MXPA01007244A - Novel cationic oxidation bases, their use for dyeing keratin fibres, dyeing compositions and dyeing methods - Google Patents

Abstract

The invention concerns novel pyrazole derivatives comprising at least a cationic group Z, Z being selected among the quaternized aliphatic chains, aliphatic chains comprising at least a saturated quaternized cycle, and aliphatic chains comprising at least an unsaturated quaternized cycle, their use as oxidation base for dyeing keratin fibres, dyeing compositions containing them, and dyeing methods using them.

Description

NEW ACOUSTIC OXIDATION BASES, ITS USE FOR THE OXIDATION TISSUE OF KERATINIC FIBERS, TINTORIAL COMPOSITIONS AND DYEING PROCEDURES DESCRIPTION OF THE INVENTION The invention relates to novel pyrazole derivatives comprising at least one cationic group Z, Z being selected from quaternized aliphatic chains, aliphatic chains comprising at least one quaternized saturated cycle, and aliphatic chains comprising at least one unsaturated cycle quaternized, its use as an oxidation base for the dye by oxidation of the keratin fibers, the dyeing compositions. contain, as well as the oxidation dyeing procedures that use them. It is known to dye keratin fibers and in particular human hair with dyeing compositions containing dye precursors by oxidation; in particular the ortho or para-phenylenediamines, the ortho or para-aminophenols, heterocyclic compounds such as diammop-razol derivatives, generally called oxidation bases. Oxidation dye precursors, or oxidation bases, are colorless or sparingly colored compounds which, when combined with REF: 131129 oxidizing products, can give rise to colored compounds and dyes by a process of oxidative condensation. It is also known that the shades obtained with these oxidation bases can be modified by associating them with copulators or color modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds. The variety of molecules used at the level of oxidation bases and copulators allows obtaining a rich range of colors. The coloration called "permanent" obtained thanks to these oxidation dyes, must on the other hand meet a certain number of requirements. Thus, it should have no drawbacks on the toxicological level, should allow obtaining tonalities in the desired intensity and present a good behavior in front of external agents (light, weather, washing, perm, perspiration, friction). The dyes should likewise make it possible to cover the white hairs, and finally to be as less selective as possible, that is to say, to obtain differences in coloration as low as possible throughout the same keratin fiber, which may, in fact, be distinctly sensitized. (ie spoiled) at its tip and its root. Now, the applicant firm has just discovered, in a totally unexpected and surprising way, that new pyrazole derivatives of formula (I) defined below comprising at least one cationic group Z, Z being selected from quaternized aliphatic chains, aliphatic chains comprising at least one quaternized saturated cycle, and aliphatic chains comprising at least one quaternized unsaturated cycle, are not only suitable for use as a base for oxidation, but also allow to obtain dyeing compositions that lead to strong colorations, within a wide range of colors , and that have excellent resistance properties to the different treatments that keratin fibers can experience. These discoveries form the basis of the present invention. The invention therefore has as its primary object new compounds of the formula (I) below, their addition salts with an acid or a base, and their possible tautomeric forms: which: • Ri represents a hydrogen atom; a group Z as defined below; an alkyl radical of C? -C6; a trifluoroalkyl radical of Ci-Cß; a monohydroxyalkyl radical of Ci-Cß; a C2-C6 polyhydroxyalkyl radical; an arylalkyl radical of Ci-Cβ in which the aryl radical can be in particular a phenyl radical or a five or six-membered aromatic heterocycle such as, for example, a pyridyl cyclo, a cycloimidazolyl, a furyl cyclo or an oxazolyl cyclo; an alkoxy (Ci- C6) alkyl radical of Ci-Cβ, * an alkyl (Ci-Cβ) thio radical of C? -C6 alkyl; an aminoalkyl radical (C? -C6) carbonylalkyl (C? -Cd); a radical N-Z-aminoalkyl (C? -C6) carbonylalkyl (C? -C6); a radical N-alkyl (C? -C6) aminoalkyl (Cx-Cs) carbonylalkyl (C? -C6); a N, N-dialkyl (C? -C6) aminoalkyl (C? -C6) carbonylalkyl radical (Ci- Ce); an aminosulfonyl-alkyl radical (C? -C0); a N-Z-aminosulfonylalkyl radical (C? -C6); a radical N-alkyl (Ci-Ce) aminosulfonylalkyl (C? -C6; an N, N-dialkyl radical (C? ~ C < aminosulfonylalkyl (C? -C0); • R2 and R3, identical or different represent a group -NHR4, a hydroxyl radical, a halogen atom, a nitro radical, a cyano radical, a carboxy radical, a carboxy alkyl radical of Ci-Cß, a carboxyl aryl radical, a carbamyl radical, an N-alkyl radical (C? -C6) carbamyl, an N, N-dialkyl (Ci-Cβ) carbamyl radical, an N-arylcarbamyl radical, a Ci-Cβ alkoxy radical, "an aryloxy radical, a C6-6 alkyl radical, a thioaryl radical or one of the meanings given above for Ri, it being understood that at least one of the radicals R2 and R3 represents a group -NHR4 or a hydroxyl radical, • R4 represents a hydrogen atom, a group Z as defined below; an alkyl radical of C? -C6, a monohydroxyalkyl radical of C? -C6, a polyhydroxyalkyl radical of C2-C6, an alkoxy radical (C? -C6) alkyl of C? C6, an aryl radical; a benzyl radical; a cyanoalkyl radical of Ci-Ce; a carbamylalkyl radical of C? -C6; an N-alkyl (C? -C6) carbamylalkyl radical of C? -C6; an N, N-dialkyl (C? -C6) carbamylalkyl radical of C? -C6; a thiocarbamylalkyl radical of C? -C5; a trifluoroalkyl radical of C? -C5; a sulfoalkyl radical of C? -C6; an alkylation-Ce) carboxyalkyl radical of C? -C6; an alkyl (Ci-C6) sulfinylalkyl radical of Ci-Ce; an aminosulfonylalkyl radical of Ci-Cß; a N-Z-aminosulfonylalkyl radical of Ci-Cß; an N-alkyl (C? -C6) aminosulfonylalkyl radical of C? -C6; a N, N-dialkyl (C? -C6) aminosulfonylalkyl radical of Ci-Cß; an aminoalkyl radical of Ci-Ce; an aminoalkyl radical of C? -C6 whose amine is substituted by one or two identical or different radicals selected from the C? -C3 alkyl radicals, C? -C6 monohydroxyalkyl, C2-C6 