FR2968962A1 - Composition, useful for dyeing keratin fibers, preferably human hair, comprises, in a medium, at least one oxidation base comprising 4,5-diaminopyrazole derivatives and at least one coupler comprising 4-aminoindole derivatives - Google Patents

Abstract

Composition, comprises, in a medium, at least one oxidation base comprising 4,5-diaminopyrazole derivatives (I) and their addition salts, or solvates and its solvates; and at least one coupler comprising 4-aminoindole derivatives (II), and their addition salts, or solvates and its salts. Composition, comprises, in a medium, at least one oxidation base comprising 4,5-diaminopyrazole derivatives of formula (I) and their addition salts, or solvates and its solvates; and at least one coupler comprising 4-aminoindole derivatives of formula (II), and their addition salts, or solvates and its salts. R1-R6 : H or 1-6C alkyl (optionally substituted with at least one substituents of OR, NHR, NRRa1, SR, SOR, SO 2R, COR, COOH, CONH 2, CONHR, CONRRa1, PO(OH) 2, SH, SO 3X, non-cationic heterocycle, Cl, Br or I); X : H, Na, K or NH 4; R, Ra1 : 1-4C alkyl, 1-4C alkenyl, 2-4C hydroxyalkyl, 2-4C aminoalkyl, phenyl (optionally substituted with a halo or 1-4C alkyl, 1-4C alkoxy, nitro, trifluoromethyl, amino or 1-4C alkylamino), benzyl (optionally substituted with a halo or 1-4C alkyl, 1-4C alkoxy, methylenedioxy or amino), or -(CH 2) m-X1-(CH(-Y1)) n-Z-; m, n : 0-3; X1 : O or NH; Y1 : H or 1-4C alkyl; Z : CH 3(when n is 0), or 1-4C alkyl, OR, or NRa2Ra3 (when n is >= 1); Ra2, Ra3 : H or 1-4C alkyl; R5 together with the N of the NR3R4 group : at least 4-membered heterocycle, where at least one of R1-R4 is H; R1aa : H, saturated 1-6C alkyl, optionally interrupted by an oxygen atom or NR7a, optionally substituted with OH, or NR7aR8a; R2aa, R3aa : H, saturated 1-6C, preferably 1-4C alkyl (optionally substituted by one or more OH), 1-6C alkyl carboxylate, carboxyl group or CONR7aaR8aa; R4aa, R5aa : H (preferred) or 1-6C alkyl; R6aa : halo, 1-10C alkyl (optionally interrupted by heteroatoms of O or NR9aa and/or optionally substituted by one or more OH or NR7aaR8aa), carboxyl group, 1-10C alkyl carboxylate, CONR7aaR8aa, 1-10C-alkoxy- or (poly)hydroxy-1-10C alkoxy, (poly)(1-10C)alkoxy(1- 10C)alkyloxy, or -O-Ak2-NR9aaR10aa; Ak1 : linear 1-8C or branched 3-8C divalent alkylene radical, optionally interrupted by one or more O and/or NR7aa; R7aa, R8aa : H or 1-8C alkyl optionally substituted by one or more OH; either R9aa, R10aa : optionally saturated 1-4C alkyl group; or NR9aaR10aa : optionally saturated 5-8 membered ring, one of the links can be an oxygen atom or a NR11a; and R11a : H or 1-4C alkyl, optionally substituted by OH or NR7aaR8aa. Independent claims are included for: (1) process for dyeing keratin fibers comprising applying the composition on the keratin fibers in the presence of at least one oxidizing agent for a sufficient time to develop the desired color; and (2) multi-compartment device in which a first compartment contains a dye composition and a second compartment contains at least one oxidizing agent. [Image].

Description

The invention relates to a dye composition comprising at least one particular diamino-pyrazole oxidation base and at least one suitably selected 4-aminoindole coupler. , as well as the dyeing process using this composition. It is known to dye keratinous fibers, and in particular human keratin fibers such as the hair, with dyeing compositions containing oxidation dye precursors, generally known as oxidation bases, such as ortho or para-phenylenediamines, ortho or or para-aminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise to colored compounds by a process of oxidative condensation.

It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as than indolic compounds.

The variety of molecules involved in oxidation bases and couplers, allows to obtain a rich palette of colors. The so-called "permanent" coloration obtained with these oxidation dyes must also meet a certain number of requirements. Thus, it must be harmless from the toxicological point of view, it must make it possible to obtain shades in the desired intensity and to have good resistance to external agents such as light, bad weather, washing, permanent undulations, sweating and friction. The dyes must also make it possible to cover the white hair, and finally be the least selective possible, that is to say, to obtain the lowest possible color differences throughout the same keratin fiber, which is in general differently sensitized (ie damaged) between its point and its root. It is already known in document EP 0 728 464 to use diaminopyrazole derivatives as oxidation bases in combination with heterocyclic couplers, and in particular indole derivatives. It is also known from WO 92/18093 to use compounds of the indole amino type, and in particular 7-methyl-1H-indol-4-amine and 7-ethyl-1H-indol-4-amine. , for dyeing keratinous fibers, and in particular the hair. However, the dyeing compositions of the prior art lead to colorations that do not give complete satisfaction in terms of intensity, chromaticity, selectivity and toughness to external agents. The object of the present invention is to obtain a hair coloring composition which has improved dyeing properties in terms of intensity and / or chromaticity and / or selectivity and / or resistance to external agents.

This object is achieved with the present invention, which relates to a dyeing composition for keratinous fibers comprising, in a suitable dyeing medium: at least one oxidation base chosen from 4,5-diaminopyrazole derivatives of formula (I) ) and their addition salts, their solvates and the solvates of their salts: R6 NRI R2 (3) R5 (I) in which: R1, R2, R3, R4, R5 and R6, which are identical or different, represent a hydrogen atom; a C1-C6 alkyl radical which is unsubstituted or substituted with at least one substituent selected from OR, NHR, NRR ', SR, SOR, SO2R, COR, COOH, CONH2, CONHR, CONRR', PO (OH) 2, SH, SO3X, a non-cationic heterocycle, Cl, Br or I, X denoting a hydrogen atom, Na, K, or NH4, and R and R ', which may be identical or different, representing a C1-C4 alkyl or alkenyl; a C2-C4 hydroxyalkyl radical; a C2-C4 aminoalkyl radical; a phenyl radical; a phenyl radical substituted by a halogen atom or a C1-C4 alkyl, C1-C4 alkoxy, nitro, trifluoromethyl, amino or C1-C4 alkylamino radical; a benzyl radical; a benzyl radical substituted with a halogen atom or with a C1-C4 alkyl, C1-C4 alkoxy, methylenedioxy or amino radical; a radical of the following formula: - (CH2) m - X - (rH), - ZY in which m and n are integers, identical or different, between 0 and 3 inclusively, X represents an oxygen atom or the group NH, Y is a hydrogen atom or an alkyl radical in (2) Nx (5) (1) NN R3R4 C1-C4, and Z represents a methyl radical when n is 0, or Z represents a C 1 -C 4 alkyl radical, a group OR or NR "R" 'when n is greater than or equal to 1, R "and R"', which are identical or different, denoting a hydrogen atom, a C 1 -C 4 alkyl radical; C4; or R5 forms with the nitrogen atom of the NR3R4 group at the 5-position a heterocycle comprising at least 4 members; at least one of R 1, R 2, R 3 and R 4 represents a hydrogen atom; and at least one coupler chosen from 4-aminoindole derivatives of formula (II), as well as their addition salts, their solvates and the solvates of their salts: R'5N, R'4 R3 in which: R ', represents: - a hydrogen atom; a saturated C1-C6 alkyl radical, linear or branched, optionally interrupted by an oxygen atom or an NR'7 radical, optionally substituted with a radical chosen from OH, NR ', R'3; R'2 and R'3, identical or different, represent: - a hydrogen atom; a C1-C6 alkyl radical, preferably a C1-C4 alkyl radical, optionally substituted with one or more hydroxyl radicals; a C1-C6 alkyl carboxylate radical; a carboxyl radical; a radical CONR ', R'3; R'4 and R'5, identical or different, represent: - a hydrogen atom; a C1-C6 alkyl radical; R'6 represents: - a halogen; a linear or branched C1-C10 alkyl radical, optionally interrupted by a heteroatom selected from O or NR'9 and / or optionally substituted with one or more radicals, which may be identical or different, chosen from OH, NR ', R'; 3; a carboxyl radical; a C1-C10 alkyl carboxylate; a radical CONR ', R'8; - a C1-C10 alkoxy radical or (poly) hydroxyalkyloxy C1-C10; a (poly) alkoxy (C1-C10) alkyl (C1-C10) oxy radical; - a radical O-Ak-NR'9R ', o with Ak = divalent linear alkylene radical, C1-C8 or branched C3-C8, optionally interrupted by one or more oxygen atoms and / or NR'7 groups; R'7 and R'8, identical or different, represent: - a hydrogen atom; - A C1-C8 alkyl radical optionally substituted with one or more hydroxyl radicals R'9 and R ', o, identical or different, represent a linear or branched, saturated or unsaturated C1-C4 alkyl; R'9 and R ', o can form with the nitrogen which carries them a saturated or unsaturated 5- to 8-membered heterocycle, one of the links possibly being an oxygen atom or a radical NR' 'with R' ' = H or C1-C4 alkyl, optionally substituted with one or more radicals selected from OH, NR ', R'8. The invention also relates to a dyeing process using this composition. Another subject of the invention is the use of the composition of the present invention for dyeing keratinous fibers, and in particular human keratinous fibers such as the hair. The invention also relates to multi-compartment devices comprising compositions using at least one oxidation base chosen from the compounds of formula (I), their addition salts, their solvates and the solvates of their salts and at least one a coupler chosen from the compounds of formula (II), as well as their addition salts, their solvates and the solvates of their salts.

