FR3006182A1 - AZOMETHINIC DIRECT DYES WITH TWO ANILINE COMPOUND ORTHO GROUPS, TINCTORIAL COMPOSITION COMPRISING AT LEAST ONE SUCH COLOR, METHOD OF IMPLEMENTATION AND USE - Google Patents

Abstract

The present invention relates to hindered aniline azomethine direct dyes of formula (I) and their leucos forms of formula (II) as well as their use for dyeing keratinous fibers, in particular human keratinous fibers such as the hair: Formula (I) or (II) in which R1, W, X and Z are as defined in the description The compounds of formula (I) according to the invention make it possible to lead to powerful, chromatic, not very selective and resistant staining. the various attacks that may suffer keratin fibers such as weather, light, washing and perspiration.

Description

The present invention relates to azomethine direct dyes having two confined aniline groups of formula (I) and their leucos forms. of formula (II) and their use for coloring keratinous fibers, in particular human keratinous fibers such as the hair.

It is known to dye keratinous fibers, and in particular the hair, with dyeing compositions containing one or more direct dyes, according to a process known as "direct dyeing". The method conventionally used in direct dyeing consists in applying to the keratinous fibers one or more direct dyes, or coloring molecules, having an affinity for said fibers, allowing them to be paused and then rinsing the fibers. The direct dyes heretofore used are generally nitrobenzene dyes, anthraquinone dyes, nitropyridine dyes, azo, xanthene, acridine, azine dyes or triarylmethane dyes. However, the resulting colorations are temporary or semi-permanent colorings, because the nature of the interactions that bind the direct dyes to the keratin fiber, and their desorption of the surface and / or the core of the fiber are responsible for their weak dye power and their poor resistance to washing, weathering or perspiration. These dyes also have the disadvantage of lack of stability vis-à-vis the light, because of the low resistance of the chromophore to photochemical attacks, which tends to lead to a fading time of the color of the keratinous fibers. There is therefore a real need for direct dyes that not only dye keratin fibers satisfactorily but are also stable in light, capable of leading to stain resistant to the various attacks that can suffer fibers such as bad weather, washing and sweating.

These objects are attained with the present invention which has particular object azométhiniques direct dyes of formula (I) following, their salts of organic or mineral acid or base, their tautomeric forms, optical isomers, geometric isomers and / or their solvates (I) Formula (I) wherein: n represents an integer of 1, 2 or 3; R 1, identical or different, preferably identical, represents: a linear or branched C 1 -C 4 alkyl radical; or - a linear or branched C1-C4 alkyl radical substituted with one or more radicals, which may be identical or different, chosen from the radicals i) hydroxy, ii) guanidine -N (R) -C (= NR ') - NR "R", iii) guanidinium -N (R) -C (= N + R'R ") - NR-R-, An-; iv) amidine -C (= NR) -NR'R", v) amidinium -C (= N + RR ') - NR "R'", An-; vi) Cationic heteroaryl, An- such as pyridinium, quinolinium, imidazolium, or benzomidazolium, An- and vi) tetraalkylammonium -N + RR'R "R", An- with R, R ', R ", R" and R " , which may be identical or different, represent a hydrogen atom or a linear or branched C 1 -C 6 alkyl group with An = denoting an anionic counterion or a cosmetically acceptable mixture of anions, such as halide; Oxygen or an NH radical, preferably oxygen, Z, identical or different, represent i) a hydroxyl group or ii) an amino group -NR2R3 with R2 and R3, identical or different, representing: a hydrogen atom, a linear or branched C 1 -C 6 alkyl group; a linear or branched C 1 -C 6 alkyl group substituted with one or more radicals selected from linear and branched C 1 -C 4 hydroxy and alkoxy; W represent i) a group OR, with R as defined above, preferably CH or ii) a nitrogen atom; - - An- denotes an anionic counterion or a mixture of cosmetically acceptable anionic counterions such as, for example, halides, such as chloride, methosulphates, nitrates; alkylsulfonates: Alk-S (O) 20- such as methylsulfonate or mesylate and ethylsulfonate; arylsulfonates: Ar-S (O) 20- such as benzenesulphonate and toluenesulphonate or tosylate; citrate; succinate; tartrate; lactate; alkyl sulphates: Alk-O-S (O) O- such as methylsulfate; aryl sulphates such as benzenesulphate and toluenesulphate; phosphate; acetate; triflate; and borates such as tetrafluoroborate. Preferably, An- is an anionic counterion selected from bromide, chloride, methylsulfate, toluenesulfonate or a mixture of these ions. Another subject of the present invention relates to the use of one or more azomethine direct dyes of formula (I) as defined above for the dyeing of keratinous fibers, in particular human keratinous fibers such as the hair. The present invention also relates to a composition for dyeing keratinous fibers, in particular human keratin fibers such as the hair, comprising, in a medium suitable for dyeing, one or more azomethine direct dyes of formula (I) such that previously defined.

In particular, the invention also relates to the use of said dye composition for dyeing keratinous fibers, especially human keratin fibers such as the hair. The invention furthermore relates to a process for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, in which said dyeing composition according to the invention is applied to said fibers for a time sufficient to obtain the desired coloration, after which it is rinsed, the fibers are optionally washed with shampoo, rinsed again and the resulting fibers are dried or allowed to dry. Similarly, the invention relates more particularly to a process for dyeing and lightening keratinous fibers, in particular human keratinous fibers such as the hair, in which said dyeing composition (i) is applied to said dyeing composition which is free from an oxidizing agent and (ii) a cosmetic composition comprising one or more oxidizing agents; the compositions (i) and (ii) being applied to said keratinous fibers sequentially or simultaneously for a time sufficient to obtain the desired lightening, after which the fibers are rinsed, washed optionally with shampoo, rinsed again and dried or the resulting fibers are allowed to dry.

The azomethine direct dyes of formula (I) according to the invention thus make it possible to lead to colorings that are resistant to the various attacks that keratin fibers such as weather, light, washing and transpiration can undergo.

