FR2968960A1 - Composition, useful for dyeing keratin fibers, comprises, in a medium, at least one oxidation base comprising diamino-N,N-dihydro-pyrazolone derivatives and at least one coupler comprising 4-aminoindole derivatives - Google Patents

Abstract

Composition (A) comprises, in a medium, at least one oxidation base comprising diamino-N,N-dihydro-pyrazolone derivatives of formula (I), and their addition salts, solvates and solvates of their salts; and at least one coupler comprising 4-aminoindole derivatives of formula (II), and their addition salts, solvates and solvates of their salts. Composition (A) comprises, in a medium, at least one oxidation base comprising diamino-N,N-dihydro-pyrazolone derivatives of formula (I), and their addition salts, solvates and solvates of their salts; and at least one coupler comprising 4-aminoindole derivatives of formula (II), and their addition salts, solvates and solvates of their salts. Either R1, R2 : 1-6C alkyl (optionally substituted by OR5, NR6R7, carboxyl, sulfonic group, carboxamido group, CONR6R7, SO 2NR6R7, heteroaryl, aryl (optionally substituted by 1-4C alkyl), hydroxy, 1-2C alkoxy, amino, or (di)alkyl(1-2C)amino)), aryl (optionally substituted by 1-4C alkyl, hydroxyl, 1-2C alkoxy, amino, (di)alkyl(1-2C)amino), or 5-6 membered heteroaryl ring (optionally substituted by (1-4C)alkyl, or (1-2C)alkoxy); and R3, R4 : H or R1; or NR1R2 : optionally saturated 5-7 membered heterocycle (optionally substituted by halo, amino, (di) alkyl(1-4C)amino, hydroxy, carboxy, carboxamido, (1-2C) alkoxy), where the 1-4C alkyl is optionally substituted by hydroxy, amino, (di)-alkylamino, alkoxy, carboxy or sulfonyl; or NR3R4 : optionally saturated 5-7 membered heterocycle ((optionally substituted by halo, amino, (di) alkyl(1-4C)amino, hydroxy, carboxy, carboxamido, (1-2C) alkoxy), where the 1-4C alkyl is optionally substituted by hydroxy, amino, (di)-alkylamino, alkoxy, carboxy or sulfonyl) or 5-7 membered heterocycle ring whose carbon atoms may be optionally substituted by O or N; R5, R6, R7 : H or 1-4C alkyl group (optionally substituted with OH, 1-2C alkoxy, carboxamido, CONR8R9, SO 2R8, or aryl (optionally substituted by 1-4C alkyl, hydroxy, 1-2C alkoxy, amino, (di)alkyl (1-2C) amino); R6, R7 : CONR8R9 or SO 2R8; R8, R9 : H or 1-4C alkyl (optionally substituted by hydroxyl or 1-2C alkoxy); R1a : H, saturated 1-6C alkyl, optionally interrupted by an oxygen atom or NR7a, optionally substituted with OH, or NR7aR8a; R2a, R3a : H, saturated 1-6C, preferably 1-4C alkyl (optionally substituted by one or more OH), 1-6C alkyl carboxylate, carboxyl group or CONR7aR8a; R4a, R5a : H or 1-6C alkyl; R6a : halo, 1-10C alkyl (optionally interrupted by heteroatoms of O or NR9a and/or optionally substituted by one or more OH or NR7aR8a), carboxyl group, 1-10C alkyl carboxylate, CONR7aR8a, 1-10C-alkoxy- or (poly)hydroxy-1-10C alkoxy, (poly)(1-10C)alkoxy(1-10C)alkyloxy, or -O-Ak1-NR9aR10a; Ak1 : linear 1-8C or branched 3-8C divalent alkylene radical, optionally interrupted by one or more O and/or NR7a; R7a, R8a : H or 1-8C alkyl optionally substituted by one or more OH; either R9a, R10a : optionally saturated 1-4C alkyl group; or NR9aR10a : optionally saturated 5-8 membered ring, one of the links can be an oxygen atom or a NR11a; and R11a : 1-4C alkyl, optionally substituted by one or more OH, NR7aR8a or H. 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 time sufficient to develop the desired coloration; and (2) multi-compartment device in which a first compartment contains a dye composition (A) and a second compartment contains at least one oxidizing agent. [Image].

Description

The subject of the invention is a dyeing composition comprising at least one oxidation base derived from diamino-N, N-diol, or a di-N-dihydroxy-N, N-DIHYDRO-PYRAZOLONE OXIDATION BASE. particular dihydro-pyrazolone and at least one 4-aminoindole coupler suitably selected, as well as the dyeing process employing 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 to use diamino-N, N-dihydro-pyrazolone oxidation bases in the field of dyeing keratinous fibers for dyeing keratinous fibers, especially the hair. In particular, such a base is described in EP 1 550 656.

It is also known in documents EP 0 425 345 and WO 92/18093 to use indole-type oxidation dyes 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 composition for hair dyeing 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 composition for staining keratinous fibers comprising, in a suitable dyeing medium: at least one oxidation base chosen from diamino-N, N-dihydro-derivatives; pyrazolone of formula (I), as well as their addition salts, their solvates and the solvates of their salts: ## STR1 ## in which: R 1, R 2, R 3 and R 4, which are identical, or different, represent: a linear or branched C1-C6 alkyl radical optionally substituted by one or more radicals chosen from the group consisting of an ORS radical, a NR6R7 radical, a carboxy radical, a sulphonic radical, a carboxamido radical CONR6R7, a sulfonamido radical SO2NR6R7, a heteroaryl, an aryl optionally substituted by one or more (C1-C4) alkyl, hydroxy, C1-C2 alkoxy, amino, (di) (C1-C2) alkylamino; an aryl radical optionally substituted by one or more (C 1 -C 4) alkyl, hydroxy, C 1 -C 2 alkoxy, amino, (di) (C 1 -C 2) alkylamino; a 5- or 6-membered heteroaryl radical, optionally substituted by one or more radicals chosen from (C 1 -C 4) alkyl, (C 1 -C 2) alkoxy; R3 and R4 may also represent a hydrogen atom;