polyhydroxyalkyl, alkyl (Ci-Ce) carbonyl, alkyl (C? ~ C6) sulfonyl, formyl, trifluoroalkyl (Ci-Ce) carbonyl, or by a group Z; the amine of the aminoalkyl radical of C? -C6 can also be replaced by two radicals which, together with the nitrogen atom of said amine, form a saturated or unsaturated cycle of five or six links and which can contain one or more heteroatoms selected between nitrogen, oxygen and sulfur, such as for example a piperidine, morpholine, imidazole or oxazole ring. is selected from the unsaturated cationic groups of formulas (II) and (III) below, and the saturated cationic groups of formula (IV) below: (") (neither) which: • D is a linking arm representing an alkyl chain preferably comprising 1 to 14 carbon atoms, straight or branched, which may be interrupted by one or more heteroatoms such as oxygen, sulfur or nitrogen atoms, and which may be to be substituted by one or more hydroxyl or C6-C6 alkoxy radicals, and which may carry one or more ketone functions; • the links E, G, J, L and M, identical or different, represent a carbon atom, oxygen, sulfur or nitrogen; • n is an integer between 0 and 4 inclusive; • m is an integer between 0 and 5 inclusive; • the radicals R, identical or different, represent a second group Z identical or different from the first group Z; a halogen atom; a hydroxyl radical; an alkyl radical of C? -C6; a monohydroxyalkyl radical of Ci-Ce; a C2-C6 polyhydroxyalkyl radical; a nitro radical; a cyano radical; a cyanoalkyl radical of C? -C6; a Ci-Cβ alkoxy radical; a trialkyl (Ci-C6) silanoalkyl radical of C? -C6; an amido radical; an aldehyde radical; a carboxyl radical; a C 1 -C 6 alkylcarbonyl radical; a radical uncle; a thioalkyl radical of Ci-Cß; an alkyl (C? -C6) thio radical; an amino radical; an amino radical protected by an alkyl (C? -C6) carbonyl or alkyl (Ci-C6) sulfonyl radical; a group NHR '' or NR''R '' 'in which R' R 'identical or different, represent an alkyl radical of C? -C6, a monohydroxyalkyl radical of C? -Cd or a polyhydroxyalkyl radical of C2-Ce; 5 represents an alkyl radical of C6-C6; a monohydroxyalkyl radical of C? -C6; a polyhydroxyalkyl radical of C2-C5; a cyanoalkyl radical of C? -C6; a trialkyl radical (C? -C6) silanoalkyl of Ci-Cß; an alkoxy radical (Ci-Cβ) alkyl of C? -C6; a C 1 -C 6 carbamylalkyl radical; a C 1 -C 6 alkylcarbyalkyl radical of Ci-Cβ; a benzyl radical; or a second group Z identical or different from the first group Z; 6, R7 and Rβ identical or different, represent an alkyl radical of C6-C6; a monohydroxyalkyl radical of Ci-Ce; a C2-C6 polyhydroxyalkyl radical; an alkoxy radical (Ci-C6) alkyl of C? -C6; a cyanoalkyl radical of Ci-C5; an aryl radical; a benzyl radical; an amidoalkyl radical of C? -C6; a trialkyl (C 1 -C 6) silanoalkyl radical of Ci-Ce or an aminoalkyl radical of Ci-Cß whose amine is protected by an alkyl (Ci-Cβ) carbonyl or alkyl (Ci-Cβ) sulfonyl radical; two of the radicals R6, R7 and Re can also form together, with the nitrogen atom to which they are attached, a saturated cycle of 5 or 6 carbon atoms or containing one or more heteroatoms such as, for example, a pyrrolidine ring, a piperidine ring , a piperazine ring or a morpholine ring, the cycle may or may not be substituted by a halogen atom, a hydroxyl radical, an alkyl radical of Ci-Ce, a monohydroxyalkyl radical of C? -C6, a polyhydroxyalkyl radical of C2- C6, a nitro radical, a cyano radical, a cyanoalkyl radical of Ci-Cß, an alkoxy radical of C? -C6, a trialkyl (Ci-Ce) silanoalkyl radical of C? ~ C6, an amido radical, an aldehyde radical, a carboxyl radical, a ketoalkyl radical of Ci-Ce, a thio radical, a thioalkyl radical of C? -C6, an alkyl (Ci-Ce) thio radical, an amino radical, an amino radical protected by an alkyl radical (C? -C6) carbonyl or alkyl (d-C6) sulfonyl; one of the radicals Re, R7 and Rβ can also represent a second group Z, identical or different from the first group Z; 9 represents an alkyl radical of Ci-Ce; a monohydroxyalkyl radical of Ci-Cß; a C2-C6 polyhydroxyalkyl radical; an aryl radical; a benzyl radical; an aminoalkyl radical of Ci-Ce, "an aminoalkyl radical of C? -C6 whose amine is protected by an alkyl (C? -C6) carbonyl or alkyl (Ci-Ce) sulfonyl radical; a carboxyalkyl radical of Ci-C?; cyanoalkyl radical of Ci-Cβ; a carbamylalkyl radical of C? -C6; a trifluoroalkyl radical of C? -C6; a trialkyl (C? ~ C6) silanoalkyl radical of C? -C6; an idoalkyl sulfone radical of C? -C6; a C 1 -C 6 alkyl (C 1 -C 6) carboxyalkyl radical; a C 1 -C 6 alkyl (Ci-C 6) sulfinylalkyl radical; an alkyl (Ci-C6) sulfonylalkyl radical of Cj.-C6; an alkyl (Ci-C6) ketoalkyl radical of C? -C6; an N-alkyl (C? ~ C6) carbamylalkyl radical of C? -C6; an N-alkyl (Ci-Cß) sulfonamidoalkyl radical of C? -C6; e and are integers equal to 0 or 1; with the following conditions: - in the unsaturated cationic groups of formula (II): when a = 0, the linking arm D is attached to the nitrogen atom, when a = 1, the linking arm D is attached to one of the links E, G, J or L, and can not take the value 1: 1) when the links E, G, J and L simultaneously represent a carbon atom, and when the radical R5 is carried by the nitrogen atom of the cycle unsaturated; or 2) when at least one of the links E, G, J and L represents a nitrogen atom in which the radical R5 is fixed; in the unsaturated cationic groups of formula (III): when a = 0, the linking arm D is attached to the nitrogen atom, when a = 1, the connecting arm D is attached to one of the links E, G, J , L or M, and can not take the value 1 more than when at least one of the links E, G, J, L and M represents a divalent atom, and when the radical R5 is supported by the nitrogen atom of the unsaturated cycle; - in the cationic groups of formula (IV): when a = 0, then the binding arm D is attached to the nitrogen atom bearing the radicals Re to R8, when a = 1, then two of the radicals Re to R8 form with the nitrogen atom to which a 5 or 6-membered saturated ring is attached as defined above, and the linking arm D is supported by a carbon atom of said saturated cycle; represents a monovalent or divalent anion and is preferably chosen from a halogen atom such as chlorine, bromine, fluorine or iodine, a hydroxide, a hydrogen sulfate, or a (C_6) alkyl sulfate such as, for example, a methylisulfate or an ethyl sulfate; it being understood that the number of cationic groups Z is at least equal to 1.