In addition, the direct dyes according to the invention make it possible to dye the keratin fibers satisfactorily, in particular by leading to powerful, chromatic and low-selective colorations. The direct dyes according to the invention have the advantage of being light-stable and can be used in the presence of an oxidizing agent, which facilitates their use in direct lightening dyeing compositions based on oxidizing agents. In other words, the direct dyes according to the present invention lead to stubborn colorations and are compatible with dye compositions which are intended to lighten the keratinous fibers. Furthermore, the invention relates to colorless or weakly colored leuco compounds, which correspond to the reduced form of the azomethine direct dyes according to the invention, of formula (II) below, their acid or base salts, organic or inorganic, their tautomeric forms, optical isomers, geometric isomers and / or their solvates: XH (II) Formula (II) in which R 1, n, X, W and Z have the same meanings as those indicated previously in the formula ( I). The compounds of the leuco type according to the invention lead in the presence of one or more oxidizing agents to the azomethine direct dyes of formula (I). Thus, the invention also relates to the use of one or more leuco-type compounds of formula (II) as precursors of direct dyes of formula (I). In particular, the invention relates to the use of one or more leuco-type compounds of formula (II) in the presence of one or more oxidizing agents for dyeing keratin fibers, in particular human keratin fibers such as hair. The invention also relates to a multi-compartment device or kit containing a first compartment comprising one or more leuco type compounds of formula (II) as defined above and a second compartment comprising one or more oxidizing agents. The leuco-type compounds of formula (II) used under oxidizing conditions thus have the advantage of leading to colorings that are resistant to the various attacks that keratinous fibers, such as weather, washing, light or sweat. Moreover, the dyeing process using the colorless or weakly colored compounds of formula (II) followed by a step of revealing the color in the presence of chemical oxidizing agent makes it possible to carry out "clean" coloring, namely which stain or very little clothes or cloths used such as towels, during said process. Other features, aspects, objects and advantages of the present invention will become more apparent upon reading the following description and examples.

I. Azomethine Direct Dyes Preferably, in the formula (I), the azomethine direct dyes according to the invention are such that, taken together or separately: R 1 represents: a linear or branched C 1 -C 3 alkyl radical, preferably methyl ; a linear or branched C 1 -C 3 alkyl radical substituted with a hydroxyl radical; n represents an integer equal to 1; X represents an oxygen atom; - W represents a CH group; Z represents: a hydroxyl radical; or - an amino radical -NR 2 R 3 with R 2 and R 3, which may be identical or different, representing a hydrogen atom or a linear or branched C 1 -C 3 alkyl radical optionally substituted by a hydroxyl radical; According to another particular embodiment of the invention, n represents 2 or 3, and more particularly n is equal to 2 and R 1 represents a linear C 1 -C 3 alkyl radical. According to a particularly advantageous embodiment of the azomethine direct dyes according to the invention of formula (I) are such that Z represents an amino radical -NR 2 R 3 with R 2 and R 3, as defined above. According to a particular embodiment of the invention, R2 and R3, which are identical or different, represent: a hydrogen atom or a linear or branched C1-C3 alkyl radical, optionally substituted with a hydroxyl radical such as methyl; and more particularly Z represents -NH2. According to one particular embodiment of the invention, R1 represents a methyl radical or a linear or branched C1-C3 alkyl radical substituted with a hydroxyl radical such as hydroxymethyl -CH2-OH. . According to one particular embodiment of the invention, the compounds are of formula (IA): ## STR3 ## as well as their acid or base salts, organic or inorganic, their tautomeric forms, optical isomers, geometric isomers and / or their solvates: formula (IA) in which: - R1 represents: - a linear or branched C 1 -C 4 alkyl radical; a linear or branched C1-C4 alkyl radical substituted with one or more hydroxyl or imidazolium radicals, An-; n represents an integer equal to 1; Z represents a radical -NR2R3 with R2 and R3 representing independently of one another: a hydrogen atom; a C 1 -C 3 alkyl radical: a C 1 -C 3 alkyl radical substituted by a hydroxyl radical. Preferably, R2 and R3 are identical and represent a hydrogen atom. An- designating a cosmetically acceptable anion such as, for example, the halides, such as chloride, methosulphates, nitrates; alkylsulfonates: Alk-S (O) 20- such as methylsulfonate or mesylate and ethylsulfonate; arylsulfonates: Ar-S (O) 20- such as benzenesulphonate and toluenesulphonate or tosylate; citrate; succinate; tartrate; lactate; alkyl sulphates: Alk-O-S (O) O- such as methylsulfate; aryl sulphates such as benzenesulphate and toluenesulphate; phosphate; acetate; triflate; and borates such as tetrafluoroborate. Preferably, An- is an anionic counterion selected from bromide, chloride, methylsulfate, toluenesulfonate or a mixture of these ions. According to another particular embodiment of the invention, the compounds are of formula (IB): (IB) Formula (IB) with Z, n, and R1 as defined above for (I) or (IA). Preferably, the compounds of formula (IB) are such that: R1 represents: a linear or branched C1-C3 alkyl radical, preferably a methyl radical; a linear or branched C 1 -C 3 alkyl radical substituted with a hydroxyl radical; n represents an integer equal to 1; Z represents a hydroxyl radical or -NR 2 R 3; - R2 and R3 represent independently of one another: - a hydrogen atom; a linear or branched C 1 -C 3 alkyl radical; a linear or branched C 1 -C 3 alkyl radical substituted with a hydroxyl radical; The compounds of formula (I), (IA) or (IB) can be directly used to perform a hair coloring. Preferably, the azomethine direct dyes of formula (I), (IA), or (IB) according to the invention are chosen from the following compounds as well as their geometric or optical isomeric forms, their tautomers, their acid or organic or inorganic base or their solvates such as hydrates: H2N lei N. NH 2 O n: 2-Amino-5- (4-amino-2 or 3-ethyl-1H-phenylamino) -444-amino-2 or 3-ethylphenylimino] -cyclohexa-2,5-dienone NH 2 H 2 N * OH NH 2 1: 2-Amino-5- (4-amino-2 or 3- (2-N el 0 21 HN OH hydroxyethyl) -phenylamino) -444- [4-2 or lee NH 2 3- (2-hydroxyethyl) -phenylimino ] -cyclohexa2,5-dienone H2N el OH NH2 2-Amino-5- (4-amino-2 or 3- (2-N-hydroxypropyl) -phenylamino) -4 [4-amino-2HN OH or 3- hydroxypropyl-phenylimino] -cyclohexa-. NH2 2,5-dienone H2N ill ° 1 N. NH 2 O L11: 2-Amino-5- (4-amino-2 or 3-propyl-1H-phenylamino) -444-amino-2 or 3-propylphenylimino] -cyclohexa-2,5-dienone NH 2 H 2 N 00 OH NNH 2 (5): 3-Amino-6- [4-amino-3- (2 or 3 '- ..., ... <: .., hydroxy-ethyl) -phenylamino] -544-amino 2- or 3- (2-Hydroxyethyl) -phenylimino] -5H-pyridin-2-one HN N-Ole NH 2 OH N HN NNH 2 O n: 3-Amino-644- [4-3- (2 or 3 ethyl) phenylamino] -5 [4-amino-2- or 3- (ethyl) -N, phenylimino] -5H-pyridin-2-one 1. NH 2 H 2 N * OH NNH 2 N 0 in: 3-amino 6- [4-amino-3- (2 or 3-OH-hydroxy-propyl) -phenylamino] -54-amino-2-I-4-NH 2 or 3- (2-hydroxy-propyl) -phenylimino] -5H-pyridin -2-one Preferably, the direct dyes of formula (I) or (IA) according to the present invention are of formula LU or 121 The azomethine direct dyes of formula (I), (IA) or (IB) can be obtained according to the procedure described below: oxidizing NH 2 (I), (IA) or (IB) NH 2 base 2 The compounds corresponding to formula (I), (IA) or (IB) are genetically obtained By reacting the derivatives la with the derivatives 2 in basic medium in the presence of an oxidizing agent. The base used is preferably an aqueous solution of ammonia or sodium hydroxide and the oxidant is preferably chosen from hydrogen peroxide, potassium ferricyanide, air, ammonium persulfate and manganese oxide. Synthetic approaches approaching that described above are described in patent applications FR2234277, FR2047932, FR2106661 and FR2121101. Synthetic approaches approaching are described in the patent application FR21189380. The invention also relates to the use of one or more azomethine direct dyes of formula (I), (IA) or (IB) as described above for the dyeing of keratinous fibers, in particular human keratin fibers such as hair. Dyeing composition NNH 2 H 2 NHN N 0 NH 2 181: 3-Amino-6 [4-amino-3- (2 or 3-propyl) phenylamino] -544-amino-2 or 3- (propyl) phenylimino] The present invention also relates to a dyeing composition for keratinous fibers, in particular human keratinous fibers such as the hair, comprising, in a medium suitable for dyeing, one or more direct dyes of formula (I). I), (IA) or (IB) as defined above. Preferably, the dyeing composition comprises one or more azomethine direct dyes of formula (I), (IA) or (IB) chosen from the compounds LU to 181 as defined above, as well as their mixtures. Even more preferably, the dyeing composition comprises one or more azomethine direct dyes of formula (I), or (IA) chosen from compounds of formula LU or 21. The direct dye (s) as defined above may be present in the dye composition according to the invention in a content ranging from 0.001% to 10% by weight, preferably in a content ranging from 0.005% to 6% by weight, relative to to the total weight of the dyeing composition. The dye composition according to the invention may further comprise one or more oxidation dyes. The oxidation dyes are generally chosen from oxidation bases optionally combined with one or more couplers.