The composition of the present invention makes it possible in particular to obtain a keratinous fiber coloring composition which is suitable for use in oxidation dyeing and makes it possible to obtain a coloring with varied, intense or chromatic shades, powerful, aesthetic, not very selective. and resistant to the various attacks that hair can undergo such as shampoos, sweat, permanent deformations and light. In particular, the composition according to the invention leads to particularly chromatic nuances.

In the context of the present invention, the expression "at least one" is equivalent to the expression "one or more". The present invention also covers the mesomeric forms and stereoisomers of the various oxidation dyes of the invention.

It should be noted that in what follows, and unless otherwise indicated, the boundaries of a domain of values are included in this area. Unless otherwise indicated, the ranges of the ranges of values which are given within the scope of the invention are included in these ranges. In the context of the invention, unless otherwise indicated, the alkyl radicals are linear or branched. An alkoxy radical is an alkyl-O- radical, the alkyl radical being as defined previously. The compounds of formula (I) may be in the form of addition salts chosen in particular from acid addition salts such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates. The compounds of formula (I) carrying an acid substituent may be in the form of addition salts with a base such as sodium, potassium, ammonium or alkanolamine salts. They may also be in the form of solvates, for example a hydrate, or a linear or branched alcohol solvate, such as ethanol or isopropanol. By way of examples of derivatives of formula (I) that may be used according to the invention, mention may be made of the compounds described in DE-A-38 43 892, DE-A-41 33 957 and patent applications WO 94/08969. , WO 94/08970, FR-A-2,733,749 and DE-A-195 43 988 such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) -pyrazole, 4,5-diamino-1,3-dimethyl-pyrazole, 4,5-diamino-3-methyl-1-phenyl-pyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazino-pyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4, 5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methyl-pyrazole, 4,5-diamino-1- (13-hydroxyethyl) -3- methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxy-phenyl) -pyrazole, 4,5-diamino-1- ethyl-3-hydroxy-methyl-pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl-pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl-pyr azole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethyl-pyrazole, and their addition salts, solvates and the solvates of their salts. According to a particular embodiment, the diaminopyrazole of formula (I) is such that R6 is hydrogen. According to this variant, R 1, R 2, R 3 and R 4 represent a hydrogen atom or a C 1 -C 4 alkyl radical and R 5 is an alkyl, hydroxyalkyl or alkoxyalkyl radical. Even more preferred is 4,5-diamino-1- (2-hydroxyethyl) -1H-pyrazole and its salts, solvates and solvates of its salts, such as 4,5-diamino-1- ( 2-hydroxyethyl) -1H-pyrazole, of the following formula: ## STR2 ## H2SO4 According to one particular embodiment of the invention, in formula (II), R 'represents a hydrogen atom or a saturated C1-C4 alkyl radical optionally substituted with a hydroxyl radical.