As indicated above, the colorations obtained with the oxidation dyeing composition containing one or more compounds of formula (I) according to the invention are potent and allow a wide range of colors to be achieved. They also have excellent resistance properties with respect to the action of the different external agents (light, weathering, washing, permanent waving, perspiration, rubbing). These properties are particularly highlighted in particular as regards the resistance of the colorations obtained in relation to the action of light, washing, permanent waving and transpiration. In the formula (I) indicated above the alkyl and alkoxy radicals can be linear or branched.

Among the cycles of the unsaturated groups Z of formula (II) indicated above, mention may be made in particular of the pyrrole, imidazole, pyrazole, oxazole, thiazole and triazole rings. Among the cycles of the unsaturated groups Z of formula (III) indicated above, the pyridinic, pyrimidine, pyrazinic, oxazinic and triazinic rings can be mentioned, for example, as an example. When the compounds of formula (I) are such that they comprise an OH group in one of positions 3 or 5, in a of a nitrogen atom, there is a tautomeric equilibrium which can be represented, for example, by the following scheme: Among the compounds of formula (I) indicated above, mention may be made in particular of: [3- (4-amino-2,5-dimethyl-2H-pyrazol-3-ylamino) -propyl) -trimethyl-ammonium chloride; [3- (4-amino-2,5-dimethyl-2H-pyrazol-3-ylamino) -propyl] - (2-hydroxy-ethyl-dimethyl-ammonium chloride; 3- [3- (4-chlorocarbonyl) chloride] -amino-2, 5-dimethyl-2H-pyrazol-3-ylamino) -propyl] -1- (2-hydroxy-ethyl) -3H-imidazol-1-io; 3- [(4-amino- 2H-pyrazol-3-ylcarbamoyl) -methyl] -l-methyl-3H-imidazole-1-io; 3- [2- (4,5-diamino-3-methyl-pyrazol-1-yl) - chloride ethyl] -l-methyl-3H-imidazole-1-io; - 3- [2- (4,5-diamino-pyrazol-1-yl) -ethyl] -1- ethyl-3H-imidazole-1 chloride -io; - [2- (4,5-diamino-3-methyl-pyrazol-1-yl) -ethyl] -trimethyl-ammonium chloride; - [2- (4,5-diamino-pyrazole -l-yl) -ethyl] -trimethyl-ammonium chloride - [2- (4-amino-5-hydroxy-pyrazol-l-yl) -ethyl] -trimethyl-ammonium chloride, [2- ( 4-amino-5-hydroxy-3-methyl-pyrazol-1-yl) -ethyl] -trimethyl-ammonium; - 3- [2- (4-amino-5-hydroxy-3-methyl-pyrazole- l -yl) -ethyl] -l-methyl-3H-imidazole-1-io; - 3- [2- (4-amino-5-hydroxy-pyrazol-1-yl) -ethyl] -1- chloride methy1-3H-imidazol-1-io; - 3- [2- (4,5-diamino-1-methyl-1H-pyrazol-3-yl) -ethyl] -l-methyl-3H-imidazol-1-yl chloride, and its addition salts with an acid or a base, and its possible tautomeric forms. Among these compounds of formula (I), more particularly preferred are: [3- (4-amino-2,5-dimethyl-2H-pyrazol-3-ylamino) -propyl] -trimethyl-ammonium chloride.; - [3- (4-amino-2,5-dimethyl-2H-pyrazol-3-ylamino) -propyl] - (2-hydroxy-ethyl) -dimethyl-ammonium chloride; 3- [3- (4-amino-2, 5-dimethyl-2H-pyrazol-3-ylamino) -propyl] -1- (2-hydroxy-ethyl) -3H-imidazol-1-yl chloride; 3- [(4-amino-2H-pyrazol-3-ylcarbamoyl) methyl] -1-methyl-3H-imidazol-1-yl chloride; - 3- [2- (4,5-diamino-3-methyl-pyrazol-1-yl) -ethyl] -1-methyl-3H-imidazol-1-yl chloride; - 3- [2- (4,5-diamino-l-methyl-lH-pyrazol-3-yl) -ethyl] -l-methyl-3H-imidazol-1-yl chloride; and their addition salts with an acid or a base, and their possible tautomeric forms. The compounds of formula (I) according to the invention can be easily obtained, according to methods well known from the state of the art: either by reduction of the corresponding nitrated or nitrated cationic compounds. In this case, the reduction in corresponding primary aromatic amine is carried out according to classical methods (J. Lehmman in "Houben-Weyl," Methoden der Organischen Chemie ", Band IV / lc: Reduktion 1 pages 491 to 537.1980). Preferred according to the invention use metals such as Zn, Sn, or Fe in acidic medium such as aqueous hydrochloric acid, or aqueous acetic acid in the presence or absence of a co-solvent such as methanol, ethanol or tetrahydrofuran.Catalytic hydrogenation is A preferred reduction method according to the invention This catalytic hydrogenation uses metals such as palladium, platinum or nickel, Palladium on carbon or Raney nickel is preferred even more particularly, or else oxides such as Pt02 in solvents such as methanol , ethanol, tetrahydrofuran or ethyl acetate in the presence or absence of an acid such as acetic acid, these catalytic reductions can also be carried out with the acid formic in the presence of a trialkylamine such as triethylamine or ammonium formate instead of hydrogen gas. (S. Ram, R.E. Ehrenkaufer, Synthesis, 1988.91). - or by reduction of the corresponding cationic azo compounds (reducing cut). The corresponding primary aromatic amine reduction is carried out according to conventional methods (J. Lehmman in "Houben-Weyl," Methoden der Organischen Chemie "Band IV / lc: Reduktion 1 _ pages 551 to 553.1980; EC Taylor &Coil., J. Amer. Chem. Soc, 80, 421, 1958) This step of reduction (obtaining a primary aromatic amine) that confers on the synthesized compound its oxidizable (oxidation-based) character, followed or not by a salification, This is generally, for convenience, the last stage of the synthesis.This reduction can occur rather in the sequence of reactions leading to the preparation of the compounds of formula (I), and according to well-known procedures it is then necessary to "protect" the primary amine created (for example by a stage of acetylation, of benzenesulfonation, etc ...), then carry out the substitution or modifications desired (including quaternization) and end by the "deprotection" (usually in acid medium) of the amine function. When the synthesis is complete, the compounds of formula (I) according to the invention can, if necessary, be recovered by methods well known in the state of the art such as crystallization, distillation. Another object of the invention is the use of the compounds of formulas (I) according to the invention as an