By way of example, the oxidation bases are chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts. Among the paraphenylenediamines, there may be mentioned by way of 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- (p-hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (13-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- (13-hydroxyethyl) amino-2-chloroaniline, 213-hydroxyethyl paraphenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (p-hydroxypropyl) -paraphenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, p-hydroxyethyl) paraphenylenediamine, N- (13,7-dihydroxypropyl) Paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl-para-phenylenediamine, 213-hydroxyethyloxy-para-phenylenediamine, 213-acetylaminoethyloxy-para-phenylenediamine, N- (p-methoxyethyl) para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl paraphenylenediamine, hydroxyethylamino 5-amino toluene, 3-hydroxy-1- (4'-aminophenyl) pyrrolidine and their addition salts with an acid. Among the para-phenylenediamines mentioned above, paraphenylenediamine, para-toluenediamine, 2-isopropyl paraphenylenediamine, 213-hydroxyethyl paraphenylenediamine, 213-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (p-hydroxyethyl) paraphenylenediamine, 2-chloro-para-phenylenediamine, 213-acetylaminoethyloxy-para-phenylenediamine, and their acid addition salts are particularly preferred. Among the bis-phenylalkylenediamines, mention may be made, for example, of N, N'-bis- (phydroxyethyl) N, N'-bis (4'-aminophenyl) -1,3-diamino propanol, N, N bis (N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (p-hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) N, N'-bis- ( 4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diamino phenoxy) -3,6-dioxaoctane, and their addition salts. Among para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-chlorophenol, 4- amino 3-hydroxymethyl phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- hydroxyethyl aminomethyl) phenol, 4-amino-2-fluoro phenol, and their addition salts with an acid. Among the ortho-aminophenols, there may be mentioned by way of example, 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-amino phenol, and their addition 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, 3,4-diamino pyridine, and their addition salts. Other pyridinic oxidation bases useful in the present invention are the 3-amino pyrazolo [1,5-4-pyridines oxidation bases or their addition salts described for example in the patent application FR 2801308. A 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-Amino-pyrazolo [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-diaminopyrazolo [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-aminopyrazolo [1,5-a] pyridin-4-ol; 3-amino-pyrazolo [1,5-a] pyridin-6-ol; 3-aminopyrazolo [1,5-a] pyridin-7-ol; as well as their addition 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 VVO 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 their addition salts and tautomeric forms, when tautomeric equilibrium exists. Among the pyrazole derivatives, mention may be made of the compounds described in DE 3843892, DE 4133957 and patent applications VVO 94/08969, VVO 94/08970, FR-A-2 733 749 and DE 195 43 988 as the 4.5 1-methyl pyrazole, 4,5-diamino-1- (13-hydroxyethyl) pyrazole, 3,4-diamino 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-methyl-pyrazole, 4,5-diamino-3-tert-butyl-1-methyl-pyrazole, 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'-methoxyphenyl) pyrazole, 4 5-diamino-1-ethyl-3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl-pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole, 4,5-diamino-3-m ethyl 1-isopropyl pyrazole, 4-amino 5- (2'-aminoethyl) amino 1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino-4- (13-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts. 4-5-Diamino-1- (methoxyethyl) pyrazole can also be used. Preferably, a 4,5-diaminopyrazole and even more preferably 4,5-diamino-1- (13-hydroxyethyl) -pyrazole and / or one of its salts will be used.