R6, R6 and R7, which may be identical or different, represent: a hydrogen atom; a linear or branched C1-C4 alkyl radical optionally substituted with one or more radicals chosen from hydroxyl, C1-C2 alkoxy, carboxamido CONR8R9, sulfonyl SO2R8, aryl optionally substituted with a (C1-C4) alkyl, hydroxy, alkoxy; C1-C2, amino, (di) (C1-C2) alkylamino; aryl optionally substituted with a (C 1 -C 4) alkyl, hydroxy, C 1 -C 2 alkoxy, amino, (di) (C 1 -C 2) alkylamino;

R6 and R7, which may be identical or different, may also represent a carboxamido radical CONR8R9; a sulphonyl radical SO2R8; R8 and R9, identical or different, represent a hydrogen atom; a linear or branched C1-C4 alkyl radical optionally substituted with one or more hydroxy, C1-C2 alkoxy;

R 1 and R 2 on the one hand, and R 3 and R 4 on the other hand can form with the nitrogen atom (s) to which they are attached, a saturated or unsaturated 5 to 7-membered heterocycle, optionally substituted with one or more radicals selected from the group consisting of halogen atoms, amino, (di) (C 1 -C 4) alkylamino, hydroxy, carboxy, carboxamido, (C 1 -C 2) alkoxy radicals, C 1 -C 4 alkyl radicals; optionally substituted with one or more hydroxy, amino, (di) alkylamino, alkoxy, carboxy, sulfonyl radicals;

R3 and R4 may also together with the nitrogen atom to which they are attached form a 5- or 7-membered heterocycle whose carbon atoms may be replaced by an optionally substituted oxygen or nitrogen 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'NR'4 R3 in which: R ' represents: - a hydrogen atom; a linear or branched C1-C6 saturated alkyl radical, optionally interrupted by an oxygen atom or an NR'7 radical, 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 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 'and R'8; ; 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 = linear divalent alkylene radical, C1-C8 or branched C3-C8, optionally interrupted by one or more oxygen atoms and / or groups N R'7 ; 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), as well as 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. 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 very powerful fundamental shades.

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 dye precursors 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. In the context of the invention, the term "alkyl radical" is intended to mean linear or branched alkyl radicals, preferably C 1 -C 10 radicals, unless otherwise indicated, preferentially C 1 -C 6, preferably C 1 -C 4, such as the methyl, ethyl or propyl radical. isopropyl, isobutyl, tert-butyl, pentyl, hexyl.

More particularly, in the formula (I), the radicals R 1 and R 2, which are identical or different, are chosen from: a C 1 -C 6 alkyl radical, preferably a C 1 -C 4 alkyl radical, optionally substituted by a hydroxyl, a (C 1 -C 4 C2) alkoxy, amino, (di) (C1-C2) alkylamino; a phenyl, methoxyphenyl, ethoxyphenyl or benzyl radical.

Preferably, the radicals R 1 and R 2, which are identical or different, are chosen from methyl, ethyl, 2-hydroxyethyl, 3-hydroxypropyl and 2-hydroxypropyl radicals, and phenyl radicals.

