethylamine dissolved in tetrahydrofuran at 80 ° C. A similar reaction is described in particular in the literature (Chem.Pharm Bull 1993, 41, 529-538).

Step 2: Synthesis of the compound (1):

In a 100 ml bicol under an inert atmosphere, 2-picoline (0.62 mL, 6.6 mmol, 1.04 equivalents) is solubilized in 30 mL of ethyl ether. The reaction mixture is maintained at 0 ° C. and 1.6M n-BuLi (3.9 mL, 6.24 mmol, 0.99 equiv.) Is added dropwise while maintaining the temperature below 5 ° C. ° C. The reaction mixture is then stirred for 1 hour at room temperature and then cooled to 0 ° C. Compound (A) (1.1 g, 6.3 mmol, 1 equivalent),

34 dissolved in 30 mL of tetrahydrofuran, is then added at 0 ° C and stirring maintained at room temperature overnight. The reaction medium is then acidified with 20 ml of a solution of 2N HCl and the stirring is maintained for 2 hours at room temperature. The aqueous phase is then extracted with ethyl acetate to remove the impurities, then basified with 1N NaOH, extracted with ethyl acetate, dried (Na 2 SO 4) and reconcentrated under reduced pressure. The compound (1) is obtained after chromatography on silica gel (eluent ethyl acetate / hexane 1/4) as a yellow solid.

Step 3: Synthesis of cyanine (2):

In a 15 ml bicol, under an inert atmosphere, the compound (1) (700 mg, 2.79 mmol, 1 equivalent) and ethyl p-toluenesulfonate (560 mg, 2.79 mmol, 1 equivalent) are solubilized in 7 ml of Anhydrous 1,2-dichloroethane. The reaction mixture is refluxed for 4 hours, cooled and reconcentrated under reduced pressure. The cyanine (2) is obtained after chromatography on silica gel (eluent MeOH / CH2Cl2 5/95) in the form of an orange-red solid. The proton NMR and mass spectra are consistent with the expected structure of the product.

EXAMPLE 2 Synthesis of 4- (5-Dimethylaminoindan-1-ylidenemethyl) -1-ethylpyridinium (4) (3) N (A) Toluene-4-sulfonate

at. Step 1: Synthesis of the compound (3)

In a 100 ml bicol under an inert atmosphere, N, N-diisopropylamine (0.89 mL, 6.6 mmol, 1.11 equivalents) is solubilized in 25 mL of anhydrous tetrahydrofuran. The reaction mixture is kept at 0 ° C. and 1.6 M n-butyllithium (4 mL, 6.4 mmol, 1.13 equivalents) is added dropwise at 0 ° C. The reaction mixture is then stirred for 15 minutes at 0 ° C., cooled to -50 ° C. and 4-picoline (5) (0.61 mL, 6.28 mmol, 1.1 equivalents) added to the reaction medium and maintained under stirring at -50 ° C for 1 hour. Compound (A), the synthesis of which is described in Example 1 (1 g, 5.71 mmol, 1 equivalent), dissolved in 10 ml of tetrahydrofuran, is then added at -50 ° C. and stirring is maintained at -50 ° C. C for 1 hour and at room temperature all night. The reaction medium is then acidified with 20 ml of a 2N HCl solution and the stirring is maintained for 2 hours at room temperature. The aqueous phase is then extracted with ethyl acetate to remove impurities.

The aqueous phase is then basified with 1N NaOH solution and extracted with ethyl acetate, dried (Na 2 SO 4) and reconcentrated under reduced pressure. 1 g of compound (3) is obtained after chromatography on silica gel (eluent ethyl acetate / hexane 3/2) in the form of a yellow solid.

b. Step 2: Synthesis of cyanine (4)

In a 15 ml bicol, under an inert atmosphere, the compound (3) (700 mg, 2.79 mmol, 1 equivalent) and ethyl p-toluenesulfonate (728 mg, 3.63 mmol, 1.3 equivalents) are solubilized. in anhydrous CH2Cl2 (7 mL). The reaction mixture is refluxed for 22 hours, cooled and reconcentrated under reduced pressure. The compound (4) (800 mg) is obtained after chromatography on silica gel (eluent MeOH / CH2Cl2 5/95) in the form of a red solid. The proton NMR and mass spectra are consistent with the expected structure of the product.