oxidation base for the oxidation dyeing of keratin fibers, and in particular of human keratin fibers such as hair. The subject of the invention is also a composition for the oxidation dyeing of keratin fibers and in particular of human keratin fibers such as hair, characterized in that it comprises as an oxidation base, in a medium suitable for the treatment of hair. dye, at least one compound of formula (I) according to the invention. The compound (s) of formula (I) according to the invention preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dyeing composition, and even more preferably from 0.005 to 6% by weight approximately of this weight. The suitable medium for the dye (or support) is generally constituted by water or by a mixture of water and at least one organic solvent to solubilize the compounds that were not sufficiently soluble in water. As the organic solvent, there may be mentioned, for example, the lower C1-C4 alkanols, such as ethanol and isopropanol; glycerol; glycols and ethers of glycols such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, analogous products and mixtures thereof. The solvents can be present in proportions preferably comprised between 1 and 40% by weight approximately with respect to the total weight of the dyeing composition, and even more preferably between 5 and 30% by weight approximately. The pH of the dyeing composition according to the invention is generally between about 3 and 12, and preferably between about 5 and about 11. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used in the dyeing of keratin fibers. Among the acidulating 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, acid lactic, sulfonic acids. Among alkalizing agents, mention may be made, by way of example, of ammonia, alkali metal carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of formula ( V) next: wherein W is a propylene moiety optionally substituted by a hydroxyl group or an alkyl radical of C? -C5; Rio, Rn, R12 and R13, identical or different, represent a hydrogen atom, an Ci-Cβ alkyl radical or Ci-C6 hydroxyalkyl. The dyeing composition according to the invention can also contain, in addition to the one or of the compounds of formula (I) defined above, at least one additional oxidation base which can be chosen from the oxidation bases conventionally used in oxidation dyeing and between the oxidation dyes. which may be particularly cited paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases other than the compounds of formula (I). Among the para-phenylenediamines, para-phenylenediamine, para-tolylene-diamine, 2,6-dimethyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-n-propyl-para-phenylenediamine and 2-isopropyl-para-phenylenediamine can be mentioned more particularly., N- (β-hydroxypropyl) paraphenylenediamine, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 4-amino N- (β-methoxyethyl) aniline, paraphenylenediamines described in French patent application FR 2,630. 438, and its addition salts with an acid. Among the bis-phenylalkylenediamines, N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) -1,3-diamine propanol, N, N'-bis- (ß-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis (β-hydroxyethyl) N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) N, N'-bis - ('-amino, 3' -methylphenyl) ethylenediamine, and its addition salts with an acid. Among the para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro-phenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methyl phenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethyl phenol, 4-amino 2- (ß-hydroxyethylaminomethyl) phenol, and its addition salts with an acid. Among the ortho-aminophenols, mention may be made, in particular, of 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-aminophenol, and their derivatives. addition salts with an acid. Among the heterocyclic bases, pyridine derivatives, pyrimidine derivatives and non-cationic pyrazole derivatives can be mentioned more particularly by way of example. Among the pyridine derivatives, the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino-3-amino, can be cited more particularly. pyridine, 2, 3-diamino-6-methoxypyridine, 2- (β-methoxyethyl) amino-3-amino-6-methoxypyridine, 3,4-diamino pyridine, and their addition salts with an acid. Among the pyrimidine derivatives, mention may be made more particularly of the compounds described, for example, in German patents DE 2,359,399 or Japanese JP 88-169 571 and JP 91-10659 or WO 96/15765, such as 2, 4, 5,6-tetra-aminopyrimidine, 4-hydroxy-2, 5,6- triaminopyrimidine, 2-hydroxy-4,5,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2 5,6-triaminopyrimidine, and pyrazolo-pyrimidine derivatives such as those mentioned in patent application FR-A-2,750,048 and among which may be mentioned pyrazolo- [1,5-a] -pyrimidine-3, 7-diamine; 2,5-dimethylpyrazolo- [1,5-a) -pyrimidine-3,7-diamine; pyrazolo- [1, 5-a] -pyrimidine-3,5-diamine; 2,7,7-dimethylpyrazolo- [1,5-a] -pyrimidine-3,5-diamine; 3-aminopyrazolo- [1, 5-a] -pyrimidin-7-ol; 3-aminopyrazolo- [1,5-a] -pyrimidin-5-ol; 2- (3-amino pyrazolo- [1, 5-a] -pyrimidin-7-ylamino) -ethanol, 2- (7-amino pyrazolo- [1, 5-a] -pyrimidin-3-ylamino) - ethanol, 2 - [(3-amino-pyrazolo [1, 5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol, 2- [(7-amino-pyrazolo [ 1, 5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol, 5,6-dimethylpyrazolo [1, 5-a] -pyrimidin-3,7-diamine, the 2,6-dimethylpyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 2,5-N7,7-tetramethylpyrazolo- [1,5-a] -pyrimidin-3,7-diamine, 3-amino-5-methyl-7-imidazolylpropylaminopyrazolo [1, 5-a] -pyrimidine, its possible tautomeric forms, and its addition salts with an acid. Among the non-cationic pyrazole derivatives, the compounds described in DE 3,843,892, DE 4,133,957 and patent applications WO 94/08969, WO94 / 08970, FR-A-2 733 749 and DE can be more particularly cited. 