According to another embodiment, the R 1 and R 2 radicals together with the nitrogen atoms to which they are attached, a 5- or 6-membered ring, saturated or unsaturated, optionally substituted. Preferably, the R 1 and R 2 radicals together with the nitrogen atoms to which they are attached, a pyrazolidine ring, pyridazolidine, optionally substituted with one or more C 1 -C 4 alkyl, hydroxy, (C 1 -C 2) alkoxy radicals. carboxy, carboxamido, amino, (di) (C 1 -C 2) alkylamino. Even more advantageously, the radicals R 1 and R 2 together with the nitrogen atoms to which they are attached form a pyrazolidine pyridazolidine ring. As regards the radicals R3 and R4, the latter, which are identical or different, are more particularly chosen from a hydrogen atom; a C1-C6 alkyl radical, preferably C1-C4, linear or branched, optionally substituted by one or more hydroxy, (C1-C2) alkoxy, amino, a (di) (C1-C2) alkylamino; a phenyl radical optionally substituted by one or more hydroxyl, amino, (C 1 -C 2) alkoxy radicals. Preferably, the radicals R3 and R4, which may be identical or different, are chosen from a hydrogen atom, a methyl, ethyl, isopropyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl and 2-carboxyethyl radical. According to a particular embodiment, the radicals R 3 and R 4 represent a hydrogen atom. According to another embodiment, the radicals R 3 and R 4 together with the nitrogen atom to which they are attached, form a 5- or 7-membered ring chosen from pyrrolidine, piperidine, homopiperidine, piperazine and homopiperazine heterocycles; said rings may be substituted by one or more hydroxy, amino, (di) (C 1 -C 2) alkylamino, carboxy, carboxamido, C 1 -C 4 alkyl radical optionally substituted by one or more hydroxy, amino, (di) alkylamino radicals; in C1-C2. More particularly, the radicals R 3 and R 4 together with the nitrogen atom to which they are attached form a 5- or 7-membered ring chosen from pyrrolidine, 2,5-dimethylpyrrolidine and pyrrolidine-2-carboxylic acid, 3-hydroxypyrrolidine-2-carboxylic acid, 4-hydroxypyrrolidine-2-carboxylic acid, 2,4-dicarboxypyrrolidine, 3-hydroxy-2-hydroxymethylpyrrolidine, 2-carboxamidopyrrolidine, 3-hydroxy-2-carboxamidopyrrolidine 2- (diethylcarboxamido) pyrrolidine, 2-hydroxymethyl pyrrolidine, 3,4-dihydroxy-2-hydroxymethyl pyrrolidine, 3-hydroxypyrrolidine, 3,4-dihydroxy pyrrolidine, 3-amino pyrrolidine, 3-methylamino pyrrolidine, 3-dimethylamino-pyrrolidine, 4-amino-3-hydroxy pyrrolidine, 3-hydroxy-4- (2-hydroxyethyl) amino-pyrrolidine, piperidine, 2,6-dimethylpiperidine, 2-carboxypiperidine, 2-carboxamidopiperidine, 2-hydroxymethylpiperidine, 3-hydroxy-2-hydroxymethylpiperidine, 3-hydroxypip eridine, 4-hydroxypiperidine, 3-hydroxymethylpiperidine, homopiperidine, 2-carboxyhomopiperidine, 2-carboxamidohomopiperidine, homopiperazine, N-methyl-homopiperazine, N- (2-hydroxyethyl) homopiperazine. Preferably, the radicals R 3 and R 4 together with the nitrogen atom to which they are attached form a 5- or 7-membered ring chosen from pyrrolidine, 3-hydroxypyrrolidine, 3-aminopyrrolidine, 3-dimethylamino-pyrrolidine, pyrrolidine-2-carboxylic acid, 3-hydroxypyrrolidine-2-carboxylic acid, piperidine, hydroxypiperidine, homopiperidine, diazepane, N-methyl homopiperazine, N R-hydroxyethylhomopiperazine. According to an even more preferred embodiment of the invention, the radicals R 3 and R 4 together with the nitrogen atom to which they are attached form a 5-membered ring such as pyrrolidine, 3-hydroxypyrrolidine, 3- aminopyrrolidine, 3-dimethylamino-pyrrolidine. The compounds of formula (I) 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. 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), mention may be made of the compounds presented below, their addition salts, their solvates and the solvates of their 4,5-diamino-1,2-dimethyl-1 salts. 2-dihydro-pyrazol-3-one; 4-amino-5-methylamino-1,2-dimethyl-1,2-dihydro-pyrazol-3-one; 4-amino-5-dimethylamino-1,2-dimethyl-1,2-dihydro-pyrazol-3-one; 4-amino-5- (2-hydroxyethyl) amino-1,2-dimethyl-1,2-dihydro-pyrazol-3-one; 4-amino-5- (pyrrolidin-1-yl) -1,2-dimethyl-1,2-dihydro-pyrazol-3-one; 4-amino-5- (piperidin-1-yl) -1,2-dimethyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one; 4-amino-5-methylamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one; 4-amino-5-dimethylamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one; 4-amino-5- (2-hydroxyethyl) amino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one; 4-amino-5- (pyrrolidin-1-yl) -1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one; 4-amino-5- (piperidin-1-yl) -1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one; ; 4,5-diamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-1,2-phenyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-1-ethyl-2-methyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-2-ethyl-1-methyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-1-phenyl-2-methyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-2-phenyl-1-methyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-1- (2-hydroxyethyl) -2-methyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-2- (2-hydroxyethyl) -1-methyl-1,2-dihydro-pyrazol-3-one; 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-amino-3-methylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-amino-3-dimethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-amino-3-ethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-amino-3-isopropylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-amino-3- (2-hydroxyethyl) amino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one 2-amino-3- (2-hydroxypropyl) amino 6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-amino-3-bis (2-hydroxyethyl) amino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one 