FR2925052A1 - AZOMETHINIC DIRECT DYES OR REDUCED PRECURSORS OF DIRECT AZOMETHINIC DYES OBTAINED FROM 4,5-DIAMINO-PYRAZOLE, PROCESS FOR CAPILLARY COLORING FROM THESE COLORANTS OR PRECURSORS - Google Patents

Abstract

The invention relates to the dyeing of keratinous fibers using azomethine direct dyes obtained from 4,5-diaminopyrazole derivatives.The subject of the invention is a dyeing composition comprising at least one azomethine direct dye or a precursor of azomethine direct dyes, a process for dyeing keratin fibers, using said composition and their uses in the dyeing of keratin fibers. This composition makes it possible to obtain a particularly stable and tenacious coloration.

Description

AZOMETHINIC DIRECT DYES OR REDUCED PRECURSORS OF DIRECT AZOMETHINIC DYES OBTAINED FROM 4,5-DIAMINO-PYRAZOLE, PROCESS FOR CAPILLARY COLORING FROM THESE COLORANTS OR PRECURSORS

The invention relates to the dyeing of keratinous fibers using azomethine direct dyes or reduced precursors of azomethine direct dyes obtained from 4,5-diaminopyrazole.

It is known to dye keratinous fibers, and in particular the hair, with dyeing compositions containing direct dyes, according to a process known as direct dyeing. The method conventionally used in direct dyeing consists in applying to the keratin fibers direct dyes, or coloring molecules, having an affinity for said fibers, allowing them to pause and then rinsing the fibers. The direct dyes heretofore used are nitrobenzene dyes, anthraquinones, nitropyridines, azo, xanthene, acridine, azine or triarylmethane benzene dyes. Other dyes are derived from oxidation bases and oxidation couplers which once condensed are applied to the hair. For example, in FR 233036, FR 2262022, FR 2262024, US 4,221,729 and FR2261750, diphenylamines such as indolein indolein indolein leucoderivatives are used either alone or in combination with other dyes in the compositions. dye. Other compounds corresponding to oxidized derivatives of leuco-derivatives such as those described in documents FR 2254557 and FR 2234277 are also known for dyeing keratinous fibers. Moreover, some direct dyes obtained from 4,5-diamino-pyrazole derivatives (FR 2746392) are known for dyeing the hair. The colorations that result from direct staining are temporary or semi-permanent staining, because the nature of the interactions that bind the direct dyes to the keratinous 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 washes or perspiration. These direct dyes are in addition generally sensitive to the action of oxidizing agents such as hydrogen peroxide, which renders them generally unusable in direct lightening dyeing compositions based on hydrogen peroxide and an alkalinizing agent, which are would bring oxidation dyes closer together.

Direct dyes also exhibit a lack of light stability due to the low resistance of the chromophore to photochemical attack. In addition, their sensitivity to light is dependent on the distribution of their molecules, uniform or aggregates, in the substrate. Consequently, there is a real need to look for direct dyes which make it possible to dye the keratinous fibers, are stable in the light, are also resistant to bad weather, washes and transpiration, sufficiently stable in the presence of oxidizing agents such as oxygenated water to be able to obtain a simultaneous lightening of the fiber with the advantages described above while presenting an improved toxicological profile and compatible with a cosmetic use on keratinous fibers.

These objects are achieved with the present invention which relates to a process for dyeing keratinous fibers from a direct dye chosen from those of formula (I) to (IV) according to: (III) (IV) their salts of organic or inorganic acid, their geometric isomers, tautomers, and solvates such as hydrates; formulas (I) to (IV) in which: R 1 represents: a hydrogen atom, a C 1 -C 5 alkyl radical, or a C 1 -C 5 alkyl radical functionalized with a group chosen from: ) hydroxyl, ii) C 1 -C 4 alkoxy iii) amino, iv) amido, v) di (C 1 -C 3) alkylamino, vi) imidazolyl, vii) phenyl optionally substituted by a chlorine atom, a trifluoromethane radical, a radical methyl; R2 represents: a hydrogen atom, a bromine atom, a C1-C5 alkyl radical, or a phenyl radical; R3 and R4 represent independently of each other: a hydrogen atom, a C1-C5 alkyl radical, or a C1-C5 alkyl radical functionalized with a group chosen from: i) hydroxyl, ii) C 1 -C 4 alkoxy, iii) amino, iv) amido, v) di (C 1 -C 3) alkylamino, and vi) imidazolyl;

R5 represents: a hydrogen atom, or a C1-C4 alkyl radical; R6 represents: a hydrogen atom, or a radical corresponding to the following formula (V); H: N (V) in which formula (V) in which R 1, R 2, R 3 and R 4 have the same meaning as above. Another subject of the invention relates to a method of staining from reduced precursors of colorless azomethine dyes, which once oxidized generate the compounds / N, N 1 R NR3R4 of formula (I) to (IV) as defined above. These precursors have the following formulas (I ') to (IV'): ## STR2 ## their organic or inorganic acid salts, their geometrical isomers, their tautomers, and their solvates such as: that hydrates; formula (II) wherein R 1 to R 6 are as previously defined.