195 43 988 such as 4, 5-diamino-1-methylpyrazole, 3,4-diamino pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1, 3 -dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinpyrazole, -benzyl-4, 5-diamino-3-methylpyrazole, 4, 5-diamino-3-tert-butyl-1-methylpyrazole, 4, 5-diamino-1-tert-butyl-3-methylpyrazole, 4, 5-diamino-l- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-ethoxyphenyl) ) pyrazole, 4, 5-diamino-l-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4, 5-diamino-3-methyl-l-isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethylpyrazole, 3, 4, 5-triaminopyrazole, l-methyl-3,4,5-triaminopyrazole, 3,5-diamino-l-methyl-4-methylaminopyrazole, 3, 5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole, and its addition salts with an acid. When used, these additional oxidation bases preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dyeing composition, and even more preferably from 0.005 to 6% by weight approximately of this weight. The oxidation dyeing compositions according to the invention can also include at least one coupler and / or at least one direct dye, in particular to modify the shades or enrich them with reflections. The copulators which can be used in the oxidation dyeing compositions according to the invention can be selected from the couplers conventionally used in oxidation dyeing, among which metaphenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic copulators, such as, for example, indole derivatives, indoline derivatives, pyridine derivatives and pyrazolones, and their addition salts with an acid. These couplers are more particularly chosen from 2-methyl-5-aminophenol, 5-N- (β-hydroxyethyl) amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy -2-methylbenzene, 4-chloro-l, 3-dihydroxybenzene, 2,4-diamino-l- (β-hydroxyethyloxy) benzene, 2-amino-4- (β-hydroxyethylamino) -1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis- (2,4-dia inophenoxy) propane, sesamol, a-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, l-H3-methylpyrazol-5-one, l-phenyl-3-methylpyrazol-5-one, and their addition salts with an acid. When present, these couplers preferably represent from 0.0001 to 10% by weight approximately of the total weight of the dyeing composition and even more preferably from 0.005 to 5% by weight approximately of this weight. In a general way, addition salts with an acid which can be used within the framework of the invention (compounds of formula (I), additional oxidation bases and couplers) are chosen in particular from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates and acetates. Addition salts with a base which can be used in the context of the invention (compounds of formula (I)), are particularly those obtained with soda, potash, ammonia or amines. The dyeing composition according to the invention can also include various adjuvants conventionally used in dyeing compositions for hair, such as anionic, cationic, non-ionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic polymers , amphoteric, zwitterionic or their mixtures, mineral or organic thickening agents, antioxidant agents, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example silicones, smoke-killing agents, preserving agents, opacifying agents. Of course, the person skilled in the art will try to choose this or these possible complementary compounds in such a way that the advantageous properties intrinsically related to the oxidation dyeing composition according to the invention are not, or substantially, altered by the addition (s) considered . The dyeing composition according to the invention can be presented in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and particularly human hair. The subject of the invention is also a process for dyeing keratin fibers and in particular human keratin fibers such as hair using the dyeing composition as defined above. According to this process, at least one dyeing composition as defined above is applied to the fibers, the color being revealed at an acid, neutral or alkaline pH with the aid of an oxidizing agent which is added at the time of use to the dye composition or that is present in an oxidizing composition applied simultaneously or sequentially separately. According to a preferred embodiment of the dyeing process of the invention, the dyeing composition described above is preferably mixed, at the time of use, with an oxidizing composition containing, in a medium suitable for dyeing, at least one agent oxidant present in an amount sufficient to develop a coloration. The mixture obtained is then applied to the keratin fibers and allowed to stand for about 3 to 50 minutes, preferably about 5 to 30 minutes after which it is rinsed, washed with shampoo, rinsed again and dried. The oxidizing agent can be chosen from the oxidizing agents conventionally used for the oxidation dyeing of keratin fibers, and among which may be mentioned hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and enzymes such as peroxidases, laccases, tyrosinases and oxido-reductases among which can be mentioned in particular pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases , and the uricasas. The pH of the oxidizing composition including the oxidizing agent as defined above is such that after mixing with the dyeing composition, the pH of the resulting composition applied to the keratin fibers preferably ranges from about 3 to about 12, and even more preferably between 5 and 11. It is adjusted to the desired value by means of acidifying or alkalizing agents usually used in the dyeing of keratin fibers and as defined above. The oxidizing composition as defined above may also include various adjuvants conventionally used in hair dyeing compositions and as defined above. The composition that is finally applied on the keratin fibers can occur under various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and particularly human hair. Another object of the invention is a device with several compartments or dyeing "equipment" or any other conditioning system of several compartments of which a first compartment includes the dye composition as defined above and a second compartment includes the oxidizing composition as defined above. These devices can be equipped with a means for dispensing the desired mixture on the hair, such as the devices described in patent FR-2,586,913 in the name of the applicant. The following examples are intended to illustrate the invention without thereby limiting the scope.