According to another particular embodiment, R'2 and R'3, identical or different, represent a hydrogen atom; a C1-C4 alkyl radical optionally substituted with one or more hydroxyl radicals; a carboxyl radical; a C1-C4 alkyl carboxylate radical; a radical CONR ', R'8, preferably in CONH2. Preferably, R'2 and R'3, identical or different, represent a hydrogen atom; a C1-C4 alkyl radical optionally substituted with one or more hydroxyl radicals. According to another particular embodiment, R'4 and R'5 are identical and represent a hydrogen atom. According to another particular embodiment, R '6 represents a linear or branched C1-C6 alkyl radical; a carboxyl radical; a C1-C6 alkyl carboxylate; a carboxamide radical; a (C 1 -C 6) alkoxy (C 1 -C 6) alkyloxy radical; a C1-C6 alkoxy or C1-C6 hydroxyalkyloxy radical; a radical O-Ak-NR'9R ', o with Ak = divalent linear C1-C6 or branched C3-C6 alkylene radical optionally interrupted by an NR'7 radical. Preferably, R '6 represents a linear or branched C1-C6 alkyl radical; a (C 1 -C 6) alkoxy (C 1 -C 6) alkyloxy radical; a C1-C6 alkoxy or C1-C6 hydroxyalkyloxy radical; a radical O-Ak-NR'9R ', o with Ak = divalent linear C1-C6 or branched C3-C6 alkylene radical optionally interrupted by an NR'7 radical. According to a particular embodiment, the compounds in accordance with the invention are chosen from 4-aminoindole derivatives of formula (II '), as well as their addition salts, their solvates and the solvates of their salts: in which R 'represents: - a hydrogen atom; a saturated C1-C4 alkyl radical optionally substituted with a hydroxyl radical; R'2 and R'3, identical or different, represent: - a hydrogen atom; a C1-C4 alkyl radical optionally substituted by one or more hydroxyl radicals, preferably optionally substituted with a hydroxyl radical; a carboxyl radical; a C1-C4 alkyl carboxylate radical; a radical CONR ', R'8, preferably a carboxamide radical CONH2; R'4 and R'5 represent a hydrogen atom; R'6 represents: a linear or branched C1-C6 alkyl radical; a carboxyl radical; a C1-C6 alkyl carboxylate; a carboxamide radical; a (C1-C6) alkoxy (C1-C6) alkyloxy radical; a C1-C6 alkoxy or C1-C6 hydroxyalkyloxy radical; - a radical O-Ak-NR'9R ', o with Ak = divalent linear C1-C6 or branched C3-C6 alkylene radical optionally interrupted by a radical NR'7; R'7 and R'8 represent a hydrogen atom or a C1-C6 alkyl radical optionally substituted with a hydroxyl radical; R'9 and R ', o, which may be identical or different, represent a saturated linear C1-C4 alkyl radical or an unsaturated linear C2-C4 alkyl radical; R'9 and R ', o can form with the nitrogen which carries them a saturated or unsaturated 5- to 8-membered heterocycle; one of the links may be an oxygen atom or a radical NR '' with R '' = H or C 1 -C 4 alkyl optionally substituted with OH. The derivatives of formula (II) may optionally be salified with strong mineral acids such as, for example, HCl, HBr, HI, H 2 SO 4, H 3 PO 4, or organic acids such as, for example, acetic, lactic, tartaric or citric acid. or succinic, benzenesulfonic, para-toluenesulfonic, formic, methanesulfonic. The derivatives of formula (II) can also be in the form of solvates, for example a hydrate or a linear or branched alcohol solvate such as ethanol or isopropanol. By way of examples of derivatives of formula (II), mention may be made of the compounds presented below: 2,3-dimethyl-7- (propan-2-yl) -1H-indol-4-amine 7-ethyl 2,3-dimethyl-1H-indol-4-amine NH 2 NH 2 3-ethyl-2,7-dimethyl-1H-indol-4-amine NH 2 2,3,7-trimethyl-1H-indol-4 -amine NH 2 7-ethyl-2,3-dimethyl-1H-indol-4-amine 3,7-diethyl-2-methyl-1H-indol-4-amine 2,3-dimethyl-7-propanediol 2-yl) -1H-indol-4-amine 3-ethyl-2-methyl-7- (propan-2-yl) -1H-indol-4-amine 7-ethyl-1,2,3-trimethyl 1H-indol-4-amine 3,7-diethyl-1,2-dimethyl-1H-indol-4-amine OH 2- (4-amino-7-ethyl-2,3-dimethyl-1H) -indol-1- 2- (4-amino-3,7-diethyl-2-methyl-1H-indol-1-yl) ethanol yl) ethanol NH 2 NH 2 1,2,3-trimethyl-7-propanol 2-yl) -1H-indol-4-amine 3-ethyl-1,2-dimethyl-7- (propan-2-yl) -1H-indol-4-amine OH 2- [4-amino-2 3-dimethyl-7- (propan-2-yl) -1H-indol-1-yl] ethanol OH 2- [4-amino- 3-ethyl-2-methyl-7- (propan-2-yl) ) -1 H -indol-1-yl] ethanol 7-methoxy-2,3-dimethyl-1H-indol-4-amine 7-methoxy-1,2,3-t 1-trimethyl-3H-indol-4-amine 3-ethyl-7-methoxy-2-methyl-1H-indol-4-amine OH 2- (4-amino-7-methoxy-2,3-dimethyl-1H) -indol-1-yl) ethanol 3-ethyl-7-methoxy-1,2-dimethyl-1H-indol-4- 3-ethyl-7-methoxy-1,2-dimethyl-1H-indol-4- amine amine OH 2- (4-amino-3-ethyl-7-methoxy-2-methyl-1H-indol-1-yl) ethanol 7-ethoxy-2,3-dimethyl-1H-indol-4-amine 7-ethoxy-1,2,3-trimethyl-1H-indol-4-amine OH 12- (4-amino-7-ethoxy-2,3-dimethyl-1H-indol-1-yl) ethanol 7 Ethoxy-3-ethyl-2-methyl-1H-indol-4-amine 7-ethoxy-3-ethyl-1,2-dimethyl-1H-indol-4-amine NH 2 H 2- (4-amino) 7-ethoxy-3-ethyl-2-methyl-1H-indol-1-yl) ethanol 2 - [(4-amino-2,3-dimethyl-1H-indol-7-yl) oxy] ethanol NH 2 NH 2 OH HOC HOC 2 - [(4-Amino-1,2,3-trimethyl-1H-indol-7-yl) oxy] ethanol NH 2 2- [4-amino-7- (2-hydoxyethoxy) -2 3-dimethyl-1H-indol-1-yl] ethanol NH 2 OH 2- (4-Amino-7- [2- (dimethylamino) ethoxy] -2,3-dimethyl-1H -indol-1-yl} ethanol 2,3-dimethyl-7- [2- (pyrrolidin-1-yl) ethoxy] -1 H -indo 1- [4-amine 7- [2- (dimethylamino) ethoxy] -2,3-dimethyl-1H-indol-4-amine NH 2 7- [2- (dimethylamino) ethoxy] -1,2,3-trimethyl 1H-indol-4-amine NH 2 13 NH 2 NH 2 2,3-dimethyl-7- [2- (piperidin-1-yl) ethoxy] -1H-2,3-dimethyl-7- [2- (morpholine) 4-yl) ethoxy] -indol-4-amine 1H-indol-4-amine N HO 2- (4- {2 - [(4-amino-2,3-dimethyl-1H-indol-7-) yl) oxy] ethyl] piperazin-1-yl) ethanol N 7- [2- (dimethylamino) ethoxy] -3-ethyl-2-methyl-1H-indol-4-amine HNN 2,3-dimethyl- 7- [2- (4-methylpiperazin-1-yl) ethoxy] -1H-indol-4-amine 2,3-dimethyl-7- [2- (morpholin-4-yl) ethoxy] -1H- indol-4-amine NH 2 3-ethyl-2-methyl-7- [2- (piperidin-1-yl) ethoxy] -1H-3-ethyl-2-methyl-7- [2- (morpholin-4) 4-Indol-4-aminyl) ethoxy] -1H-indol-4-amine NH 2 NH 2 H 3 OHNHOC 3-ethyl-2-methyl-7- [2- (pyrrolidin-1-yl) ethoxy] -1H- 2- [4-amino-7- (2-hydroxyethoxy) -1H-indol-1-indol-4-aminyl] ethanol 2 - [(4-amino-1H-indol-7-yl) oxy] ethanol NH 2 NH 2 N 7- [2- (piperidin-1-yl) ethoxy] -1H-indol-4-amine 7- [2- (morpholin-4-yl) etho] xy] -1H-indol-4-amine NN HO 7- [2- (4-methylpiperazin-1-yl) ethoxy] -1H-indol-2- (4- {2 - [(4-amino-1 H -indol-7-yl) oxy] ethyl} piperazi n-1-yl) ethanol 7- [2- (dimethylamino) ethoxy] -1H-indol-4-amine 7- [2- (1H-im)] azo 1-yl) and hoxy] -1-amino-4-amine 4-amine 16 NH 2 NH 2 7- [2- (1H-imidazol-1-yl) ethoxy] -2,3- dimethyl-1H-indol-4-amine NH2 2,3-dimethyl-7- [2- (1H-pyrrol-1-yl) ethoxy] -1H-indol-4-amine NH2 7- (2-methoxyethoxy) 1H-indol-4-amine 27- (2-methoxyethoxy) -2,3-dimethyl-1H-indol-4-amine ethyl-4-amino-3-methyl-7- (propan-2-yl) 1H-indole-2-carboxylate NH 2 4-amino-7- (propan-2-yl) -1H-indole-2-carboxylic acid NH 2 H 7 - (2 - {[2- (piperidin-1-yl)} ) ethyl] amino} ethoxy) -2,3-dimethyl-7- (2 - {[2- (pyrrolidin-1H-indol-4-aminyl) ethyl] amino} ethoxy) -1H-indol- 4-amine NH 2 NH 2 HN HN N N N '- {2 - [(4-amino-1H-indol-7-yl) oxy] ethyl} -N, N-N' - {2 - [(4-amino)} 2,3-dimethyl-1H-indol-7-dimethylethane-1,2-diaminyl) oxy] ethyl} -N, N-dimethylethane-1,2-diamine 4-amino-3,7-dimethyl-1H -indole-2-carboxamide O OH 4-friend α-2,3-dimethyl-1H-indole-7-carboxylic acid methyl 4-amino-2,3-dimethyl-1H-indole-7-carboxylate O OH 4-amino-1H-indole-7-carboxylic acid NH 2 4-amino-2,3-dimethyl-1H-indole-7-carboxamide 4-amino-1H-indole-7-carboxamide OH 2- (4-amino-7-methyl-1H-indol) 3-yl) ethanol NH 2- (4-amino-2,7-dimethyl-1H-indol-3-yl) ethanol NH 2 OH 3- (4-amino-7-methyl-1H-indol-3-yl) ) propan-1-OH 3- (4-amino-2,7-dimethyl-1H-indol-3-yl) propan-1-alNH 2 H 7 -methyl-1H-indol-4-amine 7- ethyl-1H-indol-4-amine