As pyrazole derivatives, there may also be mentioned diamino N, N-dihydropyrazolopyrazolones and in particular those described in application FR-A2 886 136 such as the following compounds and their addition salts: 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-amin-5- ( 3-Diethylamino-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. It will be preferred to use 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one and / or a salt thereof. As heterocyclic bases, use will preferably be made of 4,5-diamino-1- (13hydroxyethyl) pyrazole and / or 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one and / or a salt thereof. The dye composition may optionally comprise one or more couplers advantageously chosen from those conventionally used for dyeing keratinous fibers. Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. By way of example, mention may be made of 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene and 2,4-diamino-1- (11- hydroxyethyloxy) benzene, 2-amino 4- (11-hydroxyethylamino) 1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido-dimethylamino benzene, sesamol, 1-11-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N- (11-hydroxyethyl) amino, -3,4-methylene dioxybenzene, 2,6-bis- (11-hydroxyethylamino) toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazole-5-one 1-phenyl-3-methyl-pyrazole-5-one, 2,6-dimethyl-pyrazolo [1,5-b] -1,2,4-triazole, 2,6-dimethyl [3,2-c] - 1,2,4-triazole, 6-methyl pyrazolo [1,5-4-benzimidazole, their addition salts with an acid, and mixtures thereof. In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen in particular from acid addition salts such as hydrochlorides, hydrobromides and sulphates. citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates. The oxidation base (s) each advantageously represent from 0.001% to 10% by weight, and preferably from 0.005% to 6% by weight, relative to the total weight of the composition. The content of the coupler (s), if they are (are) present (s), are each advantageously from 0.001% to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 6% by weight relative to the total weight of the dye composition The dye composition according to the invention may also comprise one or more additional direct dyes different from the azomethine direct dyes according to the present invention. The additional direct dye (s) according to the invention are chosen from nitro dyes of the benzene series, which are neutral, acidic or cationic, acid or cationic neutral azo direct dyes, azomethine direct dyes different from those of the present invention, and in particular neutral, acidic or cationic anthraquinones, azine direct dyes, triarylmethane direct dyes, direct dyes, azomethine direct dyes and natural direct dyes.

Among the benzene direct dyes that may be used according to the invention, the following compounds may be mentioned in a nonlimiting manner: - 1,4-diamino-2-nitrobenzene, - 1-amino-2-nitro-4-hydroxyethylaminobenzene-1-amino -2-nitro-4-bis (13-hydroxyethyl) -aminobenzene-1,4-bis (11-hydroxyethylamino) -2-nitrobenzene-1-11-hydroxyethylamino-2-nitro-4-bis (13-hydroxyethylamino) - benzene - 1-11-hydroxyethylamino-2-nitro-4-aminobenzene - 113-hydroxyethylamino-2-nitro-4- (ethyl) (11-hydroxyethyl) -aminobenzene-1-amino-3-methyl-413-hydroxyethylamino-6 1-amino-2-nitro-413-hydroxyethylamino-5-chlorobenzene-1,2-diamino-4-nitrobenzene-1-amino-213-hydroxyethylamino-5-nitrobenzene-1,2-bis-nitrobenzene 4-hydroxyethylamino) -4-nitrobenzene-1-amino-2-tris (hydroxymethyl) methylamino-5-nitrobenzene 35-1-Hydroxy-2-amino-5-nitrobenzene-1-hydroxy-2-amino-4-nitrobenzene - 1-Hydroxy-3-nitro-4-aminobenzene - 1-Hydroxy-2-amino-4,6-dinitrobenzene - 113-hydrox Yethyloxy-213-hydroxyethylamino-5-nitrobenzene-1-methoxy-213-hydroxyethylamino-5-nitrobenzene-113-hydroxyethyloxy-3-methylamino-4-nitrobenzene-113,7-dihydroxypropyloxy-3-methylamino-4-nitrobenzene hydroxyethylamino-413,7-dihydroxypropyloxy-2-nitrobenzene-113,7-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene-113-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene-113-hydroxyethylamino-3-methyl-2-nitrobenzene 113-aminoethylamino-5-methoxy-2-nitrobenzene-1-hydroxy-2-chloro-6-ethylamino-4-nitrobenzene-1-hydroxy-2-chloro-6-amino-4-nitrobenzene-1-hydroxy-6- bis- (p-hydroxyethyl) -amino-3-nitrobenzene-113-hydroxyethylamino-2-nitrobenzene-1-hydroxy-413-hydroxyethylamino-3-nitrobenzene. Among the azo direct dyes that can be used according to the invention, mention may be made of the cationic azo dyes described in the patent applications VVO 95/15144, VVO 95/01772 and EP-714954, the content of which forms an integral part of the invention. Among these compounds, mention may be made of the following dyes: 1,3-dimethyl-24 [4- (dimethylamino) phenyl] azo] -1H-imidazolium chloride, 1,3-dimethyl-2-yl chloride [- 4-Aminophenyl) azo] -1H-Imidazolium, 1-methyl-4 - [(methylphenylhydrozono) methyl] -pyridinium methylsulfate.

Mention may also be made, among the azo direct dyes, of the following dyes, described in the COLOR INDEX INTERNATIONAL 3rd edition: Disperse Red 17, Acid Yellow 9, Acid Black 1, Basic Red 22, Basic Red 76, Basic Red 51, Basic Yellow 57, Basic Brown 16, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 35, Basic Brown 17, Acid Yellow 23, Acid Orange 24, Disperse Black 9.