2-amino-3- (pyrrolidin-1-yl) ) -6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-amino-3- (3-hydroxy-pyrrolidin-1-yl) -6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one 2-amino-3- (piperidin) -1-yl) -6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2,3-diamino-6-hydroxy-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2,3-diamino-6-methyl-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2,3-diamino-6-dimethyl-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2,3-diamino-5,6,7,8-tetrahydro-1H, 6H-pyridazino [1,2-a] pyrazol-1-one; 2,3-diamino-5,8-dihydro-1H, 6H-pyridazino [1,2-a] pyrazol-1-one; 4-Amino-5-dimethylamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5-ethylamino-1,2-dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5-isopropylamino-1,2-dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5- (2-hydroxyethylamino) -1,2-dihydro-pyrazol-3-one; 4-Amino-5- (2-dimethylaminoethylamino) -1,2-diethyl-1,2-dihydro-pyrazol-3-one; 4-Amino-5- [bis (2-hydroxyethyl) amino] -1,2-diethyl-1,2-dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5- (3-imidazol-1-yl-propylamino) -1,2-dihydro-pyrazol-3-one; 4-Amino-5-dimethylamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5-ethylamino-1,2-dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5-isopropylamino-1,2-dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5- (2-hydroxyethylamino) -1,2-dihydro-pyrazol-3-one; 4-Amino-5- (2-dimethylaminoethylamino) -1,2-diethyl-1,2-dihydro-pyrazol-3-one; 4-Amino-5- [bis (2-hydroxyethyl) amino] -1,2-diethyl-1,2-dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5- (3-imidazol-1-yl-propylamino) -1,2-dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5- (3-hydroxy-pyrrolidin-1-yl) -1,2-dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5-pyrrolidin-1-yl-1,2-dihydro-pyrazol-3-one; 4-Amino-5- (3-dimethylamino-pyrrolidin-1-yl) -1,2-diethyl-1,2-dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5- (4-methyl-piperazin-1-yl) -pyrazolidin-3-one; 2,3-Diamino-6-hydroxy-6,7-dihydro-5H-pyrazolo [1,2-a] pyrazol-1-one; some of which are shown below to illustrate the names by chemical structures: O \ \ ~ \ NH2 4,5-Diamino-1,2-dimethyl-1,2-dihydro-N pyrazol-3-one H3C NH ~ H 2 3 O-NH 2 C 2 H 5 NON-NH 2 4,5-Diamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one C2H5 O, CN H 2 4,5-Diamino-1,2-diphenyl-1 2-Dihydro-Ph-N- (NH 2) pyrazol-3-one Ph 2 NH 2 (NH 2 4,5-Diamino-1-ethyl-2-methyl-1,2-H 3 C N dihydro-pyrazol-3-one 4,5-Diamino-1-phenyl-2-methyl-1,2-H3C 'N dihydro-pyrazol-3-one C 2 H 5 NH 2 O 4 NH 2 4-Amino-5- (pyrrolidine) -1-yl) -1,2-diethyl-N, N-1,2-dihydro-pyrazol-3-one C 2 H 5 C 5 H 5 O 4 NH 2 4-Amino-5- (3-dimethylamino-pyrrolidin-OH-yl) -1, 2-diethyl-1,2-dihydro-pyrazol-3-one NNNN i, CH3 C2H5 O, NH2 2,3-diamino-6,7-dihydro-1H, 5H-N-pyrazolo [1] , 2-a] pyrazol-1-one / NH 2 O NH 2 1H, 5H-pyrazolo [1,2-a] pyrazol-1-one (1, NH 4 -NH 2 2-Amino-3-ethylamino-6,7 1H-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one NH 2 -NH-amino-3- (2-hydroxyethyl) amino-6,7-dihydro- 1H, 5H-pyrazolo [1,2-a] pyrazol-1-one / OH-O-CNH 2 2-amino-3- (2-hydroxypropyl) amino-6,7-NN NH dihydro-1H, 5H-pyrazolo [1,2-a] 1a-pyrazol-1-one O-NH 2 2-amino-3-bis (2-hydroxyethyl) amino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol 1- [N-O] -NH, NH 2 -amino-3-isopropylamino-6,7-dihydro-N, N -NH-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one N, 2-amino-3- (pyrrolidin-1-yl) -6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one NN, N, OH 2-Amino-3- (3-hydroxy-pyrrolidin-1-yl) -N, 6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-ol ~ NHz 2,3-diamino-6-hydroxy-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one N, N NHz HO O> ~ NHz 2,3 6-amino-6-methyl-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one NHzO-NHz 2,3-diamino-6,6-dimethyl-6, 7-Dihydro-NH 2 H, 5H-pyrazolo [1,2-a] pyrazol-1-one NO ~NHz 2,3-diamino-5,6,7,8-tetrahydro-1H, 6H-N NHz pyridazino [1,2-a] pyrazol-1-one O ~ NHz 2,3-diamino-5,8-dihydro-1H, 6H-NNHZ pyridazino [1,2-a] pyrazol-1-one O \ 4,5-diamino-1- (2-hydroxyethyl) CNH2 N-NH-methyl-1,2-dihydro-pyrazol-3-one Hsc-N-N-OH NH 2 4,5-diamino-2- (2-hydroxyethyl) -1-N-NH 2 -methyl-1,2-dihydro-pyrazol-3-one dihydro-pyrazol-3-one. Among these compounds, the diamino-N, N-dihydropyrazolone derivatives of formula (I) or their addition salts, their solvates and the solvates of their particularly preferred salts are: 2,3-Diamino-6, 7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-Amino-3-ethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-Amino-3-isopropylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-Amino-3- (pyrrolidin-1-yl) -6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 4,5-diamino-1,2-dimethyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one; 2-amino-3- (2-hydroxyethyl) amino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-amino-3-dimethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2,3-diamino-5,6,7,8-tetrahydro-1H, 6H-pyridazino [1,2-a] pyrazol-1-one; 4-Amino-1,2-diethyl-5- (pyrrolidin-1-yl) -1,2-dihydro-pyrazol-3-one; 4-Amino-5- (3-dimethylamino-pyrrolidin-1-yl) -1,2-diethyl-1,2-dihydro-pyrazol-3-one; 2,3-diamino-6-hydroxy-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one. According to one particular embodiment, the composition of the invention contains an oxidation base chosen from: 4,5-Diamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5- (pyrrolidin-1-yl) -1,2-dihydro-pyrazol-3-one; 4-Amino-5- (3-dimethylamino-pyrrolidin-1-yl) -1,2-diethyl-1,2-dihydro-pyrazol-3-one; 2,3-diamino-6-hydroxy-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2,3-diamino-5,6,7,8-tetrahydro-1H, 6H-pyridazino [1,2-a] pyrazol-1-one; their addition salts, their solvates and the solvates of their salts.