EXAMPLES OF PREPARATION PREPARATION EXAMPLE 1: Synthesis of 3- [3- (4-amino-2,5-dimethyl-2H-pyrazol-3-ylamino) -propyl] -1- (2-hydroxyethyl) -3H-imidazole chloride dihydrochloride -mess a) Preparation of (2,5-dimethyl-4-nitro-2H-pyrazol-3-yl) (3-imidazol-1-yl-propyl) -amine A 0.25 g of 5-chloro-l, 3-dimethyl-4-nitro-1H-pyrazole (Aldrich) was introduced into a three-neck flask of 25 ° C equipped with magnetic stirring, a thermometer and a refrigerant. molar equivalent of triethylamine, 1.1 molar equivalent of 3-imidazol-1-yl-propylamine and 5 n of N, -dimethylformamide. The reaction medium was brought to a temperature of about 105 ° C for 6 hours. The solvent was evaporated in vacuo. A black liquid was obtained which was purified by chromatography on silica gel (ethyl acetate / methanol = 4/1). 0.75 g of (2,5-dimethyl-4-nitro-2H-pyrazol-3-yl) - (3-imidazol-1-yl-propyl) -amine was obtained in the form of white crystals with a yield of 56.7%. b) Preparation of 3- [3- (2, 5-dimethyl-4-nitro-2H-pyrazol-3-ylamino) -propyl] -1- (2-hydroxyethyl) -3H-imidazole-1-yl chloride A 0.25 g (2, 5-dimethyl-4-nitro-2H-pyrazol-3-yl) - (3-n-3-yl) magnetic stirrer, thermometer and coolant were introduced into a three-neck flask of 10 ° C. -imidazol-1-yl-propyl) -amine and 2.2 g of 2-chloroethanol. The reaction medium was brought to reflux for 2 hours. The solvent was evaporated in vacuo. 0.7 g of 3- [3- (2, 5-dimethyl-4-nitro-2H-pyrazol-3-ylamino) -propyl] -1- (2-hydroxyethyl) -3H-imidazole-1-yl chloride were obtained. in the form of a viscous liquid with a yield of 96 ° 0. c) Preparation of 3- [3- (4-amino-2,5-dimethyl-2H-pyrazol-3-ylamino) -propyl] -1- (2-hydroxyethyl) -3H-imidazole-1-chloride dihydrochloride io 7.9 g of 3- [3- (2, 5-dimethyl-4-nitro-2H-pyrazol-3-ylamino) -propyl] -1- (2-hydroxyethyl) chloride were introduced into a 500-hydrogenation reactor. ) -3H-imidazole-1-io obtained previously in the preceding step, 150 cc of methanol and 0.97 g of 5% palladium on charcoal containing approximately 50% water. A hydrogen pressure of 10 bar was set and the reaction medium was brought to 115 ° C. After 5 hours, the catalyst was filtered over celite over 100 c of a 5 mol / liter hydrochloric ethanol solution. The solvent was evaporated under vacuum in the vane pump (0.1 bar). 6.5 g of 3- [3- (4-amino-2,5-dimethyl-2H-pyrazol-3-ylamino) -propyl] -1- (2-hydroxyethyl) -3H-imidazole-1-dihydrochloride were obtained. io in the form of a solid with a yield of 73%. The XH NMR analysis (DMSO d6 + CD3OD) was as follows: 2.03 (m; 2H); 2.13 (s; 3H); 3.03 (t, 2H); 3.57 (s; 3H); 3.72 (t; 2H); 4.24 (t; 2H); 4.34 (t; 2H); 7.73 (dd; ÍH); 9.33 (s; ÍH).