We may also mention 1- (4'-aminodiphenylazo) -2-methyl-4- bis- (p-hydroxyethyl) aminobenzene and 4-hydroxy-3- (2-methoxyphenylazo) -1-naphthalenesulfonic acid. Among the azomethine direct dyes, mention may be made of the following dyes: Disperse Red 15, Solvent Violet 13, Acid Violet 43, Disperse Violet 1, Disperse Violet 4, Disperse Blue 1, Disperse Violet 8, Disperse Blue 3, Disperse Red 11, Acid Blue 62, Disperse Blue 7, Basic Blue 22, Disperse Violet 15, Basic Blue 99 and the following compounds: -1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone -1-Aminopropylamino-4-methylaminoanthraquinone -1-Aminopropylaminoanthraquinone -513-hydroxyethyl -1,4-Diaminoanthraquinone -2-Aminoethylaminoanthraquinone -1,4-Bis - ([3,7-dihydroxypropylamino) anthraquinone. Among the azine dyes, mention may be made of the following compounds: Basic Blue 17 and Basic Red 2. Among the triarylmethane dyes that can be used according to the invention, mention may be made of the following compounds: Basic Green 1, Acid Blue 9, Basic Violet 3, Basic Violet 14, Basic Blue 7, Acid Violet 49, Basic Blue 26 and Acid Blue 7. Among the azomethine dyes that may be used according to the invention, mention may be made of the following compounds: - 213-hydroxyethylamino-54bis - ([3-4'- hydroxyethyl) amino] anilino-1,4-benzoquinone-213-hydroxyethylamino-5- (2'-methoxy-4'-amino) anilino-1,4-benzoquinone-3-N (2'-chloro-4'-hydroxy) ) phenyl-acetylamino-6-methoxy-1,4-benzoquinone imine-3-N (3'-chloro-4'-methylamino) phenyl-ureido-6-methyl-1,4-benzoquinone imine-344'-N- (Ethyl, carbamylmethyl) amino] phenyl-ureido-6-methyl-1,4-benzoquinone imine. Among the natural direct dyes that may be used according to the invention, lawsone, juglone, alizarin, purpurine, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin , curcumin, spinulosin, apigenidine. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from henna. The additional direct dye (s) may be present in the dyeing composition in a content ranging from 0.001% to 10% by weight, preferably in a content ranging from 0.005% to 6% by weight, relative to the total weight of the composition.

Preferably, the dyeing composition comprises one or more azomethine direct dyes of formula (I), (IA) or (IB) and one or more azomethine direct dyes. The medium suitable for dyeing, also called dyeing medium, is a cosmetic medium generally consisting of water or a mixture of water and at least one organic solvent. As organic solvent, there may be mentioned for example lower alkanols in Cl-04, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

The solvents when present are present in proportions preferably of between 1 and 99% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 95% by weight approximately. The dyeing composition may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic or amphoteric surfactants, or mixtures thereof, anionic, cationic, nonionic or amphoteric polymers, or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, solubilizing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or otherwise, such as aminosilicones, 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 in such a way that the advantageous properties intrinsically attached to the dyeing composition according to the invention are not, or not substantially, impaired by the or the additions envisaged.

The pH of the dye composition in accordance with the invention is generally between 3 and 12, preferably between 5 and 11, and even more particularly between 6 and 9. It can be adjusted to the desired value by means of agents. acidifying or basifying agents usually used for coloring keratinous fibers or else using conventional buffer systems.

Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids. Among the alkalinizing agents that may be mentioned, by way of example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula (III): RaRbN-W-NR, Rd; wherein W is a linear or branched (C1-C6) alkylene group, optionally substituted by one or more hydroxyl or amino groups, preferably VV = propylene optionally substituted by a hydroxyl group or a C1-C4 alkyl radical; R, Rb, R, and Rd, identical or different, represent a hydrogen atom, a C1-C4 alkyl or C1-C4 hydroxyalkyl radical. The dye composition according to the invention may be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratinous fibers, and in particular human hair.

As indicated above, the invention also relates to the use of the dye composition as defined above for the dyeing of keratinous fibers, in particular human keratinous fibers such as the hair. III. Dyeing process The dyeing process according to the present invention consists in applying to the keratin fibers, dry or wet, a dyeing composition as defined above, comprising at least one compound of formula (I), (IA) or (IB) or (II), (IIA) or (IIB) as defined below, preferably (I), (IA) or (113), for a time sufficient to obtain the desired coloration, after which the fibers are rinsed, washed optionally to the shampoo, rinsed again and dried or allowed to dry the resulting fibers. Preferably, the exposure time of the dyeing composition is between 1 and 60 minutes, preferably between 5 and 40 minutes, and even more preferably between 10 and 30 minutes. The dyeing composition is generally applied to the keratinous fibers at room temperature, preferably between 25 and 55 ° C. According to one embodiment, the dye composition according to the invention is applied to the keratinous fibers in the presence of one or more chemical oxidizing agents for a time sufficient to obtain the desired lightening. The chemical oxidizing agent may be present in the dye composition or may be used separately in a cosmetic composition. Preferably, the chemical oxidizing agent is used separately in a cosmetic composition.

Thus, the present invention also relates to a process for lightening keratinous fibers, in particular human keratinous fibers such as the hair, in which said dye composition as defined previously free of chemical oxidizing agents is applied to said fibers (i). (ii) a cosmetic composition comprising one or more chemical oxidizing agents; the compositions (i) and (ii) being applied to said keratinous fibers sequentially or simultaneously for a time sufficient to obtain the desired lightening, after which the fibers are rinsed, washed optionally with shampoo, rinsed again and dried or the resulting fibers are allowed to dry. By "sequentially" is meant in the sense of the present invention that the oxidizing composition is applied before or after the dye composition, that is to say in pre- or post-treatment, preferably in post-treatment. The chemical oxidizing agents used are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes (with their possible cofactors), among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Preferably, the chemical oxidizing agent is hydrogen peroxide. The oxidizing composition may also contain various adjuvants conventionally used in hair dye compositions and as defined above.