According to a 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 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 = linear divalent linear C1-C6 or branched C3-C6 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 = linear divalent linear C1-C6 or branched C3-C6 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: R'S ~ N.R'4 wherein: 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; R'6 - 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 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',; 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 2,3,7-trimethyl-1H-indol-4-amine 3-ethyl-2,7-dimethyl-1H-indol-4-amine 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- (2- (4-Amino-3,7-diethyl-2-methyl-1H-indol-1-yl) ethanol (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 OH OH

2- [4-Amino-2,3-dimethyl-7- (propan-2-yl) -1H-2- [4-amino-3-ethyl-2-methyl-7- (propan-2-indol)] -sub 1-yl] ethanol 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-7-methoxy-2,3-dimethyl-1H-indol-1-yl) ethanol 3-ethyl-7-methoxy-2-methyl-1H-indol 4-amine 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-7-ethoxy-2,3-dimethyl-1H-indol-4-amine 18-yl) ethanol OH NH 2 NH 2 1-ethoxy-1,2,3-trimethyl-1H-indol-4-amine 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 2- (4-amino-7-ethoxy-3) 1-ethyl-2-methyl-1H-indol-1-NH 2 NH 2 (yl) ethanol 2 - [(4-Amino-2,3-dimethyl-1H-indol-7-yl) oxy] ethanol OH HOC HOC 2 2- [4-Amino-7- (2-hydoxy)] - [(4-amino-1,2,3-trimethyl-1H-indol-7-yl) oxy] ethanol thoxy) -2,3-dimethyl-1H-indol-1-yl] ethanol H 7- [2- (dimethylamino) ethoxy] -2,3-dimethyl-1H-7- [2- imethylamino) ethoxy] -1,2,3-indol-4-amine trimethyl-1H-indol-4-amine NH 2 NH 2 Ⓒ 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- 2,3-dimethyl-7- [2- (piperidin-1-yl) ethoxy] -1H-2,3-dimethyl-7- [2- (morpholin-4-yl) ethoxy] indol-4-amine amine 1H-indol-4-amine 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 HON NH2NH2 2- (4- {2 - [(4-amino-2,3-dimethyl) -1H-indol-7- yl) oxy] ethyl} piperazin-1-yl) ethanol 7- [2- (dimethylamino) ethoxy] -3-ethyl-2-methyl-1H-indol-4-amine 3-ethyl-2-methyl 7- [2- (Piperidin-1-yl) ethoxy] -1H-3-ethyl-2-methyl-7- [2- (morpholin-4-indol-4-aminyl) ethoxy] -1H- Indol-4-amine OH HOC C N 3-ethyl-2-methyl-7- [2- (pyrrolidin-1-yl) ethoxy] -1H-2- [4-amino-7- (2 1H-indol-1-indol-4-amine 22-yl] ethanol 2 - [(4-amino-1H-indol-7-yl) oxy] ethanol NH 2 NH 2 H 7- [2- (piperidine) 1-yl) ethoxy] -1H-indol-4-amine 7- [2- (morpholin-4-yl) ethoxy] -1H-indol-4-amine NH 2 NH 2 N HO 7 2- [4 1-methylpiperazin-1-yl) ethoxy] -1H-indol-4-amine 2- (4- {2 - [(4-amino-1H-indol-7-yl) oxy] ethyl} piperazi n-1 yl) ethanol 7- [2- (dimethylamino) ethoxy] -1H-indol-4-amine 7- [2- (1H-imidazol-1-yl) ethoxy] -1H ndO l-4- amine INA / N ~ NJ 7- [2- (1H-imidazol-1-yl) ethoxy] -2,3-dimethyl-1H-indol-4-amine 2,3-dimethyl-7- [2- (1 H -pyrrol-1-yl) ethoxy] -1H-indol-4-amine NH 2 NH 2 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-methoxyethoxy) -1H-indol-4-amine 27- (2-methoxyethoxy) -2,3 1-dimethyl-1H-indol-4-amine 7- (2 - {[2- (piperidin-1-yl) ethyl] amino} ethoxy) -2,3-di methyl-7- (2 - {[2- (pyrrolidin-1H-indol-4-aminyl) ethyl] amino} ethoxy) -1H-indol-4-amine NH 2 NH 2 HNHN N '- {2 - [(4-amino-1) H-indol-7-yl) oxy] Ethy 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 4-amino-1H-indole-7-carboxylic acid 4-amino-2,3-dimethyl-1H -indole-7-carboxylic acid methyl 4-amino-2,3-dimethyl-1H-indole-7-carboxylate 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 OH NH 2- (4-amino-2,7-dimethyl-1H-indol-3) -yl) ethanol NH 2 7-methyl-1H-indol-4-amine 3- (4-amino-7-methyl-1H-indol-3-yl) propan-1-al 3- (4-amino) -2 Among these compounds, the derivatives of formula (II) which are particularly preferred are the following: 2, 7-dimethyl-1H-indol-3-yl) propan-1-ol 7-ethyl-1H-indol-4-amine 3-dimethyl-7- (propan-2-yl) -1H-indol-4-amine 7-ethyl-2,3-dimethyl-1H-indol-4-amine 2,3,7-trimethyl-1 H-indol-4-amine 3-ethyl-2,7-dimethyl-1H-indol-4-amine 7-ethyl-2,3-dimethyl-1H-indol-4-amine 3,7-diethyl-2 1-methyl-1H-indol-4-amine 2 3-dimethyl-7- (propan-2-yl) -1H-indol-4-amine-3-ethyl-2-methyl-7- (propan-2-yl) -1H-indol-4-amine 1-ethyl-1,2,3-trimethyl-1H-indol-4-amine 3,7-diethyl-1,2-dimethyl-1H-indol-4-amine OH 2- (4-amino-7-) 1,2-ethyl-2,3-dimethyl-1H-indol-1- 2- (4-amino-3,7-diethyl-2-methyl-1H-indol-1-yl) ethanol); 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 2- (4-amino) 3-Ethyl-7-methoxy-2-methyl-1H-indol-7-ethoxy-2,3-dimethyl-1H-indol-4-amin-1-yl) ethanol 7-ethoxy-1,2,3-ethanol trimethyl-1H-indol-4-amine 12- (4-amino-7-ethoxy-2,3-dimethyl-1H-indol-1-yl) ethanol HOC HOC 2 - [(4-amino-2,3) 1-dimethyl-1H-indol-7-yl) oxy] ethanol 2 - [(4-amino-1,2,3-trimethyl-1H-indol-7-yl) oxy] ethanol NH 2 NH 2 HOC OH N 2 - [4-Amino-7- (2-hydoxyethoxy) -2,3-dimethyl-1H-indol-1-yl] ethanol 7- [2- (dimethylamino) ethoxy] -2,3- dimethyl 1H-indol-4-amine 7- [2- (dimethylamino) ethoxy] -1,2,3-trimethyl-1H-indol-4-amine NH 2 NH 2 OH 1 CJN 2- {4-amino-7- [2- (dibutylamino) ethoxy] -2,3-dimethyl-1H-indol-1-yl} ethanol 2,3-dimethyl-7- [2- (pyrrolidin-1-yl) ) ethoxy] -1H-indol-4-amine NH 2 NH 2 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 N 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 HON 2- (4- {2 - [(4-amino-2, 3-dimethyl-1H-indol-7-yl) oxy] ethyl} piperazin-1-yl) ethanol OH HOC2 - [(4-amino-1H-indol-7-yl) oxy] ethanol 2- [4 amino-7- (2-hydroxyethoxy) -1H-indol-1-yl] ethanol NH 2 NH 2 HH 7- [2- (piperidin-1-yl) ethoxy] -1H-indol-4-amine 7- [ 2- (Morpholin-4-yl) ethoxy] -1H-indol-4-amine N HO 7- [2- (4-methylpiperazin-1-yl) ethoxy] -1H-indol-4-amine NH 2 NH 2 / N (N2- (4- {2 - [(4-amino-1 H -indol-7-yl) oxy] ethyl} piperazin-1-yl) ethanol 7- [2- (dimethylamino) ethoxy] -1H - indol-4-amine 7- [2- (1H-imidazol-1-yl) ethoxy] -1H-di-4-amine H 7- [2- (1H-imidazol-1-yl)) ethoxy] -2,3-dimethyl-1H-indol-4-amine 2,3-dimethyl-7- [2- (1H-pyrrol-1-yl) ethoxy] -1H-indol-4-amine 7 (2-methoxyethoxy) -1H-indol-4-amine 27- (2-methoxyethoxy) -2,3-dimethyl-1H-indol-4-amine NH 2 NH 2 OH 2- (4-amino-7-) methyl-1H-indol-3-yl) ethanol 3- (4-amino-7-methyl-1H-indol-3-yl) propan-1-ol 7-methyl-1H-indol-4-amine 7 The compounds of formula (I), the compounds of formula (II), as well as their addition salts, their solvates and the solvates of their salts, are generally present in each case. an amount of between 0.001 to 10% by weight of the total weight of the dyeing 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), their addition salts, their solvates and the 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 and 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-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-3-methyl-phenylenediamine, N, N- (ethyl, [3-hydroxyethyl) para-phenylenediamine, N - (( 3, γ-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-hydroxy-3-hydroxyethyl-para-phenylenediamine, 2- [3-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl paraphenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis- (3-hydroxyethyl) para-phenylenediamine, 2-chloro-para-phenylenediamine, 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, the N, N'-bis - ([3-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis; - (13-hydroxyethyl) N, N'-bis- (4- (13-hydroxyethyl) para-phenylenediamine, 4-N, N-bis- (13-hydroxyethyl) amino-2-methyl aniline, 4-N, N-bis - ((3-hydroxyethyl) amino-2-chloroaniline, aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) N N, N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diamino phenoxy) -3,6-dioxaoctane, their addition salts with an acid, their solvates and the solvates of their salts.