Example 3 Synthesis of 1- (2-Chloro-ethyl) -4- (5-20-dimethylaminoindan-1-ylidenemethyl) -pyridinium chloride

(3) The same procedure as in Example 2 is carried out with 1,2-dichloroethane as the reaction solvent. The proton NMR and mass spectra are consistent with the expected structure of the product. Example 4 Synthesis of cyanine (7) oo, o o- (7) Step 1: Synthesis of Compound (5): In a 3-necked 500 ml, under an inert atmosphere, the compound (4) (3.9 g; 18.6mmol, 3.1 equiv) is solubilized in anhydrous Et2O (100mL). TMEDA (3.05 mL, 20.1 mmol, 3.4 equiv) is added and the reaction medium is cooled to -60 ° C. NBuLi (1.6M in hexane) (12.8 mL, 20.1 mmol, 3.4 equiv) is added dropwise at -60 ° C to -55 ° C. The reaction medium is stirred for 30 minutes and a solution of compound (2) (1.03 g, 5.9 mmol, 1.0 equiv) in anhydrous THF (12 mL) is added dropwise over 5 minutes between -60. ° C and -55 ° C. The reaction mixture is stirred for 16 hours, allowing the temperature to rise gradually to room temperature. A 2N aqueous HCl solution (12mL) is added and stirring is continued for an additional 2.5 hours at room temperature. The mixture is concentrated under reduced pressure at room temperature and then basified by the addition of a 2N aqueous sodium hydroxide solution to a pH-12. The aqueous phase is extracted with AcOEt (3x200mL). The combined organic phases are dried over MgSO 4, filtered and then concentrated under reduced pressure. The solid obtained is

38 purified by chromatography on silica gel (eluent AcOEt / cyclohexane: 50/50). The compound (5) corresponding to a mixture of compounds (5) and (6) (ratio 1/1) is obtained in the form of a beige solid. Step 2: Synthesis of cyanine (7) In a 100mL monocol, the compound (5) (450mg, 1.44mmol, 1.0 equiv) is solubilized in anhydrous toluene (50mL). PBr 3 (1.75mL, 17.3mmol, 12.0 equiv) is added and the mixture is heated at -90 ° C for 16 hours. After returning to ambient temperature, MeOH (50 mL) is added and the mixture is then evaporated to dryness under reduced pressure. Water (40 ml) is added, the resulting aqueous phase is washed with DCM (3 × 100 ml) and then basified by adding saturated aqueous NaHCO 3 solution to pH 9. A saturated aqueous solution of NaCl (80 mL) is added and the resulting aqueous phase is extracted with DCM (4x250mL). The organic phases are combined, dried over MgSO 4, filtered and concentrated under reduced pressure. The crude solid obtained is purified by passage over a pad of silica gel (eluent: DCM / MeOH 90/10). The red solid obtained is taken up in EtOH and the solution is concentrated under reduced pressure. The compound (7) is obtained in the form of a red solid. EXAMPLES OF TINCTORIAL COMPOSITIONS The dye (2) has the following structure: (2) The compound (2) is used in the following dyeing compositions (A) ) and (B): Composition Composition AB Colorant (2) 0.5% 0.5% Alkyl (C8 / C10 50/50) Polyglucoside 5% 5% PEG-8 6% 6% Benzyl alcohol 4% 4% Hydroxyethyl cellulose (MW 720,000) 2% 2% Buffer pH4, pH7 or pH9 50% - Ammonia 20% - 13% Water Qsp 100 Qsp 100 The compositions (A) and (B) are applied for 30 minutes at room temperature (23 ° c + / - 3 ° C) on locks of hair 90% natural white. After rinsing, shampooing and drying with a helmet for 30 minutes, the hair has an intense coppery color. Similar formulations were made by replacing the pH9 buffer with pH4 and pH7 buffers. The intense copper is found. Example 2: The dyes (4) and (5) have the following structures: (4) (5) The compounds (4) and (5) are used in the following compositions (C) and (D): Composition Composition CD Colorant 4 0.5% - Color 5 -0.5% Alkyl (C8 / C10 50/50) Polyglucoside 5% 5% PEG-8 6% 6% Benzyl alcohol 4% 4% Hydroxyethyl cellulose (MW 720,000) 2 Buffer pH4, pH7 or pH9 50% Ammonia 20% 13% Water Qsp 100 Qsp 100 The compositions (C) and (D) are applied for 30 minutes at room temperature (23 ° C +/- 3 ° C) on 90% natural white hair locks.