Among these compounds, the particularly preferred derivatives of formula (II) are the following: 2,3-dimethyl-7- (propan-2-yl) -1H-indol-4-amine 7-ethyl-2,3-dimethyl 1H-indol-4-amine NH 2 NH 2 3-ethyl-2,7-dimethyl-1H-indol-4-amine NH 2 2,3,7-trimethyl-1H-indol-4-amine NH 2 7 -ethyl 2,3-dimethyl-1H-indol-4-amine 3,7-diethyl-2-methyl-1H-indol-4-amine 2,3-dimethyl-7- (propan-2-yl) -1 H-Indol-4-amine 3-ethyl-2-methyl-7- (propan-2-yl) -1H-indol-4-amine 7-ethyl-1,2,3-trimethyl-1H-indol 4-amine 3,7-diethyl-1,2-dimethyl-1H-indol-4-amine OH 2- (4-amino-7-ethyl-2,3-dimethyl-1H-indol-1-yl) Ethanol NH 2 OH 2- (4-amino-3,7-diethyl-2-methyl-1H-indol-1-yl) ethanol NH 2 OH 1,2,3-trimethyl-7- (propan-2-yl) 1H-indol-4-amine 2- [4-amino-2,3-dimethyl-7- (propan-2-yl) -1H-indol-1-yl] ethanol 7-methoxy-2,3-dimethyl 1H-indol-4-amine 7-methoxy-1,2,3-trimethyl-1H-indol-4-amine OH 2- (4-amino-3-ethyl-7-methoxy-2-methyl-1H) indol-1-yl) ethanol 7-ethoxy-2,3-dimethyl-1H-indol-4-amin 7-Ethoxy-1,2,3-trimethyl-1H-indol-4-amine OH 12- (4-amino-7-ethoxy-2,3-dimethyl-1H-indol-1-yl) ethanol NH 2 NH 2 HOC HOC 2 - [(4-amino-2,3-dimethyl-1H-indol-7-yl) oxy] ethanol NH 2 - [(4-amino-1,2,3-trimethyl-1H-indol) Yl) oxy] ethanol NH 2 HOC OH N 2- [4-amino-7- (2-hydroxyethoxy) -2,3-dimethyl-1H-indol-1-yl] ethanol 7- [2- (d) imethylamino) ethoxy] -2,3-dimethyl-1H-indol-4-amine 22 N 7- [2- (dimethylamino) ethoxy] -1,2,3-trimethyl-1H-N OH 2- {4 amino-7- [2- (dimethylamino) ethoxy] -2,3-dimethyl-1H-indol-1-yl} ethanol 2,3-dimethyl-7- [2- (pyrrolidine) In-1-yl) ethoxy] -1H-indol-4-amine NH2 2,3-dimethyl-7- [2- (piperidin-1-yl) ethoxy] -1H-2,3-dimethyl-7- [2- (Morpholin-4-yl) ethoxy] -indol-4-amine 1H-indol-4-amine 23 NH 2 NH 2 2,3-dimethyl-7- [2- (4-methylpiperazin-1, 2,3 dimethyl-7- [2- (morpholin-4-yl) ethoxy] -yl) ethoxy] -1H-indol-4-amine 1H-indol-4-amine NH2HHO 2- (4- {2- [(4-Amino-2,3-dimethyl-1H-indol-7-yl) oxy] ethyl} piperazin-1-yl) ethanol OH HOC 2 - [(4-amino-1H) -1- indol-7-yl) oxy] ethanol 2- [4-amino-7- (2-hydroxyethoxy) -1H-indol-1-yl] ethanol NH 2 NH 2 7- [2- (piperidin-1-yl) ethoxy] 1H-indol-4-amine 7- [2- (morpholin-4-yl) ethoxy] -1H-indol-4-amine HNN HO 7- [2- (4-methylpiperazin-1-yl) ethoxy] 1H-indol-2- (4- {2 - [(4-amino-1H-indol-7-yl-4-aminyl) oxy] ethyl} piperazin-1-yl) ethanol 7- [2- ( dimethylamino) ethoxy] -1H-indol-4-amine 7- [2- (1H-imidazo l-1-yl) and hoxy] -1H ndO-l-4-amine NH 2 NH 2 7- [ 2- (1H-imidazol-1-yl) ethoxy] -2,3-dimethyl-1H-indol-4-amine NH 2 O 7- (2-methoxyethoxy) -1H-indol-4-amine OH 2 (4-amino-7-methyl-1H-indol-3-yl) ethanol 7-methyl-1H-indol-4-amine 27- (2-methoxyethoxy) -2,3-dimethyl-1H - indol-4-amine 3- (4-amino-7-methyl-1H-indol-3-yl) propan-1-ol NH 2 7-ethyl-1H-indol-4-amine 2,3-dimethyl- 7- [2- (1H-pyrrol-1-yl) ethoxy] -1H-indol-4-amine NH 2 OH The compounds of formula (I), the compounds of formula (II), and their salts of addition, their solvates and the solvates of their salts, are generally present each in one amount of between 0.001 to 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6%.

The dye composition of the invention may optionally comprise one or more additional oxidation bases conventionally used for dyeing keratinous fibers, different from the compounds of formula (I) or their addition salts, their solvates and the solvates of their salts. . By way of example, these additional oxidation bases are chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols and heterocyclic bases other than the bases of formula (I). ) and their addition salts, solvates and solvates of their salts. Among the para-phenylenediamines, there may be mentioned, for example, para-phenylenediamine, para-toluenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl para phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N-dipropyl para phenylenediamine, 4-amino N, N-diethyl-3-methylaniline, N, N-bis- (13-hydroxyethyl) para-phenylenediamine, 4-N, N-bis- (13-hydroxyethyl) amino 2- methyl aniline, 4-N, N-bis - ((3-hydroxyethyl) amino-2-chloroaniline, 2-13-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (13-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-methyl-para-phenylenediamine, N, N- (ethyl, [3-hydroxyethyl) para-phenylenediamine, the N- ((3-y-dihydroxypropyl) para-phenylenediamine, N- (4'-aminophenyl) para-phenylenediamine, N-phenyl para-phenylenediamine, 2-hydroxyethyloxy-para-phenylenediamine, 2-13-acetylaminoethyloxy para phenylenediamine, N- (13-methoxyethyl) para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl para-phenylenediamine, 2- (3-hydroxyethylamino 5-amino toluene, 3-hydroxy-1- (4 ') aminophenyl) pyrrolidine, their addition salts with an acid, their solvates and the solvates of their salts. Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-toluenediamine, 2-isopropyl para-phenylenediamine, 2-13-hydroxyethyl para-phenylenediamine, 2-13-hydroxyethyloxy paraphenylenediamine, 2 , 6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis- (3-hydroxyethyl) para-phenylenediamine, 2-chloro-para-phenylenediamine , 2- [3-acetylaminoethyloxy para-phenylenediamine, their addition salts with an acid, their solvates and the solvates of their salts are particularly preferred. Among the bis-phenylalkylenediamines, mention may be made, by way of example, of N, N'-bis ((3-hydroxyethyl) N, N'-bis (4'-aminophenyl) -1,3-diamino propanol, N, N'-bis - ([3-ethylenediamine, 1,8-bis (2,5-diamino phenoxy) -3,6-dioxaoctane, their addition salts with an acid, their solvates and solvates Among their para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-hydroxymethylphenol, 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, 1-hydroxy-4-methylamino-benzene, 2-2'-methylenebis-4-amino phenol, their addition salts with an acid, their solvates and the solvates of their Among the ortho-aminophenols, mention may be made, for example, of 2-amino phenol, 2-amino-5-methyl n-alkyl, 2-amino-6-methyl phenol, 5-acetamido-2-amino phenol, their addition salts with an acid, their solvates and the solvates of their salts. Among the heterocyclic bases that may be mentioned by way of example are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives. Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2- (4-methoxyphenyl) amino 3-amino pyridine, 2,3-diamino-6-methoxy pyridine, 2 - ([3-methoxyethyl) amino-3-amino-6-methoxy pyridine, 3,4-diamino pyridine, their addition salts with an acid, their solvates and the solvates of their salts. Other pyridinic oxidation bases useful in the present invention are the 3-amino pyrazolo [1,5-a] pyridines oxidation bases or their addition salts described, for example, in the FR 2 patent application. 801 308. By way of example, mention may be made of pyrazolo [1,5-a] pyridin-3-ylamine; 2-acetylamino pyrazolo [1,5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 3-amino-pyrazolo [1,5-a] pyridin-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-a] pyridin-3-ylamino; (3-amino-pyrazolo [1,5-a] pyridin-7-yl) -methanol; 2- (3-aminopyrazolo [1,5-a] pyridin-5-yl) -ethanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-7-yl) -ethanol; (3-Amino-pyrazolo [1,5-a] pyridin-2-yl) -methanol; 3,6-diaminohydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- ([3 hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) N, N'- bis- (4'-amino, 3'-methylphenyl) pyrazolo [1,5-a] pyridine; 3,4-diamino-pyrazolo [1,5-a] pyridine; pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; pyrazolo [1,5-a] pyridine-3,5-diamine; 5-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 2 - [(3-amino-pyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) amino] ethanol; 2 - [(3-Amino-pyrazolo [1,5-a] pyridin-7-yl) - (2-hydroxyethyl) amino] ethanol; 3-amino-pyrazolo [1,5-a] pyridin-5-ol; 3-amino-pyrazolo [1,5-a] pyridin-4-ol; 3-amino-pyrazolo [1,5-a] pyridin-6-ol; 3-amino-pyrazolo [1,5-a] pyridin-7-ol; as well as their addition with an acid or a base, their solvates and the solvates of their salts.

Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in DE 2359399; JP 88-169571; JP 05-63124; EP 0770375 or patent application WO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4 dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in the patent application FR-A-2750048 and among which mention may be made of pyrazolo [1,5- a] -pyrimidine-3,7-diamine; 2,5-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; pyrazolo [1,5-a] pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-amino pyrazolo [1,5-a] pyrimidin-7-ol; 3-amino pyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-amino pyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol, 2- (7-amino pyrazolo [1,5-a] pyrimidin-3-ylamino) - ethanol, 2 - [(3-amino-pyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol, 2 - [(7-amino-pyrazolo [ 1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol, 5,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5-N, 7-N-7-tetramethyl-pyrazolo [1,5-a] -pyrimidine-3, 7-diamine, 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo [1,5-a] pyrimidine, their addition salts with an acid, their solvates and the solvates of their salts. Mention may also be made of diaminopyrazolinones described in patent application FR2886137 and in particular 2,3-diamino-6,7-dihydro-1H, 5H-pyrazol-1-one and its salts, solvates and solvates thereof. salts. The additional oxidation base or bases are generally each present in an amount of between 0.001 to 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6%.

The dye composition according to the invention may contain one or more additional couplers conventionally used for dyeing the different keratin fibers of the compounds of formula (II), as well as their addition salts, their solvates and the solvates of their salts. Among these couplers, particular mention may be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers other than the compounds of formula (II), their addition salts, their solvates and the solvates of their salts.

By way of example of a coupler, mention may be made of 2-methyl-5-aminophenol, 5-N- (13-hydroxyethyl) amino-2-methylphenol, 6-chloro-2-methyl-5-aminophenol and 2-methyl-5-aminophenol. , 4-dichloro-3-aminophenol, 5-amino-4-chloro-o-cresol, 4-chloro-1,3-dihydroxy benzene, 2,4-diamino-1- (13-hydroxyethyloxy) benzene, 2 amino-4- (R-hydroxyethylamino) -1-methoxybenzene, 1,3-bis- (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol, 1- R-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxy naphthalene, 2,7-naphthalenediol, 1-acetoxy-2-methylnaphthalene, 6 -hydroxyindole, 4-hydroxyindole, 4-hydroxy N-methylindole, 3,5-diamino-2,6-dimethoxypyridine, 2,6-dihydroxy-3-4-dimethylpyridine, 3-amino 2-methylamino-6-methoxypyridine, 1-N- (R-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- (R-hydroxyethylamino) toluene, 3-methyl-1-phenyl -5-pyrazolone their addition salts with an acid, their solvates and the solvates of their salts. The preferred additional couplers are chosen from 2-methyl-5-aminophenol, 5-N- (13-hydroxyethyl) amino-2-methylphenol and 6-chloro-2-methyl-5-aminophenol. The additional coupler or couplers are generally present each in an amount of between 0.001 to 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6%.

In general, the addition salts of the additional oxidation bases and additional couplers that can be used in the context of the invention are chosen especially from acid addition salts such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines. The dye composition in accordance with the invention may also contain one or more direct dyes that may be chosen in particular from nitro dyes of the benzene series, azo direct dyes and methine direct dyes. These direct dyes may be nonionic, anionic or cationic in nature. They can be synthetic or of natural origin. The medium suitable for dyeing, also known as a dyeing medium, generally comprises water or a mixture of water and of one or more organic solvents such as, for example, lower C 1 -C 4 alkanols, such as ethanol and isopropanol, polyols such as propylene glycol, dipropylene glycol or glycerol, and polyol ethers such as dipropylene glycol monomethyl ether.

The solvent or solvents are generally present in proportions which can be between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 3 and 30% by weight approximately. The dyeing composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants, or mixtures thereof, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or their mixtures, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents. The adjuvants above are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the composition. Of course, one skilled in the art will take care to choose this or these optional additional compounds such that the advantageous properties intrinsically attached to the oxidation dyeing composition according to the invention are not, or not substantially impaired by the addition or additions envisaged. The pH of the dye 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 alkalizing agents usually used for dyeing keratin fibers or else using conventional buffer systems. Acidifying agents include, for example, inorganic or organic acids such as hydrochloric acid, (ortho) phosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids. Among the alkalinizing agents, mention may be made by way of example of ammonia, alkaline carbonates, sodium metasilicate, sodium silicate, alkanolamines such as mono-, di- and triethanolamines and their derivatives, for example monoethanolamine, aminomethylpropanol, triethanolamine, hydroxides of sodium or potassium, for example sodium hydroxide, sodium pyrrolidine carboxylate, and the compounds of formula (III) below: Ra Rb NW-N i \ R ~ Rd ( III) wherein W is a propylene residue optionally substituted with a hydroxyl group or a C1-C4 alkyl radical; Ra, Rb, Rd and Rd, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.

The composition according to the invention may comprise one or more oxidizing agents. The oxidizing agents are those conventionally used for the oxidation dyeing of keratin fibers, for example hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and the like. oxidase enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred. The composition with or without an oxidizing agent according to the invention may be in various forms, such as in the form of liquids, creams, gels, or in any other form that is suitable for dyeing keratinous fibers, and in particular hair humans. It can result from mixing at the time of use of several compositions.

In a particular variant, it results from the mixture of two compositions, one comprising at least one oxidation base chosen from the compounds of formula (I) and their addition salts, their solvates and the solvates of their salts and at least one at least one coupler chosen from the compounds of formula (II), as well as their addition salts, their solvates and the solvates of their salts, and another composition comprising at least one oxidizing agent as described above. The composition of the invention is therefore applied to the hair for dyeing keratinous fibers either as such or in the presence of at least one oxidizing agent, for dyeing keratinous fibers. The process of the present invention is a process in which the non-oxidizing composition according to the present invention as defined above is applied to the fibers in the presence of an oxidizing agent for a time sufficient to develop the desired coloration. The color can be revealed at acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition of the invention just at the time of use or it can be used from an oxidizing composition containing it applied simultaneously or sequentially to the composition of the invention. According to a particular embodiment, the composition without oxidant according to the present invention is mixed, preferably at the time of use, with a composition containing, in a medium suitable for dyeing, at least one oxidizing agent. The mixture obtained is then applied to the keratinous fibers. After a residence time of about 3 to 50 minutes, preferably about 5 to 30 minutes, the keratinous fibers are rinsed, optionally washed with shampoo, rinsed again and then dried. The oxidizing agents are those described above.

The oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing hair and as defined above. The pH of the oxidizing composition containing the oxidizing agent is such that, after mixing with the dyeing composition, the pH of the resulting composition applied to the keratinous fibers preferably varies between 3 and 12 approximately, and even more preferably between 5 and 11. It can be adjusted to the desired value by means of acidifying or basifying agents usually used for dyeing keratinous fibers and as defined above. The invention also relates to a multi-compartment device or "kit" for dyeing in which a first compartment contains the oxidation-free dye composition of the present invention defined above comprising at least one oxidation base chosen from the compounds of formula (I), their addition salts, their solvates and the solvates of their salts, and at least one coupler chosen from the compounds of formula (II), as well as their addition salts, their solvates and the solvates of their salts, and a second compartment contains at least one oxidizing agent. A second device is constituted by a first compartment containing a composition comprising at least one oxidation base chosen from the compounds of formula (I), their addition salts, their solvates and the solvates of their salts, a second compartment containing a composition comprising at least one coupler chosen from the compounds of formula (II) as well as their addition salts, their solvates and the solvates of their salts.

A third device may optionally comprise the two compartments of the second device plus a third compartment containing a composition comprising at least one oxidizing agent. These devices may be equipped with means for delivering the desired mixture onto the hair, such as the devices described in patent FR-2 586 913 in the name of the applicant. According to one particular embodiment, the synthesis of the compounds of formula (II) is carried out according to the following scheme: ## STR1 ## in which wherein: Pg is an amine protecting group selected from those cited in Protective Groups in Organic Synthesis, TW Greene, PGM.Wutz, John Wiley & Sons, 2nd Ed, 1991, X is a halogen atom such as A fluorine, chlorine, bromine or iodine atom According to another particular embodiment, the synthesis of the compounds of formula (II) is carried out according to the following scheme: HN Rs Ra ~ N.R5R '( I) Deprotection Protection HN i Ra Protection HN Ra Alkylation R4X or RSX HN Rs (10) NH2 (12) Cyclization Alkylation R, X R1X R, Cyclization NH Alkylation R 6 RI Compounds (2) are obtained from protected amines ( 1) by Bischler-type cyclization reaction carried out in a dipolar solvent such as DMF, NMP, acetonitrile, THF, or in an alcohol such as ethanol for example, optionally in the presence of an organic or inorganic base such as triethylamine, ethyldiisopropylamine, sodium hydroxide or potassium hydroxide, with 0.5 to 1 or more equivalents of R 2 -CO-CHX-R 3 carbonyl halide for 1 to 24 hours at a temperature of from 20 ° C to the reflux temperature of the solvent.