Among the para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-hydroxymethylphenol, 4-amino-2 are exemplified. 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 salts. Among the ortho-aminophenols, mention may be made, for example, of 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-aminophenol and their salts. acid addition, solvates and 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-diamino pyridine, 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 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 patent application FR 2 801. 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-Amino-pyrazolo [1,5-a] pyridin-5-yl) -ethanol; 2- (3-aminopyrazolo [1,5-a] pyridin-7-yl) -ethanol; (3-Amino-pyrazolo [1,5-a] pyridin-2-yl) -methanol; 3,6-diamino-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 and their addition salts with an acid, their solvates and the solvates of their salts. As examples of diaminopyrazole bases, 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-tertbutyl-3-methyl-pyrazole, 4,5-diamino-1 - ([3-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-pyrazole, 4,5-diamino-3-methyl-1-is opropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethyl-pyrazole, their addition salts, their solvates and the solvates of their 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), their addition salts, their solvates and the solvates of their salts. Among these couplers, mention may especially 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 additional preferred couplers are chosen from 2-methyl-5-aminophenol, 5-N- (13-hydroxyethyl) amino-2-methylphenol, 6-chloro-2-methyl-5-aminophenol, and their addition salts. their solvates and the solvates of their salts. 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 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%.

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, sodium hydroxide or potassium hydroxide, 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 by 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 mixing of two compositions, one comprising at least one oxidation base chosen from the compounds of formula (I), as well as 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 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), as well as 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 consists of a first compartment containing a composition comprising at least one oxidation base chosen from the compounds of formula (I) as well as 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.

The compounds of formula (I) are synthesized according to a procedure such as those described in document EP 0 550 656. According to one particular embodiment, the synthesis of the compounds of formula (II) is carried out according to the following scheme: Alkylation o, Pg (2) 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 denotes 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 R4 HN ~ R4 Cyclization ® NH Rs RI Compounds (2) are obtained from protected amines (1) by a 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 R2-CO-CHX-R3 carbonyl halide for 1 to 24 hours at a temperature ranging 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. NH2 (12) Protection HN Rs R, HN Rs Deprotection Alkylation R4X or R5X s R1X Alkylation Cyclization The alkylation of 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 varying from 15 ° C at 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 Example 1: Synthesis of 2,3,7-trimethyl-1H-indol-4-amine hydrochloride NH 2 Step 1: Synthesis of N- (2,3,7-trimethyl-1H-indol-4-yl) acetamide + Br'o DMF reflux In a 25 ml tricol, equipped with a refrigerant, a thermometer and magnetic stirring, 5 g (30 mmol) of N- (3-amino-4-methylphenyl) acetamide in 12 ml of dimethylformamide are introduced and 3.24 ml (30 mmol) of 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 yield 1.15 g of a gray powder corresponding to the expected compound (yield = 64%). Analysis by mass spectrometry 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-propanediol 2-yl) -1H-indol-4-yl] acetamide

HN ~) LNH NH2 DMF reflux In a tricolor of 25 ml, equipped with a condenser, a thermometer and a magnetic stirrer, 6.7 g (34.8 mmol) of N- [3-amino are introduced. 4- (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 off 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%) . The NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are consistent 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 STAIN

The following Cl composition was prepared. 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one 0.005 mole dimethanesulfonate 7-methyl-1H-indol-4-amine 0.005 mole Oleic alcohol polyglycerol containing 2 moles of glycerol 4 g MA Oleyl alcohol polyglycerolated with 4 moles of glycerol (78% MA) 6 g MA Oleic acid 3 g Oleic amide 2 EO marketed under the name 7 g MA of ETHOMEEN 012 by the company AKZO Laurylamino succinamate of 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 (20E) 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 qs Ammonia at 20% NH3 10.2 g Demineralised 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 Tone Height Reflection Cl Golden Blonde 15 The following composition C2 was prepared. Cl 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one 0.005 mole dimethanesulfonate 2,3,7-trimethyl-1H-indol-4-amine , HCl 0.005 mole Oleyl 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 sold under the name 7 g MA of ETHOMEEN 012 by the company AKZO Laurylamino diethylaminopropyl succinamate, sodium salt 3 g MA at 55% MA 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 qs Ammonia at 20% NH3 10.2 g Demineralised 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 Golden Blonde

Claims (16)