After rinsing, shampooing and drying with a helmet for 30 minutes, the hair has a deep red coppery color. Analogous formulations were made by replacing the pH9 buffer with pH4 and pH7 buffers. The intense red copper is found. Example 3: The dye (7) has the following structures N (7) The compound (7) is used in the following dyeing compositions (E) and (F): Composition Composition EF Colorant (7) 0.5% 0 , 5% Alkyl (C8 / C10 50/50) 5% 5% polyglucoside PEG-8 6% 6% Benzyl alcohol 4% 4% Hydroxyethyl cellulose (MW 2% 2% 720,000) Buffer pH4, pH7 or pH9 50% - Ammonia at 20% - 13% Water Qs 100 Qs 100

The compositions (E) and (F) are applied for 30 minutes at room temperature (23 ° C +/- 3 ° C) on locks of hair 90% natural white.

After rinsing, shampooing and drying with a helmet for 30 minutes, the hair has an intense coppery color. Analogous formulations were made by replacing the pH9 buffer with pH4 and pH7 buffers. The intense copper is found.

Claims (36)

1. Use of one or more compounds of formula (I) below (I) X in which: A represents an aromatic heterocycle comprising 5 to 12 members, comprising at least one cationic charge on a nitrogen atom and optionally comprising one or several other heteroatoms selected from nitrogen, oxygen and / or sulfur; said aromatic heterocycle being optionally substituted and / or condensed with one or more aromatic rings; B represents an alkylene group CH 2 or (CH 2) 2; R1 represents a hydrogen atom; a halogen atom; a hydroxyl group; a linear, branched or cyclic C1-C24 alkyl radical which may be interrupted by one or more heteroatoms and / or may be substituted; an optionally substituted benzyl or aryl radical; a linear or branched C1-C24 alkoxy group which may be interrupted by one or more heteroatoms and / or may be substituted; an unsubstituted amino group, mono- or disubstituted with one or more linear or branched C1-C24 alkyl groups, which may be interrupted by one or more heteroatoms and / or may be substituted, the substituent or substituents of the amino group which may form together a saturated or unsaturated heterocycle comprising 5 to 12 members 44 optionally substituted and / or fused with one or more optionally aromatic rings; R1 may form with a carbon atom of the alkylene group B, an aromatic or non-aromatic ring, C6-C30 or a heterocycle, saturated or unsaturated, comprising from 5 to 12 members and one or more heteroatoms; said ring or heterocycle being optionally substituted and / or fused; R2 represents a hydrogen or halogen atom; a linear or branched C1-C24 alkoxy group which may be interrupted by one or more heteroatoms and / or may be substituted; a linear or branched C1-C24 alkyl radical which may be interrupted by one or more heteroatoms and / or may be substituted; R3 represents a hydrogen atom or a linear or branched, substituted or unsubstituted C1-C6 alkyl radical which may be interrupted by one or more heteroatoms or one or more carbonyl groups; R3 can form with a ring A carbon atom a saturated or unsaturated 5- to 6-membered ring optionally comprising one or more heteroatoms; R4 represents a linear, branched or cyclic, substituted or unsubstituted C 1 -C 24 alkyl radical which may be interrupted by one or more heteroatoms or one or more carbonyl groups and / or by one or more heterocycles; a substituted or unsubstituted aryl radical; R4 can form with the nitrogen atom carrying it and with the substituent R3, a heterocycle comprising 5 to 10 members, saturated or unsaturated, substituted or unsubstituted, and optionally comprising one or more heteroatoms other than the nitrogen atom R4 carrier; X represents an organic or mineral anion. as a coloring agent for keratinous fibers, in particular human fibers, and / or as an agent for the optical lightening of these fibers. 45 2. Use according to claim 1, characterized in that A is chosen from imidazolium rings, pyridinium, indolinium, quinolinium, benzothiazolium and benzoxalium optionally substituted. 