Another subject of the invention is a dye chosen from those of formulas (I) to (IV) and a reduced coloring precursor chosen from those of formulas (I ') to (IV').

Another subject of the invention is a dyeing composition for dyeing keratinous fibers, in a cosmetic medium, comprising at least one compound of formula (I) to (IV) or (I ') to (IV') as defined previously.

The direct dyes of formula (I) to (IV) make it possible to overcome the drawbacks of the direct dyes conventionally used previously, and lead to dyeings by direct dyeing, endowed with very good resistance to light, bad weather, washes, sweating and rubbing. Their good stability vis-à-vis oxidizing agents such as hydrogen peroxide also allows them to be used in a direct lightening dyeing process.

In addition, it has been discovered that the reduced forms of the azomethine derivatives obtained from 4,5-diaminopyrazole derivatives of formulas (I ') to (IV'), used in an oxidizing condition, can also lead to colorings provided with very good resistance to light, weather, washing, perspiration and friction.

For the purposes of the present invention, and unless a different indication is given: an organic or inorganic acid salt is for example chosen from a salt derived i) hydrochloric acid HCl, ii) hydrobromic acid HBr iii) sulfuric acid H2SO4; iv) alkylsulfonic acids: Alk-S (O) 2OH such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S (O) 2OH such as benzene sulfonic acid and toluene sulfonic acid; (vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid, x) alkoxysulfinic acids: Alk-O-S (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid H3PO4i xiii) acetic acid CH3C (O) OH; xiv) triflic acid CF3SO3H and xv) tetrafluoroboric acid HBF4; an alkyl radical is a hydrocarbon radical, linear or branched, saturated, comprising from 1 to 6 carbon atoms, particularly from 1 to 3 carbon atoms such as the methyl or ethyl radical; an alkoxy radical is an alkyl-oxyalkyl-O- radical in which the alkyl part is as defined above; benzyl or phenyl radicals followed by optionally substituted by

. means that said radicals may have one or more hydrogen atoms substituted by one or more substituents in question, particularly one or two substituents in question ... DTD: An object of the invention relates to direct dyes of formula (I) to (IV) or staining precursors of formula (I ') to (IV'). A particular embodiment of the invention relates to compounds of formula (I) to (IV) or (I ') to (IV') for which n is zero.

According to one particular embodiment of the invention, the compounds of formula (I) to (IV) or (I ') to (IV') contain a radical R, representing a C1-C5 alkyl radical, or an alkyl radical. in Cl-05 functionalized with a hydroxyl group.

One variant relates to the compounds of formula (I) to (IV) or (I ') to (IV') for which R3 and R4 represent a hydrogen atom. Another variant of the invention uses dyestuffs of formula (I) and (IV) or (I ') and (IV') for which R6 represents a radical (V) as defined above in which R2, R3 and R4 represents a hydrogen atom and R5 represents a C1-C5 alkyl radical functionalized with a hydroxyl group.