The pH of the oxidizing composition containing the chemical 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, more preferably between 5 and 11. and even more particularly between 6 and 8.5. It can be adjusted to the desired value by means of acidifying or basifying agents usually used for coloring keratinous fibers and as defined above. IV. The present invention also relates to compounds of the leuco type of formula (II) below, their acid or base salts, organic or inorganic, their tautomeric forms, optical isomers, geometrical isomers and / or their solvates. (II) Formula (II) wherein R1, n, X, W and Z have the same meanings as previously indicated in formula (I). In particular, the preferred variants of n, Y, and R 1 in the formula (II) of the leuco compounds correspond to those indicated in the formula (I) of the direct dyes. More particularly, the compounds of formula (II) are chosen from (IIA) and (IIB): OH HN Formula (IIA) and (IIB) with R1, n and Z as defined previously for (IA) and (IB). The leuco compounds of formula (II) are obtained generally by reacting the azomethine compounds of formula (I) with a reducing agent according to the reaction scheme below: HN Reducer (I) XN H2 Il is the same to obtain the compounds of formula (IIA) and (IIB) as defined above from (IA) and (IB) respectively. Indeed (IIA) is obtained by reduction of (IA) from conventional reductant known to those skilled in the art, and (IIB) is synthesized from (IB) which is reduced by conventional reductant. Synthetic approaches approaching this scheme are described in patent applications FR2056799, FR2047932, FR2165965 and FR2262023. The leuco compounds of formula (I1), (IIA) and (IIB) are used as precursors of direct dyes of formula (I), (IA) and (IB) respectively.

Preferably, the compounds of the leuco type of formula (I1), and (IIA) are chosen from compounds corresponding to the reduced form of the direct azomethine dyes with Lin as defined above, as well as their mixtures. Even more preferentially, the dye composition comprises one or more azomethine direct dyes of formula (II) corresponding to the reduced form of those chosen from the compounds of formula LU or L21 mentioned above. In particular, the invention relates to a cosmetic composition comprising one or more leuco type compounds of formula (II) as defined above. The present invention also relates to a dyeing process in which a cosmetic composition comprising one or more leuco-type compounds of formula (II) above, in the presence of one or more oxidizing agents, is applied to the keratin fibers for a time sufficient to develop the desired coloring, after which the fibers are rinsed, washed optionally with shampoo, rinsed again and dried or allowed to dry the resulting fibers. According to a particular embodiment of the invention, when the staining process does not use chemical oxidizing agent, the staining from the leucos compounds of formula (II) is carried out with the oxygen of the air. The simple air exposure of the keratin fibers treated with the composition comprising the leuco-type compound (s) makes it possible to generate the coloring species and, consequently, to color the fibers. According to one variant, the oxidizing agent (s) may be applied simultaneously or sequentially to the cosmetic composition comprising the leuco type compounds. According to an advantageous variant, the dyeing process is a sequential process which consists firstly of applying to the keratinous fibers, in particular human fibers such as the hair, one or more leucos compounds of formula (II), then of revealing the color in applying an oxidizing composition comprising one or more chemical oxidizing agents. This process makes it possible in particular to carry out clean staining, ie not staining or very little cloths and clothing since the first composition uses compounds of formula (II), (IIA) or (IIB) not colored or very weakly colored, then the color is revealed once said colorless (II), (IIA) or (IIB) compounds have been applied to the hair so that staining is avoided on the tissues during the staining process. The cosmetic composition comprising the chemical oxidizing agent (s) may be applied to the keratin fibers before, simultaneously with or after the cosmetic composition comprising the leuco type compounds of formula (II), (IIA) or (IIB) according to the invention. According to another variant, a ready-to-use composition is applied to the keratinous fibers which results from the mixing of a cosmetic composition comprising one or more leuco-type compounds of formula (II), (IIA) or (IIB) above and a cosmetic composition comprising one or more chemical oxidizing agents. According to one embodiment, the invention relates to a composition, in particular for dyeing keratinous fibers such as the hair, comprising one or more compounds of formula (II), (IIA) or (IIB) as defined above and comprising optionally one or more chemical oxidizing agents. The ready-to-use composition which is thus applied to the keratinous fibers may be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratinous fibers, and including human hair.

The exposure time of the composition (s) varies from 1 to 60 minutes, preferably from 5 to 40 minutes, and even more preferably from 10 to 30 minutes. The cosmetic composition comprising such leuco type compounds is generally applied to the keratin fibers at room temperature, preferably between 25 and 55 ° C.

V. Dyeing Device The present invention further relates to a multi-compartment device or "kit" comprising a first compartment containing a cosmetic composition comprising one or more dyes of formula (I), (IA) or (IB) as defined previously. or containing one or more leuco type compounds of formula (II), (IIA) or (IIB) as defined above, and optionally a second compartment comprising one or more chemical oxidizing agents. In particular, the invention relates to a multi-compartment device or dyeing kit comprising a first compartment containing a cosmetic composition comprising one or more direct dyes of formula (I), (IA) or (IB) as defined previously or containing one or more leuco type compounds of formula (II), (IIA) or (IIB) as defined above, and a second compartment comprising one or more chemical oxidizing agents. More particularly, the invention relates to a multi-compartment device or dyeing kit comprising a first compartment containing a cosmetic composition comprising one or more direct dyes of formula (I), (IA) or (IB) as defined above, free from chemical oxidizing agent and a second compartment containing a cosmetic composition comprising one or more chemical oxidizing agents. The invention also relates to a multi-compartment device or dyeing kit comprising a first compartment containing a cosmetic composition comprising one or more leuco type compounds of formula (II), (IIA) or (IIB) above, and a second compartment containing a cosmetic composition comprising one or more chemical oxidizing agents. According to a particular embodiment, the device may comprise at least one compartment comprising a cosmetic composition comprising one or more leuco type compounds of formula (II), (IIA) or (IIB) above. In this case, the composition comprising the leuco type compound (s) as defined above is applied to the keratinous fibers which are colored by virtue of their exposure to air.