3. Use according to claim 1 or 2, characterized in that R2 represents a hydrogen atom, R3 represents a hydrogen atom or forms with a ring A carbon atom, a saturated or unsaturated 5-membered ring, R1 represents a hydrogen atom, a C1-C24 alkoxy radical, preferably a C1-C4 radical, an unsubstituted amino radical, an amino radical substituted by one or more C1-C4 alkyl radicals or forms with a carbon atom of alkylene group B, a C 6 -C 30 aryl radical, R 4 represents a C 1 -C 24, preferably C 1 -C 4, alkyl radical optionally substituted in particular by one or more halogen atoms, a phenylcarbonyl radical and B denotes a radical; methylene or ethylene 4. Use according to any one of claims 1 to 3, characterized in that B represents (CH2) 2; A represents a pyridinium radical optionally substituted with one or more C1-C4 alkyl groups, preferably with a methyl group; R2 and R3 represent a hydrogen atom; R1 represents a hydrogen atom or a C1-C6 alkoxy group, preferably a methoxy group, and R4 represents a C1-C4 alkyl group, preferably a methyl group. 5. Use according to any one of claims 1 to 3, characterized in that B represents (CH2) 2; A represents a benzothiazolium radical optionally substituted with one or more C1-C4 alkyl groups, preferably with a methyl group; R2 and R3 represent a hydrogen atom; R1 represents a hydrogen atom or a C1-C6 alkoxy group, preferably a methoxy group, and R4 represents a C1-C4 alkyl group, preferably an ethyl group. 6. Use according to any one of claims 1 to 3, characterized in that B represents CH2; A represents a benzothiazolium radical optionally substituted with one or more C1-C4 alkyl groups, preferably with a methyl group; R2 and R3 represent a hydrogen atom; R1 represents an unsubstituted amino group and R4 represents a C1-C4 alkyl group, preferably a methyl group. 7. Use according to any one of claims 1 to 3, characterized in that B represents CH2; A represents a pyridinium radical optionally substituted with one or more C1-C4 alkyl groups, preferably with a methyl group, or with one or more phenyl radicals; R1 denotes a dialkyl (C1-C4) amino group or forms with the carbon atom of the group B an aromatic ring; R2 and R3 represent a hydrogen atom or R3 forms with a ring A carbon atom, a saturated or unsaturated 5-membered ring and R4 represents a C1-C6 alkyl radical optionally substituted in particular by one or more atoms of halogen or a phenylcarbonyl radical. 8. Use according to claim 1, characterized in that the compounds of formula (I) are chosen more particularly from compounds of formula (II): NX wherein: R2, R3, R4, A, B and X- have the same meanings as in the case of formula (I); R6 and R7 represent, independently of one another, a hydrogen atom; a linear or branched C1-C24 alkyl radical which may be interrupted by one or more heteroatoms and / or may be substituted; when R6 and R7 represent a linear C1-C24 alkyl radical which may be interrupted by one or more heteroatoms and / or may be substituted, said alkyl radicals may together form a saturated or unsaturated heterocycle comprising 5 to 12 optionally substituted and / or condensed with one or more optionally aromatic rings. 9. Use according to claim 8, characterized in that B represents CH2; A represents a pyridinium radical optionally substituted with one or more C1-C4 alkyl groups, preferably unsubstituted; R2 and R3 represent a hydrogen atom; R6 and R7 represent, independently of one another, a linear or branched C1-C6 alkyl radical, preferably a methyl group, and R4 represents a C1-C4 alkyl radical optionally substituted with a halogen atom, preferably chlorine, or can form with the nitrogen atom carrying it and with the substituent R3, a 5-membered heterocycle, saturated or unsaturated, substituted or unsubstituted, and optionally comprising one or more heteroatoms. 10.Use according to any one of the preceding claims, characterized in that the anion of mineral origin is chosen from halides, perhalogenates, sulphates, bisulphates, nitrates, phosphates, hydrogenphosphates, dihydrogenphosphates, boronates, carbonates, bicarbonates; and in that the anion of organic origin is chosen from those originating from salts of mono- or polycarboxylic acids, sulphonic acids, sulfuric acids, saturated or unsaturated acids, aromatic or otherwise, optionally substituted by at least one hydroxyl radical, amino , or halogen atoms. 