By way of example, the compounds of formula (I) to (IV) or (I ') to (IV') according to the invention, dyes (la) to (1j) and precursors (2a) to 2j), as well as their salts of organic or inorganic acid, their geometric isomers, tautomers and solvates such as hydrates: Dyestuffs of formula (I) to (IV): O 2- [5-Amino-1- ( 2-Hydroxyethyl) -1H-pyrazol-4-ylamino] -5- (2-hydroxyethylamino) -NN [1,4] benzoquinone / Formula (III) N-NH 2 OH (1 a) H 2 N CI 3-Amino-4- [5-amino-1- (2-hydroxyethyl) -1H-pyrazol-4-ylimino] -2-chloro-6-methylcyclohexa-2,5-dienone N, N NH 2 Contains Formula (II) OH (1b) HO 4- [5-Amino-1- (2-hydroxyethyl) -1H-pyrazol-4-N-ylimino] -3-hydroxy-cyclohexa-2,5- dienone N NH 2 Contains formula (I) OH (1c) HO 2- [5-Amino-1- (2-hydroxyethyl) -1H-pyrazol-4-yl] amino] -4- [5-amino-1] - (2-hydroxy-ethyl) -1H-N NNH 2 N ~ N pyrazol-4-ylimino] -5-hydroxy-cyclohexa-2,5-HN dienone I H2N OH Formula (I) HO (Id) 6H 4- [5-Amino-1- (2-hydroxyethyl) -1H-pyrazol-4-ylimino] -3-hydroxy-2-methyl-cyclohexa-2,5-N-NH Dienone N 2 Contains formula (I) OH (1 e) NO 1 N / N NH 2 NH 2 2-Amino-6- [5-amino-1- (2-hydroxyethyl) -1H-OH pyrazol-4-ylimino] -6H -pyridin-3-one (1f) Contains formula (IV) CN'N ', OH 2-Amino-5- [5-amino-1- (2-hydroxyethyl) -1H-C-pyrazol-4-ylamino] 6-Amino-1- (2-hydroxyethyl) -NH 2 H -pyrazol-4-ylimino] -6H-pyridin-3-one [5-amino-1- (2-hydroxyethyl) -N-O-N-NH-NH 2 2 OIH Formula (IV) (1g) O 2- (5-Amino-1,3-dimethyl-1H-pyrazol-HH-4-ylamino) -5- (2-hydroxyethylamino) -NH 2 OH - [1,4] benzoquinone (1h) Belongs Formula (III) N2NH NNLNH2,2,5-Dienone N, 3-Amino-4- (5-amino-1,3-dimethyl-1H-pyrazol-4-ylimino) -2-chloro-6-methyl- Cyclohexa- (1i) Formula (II) HO 4- (5-Amino-1,3-dimethyl-1H-pyrazol-4-ylimino) -3-hydroxy-cyclohexa-2,5-dienone N i NH 2 Contains Formula (I) (1j) n-4- (5-Amino-1,3-dimethyl-1H-pyrazol-4-ylimino) -3-hydroxy-2-methyl-cyc 2,5-N-phenyl N 2 H 2 O 2 N 2 O 2 N- (2-amino) -6- (5-amino-1,3-dimethyl-1H-pyrazol-4-ylimino) -6H-pyridin-3-one N NH NH Contains formula (IV) 2 2 (11) HN NH 2 2-Amino-5- (5-amino-1,3-dimethyl-1H-pyrazol-4-ylamino) 6 (5-amino-1,3-dimethyl-1H-N-pyrazol-4-ylimino) -6H-pyridin-3-one N NH 2 NH 2 Contains formula (IV) 1 (1 m) Precursors of staining of formula (1 ') to (IV'): HO 2- [5-Amino-1- (2-hydroxyethyl) -1H-pyrazol-4-ylamino] -5- (2-hydroxyethylamino) - benzene-1,4-NN diol / pertains to formula (III ') N' NH 2 OH (2a) H 2 N and H 3-Amino-4- [5-amino-1- (2-hydroxyethyl) -1H) Pyrazol-4-ylamino] -2-chloro-6-methyl-phenol N le, pertains to formula (II ') N / N-NH 2 OH (2b) HO 4- [5-Amino-1- (2- hydroxyethyl) -1H-pyrazol-4-H ~ N-OH N- [NH2-ylamino] -benzene-1,3-diol H Formula (1 ') OH (2c) / HO 4,6-Bis- [5-Amino-1- (2-hydroxyethyl) -1H-pyrazol-4-NNH ylamino] -benzene-1,3-diol HO N OH Contains formula (I ') NH 2 H - H2N OH ( 2d) HO 4- [5-Amino-1- (2-hydroxyethyl) -1H-pyrazol-4-ylamino] -2-methyl-benzene-1,3-diol / N OH Formula (I ') N NH 2 OH (2e) N, N-, OH 2-Amino-5,6-bis- [5-amino-1- (2-hydroxyethyl) -1H-pyrazol-4-ylamino] -pyridine 3-ol is as formula (IV ') ## STR2 ## More particularly the dyes contained in the composition are chosen from the foregoing dyes (1a), (Ib), (1c), (1c), 1d), (1e), (1f), (1g), (2b) and their organic or inorganic acid salts, their geometrical isomers, their tautomers, and their solvates such as hydrates. The compounds of formula (I) to (IV) and (I ') to (IV') of the invention are prepared according to the following general routes of synthesis: 1- Access to compounds corresponding to formula (I) to (IV ):