REVENDICATIONS1. Coloring composition of keratinous fibers comprising, in a suitable dyeing medium: at least one oxidation base chosen from the diamino-N, N-dihydro-pyrazolone derivatives of formula (I), and also their dicarboxylic acid salts; addition, their solvates and the solvates of their salts: NRN ~ NR3R4 R2 (I) in which: R1, R2, R3 and R4, identical or different, represent: a linear or optionally branched C1-C6 alkyl radical substituted with one or more radicals selected from the group consisting of an ORS radical, a NR6R7 radical, a carboxy radical, a sulfonic radical, a carboxamido radical CONR6R7, a sulfonamido radical SO2NR6R7, a heteroaryl, an aryl optionally substituted by one or more groups (C 1 -C 4) alkyl, hydroxy, C 1 -C 2 alkoxy, amino, (di) (C 1 -C 2) alkylamino; an aryl radical optionally substituted by one or more (C 1 -C 4) alkyl, hydroxy, C 1 -C 2 alkoxy, amino, (di) (C 1 -C 2) alkylamino; a 5- or 6-membered heteroaryl radical, optionally substituted by one or more radicals chosen from (C 1 -C 4) alkyl, (C 1 -C 2) alkoxy; R3 and R4 may also represent a hydrogen atom; R6, R6 and R7, which may be identical or different, represent - a hydrogen atom; A linear or branched C1-C4 alkyl radical optionally substituted with one or more radicals chosen from hydroxyl, C1-C2 alkoxy, carboxamido CONR8R9, sulfonyl SO2R8, aryl optionally substituted with a (C1-C4) alkyl, hydroxy, C 1 -C 2 alkoxy, amino, (di) (C 1 -C 2) alkylamino; aryl optionally substituted with a (C 1 -C 4) alkyl, hydroxy, C 1 -C 2 alkoxy, amino, (di) (C 1 -C 2) alkylamino; R6 and R7, which may be identical or different, may also represent a carboxamido radical CONR8R9; a sulphonyl radical SO2R8; O NH / 2R8 and R9, which may be identical or different, represent a hydrogen atom; a linear or branched C1-C4 alkyl radical optionally substituted with one or more hydroxy, C1-C2 alkoxy; R 1 and R 2 on the one hand, and R 3 and R 4 on the other hand can form with the nitrogen atom (s) to which they are attached, a saturated or unsaturated 5 to 7-membered heterocycle, optionally substituted with one or more radicals selected from the group consisting of halogen atoms, amino, (di) (C 1 -C 4) alkylamino, hydroxy, carboxy, carboxamido, (C 1 -C 2) alkoxy radicals, C 1 -C 4 alkyl radicals; optionally substituted with one or more hydroxy, amino, (di) alkylamino, alkoxy, carboxy, sulfonyl radicals; R3 and R4 may also together with the nitrogen atom to which they are attached form a 5- or 7-membered heterocycle whose carbon atoms may be replaced by an optionally substituted oxygen or nitrogen 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'NR'4 R3 in which: R ', represents: - a hydrogen atom; a linear or branched C1-C6 saturated alkyl radical, optionally interrupted by an oxygen atom or an NR'7 radical, 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 by one or more radicals, which may be identical or different, chosen from OH and N R '; , 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'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'10, identical or different, represent 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 C1-C4 alkyl, optionally substituted by one or more radicals selected from OH, NR ', R'8. 2. Composition according to claim 1, in which R 1 and R 2 are chosen from a C 1 -C 6 alkyl radical optionally substituted with a hydroxy, (C 1 -C 2) alkoxy, amino, (di) (C 1 -C 2) alkylamino ; a phenyl radical, a methoxyphenyl, ethoxyphenyl or benzyl radical, preferably a methyl, ethyl or 2-hydroxyethyl radical, 3-hydroxypropyl, 2-hydroxypropyl, phenyl. 3. Composition according to claim 1, in which R 1 and R 2 together with the nitrogen atoms to which they are attached form an optionally substituted 5 or 6-membered saturated or unsaturated ring, preferably a pyrazolidine or pyridazolidine ring, optionally substituted with a or more C 1 -C 4 alkyl radicals, hydroxy, (C 1 -C 2) alkoxy, carboxy, carboxamido, amino, (di) (C 1 -C 2) alkylamino. 4. Composition according to any one of claims 1 to 3 wherein R3 and R4 are selected from a hydrogen atom; a linear or branched C 1 -C 6 alkyl radical optionally substituted with one or more hydroxy, (C 1 -C 2) alkoxy, amino, a (di) (C 1 -C 2) alkylamino; a phenyl radical optionally substituted with one or more hydroxyl, amino, (C 1 -C 2) alkoxy radicals, preferably a hydrogen atom, a methyl, ethyl, isopropyl, 2-hydroxyethyl, 3-hydroxypropyl or 2-hydroxypropyl radical, 2 -carboxyéthyle. 5. Composition according to any one of claims 1 to 3 wherein R3 and R4 form together with the nitrogen atom to which they are attached a 5- or 7-membered ring selected from heterocycles pyrrolidine, piperidine, homopiperidine, piperazine, homopiperazine; said rings may be substituted with one or more hydroxyl, amino, (di) (C 1 -C 2) alkylamino, carboxy, carboxamido, C 1 -C 4 alkyl radical optionally substituted with one or more hydroxy, amino, (di) alkylamino C1-C2, preferably a 5- or 7-membered ring selected from pyrrolidine, 2,5-dimethylpyrrolidine, pyrrolidine-2-carboxylic acid, 3-hydroxypyrrolidine-2-carboxylic acid, 4- hydroxypyrrolidine-2-carboxylic acid, 2,4-dicarboxypyrrolidine, 3-hydroxy-2-hydroxymethylpyrrolidine, 2-carboxamidopyrrolidine, 3-hydroxy-2-carboxamidopyrrolidine, 2- (diethylcarboxamido) pyrrolidine, 2-hydroxymethyl pyrrolidine, 3,4-dihydroxy-2-hydroxymethylpyrrolidine, 3-hydroxypyrrolidine, 3,4-dihydroxypyrrolidine, 3-aminopyrrolidine, 3-methylaminopyrrolidine, 3-dimethylamino-pyrrolidine, 4-amino-3-hydroxy pyrrolidine, 3-hydroxy-4- (2-hydroxyethyl) amino-pyrrolidine, piperidine, 2,6-dimethylpiperidine, 2- carboxypiperidine, 2-carboxamidopiperidine, 2-hydroxymethylpiperidine, 3-hydroxy-2-hydroxymethylpiperidine, 3-hydroxypiperidine, 4-hydroxypiperidine, 3-hydroxymethylpiperidine, homopiperidine, 2-carboxyhomopiperidine, 2-carboxamidohomopiperidine, homopiperazine, N-methyl-homopiperazine, N- (2-hydroxyethyl) -homopiperazine. 