11. Use according to any one of the preceding claims, characterized in that the anion is chosen from chloride, bromide, iodide, perchlorate, sulfate, methosulphate or ethosulphate. 12.Use according to any one of the preceding claims, characterized in that the compound of formula (I) is selected from the group consisting of: - salt of 2 - [(3,4-dihydro-1 (2H) - naphthalenylidene) methyl] -3-ethylbenzothiazolium; 3 - [(3,4-dihydro-6-methoxy-1 (2H) -naphthalenylidene) methyl] -1,4-dimethyl-, (Z) -pyridinium salt, - the salt of 3 - [(3 4-dihydro-1 (2H) -naphthalenylidene) methyl] -1,4-dimethyl-, (Z) -pyridinium, salt of 3 - [(3,4-dihydro-6-methoxy-1 (2H)) naphthalenylidene) methyl] -1,4-dimethyl- (E) -pyridinium, - salt of 3 - [(3,4-dihydro-1 (2H) -naphthalenylidene) methyl] -1,4-dimethyl- (E) ) -pyridinium, - 3 - [(3,4-dihydro-6-methoxy-1 (2H) -naphthalenylidene) methyl] -1,4-dimethyl- (E) -pyridinium iodide, - iodide 3 - [(3,4-dihydro-6-methoxy-1 (2H) -naphthalenylidene) methyl] -1,4-dimethyl- (Z) -pyrridinium, - iodide 3 - [(3,4-dihydro-6) -methoxy-1 (2H) -naphthalenylidene) methyl] -1,4-dimethyl- (Z) -pyridinium, - iodide 3 - [(3,4-dihydro-1 (2H) -naphthalenylidene) methyl] -1 4-dimethyl- (E) -pyridinium, - 3 - [(3,4-dihydro-1 (2H) -naphthalenylidene) methyl] -1,4-dimethyl- (Z) -pyridinium iodide, 2 - [(3,4-Dihydro-1 (2H) -naphthylidene) methyl] -3-ethylbenzothiazolium iodide; 2- [2- [ [5- (Dimethylamino) -2,3-dihydro-1H-indenylidene] methyl] -3-methyl-benzathiazolium, - 4 - [[5- (dimethylamino) -2,3-dihydro-1H-salt] inden-1-ylidene] methyl] -1-methyl-2,6-diphenyl-pyridinium, 4- (1 (2H) -acenaphthylenylidenemethyl) -1- (2-oxo-2-phenylethyl) -pyridinium bromide; ; [5-dimethylamino) -2,3-dihydro-1H-inden-1-ylidene] -6,7-dihydro-2-methyl-1,3-diphenyl-5H-cyclopenta [c] pyrridinium salt; 2- (5-Dimethylamino-indan-1-ylidenemethyl) -1-ethyl-pyridinium toluene-4-sulfonate; 4- (5-dimethylaminoindan-1-ylidenemethyl) toluene-4-sulfonate; ethyl-pyridinium, 1- (2-chloro-ethyl) -4- (5-dimethylamino-indan-1-ylidenemethyl) -pyridinium chloride, 1- (5-dimethylamino) toluene-4-sulfonate 1-indan-1-ylidine) -2,3-dihydro-1H-indolizinylium. 13. Cosmetic composition comprising, in a medium suitable for staining, one or more direct dyes defined in any one of the preceding claims. 14.Composition according to claim 13, characterized in that the direct dye (s) content (s) is between 0.001 to 10% by weight relative to the total weight of the composition. 15. Cosmetic composition according to any one of the preceding claims, characterized in that the medium suitable for coloring consists of water or a mixture of water and one or more organic solvents. 16. Cosmetic composition according to any one of claims 13 to 15, characterized in that it comprises one or more additional direct dyes of nonionic, cationic or anionic nature. 17. The composition as claimed in claim 16, characterized in that the additional direct dye or dyes are chosen from nitro dyes of the benzene series, which are neutral, acidic or cationic, neutral azoic acid or cationic direct dyes, quinone direct dyes, and neutral, acidic or cationic anthraquinone compounds, direct azine dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes. 18. Cosmetic composition according to claim 16 or 17, characterized in that the additional direct dye or dyes are present in an amount of between 0.001% to 10% by weight and preferably between 0.1% to 8% by weight relative to the weight. total of the composition. 19. Cosmetic composition according to any one of claims 13 to 18, characterized in that it comprises one or more oxidation dye precursors chosen from oxidation bases and couplers. 20. Cosmetic composition according to claim 19, characterized in that the oxidation base (s) are chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts. 21. Cosmetic composition according to claim 19 or 20, characterized in that the oxidation base (s) are present in an amount of between 0.001% to 10% by weight and preferably between 0.01% to 8% by weight relative to the total weight of the composition. 