The cyclization reactions of (3) to lead to (4), or (5) to lead to (6), or (7) to lead to (8), or (9) to lead to (10) , or (11) to lead to (I) are performed in the same way. The alkylation of the compounds (4) is carried out with at least one equivalent of alkyl halide R1-X in a solvent such as THF or acetonitrile or dioxane or ethyl acetate, in the presence of an organic or inorganic base such as triethylamine, ethyldiisopropylamine, sodium hydroxide or potassium hydroxide for 15 minutes to 24 hours at a temperature ranging from 15 ° C to the reflux temperature of the solvent and leads to the compounds (6). The alkylation of compounds (2) to give compounds (8), or (9) to lead to (11), or (10) to lead to (I), is carried out according to an identical protocol.

The reduction of the nitro group of the compounds (4) and (6) is carried out under standard conditions, for example by carrying out a hydrogenation reaction by heterogeneous catalysis in the presence of catalyst such as Pd / C, Pd (II) / C, Ni / Ra, or by performing a reduction reaction with a metal, for example with zinc, iron, or tin (see Advanced Organic Chemistry, 3rd Edition, J. March, 1985, Willey Interscience and Reduction in organic Chemistry, M. Hudlicky, 1983, Ellis Horwood Chemical Science Series). Cleavage of the protecting group Pg can be carried out in an acidic or basic medium in a very conventional manner, depending on their nature (see Protective Groups for Organic Synthesis, TW Greene, PGM.Wutz, John Wiley & Sons, 2nd Ed, 1991). When the compounds (9) are not commercial, they may for example be obtained from the diamines (12) or (13). The examples which follow serve to illustrate the invention without, however, being limiting in nature.

EXAMPLES EXAMPLES OF SYNTHESIS Step 1: Synthesis of N- (2,3,7-trimethyl-1H-indol-4-yl) acetamide

In a 25 ml three-necked flask equipped with a condenser, a thermometer and a magnetic stirrer, 5 g (30 mmol) of N- (3-amino-4) were added. -methylphenyl) acetamide in 12 ml of dimethylformamide and dropwise to Example 1: synthesis of 2,3,7-trimethyl-1H-indol-4-amine hydrochloride. NH 2 NH 2 DMF reflux drop 3.24 ml (30 mmol) of 3-bromo-2-butanone. The whole is then heated at 100 ° C. for 8 hours until the total disappearance of the starting product. The reaction medium is cooled and then poured into a mixture of water and ice. The gummy precipitate formed is taken up in dichloromethane.

The organic phase is then washed with water before being dried over sodium sulfate and the solvents are removed on a rotary evaporator under vacuum. The crude product thus obtained is purified by flash chromatography on a silica column (eluent: dichloromethane) to yield, after removal of the solvent, 1.4 g of a beige powder corresponding to the expected product (yield = 21.2%).

The NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are in accordance with the expected structure. Mass spectrometry analysis confirms the structure of the expected compound C13H16N2O. The quasi-molecular ions [M + H] +, [M + Na] +, [M-H] - of the expected molecule are mainly detected.

Step 2: Synthesis of 2,3,7-trimethyl-1H-indol-4-amine o isopropanol hydrochloride / HCl reflux In a 25 ml three-neck, equipped with a condenser, a thermometer and stirring magnetic material, 1.4 g (30 mmol) of N- (2,3,7-trimethyl-1H-indol-4-yl) acetamide are introduced into 8 ml of isopropanol solution of 50% HCl. The medium is refluxed for 48 hours. The solvent is then removed under vacuum on a rotary evaporator to give 1.15 g of a gray powder corresponding to the expected compound (yield = 64%).

Mass spectrometry analysis confirms the expected structure C11H14N2. The quasi-molecular ions [M + H] +, [M + Na] +, [M-H] - of the expected molecule are mainly detected. Example 2: Synthesis of 2,3-dimethyl-7- (propan-2-yl) -1H-indol-4-amine hydrochloride Step 1: Synthesis of N- [2,3-dimethyl-7- (propan) 2-yl) -1H-indol-4-yl] acetamide (NH 3) NH 4 DMNHF reflux In a 25 ml three-necked flask, equipped with a condenser, a thermometer and a magnetic stirrer, introduced 6.7 g (34.8 mmol) of N- [3-amino-4- (1-methylethyl) phenyl] acetamide in 20 ml of dimethylformamide and then 1.4 ml (13 mmol) of 3-bromo-2- butanone are added dropwise.

The medium is then heated at 100 ° C. for 48 hours and is then cooled and poured onto a mixture of water and ice, with stirring. The precipitate formed is filtered and washed very abundantly with water and then dried under vacuum in the presence of desiccant. The product thus obtained is purified by flash chromatography on a silica column (eluent: dichloromethane 95 / methanol 5) to yield, after removal of the solvent, 2.87 g of a brown powder corresponding to the expected product (yield = 51%) .

NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are in accordance with the expected structure. Mass spectrometry analysis confirms the structure of the expected compound C15H2ON20. The quasi-molecular ions [M + H] +, [M + Na] +, [M-H] - of the expected molecule are mainly detected.

Step 2: Synthesis of 2,3-dimethyl-7- (propan-2-yl) -1H-indol-4-amine hydrochloride. o This compound is obtained according to a protocol identical to that described for Example 1, replacing the isopropanol solution of HCI 6N) with 6 ml of a 37.5% hydrochloric acid solution. For this example, the reaction of 2.87 g of N- [2,3-dimethyl-7- (propan-2-yl) -1H-indol-4-yl] acetamide gives 2.8 g of powder corresponding to the expected product (Yield = 89%).

The NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are in accordance with the expected structure. Mass spectrometry analysis confirms the structure of the expected compound C13H18N2. The quasi-molecular ions [M + H] +, [M + Na] +, [M-H] - of the expected molecule are mainly detected.

EXAMPLES OF DYEING The following composition C1 was prepared. Cl 2- (4,5-diamino-1H-pyrazol-1-yl) ethanol sulfate 0.005 mole 7-methyl-1H-indol-4-amine 0.005 mole Oleic alcohol polyglycerolated with 2 moles of glycerol 4 g MA Oleic alcohol polyglycerol with 4 moles of glycerol (78% MA) 6 g MA Oleic acid 3 g Oleic amine 2 E 3 marketed under the name 7 g MA ETHOMEEN 012 by AKZO Laurylamino succinamate diethylaminopropyl, sodium salt 3gM.A. to 55% M.A. Oleyl alcohol 5 g Monoethanolamide of alkyl acid (C13 / C15 70/30, 50% linear) 10 g MA carboxylic ether (2OE) Propylene glycol 9.5 g Ethyl alcohol 5 g Hexylene glycol 9.3 g Sodium metabisulphite in solution 35% aqueous MA 0.455 g MA Ammonium acetate 0.8 g Antioxidant, sequestering qs Fragrance, preservative q.s15 Ammonia at 20% NH3 Demineralized water MA: active ingredient 10.2 g qs 100 g Application method composition was diluted extemporaneously with 1 times its weight of oxygenated water at 20 volumes. The mixture was applied to gray hair with 90% white hair at the rate of 10 g of mixture per 1 g of hair. After 30 minutes of resting at room temperature, the hair was then rinsed, washed with standard shampoo and dried. Results Hair coloration was evaluated visually. Composition Height of tone Reflection Cl Chestnut Violine The coloration obtained is particularly chromatic. The following composition C2 was prepared. C2 2- (4,5-diamino-1H-pyrazol-1-yl) ethanol sulfate 0.005 mole 2,3,7-trimethyl-1H-indol-4-amine, HCl 0.005 mole Oleic alcohol polyglycerolated with 2 moles of glycerol 4 g MA oleic alcohol polyglycerolated with 4 moles of glycerol (78% MA) 6 g MA Oleic acid 3 g Oleic amine 2 EO marketed under the name 7 g MA of Ethhomeen 012 by the company AKZO Laurylamino diethylaminopropyl succinamate, salt of sodium 3 g MA 55% MA Alcoholic oleic 5 g Monoethanolamide of alkyl acid (C13 / C15 70/30, 50% linear) 10 g MA carboxylic ether (20E) Propylene glycol 9.5 g 15 Ethyl alcohol 5 g Hexylene glycol 9.3 g Sodium metabisulphite in 35% aqueous solution MA 0.455 g MA Ammonium acetate 0.8 g Antioxidant, sequestering qs Fragrance, preservative qs Ammonia at 20% NH3 10.2 g Demineralized water qs 100 g MA: active ingredient

Mode of application The composition was diluted extemporaneously with 1 time its weight of oxygenated water at 20 volumes. The mixture was applied to gray hair with 90% white hair at the rate of 10 g of mixture per 1 g of hair. After 30 minutes of resting at room temperature, the hair was then rinsed, washed with standard shampoo and dried.