EXAMPLE OF PREPARATION 2 Synthesis of [3- (4-amino-2,5-dimethyl-2H-pyrazol-3-ylamino) -propyl] - (2-hydroxyethyl) -dimethyl-ammonium chloride dihydrochloride a) Preparation of [3- (2, 5-dimethyl-4-nitro-2H-10 pyrazol-3-ylamino) -propyl] - (2-hydroxyethyl) -dimethylammonium chloride A 0.5 g of N- (2,5-dimethyl-4-nitro-2H-pyrazole-3-20 yl) was introduced into a three-necked flask of 10 ° C equipped with magnetic stirring, a thermometer and a condenser. -N ', N' -dimethyl-propan-1,3-diamine and 2.2 g of 2-chloroethanol. The reaction medium was brought to reflux for 2 hours. The medium was allowed to cool to room temperature and was diluted with 50 g of ethyl acetate. The precipitate was filtered. 0.55 g of [3- (2, 5-dimethyl-4-nitro-2H-pyrazol-3-ylamino) -propyl] - (2-hydroxyethyl) -dimethylammonium chloride in the form of yellow crystals were obtained in a yield 82% b) Preparation of [3- (4-amino-2,5-dimethyl-2H-pyrazol-3-ylamino) -propyl] - (2-hydroxyethyl) dimethylammonium chloride dihydrochloride. They were introduced into a hydrogenation reactor. of 250 g, 3.22 g of [3- (2, 5-dimethyl-4-nitro-2H-pyrazol-3-ylamino) -propyl] - (2-hydroxyethyl) -dimethylammonium chloride., 150 cc of methanol and 0.42 g of 5% palladium on charcoal containing approximately 50% water. The reactor was subjected to a hydrogen pressure of 11.7 bar and the reaction medium was brought to 60 ° C. After 2 hours, the hydrogen pressure was 8.3 bar. The catalyst was filtered over celite. A stream of gaseous hydrochloric acid was passed through the filtrate and the solvent was evaporated in vacuo. 3 g of viscous liquid were obtained which were diluted in 100 cc of water and then lyophilized. 1.54 g of [3- (4-amino-2,5-dimethyl-2H-pyrazol-3-ylamino) -propyl] - (2-hydroxyethyl) -dimethyl-ammonium chloride dihydrochloride (containing 1.3 moles of water), in the form of a solid with a yield of 40%, and whose elemental analysis calculated for C? 2 H2e N5 O Cl, 2 HCl, 1.3 H20, (MW = 388.15 g / mol) was as follows: H N O Cl Calculated: 37.09 7.88 18.03 9.4Í 27.43 Found: 37.46 7. 17.79 9.68 26.85 EXAMPLES OF APPLICATION EXAMPLES 1 to 8 OF DYEING IN BASIC MEDIUM The following dyeing compositions were prepared (contained in grams): or WHAT IT OR CM (*) Common dyeing support n 1: Ethyl alcohol of 96 18 g Sodium metabisulfite in 35% aqueous solution 0.68 g Pentasodic salt of diethylenetriaminepentaacetic acid 1.1 g Ammonia at 20% 10.0 g At the time of use, weight per weight each of the dyeing compositions indicated above was mixed with a solution of hydrogen peroxide in 20 volumes (6% by weight) with a pH of 3. The obtained mixture was applied on wicks of gray hair persisted with 90% of whites for 30 minutes. The wicks were then rinsed, washed with a standard shampoo, rinsed again and then dried. The shades obtained are shown in the table given below: EXAMPLES 9 TO 12 OF DYEING IN MIDDLE NEUTRAL They were plowed (**) Common dyeing support n 2: Ethanol 96 ° 18 g Buffer K2HP04 / KH2PO4 (1.5 M / l M) 10 g Sodium metabisulphite 0. 68 g Pentasodic salt of a-ethylenetriaminepentaacetic acid 1. 1 g At the time of use, weight per weight each of the dyeing compositions indicated above was mixed with a solution of hydrogen peroxide in 20 volumes (6% by weight) of pH 3.

The obtained mixture was applied on wicks of natural gray hair with 90% of whites during 30-minutes. The wicks were then rinsed, washed with a conventional shampoo, rinsed again and then dried.

The shades obtained are shown in the table given below: It is noted that in relation to this date, the best method known to the applicant, to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (22)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. Compounds of formula (I) below, their addition salts with an acid or a base, and their possible tautomeric forms: characterized in that: Ri represents a hydrogen atom; a group Z as defined below; an alkyl radical of Ci-Cß, "a trifluoroalkyl radical of C? -C6, a monohydroxyalkyl radical of Ci-Cß, a polyhydroxyalkyl radical of C2-C6, an arylalkyl radical of Ci-Ce in which the aryl radical can be particularly a phenyl radical or a five or six-membered aromatic heterocycle, an alkoxy radical (C? -C6) C? -C6 alkyl, a C6-C6 alkylthioalkyl radical of C? -C6, an aminoalkyl radical (C) ? -C6) carbonylalkyl (C? -C6), a NZ-aminoalkyl (C? -C6) carbonylalkyl radical (C? -C?), An N-alkyl (CL-C6) aminoalkyl (C-Ce) carbonylalkyl radical ( C? -C6), an N, N-dialkyl (C? -C6) aminoalkyl (C? -C6) carbonylalkyl (Ci- C6) radical, an aminosulfonylalkyl radical (C? -C6), a NZ-aminosulfonylalkyl radical (C) -C6), a radical N-alkyl (Ci-Ce) aminosulfonylalkyl (C? -C3; an N, N-dialkyl (Ci- Cs) aminosulfonylalkyl (C? -Cd) radical; R2 and R3, identical or different represent a group -NHR4, a hydroxyl radical, a halogen atom, a rad ical nitro, a cyano radical; a carboxy radical; a carboxyalkyl radical of C? -C6; a carboxyl aryl radical; a carbamyl radical; a radical N-alkyl (C? -C6) carbamyl; a N, N-dialkyl (Ci-Ce) carbamyl radical; an N-arylcarbamyl radical; a Ci-Cβ alkoxy radical, "an aryloxy radical, a thioalkyl radical of Ci-Cß, a thioaryl radical or one of the meanings given above for Ri, it being understood that at least one of the radicals R2 and R3 represents a group -NHR or a hydroxyl radical, R4 represents a hydrogen atom, a group Z as defined below, an alkyl radical of Ci-Cß, a monohydroxyalkyl radical of C? -C6, a polyhydroxyalkyl radical of C; -Ce; alkoxy radical (C? -C6) alkyl of dC6, an aryl radical, a benzyl radical, a cyanoalkyl radical of Ci-Cß / a carbamylalkyl radical of C? -C5, a radical N-alkyl (C? -C5) Carbamylalkyl of C 1 -Ce, an N, N-dialkyl (C 6 -C) carbamylalkyl radical of C 6 -C 6, a thiocarbamylalkyl radical of C 6 -C 6, a trifluoroalkyl radical of C 6 -C 6, a sulfoalkyl radical of Ci -Cβ, an alkyl (Ci-Ce) carboxyalkyl radical of C?