The devices mentioned above are suitable for dyeing keratinous fibers. The examples below are there to illustrate the invention and in no way limit the scope. The compounds have been fully characterized by standard spectroscopic or spectrometric methods known to those skilled in the art. Synthetic Example 1 Compound 1: Synthesis of 2-Amino-5- (4-amino-2 or 3-ethyl-phenylamino) -4- [4-amino-2 or 3-ethyl-phenylimino] -cyclohexa-2,5-dienone: 2H01 + NH 2 H 2 O 2 O 2 -NH 2 NH 2 III NH 2 to a solution of 4.18 g of 2-ethyl-benzene-1,4-diamine dihydrochloride (20 mmol) and 1.095 g of 2-amino-phenol (10 mmol) in 20 ml of ethanol and 20 ml of water are added 7 ml of a solution. of 30% hydrogen peroxide and then the pH is adjusted to a pH of 9.5 with a 20% aqueous ammonia solution. The reaction medium is stirred at room temperature for 6 hours. The gum formed isolated, washed with water with stirring becomes a powder which is filtered and dried under reduced pressure. 2 g of the mixture of 2-amino-5- (4-amino- (2 or 3) -ethyl-phenylamino) -444-amino- (2 or 3-ethylphenylimino] -cyclohexa-2,5-dienone isomers are obtained in the form of black powder. This compound has been fully characterized by spectroscopic and spectrometric methods. MS (ES +): [M + H] = 376, (ES-): [M-H] = 374 Compound 2: Synthesis of 2-Amino-5- (4-amino-2 or 3- (2-hydroxyethyl) phenylamino) -4- [4-amino-2 or 3-ethyl-phenylimino] -cyclohexa-2,5-dienone: OH H 2 SO 4 + NH H 2 O 2 OH 2 NH 2 NH 2 A mixture of 2-hydroxyethyl-benzene-1 sulfate, 4-diamine (5 g, 0.02 mol, 2 eq) and 2-aminophenol (1.09 g, 0.01 mol, 1 eq) are suspended in ethanol (20 ml) and water (10 ml). The pH of the solution was adjusted to 9.5 with 4M sodium hydroxide solution (9.5 ml) and then 10% aqueous H 2 O 2 solution (17 ml, 0.06 mol, 6 eq) was added. The reaction mixture is stirred for 6 hours at room temperature, then water is added and the mixture is lyophilized. Purification by chromatography on silica (eluent: acetone / MeOH 98/2 to 95/5) leads to 2-amino-5- (4-amino-2 or 3- (2-hydroxyethyl) -phenylamino) -444-amino 2 or 3-ethyl-phenylimino] -cyclohexa-2,5-dienone expected in the form of a black powder. This compound has been fully characterized by spectroscopic and spectrometric methods. MS (ES +): [M + 1-1] = 408, (ES-): [M-I-1] = 406 II- Dye evaluations of the synthesized molecules: The following dye compositions were prepared: - 500 mg of compound L11 - 74.5 g of water; 15 g of ethanol; - 5 g of benzyl alcohol; 5 g of a 30% aqueous solution of oleocetyldimethyl hydroxyethyl ammonium chloride. 1.25 g of the resulting mixture is applied to a lock of 0.25 g gray hair at 90% white. After 30 minutes of exposure to room temperature, the wick is rinsed, washed with a standard shampoo, rinsed again and then dried. The resulting color of the lock thus treated is a very attractive dark brown. Moreover, it appears that the color is homogeneous along the fiber.

Claims (15)