Results Hair coloration was evaluated visually. Composition Height of tone Reflex C2 Violine The coloring obtained is particularly chromatic.

Claims (13)

REVENDICATIONS1. Coloring composition of keratinous fibers comprising, in a suitable dyeing medium: at least one oxidation base chosen from 4,5-diaminopyrazole derivatives of formula (I), their addition salts, their solvates and the solvates of their salts: R 6 NRIR 2 (3) (2) N x (5) (1) N NR 3 R 4 R 5 (I) in which: R 1, R 2, R 3, R 4, R 5 and R 6, which are identical or different, represent an atom of hydrogen; a C1-C6 alkyl radical which is unsubstituted or substituted with at least one substituent selected from OR, NHR, NRR ', SR, SOR, SO2R, COR, COOH, CONH2, CONHR, CONRR', PO (OH) 2, SH, SO3X, a non-cationic heterocycle, Cl, Br or I, X denoting a hydrogen atom, Na, K, or NH4, and R and R ', which may be identical or different, representing a C1-C4 alkyl or alkenyl; a C2-C4 hydroxyalkyl radical; a C2-C4 aminoalkyl radical; a phenyl radical; a phenyl radical substituted by a halogen atom or a C1-C4 alkyl, C1-C4 alkoxy, nitro, trifluoromethyl, amino or C1-C4 alkylamino radical; a benzyl radical; a benzyl radical substituted with a halogen atom or with a C1-C4 alkyl, C1-C4 alkoxy, methylenedioxy or amino radical; a radical of the following formula: - (CH2) m - X - (VH), - ZY in which m and n are integers, identical or different, between 0 and 3 inclusive, X represents an oxygen atom or the NH group, Y represents a hydrogen atom or a C1-C4 alkyl radical, and Z represents a methyl radical when n is 0, or Z represents a C1-C4 alkyl radical, a group OR or NR "R" 'when n is greater than or equal to 1, R "and R"', which may be identical or different, denoting a hydrogen atom or a C1-C4 alkyl radical; or R5 forms with the nitrogen atom of the NR3R4 group at the 5-position a heterocycle comprising at least 4 members; at least one of R 1, R 2, R 3 and R 4 represents a hydrogen atom; and at least one coupler chosen from 4-aminoindole derivatives of formula (II), as well as their addition salts, their solvates and the solvates of their salts: in which: R 'represents: - an atom of hydrogen; a linear or branched C1-C6 saturated alkyl radical, optionally interrupted by an oxygen atom or an NR'7 radical, which is optionally substituted with a radical chosen from OH, NR ', R'8; R'2 and R'3, identical or different, represent: - a hydrogen atom; a C1-C6 alkyl radical, preferably a C1-C4 alkyl radical, optionally substituted with one or more hydroxyl radicals; a C1-C6 alkyl carboxylate radical; a carboxyl radical; a radical CONR ', R'8; R'4 and R'5, identical or different, represent: - a hydrogen atom; a C1-C6 alkyl radical; R'6 represents: - a halogen; a linear or branched C 1 -C 10 alkyl radical, optionally interrupted by a heteroatom selected from O or NR'9 and / or optionally substituted with one or more radicals, which may be identical or different, chosen from OH and NR ', R'8; a carboxyl radical; a C 1 -C 10 alkyl carboxylate; a radical CONR ', R'8; a C1-C10 alkoxy radical or (C1-C10) poly (poly) hydroxyalkyloxy; a (poly) alkoxy (C1-C10) alkyl (C1-C10) oxy radical; an O-Ak-NR'9R'19 radical with Ak = divalent alkylene radical, linear in C1-C8 or branched in C3-C8, optionally interrupted by one or more oxygen atoms and / or groups N R'7; R'7 and R '$, identical or different, represent: - a hydrogen atom; a C1-C8 alkyl radical optionally substituted with one or more hydroxyl radicals R'9 and R'10, which may be identical or different, represents a linear or branched, saturated or unsaturated C1-C4 alkyl; R'9 and R'10 can form with the nitrogen which carries them a saturated or unsaturated 5- to 8-membered heterocycle, one of the links possibly being an oxygen atom or a radical NR '' with R '' = H or C 1 -C 4 alkyl, optionally substituted by one or more radicals selected from OH, NR ', R' 6. 2. Composition according to claim 1 wherein, in the formula (I), R6 is hydrogen, R1, R2, R3, R4 represents a hydrogen atom or a C1-C4 alkyl radical and R5 is a radical. alkyl, hydroxyalkyl or C1-C4 alkoxyalkyl. 3. Composition according to any one of claims 1 and 2 wherein the compound of formula (I) is selected from 4,5-diamino-1- (2-hydroxyethyl) -1H-pyrazole and its addition salts , its solvates and the solvates of its salts, such as 4,5-diamino-1- (2-hydroxyethyl) -1H-pyrazole sulfate. 4. Composition according to any one of claims 1 to 3 wherein, in the formula (II), R 'represents a hydrogen atom or a saturated alkyl radical C1-C4 optionally substituted with a hydroxyl radical. 5. Composition according to any one of claims 1 to 4 wherein, in the formula (II), R'2 and R'3, identical or different, represent a hydrogen atom; a C1-C6 alkyl radical optionally substituted by one or more hydroxyl radicals; a carboxyl radical; a C1-C4 alkyl carboxylate radical; a radical CONR ', R'6. 6. Composition according to any one of claims 1 to 5 wherein, in formula (II), R'4 and R'5 are identical and represent a hydrogen atom. 7. Composition according to any one of claims 1 to 6 wherein, in formula (II), R '6 represents a linear or branched C1-C6 alkyl radical; a carboxyl radical; a C1-C6 alkyl carboxylate; a carboxamide radical; a (C 1 -C 6) alkoxy (C 1 -C 6) alkyloxy radical; a C1-C6 alkoxy or C1-C6 hydroxyalkyloxy radical; an O-Ak-NR'9R'10 radical with Ak = linear divalent linear C1-C6 or branched C3-C6 radical optionally interrupted by an NR'7 radical. 