The compounds corresponding to the formula (I) to (IV) are obtained generally by reacting the derivatives 1, 2, 3 or 4 with a 4,5-diaminopyrazole derivative, preferably in a 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. oxidant base oxidant base oxidant base N`NR3R4 O OH R1 OH 2 H 3 oxidizing base Synthetic approaches approaching are described in patents FR2234277, FR2047932, FR2106661 and FR2121101. 2- Access to compounds corresponding to formula (I ') to (IV'): The compounds corresponding to formulas (I ') to (IV') are obtained in a general manner by reacting the compounds of formula (I) with ( IV) with a reducer. This reducing agent is preferably sodium hydrosulfite. (I) OH OH reducing agent N = N, NNR, R 4 NH 2 R, OH reducing reducing agent N = (reducing agent N, N -NR, R 4 NH 2 R, Synthetic approaches approaching are described in patents FR2056799, Another object of the invention is a dyeing composition for dyeing keratinous fibers in a cosmetic medium, comprising at least one compound of formula (I) to (IV), or of formula (I). ) to (IV ').

The dyeing composition useful in the invention generally contains a quantity of dye of formula (I) to (IV), or of precursor of formula (I ') to (IV') of between 0.001 and 30% relative to the total weight. of the composition. Preferably, this amount is between 0.005 and 10% by weight and even more preferably between 0.01 and 6% by weight relative to the total weight of the composition.

The dye composition containing the dye of formula (I) to (IV), or the precursor of formula (I ') to (IV'), in particular the precursor of formula (I ') to (IV'), may also contain a oxidizing agent such as hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes.

The dye composition may further contain additional direct dyes other than those of formula (I) to (IV) or (I ') to (IV'). These direct dyes are, for example, chosen from neutral, acidic or cationic nitro-benzene direct dyes, neutral azo, acid or cationic direct dyes, tetraazapentamethine dyes, neutral or acidic or cationic quinone dyes, in particular neutral anthraquinone dyes and direct azine dyes. , triarylmethane direct dyes, indoamine direct dyes and natural direct dyes. Among the nitrobenzene direct dyes, mention may be made in a nonlimiting manner of the following compounds: 1,4-diamino-2-nitrobenzene, 1-amino-2-nitro-4-13-hydroxyethylaminobenzene, 1-amino-2-nitro-4- bis (13-hydroxyethyl) -aminobenzene, 1,4-bis (13-hydroxyethylamino) -2-nitrobenzene, 1-13-hydroxyethylamino-2-nitro-4-bis (13-hydroxyethylamino) -benzene, 1-13- hydroxyethylamino-2-nitro-4-aminobenzene, 1-13-hydroxyethylamino-2-nitro-4- (ethyl) (13-hydroxyethyl) aminobenzene, 1-amino-3-methyl-4-13-hydroxyethylamino-6-nitrobenzene 1-amino-2-nitro-4-13-hydroxyethylamino-5-chlorobenzene, 1,2-diamino-4-nitrobenzene, 1-amino-2-13-hydroxyethylamino-5-nitrobenzene, 1,2-bis- ( 13-hydroxyethylamino) -4-nitrobenzene, 1-amino-2-tris (hydroxymethyl) methylamino-5-nitrobenzene, 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, 1-13-hydroxyethyloxy-2-13-hydroxyethylamino-5-nitro benzene, 1-methoxy-2-13-hydroxyethylamino-5-nitrobenzene, 1-13-hydroxyethyloxy-3-methylamino-4-nitrobenzene, 1-13, y-dihydroxypropyloxy-3-methylamino-4-nitrobenzene, 1- R-hydroxyethylamino-4-R, γ-dihydroxypropyloxy-2-nitrobenzene, 1-β, γ-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene, 1 -13-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene, 1-13- hydroxyethylamino-3-methyl-2-nitrobenzene, 1-13-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- (13-hydroxyethyl) -amino-3-nitrobenzene, 1-13-hydroxyethylamino-2-nitrobenzene, 1-hydroxy-4-13-hydroxyethylamino-3-nitrobenzene. Among the azo direct dyes, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO-95/01772 and EP-714954, the content of which forms an integral part of the invention. Among these compounds, mention may be made in particular of the following dyes: 1,3-dimethyl-2 - [[4- (dimethylamino) phenyl] azo] -1H-imidazolium chloride, 1,3-dimethyl-2-chloride [(4-Aminophenyl) azo] -1H-Imidazolium, 1-methyl-4 - [(methylphenylhydrazono) methyl] -pyridinium methylsulfate. 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 Yellow 57, Basic Brown 16 may also be mentioned among the azo direct dyes. , Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 35, Basic Brown 17, Acid Yellow 23, Acid Orange 24, Disperse Black 9. Mention may also be made of 1- (4'-aminodiphenylazo) -2-methyl -4bis-03-hydroxyethyl) aminobenzene and 4-hydroxy-3- (2-methoxyphenylazo) -1-naphthalene sulfonic acid. Among the quinone 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, as well as the following compounds: 1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone, 1-Aminopropylamino-4-methylaminoanthraquinone, 1-Aminopropylaminoanthraquinone, 5- 13-hydroxyethyl-1,4-diaminoanthraquinone, 2-aminoethylaminoanthraquinone, 1,4-bis-03, γ-dihydroxypropylamino) anthraquinone. Among the azine dyes, mention may be made of the following compounds: 20 -Basic Blue 17 and Basic Red 2. Among the triarylmethane dyes, 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, Acid Blue 7. Among the indoamine dyes, mention may be made of the following compounds: -2- [3-hydroxyethlyamino-5- [bis- ([3-4'- hydroxyethyl) amino] anilino-1,4-benzoquinone; -2- [3-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; -3- [4'-N- (ethyl, carbamylmethyl) amino] -phenyl-ureido-6-methyl-1,4-benzoquinone imine. Among the natural direct dyes that may be mentioned are lawsone, juglone, alizarin, purpurin, 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 dyeing composition may contain one or more oxidation bases and / or one or more couplers conventionally used for dyeing keratinous fibers.