22. Cosmetic composition according to claim 19, characterized in that the coupler or couplers are chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. 23. Cosmetic composition according to claim 22, characterized in that the coupler or couplers are chosen from 1,3-dihydroxy benzene, 1,3-dihydroxy-2-methyl benzene, 4-chloro-1,3-dihydroxy benzene, 2,4-diamino 1- (13-hydroxyethyloxy) benzene, 2-amino-4- (13-hydroxyethylamino) -1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol, 1-B-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6 4-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, N- (β-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- (β-hydroxyethylamino) toluene and their addition salts. 24. Cosmetic composition according to claim 22 or 23, characterized in that the coupler or couplers are present in an amount of between 0.001 to 10% by weight, preferably between 0.01 to 8% by weight relative to the total weight of the composition. 25. Cosmetic composition according to any one of claims 13 to 24, characterized in that it further comprises one or more one or more surfactants. 26. Cosmetic composition according to claim 25, characterized in that the surfactant is nonionic, anionic, cationic or amphoteric. 27. Cosmetic composition according to claim 25 or 26, characterized in that the amount of surfactants varies from 0.01 to 40% by weight, preferably from 0.5 to 30% by weight, relative to the total weight of the composition. 52 28. Cosmetic composition according to any one of claims 13 to 27, characterized in that it comprises one or more cosmetic adjuvants chosen from surfactants, polymers, ceramides and pseudo-ceramides, vitamins and vitamins. vitamins, sunscreens, solid compounds such as pigments, pearlescent or opacifying agents, sequestering agents, plasticizers, solubilizing agents, acidifying agents, basifying agents, neutralizing agents, mineral and organic thickeners antioxidants, hydroxy acids, solvents, penetrating agents, buffers, dispersing agents, conditioning agents and preservatives. 29. Cosmetic composition according to one of claims 13 to 28, characterized in that it comprises one or more oxidizing agents. 30. Cosmetic composition according to claim 29, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and enzymes. such as peroxidases and oxido-reductases with two or four electrons. 31. A process for treating keratinous fibers, more particularly human keratinous fibers, characterized in that a composition as defined according to any one of claims 13 to 30 for a period of time is applied to said fibers, dry or wet. sufficient to obtain coloring, after which it is rinsed, washed optionally with shampoo, rinsed again and dried or allowed to dry the resulting fibers. 32. Process for treating keratinous fibers, more particularly human keratinous fibers, characterized in that a composition as defined according to any one of Claims 13 to 30 is applied to said fibers, dry or wet, without final rinsing. . 53 33.Dispositif several compartments or Kit dyeing, characterized in that it comprises a first compartment containing a composition as defined in any one of claims 13 to 28 and a second compartment containing a composition comprising one or more oxidizing agents . 34.Use of the composition as defined in any one of claims 13 to 30 for dyeing keratinous fibers, in particular human keratin fibers such as the hair. 35. A compound of the following formula (II): embedded image in which: R2, R4, A, B and X- have the same meanings as in the case of formula (I); R3 represents a hydrogen atom; R6 and R7 represent, independently of each other, a linear or branched C1-C24 alkyl radical which may be interrupted by one or more heteroatoms and / or may be substituted; 36.The compound according to claim 35, characterized in that A denotes a pyridinium ring optionally substituted with one or more C 1 -C 4 alkyl or C 6 -C 30 aryl groups.