6. Composition according to claim 1 to 5 wherein the compound of formula (I) or an addition salt thereof is chosen from: 2,3-Diamino-6,7-dihydro-1H, 5H-pyrazolo [1 2-a] pyrazol-1-one; 2-Amino-3-ethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-Amino-3-isopropylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-Amino-3- (pyrrolidin-1-yl) -6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 4,5-diamino-1,2-dimethyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol 3-one; 2-amino-3- (2-hydroxyethyl) amino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-amino-3-dimethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2,3-diamino-5,6,7,8-tetrahydro-1H, 6H-pyridazino [1,2-a] pyrazol-1-one; 4-Amino-1,2-diethyl-5- (pyrrolidin-1-yl) -1,2-dihydro-pyrazol-3-one; 4-Amino-5- (3-dimethylamino-pyrrolidin-1-yl) -1,2-diethyl-1,2-dihydro-pyrazol-3-one; 2,3-diamino-6-hydroxy-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one. 7. Composition according to any one of claims 1 to 6 wherein, in the formula (II), R 'represents a hydrogen atom or a saturated C1-C4 alkyl radical optionally substituted with a hydroxyl radical. 8. Composition according to any one of claims 1 to 7 wherein, in the formula (II), 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. 9. Composition according to any one of claims 1 to 8 wherein, in formula (II), R'4 and R'5 are identical and represent a hydrogen atom. 10. Composition according to any one of claims 1 to 9 wherein, in the 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; 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. 11. Composition according to any one of claims 1 to 10 wherein the 4-aminoindole 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. 12. Composition according to any one of claims 1 to 11 wherein the 4-amino indole derivatives are chosen from: NH 2 NH 2 2,3-dimethyl-7- (propan-2-yl) -1H-indol-4 7-ethyl-2,3-dimethyl-1H-indol-4-amine-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 NH 2 3,7-diethyl-2-methyl-1H-indol-4-amine NH 2 2,3-dimethyl-7 - (propan-2-yl) -1H-indol-4-amine-3-ethyl-2-methyl-7- (propan-2-yl) -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 NH 2 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) ethanol1,2,3-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-aminomo-3-ethyl-2-methyl-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 NH 2 NH 2 OH 2- (4-amino-7-methoxy-2,3-dimethyl) 1H-indol-1-yl) ethanol 3-ethyl-7-methoxy-2-methyl-1H-indol-4-amine-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-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-amineOH 2- (4-amino-7-ethoxy-3-ethyl-2-methyl-1H-indol-1-yl) ethanol 2 - [(4-amino) -2- 2,3-dimethyl-1H-indol-7-yl) oxy] ethanol 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-hydroxyethoxy) -2,3-dimethyl-1H-indol-1-yl] ethanol NH 2 N ~ N 7- [2- (dimethylamino) ethoxy] -2 3-dimethyl-1H-7- [2- (dimethylamino) ethoxy] -1,2,3-trimethane hylindol-4-amine 1H-indol-4-amineNH 2 NH 2 NH 2- {4-amino-7- [2- (dimethylamino) ethoxy] -2,3-dimethyl-1H-indol-1 2,3-dimethyl-7- [2- (pyrrolidin-1-yl) ethoxy] -1H-indol-4-amine NH2 2,3-dimethyl-7- [2- (piperidin-1)] ethanol -yl) ethoxy] -1H-2,3-dimethyl-7- [2- (morpholin-4-yl) ethoxy] indol-4-amine 1H-indol-4-amine 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 61NH 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 OH CJNHOC 3-ethyl-2-methyl-7- [2- (pyrrolidin-1-yl) ethoxy] -1H-2- [4-amino-7- (2-hydroxyethoxy) -1H-indol-1-indol 4-amino-1-yl] ethanol 62 - [(4-amino-1H-indol-7-yl) oxy] ethanol NH 2 NH 2 7- [2- (piperidin-1) 1H-indol-4-amine 7- [2- (morpholin-4-yl) ethoxy] -1H-indol-4-amine HH / N 'HO 7- [2- (4-aminopropyl) -1H-indol-4-amine) Methylpiperazin-1-yl) ethoxy] -1H-indol-2- (4- {2 - [(4-amino-1H-indol-7-yl-4-aminyl) oxy] ethyl} piperazin-1-yl ) ethanolNH 2 NH 2 7- [2- (dimethylamino) ethoxy] -1H-indol-4-amine 7- [2- (1H-imidazol-1-yl) ethoxy] -1H ndO l-4- amine 7- [2- (1H-imidazol-1-yl) ethoxy] -2,3-dimethyl-1H-indol-4-amine 2,3-dimethyl-7- [2- (1H-pyrrol 1-yl) ethoxy] -1H-indol-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 acid7- (2-methoxyethoxy) -1H-indol-4-amine 27- (2-methoxyethoxy) -2,3-dimethyl-1H-indol- 4-amine NH 2 NH 2 NH N N H 7- (2 - {[2- (pIl-1-yl) ethyl] amino} ethoxy) -2,3-di methyl-7- (2 - {[2- ( pyrrolidin-1H-indol-4-aminyl) ethyl] amino} ethoxy) -1H-indol-4-amine HNHN 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-diamino-4-amino-3, 7-dimethyl-1H-indole-2-carboxamide OH 4-amino-1H-indole-7-carboxylic acid NH 2 4-amino-2,3-dimethyl-1H-indole-7-carboxylic acid methyl 4-amino 2,3-dimethyl-1H-indole-7-carboxylate 4-amino-2,3-dimethyl-1H-indole-7-carboxamide 4-amino-1H-indole-7-carboxamideNH 2 NH 2 7 -methyl 1H-indol-4-amine 7-ethyl-1H-indol-4-amine 13. Composition according to any one of claims 1 to 12 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. 14. Composition according to any one of claims 1 to 13 comprising at least one oxidizing agent. 15. A process for dyeing keratin fibers in which the composition as defined in any one of claims 1 to 13 is applied to the keratinous fibers in the presence of at least one oxidizing agent for a time sufficient to develop the desired coloration. 16. Multi-compartment device in which a first compartment contains a dye composition as defined in any one of claims 1 to 13 and a second compartment contains at least one oxidizing agent.