Among the oxidation bases that may be mentioned are para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts. Among the couplers, mention may notably be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. The coupler (s) are each generally present in an amount of between 0.001 and 10% by weight relative to the total weight of the dyeing composition, preferably between 0.005 and 6%.

The oxidation base (s) present in the dyeing composition are in general each present in an amount of between 0.001% and 10% by weight relative to the total weight of the dyeing composition, preferably between 0.005% and 6% by weight. In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines. The medium suitable for dyeing, also called dyeing medium, is a cosmetic medium generally comprising water or a mixture of water and at least one organic solvent. As organic solvent, there may be mentioned for example lower alkanols C1-C4, 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 they are present are preferably present in proportions preferably of between 1 and 50% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 40% by weight approximately. The dye composition may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric and zwitterionic 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, 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, conductive polymers. 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 dyeing composition is generally between 3 and 14 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. According to one particular embodiment of the invention, when the dyeing composition comprises at least one dye of formula (I) to (IV), the composition has a pH of between 6 and 11.

According to another particular embodiment of the invention when the composition comprises at least one dye precursor of formula (I ') to (IV'), the composition has a pH of between 6 and 11. Among the acidifying agents, mention may be made of by way of example, inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid , sulfonic 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 (y): R 1 R a 2 N-Wa-N-Ra 4 Rai (Y) in which Wa is a propylene residue optionally substituted with a hydroxyl group or a C 1 -C 4 alkyl radical; Raii Ra2i Rai and Ra4i, which are identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.

The dye composition may be in various forms, such as in the form of liquid, cream, gel, or in any other form suitable for dyeing keratinous fibers, and in particular hair. Another subject of the invention is a method for dyeing keratinous fibers, in particular the hair, consisting in applying to the keratin materials, in the presence or absence of an oxidation agent, a dyeing composition, comprising in a cosmetic medium at minus an azomethine dye of formula (I) to (IV) or a staining precursor of formula (I ') to (IV') as defined above.

After a pause, the keratinous fibers are rinsed revealing colored fibers. The pause time is generally between 3 and about 50 minutes, preferably about 5 to 40 minutes. The application of the dye composition according to the invention is generally carried out at room temperature. It can, however, be carried out at temperatures ranging from 20 to 80 ° C.

The examples which follow serve to illustrate the invention without, however, being limiting in nature. The dyes of the examples below have been fully characterized by standard spectroscopic and spectrometric methods. EXAMPLES EXAMPLES OF SYNTHESIS Example 1 Synthesis of 2- [5-Amino-1- (2-hydroxyethyl) -1H-pyrazol-4-ylamino] -5- (2-hydroxyethylamino) - [1,4] benzoquinone 1 ( compound (1a)). In a three-necked flask equipped with a thermometer, a condenser and a dropping funnel, 1.4 g of 2- (4,5-diamino-pyrazole) sulphate are introduced respectively. -1-yl) -ethanol (1 eq), 24 ml of water, 880 mg of 3,4-dihydro-2H-benzo [1,4] oxazin-6-ol (1 eq) and 24 ml of ethanol. After stirring, the pH is adjusted to 9.7 with a 20% aqueous ammonia solution. 2 ml of 9% hydrogen peroxide are then added and the reaction mixture is stirred for 4 hours at room temperature. The solid formed is filtered, washed with water and then dried under vacuum. 440 mg of 2- [5-30 Amino-1- (2-hydroxyethyl) -1H-pyrazol-4-ylamino] -5- (2-hydroxyethylamino) - [1,4] benzoquinone (1 a) are obtained.