REVENDICATIONS1. Compound of formula (I) or (II) below, their acid or base salts, organic or inorganic, their tautomeric forms, optical isomers, geometric isomers and / or their solvates: HN XH (I) Formula (I) or (II) wherein: - n represents an integer equal to 1, 2 or 3; - R1, identical or different, preferably identical, represents: - a linear or branched C1-C4 alkyl radical; or - a linear or branched C1-C4 alkyl radical substituted with one or more radicals, which may be identical or different, chosen from the radicals i) hydroxy, ii) guanidine -N (R) -C (= NR ') - NR "R", iii) guanidinium -N (R) -C (= N + R'R ") - NR-R-, An-; iv) amidine -C (= NR) -NR'R", v) amidinium -C (= N + RR ') - NR "R", An-; vi) Cationic heteroaryl, An- such as pyridinium, quinolinium, imidazolium, or benzomidazolium, An- and vi) tetraalkylammonium -N + RR'R "R", An- with R, R ', R ", R" and R " , which may be identical or different, represent a hydrogen atom, a linear or branched C 1 -C 6 alkyl group, with An - denoting an anionic counterion or a mixture of cosmetically acceptable anions such as halide; oxygen or an NH radical, preferably oxygen; Z, identical or different, represent i) a hydroxyl group or ii) an -NR 2 R 3 amino group with R 2 and R 3, identical or different, representing: a hydrogen atom a linear or branched C1-C6 alkyl group; a linear or branched C1-C6 alkyl group substituted with one or more radicals selected from hydroxyl and alkoxy, linear or branched, at Cl-04; , represent i) a group OR, with R as defined above, preferably CH or ii) a nitrogen atom; - denotes an anionic counterion or a mixture of cosmetically acceptable anionic counterions. 2. Compound of formula (I) or (II) according to the preceding claim, characterized in that R1 represents a linear or branched C1-C3 alkyl radical; preferably methyl or a linear or branched C 1 -C 3 alkyl radical substituted with a hydroxyl radical such as hydroxymethyl -CH 2 -OH. 3. Compound of formula (I) or (II) according to any one of the preceding claims, characterized in that Z represents an amino group -NR2R3, with R2 and R3 as defined in claim 1, preferably: R2 and R3 , identical or different, represent a hydrogen atom or a linear or branched C 1 -C 3 alkyl radical, optionally substituted with a hydroxyl radical such as methyl; and more particularly Z represents -NH2. 4. Compound of formula (I) or (II) according to claim 1 or 2, characterized in that, Z represents a hydroxy group. 5. Compound of formula (I) or (II) according to any one of the preceding claims, characterized in that they are chosen from compounds of formula (IA) or (IIA), their acid or base salts, organic or mineral, their tautomeric forms, optical isomers, geometric isomers and / or their solvates: ## STR1 ## . Wherein R1, n and Z are as defined in any one of the preceding claims; preferably: - R 1 represents a linear or branched C 1 -C 4 alkyl radical or a C 4 linear or branched C 4 alkyl radical substituted with one or more hydroxyl or imidazolium radicals, An "with An- representing a counterion anionic compound; n represents an integer ranging from 1 to 3, preferably equal to 1; Z represents an -NR 2 R 3 radical with R 2 and R 3 representing, independently of one another, a hydrogen atom; -C3 optionally substituted by a hydroxyl radical, particularly R2 and R3 are identical and represent a hydrogen atom. 6. Compound of formula (1) or (11) according to any one of the preceding claims, characterized in that they are chosen from compounds of formula (1B) or (11B), their acid or base salts, organic or mineral, their tautomeric forms, optical isomers, geometric isomers and / or their solvates: 110. ## STR2 ## wherein R 1 is N, OH, R 1, N (1B) (11B) R1, n and Z are as defined in any one of the preceding claims; preferably: R1 represents: a linear or branched C1-C3 alkyl radical, preferably a methyl radical; a linear or branched C1-C3 alkyl radical substituted with a hydroxyl radical; n represents an integer equal to 1; Z represents a hydroxyl radical or -NR 2 R 3; R2 and R3 represent, independently of one another, a hydrogen atom, a linear or branched C1-C3 alkyl radical; a linear or branched C 1 -C 3 alkyl radical substituted with a hydroxyl radical. 7. Compound of formula (I) or (II), or (IA), or (113), or (IIA), or (IIB), according to any one of the preceding claims, characterized in that it is chosen from the compounds LU at 181 as well as their reduced leucos forms, their geometric or optical isomers, their tautomers, their organic or inorganic acid or base salts or their solvates such as hydrates: H2N lei N. NH 2 O: HN 2-Amino-5- (4-amino-2- or 3-ethylphenylamino) -444-amino-2 or 3-ethylphenylimino] -cyclohexa-2,5-dienone NH 2 H 2 N NH 2 NH 2 el 2-Amino-5- (4-amino-2- or 3- (2-hydroxyethyl) -NH-phenylamino) -444-amino-2 or 3- (2-hydroxy-NH) -phenylimino] -cyclohexa-2,5 - 2N-amino-2-amino-5- (4-amino-2 or 3- (2-N-OH-NH 2 -hydroxypropyl) -phenylamino) -4-amino-2 or 3-hydroxypropyl dienone phenylimino] -cyclohexa- 2,5-dienone H2N ill. NH 2 O L11: 2-Amino-5- (4-amino-2 or 3-propyl-1H-phenylamino) -444-amino-2 or 3-propylphenylimino] -cyclohexa-2,5-dienone NH 2 H 2 N 00 OH NNH 2 (5): 3-Amino-6- [4-amino-3- (2 or 3 '- ..., ... <: .., hydroxy-ethyl) -phenylamino] -544-amino 2- or 3- (2-Hydroxyethyl) -phenylimino] -5H-pyridin-2-one HN N-Ole NH 2 OH N HN NNH 2 O n: 3-Amino-644- [4-3- (2 or 3 ethyl) phenylamino] -5 [4-amino-2- or 3- (ethyl) -N, phenylimino] -5H-pyridin-2-one 1. NH 2 H 2 N * OH NNH 2 N 0 in: 3-amino 6- [4-amino-3- (2 or 3-OH-hydroxy-propyl) -phenylamino] -54-amino-2-I-4-NH 2 or 3- (2-hydroxy-propyl) -phenylimino] -5H-pyridin -2-one 8. Composition, in particular for dyeing keratinous fibers such as the hair, characterized in that it comprises, in a medium suitable for dyeing, one or more compounds of formula (I) or (II), or (IA ), or (113), or (IIA), or (IIB) as defined in any one of claims 1 to 7. 9. Composition according to the preceding claim characterized in that it further comprises one or more chemical oxidizing agents, in particular chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes (with their possible cofactors), among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases, preferably chemical oxidizing agent is hydrogen peroxide. 10. A process for dyeing keratinous fibers, in particular human keratin fibers such as the hair, in which a dyeing composition comprising, in a medium which is suitable for dyeing, one or more compounds of formula (I) is applied to said fibers. or (IA), or (113), as defined according to any one of claims 1 to 7, for a time sufficient to obtain the desired coloration after which it is rinsed, the fibers are optionally washed with shampoo, rinsed again and drying or allowing to dry the resulting fibers. 11. A process for lightening keratinous fibers, in particular human keratinous fibers such as the hair, in which a dyeing composition comprising, on a medium which is suitable for dyeing, (i) one or more formula (I) or (IA), or (113), as defined according to any one of claims 1 to 7 free of chemical oxidizing agent and (i) a cosmetic composition comprising one or more chemical oxidizing agents such as NN H2H2NHNNO NH2 181: 3-Amino-6 [4-amino-3- (2 or 3-propyl) phenylamino] -544-amino-2 or 3 (propyl) phenylimino] -5H-pyridin 2-undefined in claim 9; the compositions (i) and (ii) being applied to said keratinous fibers sequentially or simultaneously for a time sufficient to obtain the desired lightening, after which the fibers are rinsed, washed optionally with shampoo, rinsed again and dried or the resulting fibers are allowed to dry. 12. A process for dyeing keratinous fibers, characterized in that a dyeing composition comprising one or more compounds of formula (II) or (IIA) or (IIB) is applied simultaneously to said fibers, dry or wet. as defined in any one of claims 1 to 7 and an oxidizing composition comprising one or more chemical oxidizing agents as defined in claim 9. 13. A process for dyeing keratinous fibers, characterized in that a dyeing composition comprising one or more compounds of formula (II) or (IIA) or (IIB) is applied sequentially to said fibers, dry or wet. ), as defined in any one of claims 1 to 7 and secondly an oxidizing composition, comprising one or more chemical oxidizing agents as defined in claim 9. 14. Use of one or more compounds of formula (I) or (IA), or (IB) or (II) or (IIA), or (IIB) as defined according to any one of claims 1 to 7 for the coloration of the keratinous fibers, in particular human keratinous fibers such as the hair, optionally, in the presence of one or more chemical oxidizing agents as defined in claim 9, for the coloration of the keratinous fibers, in particular human keratinous fibers such as hair. 15. Multi-compartment device or "kit" comprising a first compartment containing a composition comprising one or more compounds of formula (I) or (IA), or (IB) as defined in any one of claims 1 to 7 or containing a or more compounds of formula or (II) or (IIA), or (IIB) as defined in any one of claims 1 to 7, and a second compartment comprising one or more chemical oxidizing agents as defined in claim 9.