8. Composition according to any one of claims 1 to 7 wherein the 4-amino indole derivatives are chosen from the derivatives of formula (II '): in which: R', represents: - a hydrogen atom; a saturated C1-C4 alkyl radical optionally substituted with a hydroxyl radical; R'2 and R'3, identical or different, represent: - a hydrogen atom; a C1-C6 alkyl radical optionally substituted with one or more hydroxyl radicals; a carboxyl radical; a C1-C4 alkyl carboxylate radical; a radical CONR ', R'8, preferably a carboxamide radical CON H2; R'4 and R'5 represent a hydrogen atom; R'6 represents: a linear or branched C1-C6 alkyl radical; a carboxyl radical; a C1-C6 alkyl carboxylate; a carboxamide radical; a (C1-C6) alkoxy (C1-C6) alkyloxy radical; a C1-C6 alkoxy or C1-C6 hydroxyalkyloxy radical; - a radical O-Ak-NR'9R ', o with Ak = divalent linear C1-C6 or branched C3-C6 alkylene radical optionally interrupted by a radical NR'7; R'7 and R'8 represent a hydrogen atom or a C1-C6 alkyl radical optionally substituted with a hydroxyl radical; R'9 and R ', o, which may be identical or different, represent a saturated linear C1-C4 alkyl radical or an unsaturated linear C2-C4 alkyl radical; R'9 and R ', o can form with the nitrogen carrying them a saturated or unsaturated 5- to 8-membered heterocycle; one of the links may be an oxygen atom or a radical NR "with R '' = H or C 1 -C 4 alkyl optionally substituted with OH. 9. Composition according to any one of claims 1 to 8 wherein the 4-amino indole derivatives are chosen from: NH 2 NH 2 2,3-dimethyl-7- (propan-2-yl) -1H-indol-4 -amine 7-ethyl-2,3-dimethyl-1H-indol-4-amine NH 2 NH 2 3-ethyl-2,7-dimethyl-1H-indol-4-amine NH 2 2,3,7-trimethyl-1 H-indol-4-amine NH 2 7-ethyl-2,3-dimethyl-1H-indol-4-amine NH 2 3,7-diethyl-2-methyl-1H-indol-4-amine NH 2 7-ethyl 1,2,3-trimethyl-1H-indol-4-amine 3,7-diethyl-1,2-dimethyl-1H-indol-4-amine 2,3-dimethyl-7- (propan-2-yl) ) -1 H -indol-4-amine 3-ethyl-2-methyl-7- (propan-2-yl) -1H-indol-4-amine NH 2 OH 2- (4-amino-7-ethyl-2, 3-dimethyl-1H-indol-1-yl) ethanol OH 2- (4-Amino-3,7-diethyl-2-methyl-1H-indol-1-yl) ethanol 1,2,3-trimethyl- 7- (propan-2-yl) -1H-indol-4-amine 3-ethyl-1,2-dimethyl-7- (propan-2-yl) -1H-indol-4-amine NH 2 OH 2- [4-Amino-2,3-dimethyl-7- (propan-2-yl) -1H-indol-1-yl] ethanol OH 2- [4-aminodo-3-ethyl-2-methyl] -7- (1-propan-2-yl) 1H-indol-1-yl] ethanol 7-methoxy-2,3- 1-dimethyl-1H-indol-4-amine 7-methoxy-1,2,3-trimethyl-1H-indol-4-amine3-ethyl-7-methoxy-2-methyl-1H-indol-4-amine OH 2- (4-Amino-7-methoxy-2,3-dimethyl-1H-indol-1-yl) ethanol 3-ethyl-7-methoxy-1,2-dimethyl-1H-indol-4--3- ethyl-7-methoxy-1,2-dimethyl-1H-indol-4-amine amine NH 2 NH 2 OH 2- (4-amino-3-ethyl-7-methoxy-2-methyl-1H-indol-1 yl) ethanol 7-ethoxy-2,3-dimethyl-1H-indol-4-amine 7-ethoxy-1,2,3-trimethyl-1H-indol-4-amine OH 12- (4-amino-7) 2-ethoxy-2,3-dimethyl-1H-indol-1-yl) ethanol7-ethoxy-3-ethyl-2-methyl-1H-indol-4-amine 7-ethoxy-3-ethyl-1,2- 1-dimethyl-H-indol-4-amine NH 2 2 - [(4-amino-2,3-dimethyl-1H-indol-7-yl) oxy] ethanol NH 2 OH 2- (4-amino-7-ethoxy) 3-ethyl-2-methyl-1H-indol-1-yl) ethanol OH HOC HOC 2 - [(4-amino-1,2,3-trimethyl-1H-indol-7-yl) oxy] ethanol NH22 - [4-Amino-7- (2-hydroxyethoxy) -2,3-dimethyl-1H-indol-1-yl] ethanol NH27- [2- (dimethylamino) ethoxy] -2,3-dimethyl-1 H- [2- (dimethylamino) ethoxy] -1,2,3-trimethylindol 4-amine 1H-indol-4-amine NH 2 NH 2 N OH 2- {4-Amino-7- [2- (dimethylamino) ethoxy] -2,3-dimethyl-1H-indol-1-yl} ethanol 2,3-dimethyl-7- [2- (pyrrolidin-1-yl) ethoxy] -1H-indol-4-amine NH2H 2,3-dimethyl-7- [2- (piperidin-1-yl) ) ethoxy] -1H-2,3-dimethyl-7- [2- (morpholin-4-yl) ethoxy] indol-4-amine 1H-indol-4-amine NH 2 NH 2 N -NN Omo / 2, 3-dimethyl-7- [2- (4-methylpiperazin-1, 2,3-dimethyl-7- [2- (morpholin-4-yl) ethoxy] -yl) ethoxy] -1H-indol-4-amine 1H-indol-4-amine 50NH 2 NH 2 N 7- [2- (dimethylamino) ethoxy] -3-ethyl-2-methyl-1H-indol-4-amine 3-ethyl-2-methyl-7 [2- (pi-peridin-1-yl) ethoxy] -1H-3-ethyl-2-methyl-7- [2- (morpholin-4-indol-4-aminyl) ethoxy] -1H-indol- 4-amine NH 2 NH 2 N HO 2- (4- {2 - [(4-amino-2,3-dimethyl-1H-indol-7-yl) oxy] ethyl} piperazin-1-yl) ethanol NH 2 H 3-Ethyl-2-methyl-7- [2- (pyrrolidin-1-yl) ethoxy] -1H-2- [4-amino-7- (2-hydroxyethoxy) -1H-indol-1 Indol-4-amine-yl] ethanol 51 - [(4-amino-1H-indol-7-yl) oxy] ethanol NH 2 7- [2- (piperidin-1-y)] 1) ethoxy] -1H-indol-4-amine 7- [2- (morpholin-4-yl) ethoxy] -1H-indol-4-amine NN HO 7- [2- (4-methylpiperazin-1) yl) ethoxy] -1H-indol-2- (4- {2 - [(4-amino-1H-indol-7-yl-4-yl) oxy] ethyl} piperazin-1-yl) ethanolNH 2 NH 2 [2- (Dimethylamino) ethoxy] -1H-indol-4-amine 7- [2- (1H-imidazol-1-yl) ethoxy] -1H-amino-4-amine ethyl-4-amino 3-methyl-7- (propan-2-yl) -1H-indole-2-carboxylate 4-amino-7- (propan-2-yl) -1H-indole-2-carboxylic acid 7- [2] - (1 H-imidazol-1-yl) ethoxy] -2,3-dimethyl-1H-indol-4-amine NH2 2,3-dimethyl-7- [2- (1H-pyrrol-1-yl) ) ethoxy] -1H-indol-4-amine NH27- (2-methoxyethoxy) -1H-indol-4-amine 27- (2-methoxyethoxy) -2,3-dimethyl-1H-indol-4-amine NH 2 NH 2 NNH 7- (2 - {[2- (pIl-1-yl) ethyl] amino} ethoxy) -1H-indol-4-amine 2,3-dimethyl-7- (2 - {[ 2- (Pyrrolidin-1-yl) ethyl] amino} ethoxy) -1H-indol-4-amine NH 2 HHNH HNHN N '- {2 - [(4-amino-1H-indol-7-yl) oxy} ] ethyl-N, N-N '- {2 - [(4-amino-2,3-dimethyl-1H-indol-7-dimethylethan-1,2-diaminyl) oxy] ethyl} -N, N -dimethylethane-1,2-diamine4-amino-3, 7-dimethyl-1H-indole-2-carboxamide NH 2 O OH 4-amino-2,3-dimethyl-1H-indole-7-carboxylic acid methyl 4-amino-2,3-dimethyl-1H-indole 7-carboxylate NH 2 4-amino-1H-indole-7-carboxylic acid NH 2 4-amino-2,3-dimethyl-1H-indole-7-carboxamide NH 2 4-amino-1H-indole-7-carboxamide 7 1-methyl-1H-indol-4-amine 7-ethyl-1H-indol-4-amine their addition salts, solvates and solvates of their salts. 10. Composition according to any one of claims 1 to 9 further comprising at least one additional coupler selected from 2-methyl-5-aminophenol, 5-N- (13-hydroxyethyl) amino 2-methyl phenol, the 6- chloro-2-methyl-5-aminophenol. 11. Composition according to any one of claims 1 to 10 comprising at least one oxidizing agent. 12. A process for dyeing keratin fibers in which the composition as defined in any one of claims 1 to 10 is applied to the keratinous fibers in the presence of at least one oxidizing agent for a time sufficient to develop the desired coloration. 13. A multi-compartment device in which a first compartment contains a dye composition as defined in any one of claims 1 to 10 and a second compartment contains at least one oxidizing agent.