Example 2 Synthesis of 3-Amino-4- [5-amino-1- (2-hydroxy-ethyl) -1H-pyrazol-4-yliminol-2-chloro-6-methyl-cyclohexa-2,5-dienone 2 (compound (1b)). In a three-necked flask equipped with a thermometer, a condenser and a dropping funnel, 4.7 g (19.6 mmol) of 2- (4,5-diamino) sulphate are added. pyrazol-1-yl) ethanol (1 eq), 40 ml of water, 3.9 g (20.2 mmol) of 3,4-dihydro-2H-benzo [1,4] oxazin-6-ol (1 eq.) Then 40 ml of water and 80 ml of ethanol, all with stirring. The pH is adjusted to 9.7 with 14 ml of a 20% aqueous ammonia solution.

A solution of 9 g of ammonium persulfate in 30 ml of water is then added over 10 minutes. The reaction mixture is stirred at room temperature for 4 hours and the solid formed is filtered, washed with water, with water / ethanol 50/50 and then dried under vacuum. 5.6 g of 3-Amino-4- [5-amino-1- (2-hydroxyethyl) -1H-pyrazol-4-ylimino] -2-chloro-6-methyl-cyclohexa-2,5- are obtained. dienone (1b).

Example 3 Synthesis of 2- [5-Amino-1- (2-hydroxy-ethyl) -1H-pyrazol-4-ylaminol-4- [5-amino-1 - (2-hydroxy) -1H-pyrazol-4) -yliminol-5-hydroxy-cyclohexa-2,5-dienone 3 (compound (1d HO N H 2 N NNH 2 + N. NH 2 N N OH H 2 HSO H 2 N OH HO .24 HO (Id)

12 g (50 mmol) of 2- (4,5-diaminopyrazol-1-yl) ethanol sulfate (1 eq.), 2.8 g (25 mmol) of 3-hydroxyphenol are introduced into a flask respectively. (0.5 eq.), 250 ml of water and 250 ml of ethanol. The whole is stirred at room temperature, the pH is adjusted to 9.6 with 20 ml of a 20% ammonia solution and bubbling air is carried out in the reaction medium.

After 24 h, the ethanol of the reaction mixture is evaporated and the solid formed is filtered, washed with water and then dried under vacuum.

700 mg of 2- [5-Amino-1- (2-hydroxyethyl) -1H-pyrazol-4-ylamino] -4- [5-amino-1- (2-hydroxy-ethyl) -1H- are obtained. pyrazol-4-ylimino] -5-hydroxycyclohexa-2,5-dienone (1d).

Example 4 Synthesis of 4- [5-Amino-1- (2-hydroxyethyl) -1H-pyrazol-4-yliminol-3-hydroxy-2-methyl-cyclohexa-2,5-dienone 4 (compound (1)) In a flask containing 30 ml of ethanol, 120 mg (0.5 mmol) of 2- (4,5-diamino-pyrazol-1-yl) -ethanol are introduced into a flask containing 30 ml of ethanol (## STR2 ## 1 eq.), 2 ml of water, 62 mg (0.5 mmol) of 2-methyl-3-hydroxy phenol and then 2 ml of ethanol. The whole is stirred at room temperature, the pH is adjusted to 9.6 with 20 ml of a 20% ammonia solution and 228.2 mg (1 mmol) of ammonium persulfate (2 eq.) are added together.

After stirring for 3 h, the solid formed is filtered off, washed with water and then dried under vacuum. 85 mg of 4- [5-Amino-1- (2-hydroxyethyl) -1H-pyrazol-4-ylimino] -3-hydroxy-2-methylcyclohexa-2,5-dienone (1e) are obtained.

Example 5 Synthesis of 3-Amino-4- [5-amino-1- (2-hydroxyethyl) -1H-pyrazol-4-ylaminol-2-chloro-6-methylphenol 5 (Compound (2b)) NH 2 (2b) In a flask containing 1.5 ml of 0.5M sodium hydroxide, argon is bubbled and 30 mg (0.1 mmol) of 3-amino-4 are added. [5-Amino-1- (2-hydroxy-ethyl) -1H-pyrazol-4-ylimino] -2-chloro-6-methyl-cyclohexa-2,5-dienone 2 (1 eq). The reaction medium is stirred at ambient temperature and then 0.5 ml of ethanol is added to solubilize the whole. 250 mg (1.42 mmol) of sodium hydrosulfite (14 eq) are then added. After stirring for 5 minutes, the solution becomes discolored. The pH of the reaction medium is then brought back to 6 with acetic acid and then the ethanol is evaporated. The precipitate obtained is filtered under argon and then dried under vacuum. 9 mg of 3-Amino-4- [5-amino-1- (2-hydroxy-ethyl) -1H-pyrazol-4-ylamino] -2-chloro-6-methyl-phenol (2b) are obtained.

Claims (15)

1. Compound chosen from those of formula (I) to (IV) or (I ') to (IV'): HO R3R4N and (I) OH OH OH (III ') their salts of organic or mineral acid, their isomers geometric, their tautomers, and their solvates such as hydrates; formulas (I) to (IV) or (I ') to (IV') in which: • R, represents: a hydrogen atom, a C1-C5 alkyl radical, or a C1-C18 alkyl radical; Functionalized with a group chosen from: i) hydroxyl, ii) C 1 -C 4 alkoxy, iii) amino, iv) amido, v) di (C 1 -C 3) alkylamino, vi) imidazolyl, vii) phenyl optionally substituted by a chlorine atom, a trifluoromethane radical, a methyl radical; R2 represents: a hydrogen atom, a bromine atom, a C1-C5 alkyl radical, or a phenyl radical; R3 and R4 represent independently of each other: a hydrogen atom, a C1-C5 alkyl radical, or a C1-C5 alkyl radical functionalized with a group chosen from: i) hydroxyl, ii) C 1 -C 4 alkoxy, iii) amino, iv) amido, v) di (C 1 -C 3) alkylamino, and vi) imidazolyl; R5 represents: a hydrogen atom, or a C1-C4 alkyl radical; R6 represents: a hydrogen atom, or a radical corresponding to the following formula (V); (V) formula (V) wherein R 1, R 2, R 3 and R 4 have the same meaning as above. // N N 1 R 2. Compound according to the preceding claim wherein R2 represents a hydrogen atom or a C1-05 alkyl radical. 3. A compound according to claim any one of the preceding claims wherein R, represents a C1-C5 alkyl radical, or a C1-C5 alkyl radical functionalized with a hydroxyl group. 4. A compound according to any one of the preceding claims wherein R3 and R4 represent a hydrogen atom. 5. Compound of formula (I) and (IV) or (I ') and (IV') according to any one of the preceding claims wherein R6 represents a radical (V) in which R2, R3 and R4 represent a d hydrogen and R, represents a C1-C5 alkyl radical functionalized with a hydroxyl group. 6. Compound according to any one of the preceding claims of formula (I) to (IV) and (I ') to (IV') selected from the following compounds: OH 2- [5-Amino-1- (2-hydroxyethyl) - 1H-pyrazol-4-NN ylamino] -5- (2-hydroxyethylamino) - [[1,4] benzoquinone N ~ NH O. Contains Formula (III) N 2 OH (1 a) H 2 N 3-Amino-4 - [5-amino-1- (2-hydroxyethyl) -1H-N-O-pyrazol-4-ylimino] -2-chloro-6-methyl-cyclohexan-NH-2,5-dienone N 2 ) OH 4- (5-Amino-1- (2 (2-hydroxyethyl) -1H-pyrazol-4-ylimino] -3-hydroxycyclohexa-2,5-dienone It belongs to formula (I) NN NH 2 OH (1c) HO N 2 - [5-Amino-1- (2-hydroxyethyl) -1H-pyrazol-4-NN NH 2 N -N ylamino] -4- [5] amino-1- (2-hydroxy-ethyl) -1H-HN-pyrazol-4-ylimino] -5-hydroxy-cyclohexa-2,5-H2N OH dienone HO Contains formula (I) (1d) HO 4- [5-Amino-1- (2-hydroxyethyl) -1H-pyrazol-4-N-ylimino] -3-hydroxy-2-methyl-cyclohexa-2,5-N / NH 2 -dienone N 2 Contains Formula (I ) OH (1 e) / N-O 2-Amino-6- [5-amino-1- ( 2-hydroxyethyl) -1H-pyrazol-4-ylimino] -6H-pyridin-3-one NN NH 2 NH 2 Contains formula (IV) OH (1f) NNOH 2-Amino-5- [5-amino-1- (2 hydroxyethyl) -1H-OH pyrazol-4-ylamino] -6- [5-amino-1- (2-hydroxyethyl) -NH 2 H -pyrazol-4-ylimino] -6H-pyridin-3-one / Embedded image Nitrogen (N) O (NH) 2 O (1g) O 2- (5-Amino-1,3-dimethyl-1H-pyrazol-HH-4-ylamino) -5- (2-hydroxyethylamino) NN - [1,4] benzoquinone> n- (3-Amino-4- (5-amino-1,3-dimethyl-1H-N-pyrazol-4-ylimino) 2-Chloro-6-methyl-cyclohexa-2,5-dienone NNH 2 O. Contains Formula (II) (1i) O-O-4- (5-Amino-1,3-dimethyl-1H) pyrazol-N / NH 4-ylimino) -3-hydroxy-cyclohexa-2,5-dienone N 2 Contains formula (I) I (1j) HO 4- (5-Amino-1,3-dimethyl-1H) P-pyrazol-N- (4-ylimino) -3-hydroxy-2-methyl-cyclohexa-2,5-dienone N / C C- belonging to formula (I) N NH2 (1k) N2-Amino-6- (5) 1-amino-1,3-dimethyl-1H- / pyrazol-4-ylimino) -6H-pyridin-3-one N NH NH Contains Formula (IV) 2 2 (11) HN NH 2 2-Amino-5- (5-amino-1,3-dimethyl-1H-pyrazol-4-ylamino) -6- (5-amino-1,3-dimethyl) -1H- ~ / N pyrazol-4-ylimino) -6H-pyridin-3-one N NH H It belongs to formula (IV) 2 N2 1 (1 m) HO 2- [5-Amino-1- (2-hydroxyethyl) 1H-pyrazol-4-ylamino] -5- (2-hydroxy-ethylamino) -benzene-1,4-NN diol / Formula (III ') N -NH 2 OH (2a) H2N and 3-Amino-4- [5-amino-1- (2-hydroxyethyl) -1H-pyrazol-4-ylamino] -2-chloro-6-methylphenol OH Contains formula (II ') N / N 4- [2- (5-Amino-1- (2-hydroxyethyl) -1H-pyrazol-4-yl] amino] -benzene-1,3-diol-N-OH (2b) HO- Contains Formula (I ') N / N NH 2 OH (2c) HO 4,6-Bis [5-amino-1- (2-hydroxyethyl) -1H-pyrazol-4-ylamino] -benzene-1,3-diol OH Formula ( (4- (4-Amino-1- (2-hydroxyethyl) -1H-pyrazol-4-ylamino] -2-methyl-benzene-1,3-dihydroxybenzene Diol ~ N OH Nitrogen Formula (1 ') N / N ~ NH 2 OH (2e) CN'N', OH 2-Amino-5,6-bis- [5-amino-1- (2-hydroxyethyl) -1 H-C pyrazol-4-ylamino] -pyrid in-3-ol HN NH2 Contains formula (IV ') H NHH N / N N NH2 NH2H OH (2q) 7. dye composition comprising in a suitable cosmetic medium, at least one compound of formula (I) to (IV) or (I ') to (IV') according to any one of the preceding claims. 8. Composition according to the preceding claim, wherein the compound of formula (I) to (IV) or (I ') to (IV') is present in an amount of between 0.001 and 30% by weight relative to the total weight of the composition. 10 9. Composition according to any one of claims 7 or 8 wherein when the composition comprises at least one compound of formula (I) to (IV) the composition has a pH of between 6 and 11. 10. Composition according to any one of claims 7 to 8 wherein when the composition comprises at least one compound of formula (I ') to (IV') the composition has a pH of between 6 and 11. The composition of any one of claims 7 to 10 which further comprises at least one oxidizing agent. 12. Composition according to the preceding claim wherein the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes. 13. Composition according to any one of claims 7 to 12 which further comprises at least one adjuvant chosen from anionic surfactants, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, inorganic or organic thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents, film-forming agents, ceramides, preservatives, opacifying agents, and conductive polymers. 14. A process for dyeing keratinous fibers, wherein a suitable dye composition according to any one of the preceding claims 7 to 13 is applied to the materials. 15. Use of a compound of formula (I) to (IV) or (I ') to (IV') as defined in any one of claims 1 to 6 for dyeing keratinous fibers. 25