-C5, an alkyl (Ci-Cβ) sulfinylalkyl radical of C?-C6, an aminosulfonylalkyl radical of Ci-Ce, a radical l N-Z-aminosulfonylalkyl of Ci-Cß; an N-alkyl (Ci-Cβ) aminosulfonylalkyl radical of C? -C6; an N, N-dialkyl (C? -C6) aminosulfonylalkyl radical of C? -C6; an aminoalkyl radical of C? -C6; an aminoalkyl radical of Ci-Ce whose amine is substituted by one or two identical or different radicals selected from the C rad-C6 alkyl, C-C6 monohydroxyalkyl, C2-C6 polyhydroxyalkyl, alkyl (Ci-Ce) carbonyl radicals, alkyl (dC 6) sulfonyl, formyl, trifluoroalkyl (C 1 -C 2) carbonyl, or by a group Z; the amine of the aminoalkyl radical of d-C6 can also be replaced by two radicals which form, together with the nitrogen atom of the said amine, a saturated or unsaturated cycle of five or six links and which may contain one or more heteroatoms selected from nitrogen, oxygen and sulfur; • Z is chosen from the following unsaturated cationic groups of formulas (II) and (III), and the saturated cationic groups of formula (IV) below: (II) (iil) which: • D is a linking arm representing an alkyl chain preferably comprising 1 to 14 carbon atoms, straight or branched, which may be interrupted by one or more heteroatoms such as oxygen atoms, sulfur or nitrogen, and which can be substituted by one or more hydroxyl or Ci-Ce alkoxy radicals, and which can carry one or several ketone functions; • the links E, G, J, L and M, identical or different, represent a carbon atom, oxygen, sulfur or nitrogen; • n is an integer between 0 and 4 inclusive; • m is an integer between 0 and 5 inclusive; • the radicals R, identical or different, represent a second group Z identical or different from the first group Z; a halogen atom; a hydroxyl radical; an alkyl radical of C? -C6; a monohydroxyalkyl radical of C? -C6; a C2-C6 polyhydroxyalkyl radical; a nitro radical; a cyano radical; a cyanoalkyl radical of Ci-Ce; an alkoxy radical of C? -C6; a trialkyl (Ci- C6) silanoalkyl radical of C? -C6; an amido radical; an aldehyde radical; a carboxyl radical; an alkylcarbonyl radical of Ci-Ce, a thio radical, a thioalkyl radical of C? -C6, an alkyl radical (C? -C6) thio, an amino radical, an amino radical protected by an alkyl radical (Ci-Ce) carbonyl or alkyl (Ci- C6) sulfonyl, an NHR group "or NR" R '"in which R" and R "', identical or different, represent an alkyl radical of C? -C6, a monohydroxyalkyl radical of Ci-Ce or a polyhydroxyalkyl radical of d-; • R5 represents an alkyl radical of Ci-Ce; a monohydroxyalkyl radical of Ci-Ce; a polyhydroxyalkyl radical of -; a cyanoalkyl radical of C? -C6; a trialkyl (C? -C6) silanoalkyl radical of Ci-; an alkoxy radical (C? -C6) alkyl of Ci-; a carbamylalkyl radical Ci-d; a C 1 -C 6 alkylcarbyalkyl radical of C 1; a benzyl radical; or a second group Z identical or different from the first group Z; • R6, R7 and Rs identical or different represent an alkyl radical of C6-C6; - a monohydroxyalkyl radical of C? -C6; a polyhydroxyalkyl radical of d-; an alkoxy radical (d-C6) alkyl of C? -C6; a cyanoalkyl radical of d-C6; an aryl radical; a benzyl radical; an amidoalkyl radical of Ci-; a trialkyl (Ci-C6) silanoalkyl radical of C? -C6 or an aminoalkyl radical of Ci-Ce whose amine is protected by an alkyl (Ci-Cβ) carbonyl or alkyl (Ci-Ce) sulfonyl radical; two of the radicals Rs, 7 and Rβ can also form together, with the nitrogen atom to which they are attached, a saturated cycle of 5 or 6 carbon atoms or containing one or more heteroatoms, the cycle may or may not be substituted by a halogen atom, a hydroxyl radical, an alkyl radical of Ci-Cß, a monohydroxyalkyl radical of C? -C6, a polyhydroxyalkyl radical of C2-C6, a nitro radical, a cyano radical, a cyanoalkyl radical of Ci-, a C 1 -C 5 alkoxy radical, a trialkyl (C 1 -C 6) silanoalkyl radical of Ci-Cß, an amido radical, an aldehyde radical, a carboxyl radical, a C 6 -C 6 ketoalkyl radical, a thio radical, a radical thioalkyl of C? -C6, an alkyl radical (C? -C6) thio, an amino radical, an amino radical protected by an alkyl (C-Ce) carbonyl or alkyl (Ci-d) sulfonyl radical; one of the radicals R6, 7 and Rs can also represent a second group Z, identical or different from the first group Z; 9 represents an alkyl radical of C6-C6; a monohydroxyalkyl radical of C? -C6; a C2-C6 polyhydroxyalkyl radical; an aryl radical; a benzyl radical; an aminoalkyl radical of C? -C6; an aminoalkyl radical of C? -C6 whose amine is protected by an alkyl (C? -C6) carbonyl or alkyl (Ci-Ce) sulfonyl radical; a carboxyalkyl radical of Ci-; a cyanoalkyl radical of C? -C6; a carbamylalkyl radical of Ci-; a trifluoroalkyl radical of Ci-Ce; a trialkyl (C? d) silanoalkyl d-C6 radical; a sulfonamidoalkyl radical of C? -C6; an alkyl (C? d) carboxyalkyl radical of C? -C6; an alkyl (Ci-d) sulfinylalkyl radical of C? -C6; an alkyl (Ci-d) sulfonylalkyl radical of C? -C6; an alkyl (C? -C5) ketoalkyl radical of C? -C6; an N-alkyl (Ci-C6) carbamylalkyl radical of C? -C6; an N-alkyl (Ci- Ce) sulfonamidoalkyl radical of Ci-; a and y are integers equal to 0 or 1; with the following conditions: - in the unsaturated cationic groups of formula (II): when a = 0, the linking arm D is attached to the nitrogen atom, when a = 1, the linking arm D is attached to one of the links E, G, J or L, and can not take the value 1: 3) when the links E, G, J and L simultaneously represent a carbon atom, and when the radical R5 is carried by the nitrogen atom of the cycle unsaturated; or 4) when at least one of the links E, G, J and L represents a nitrogen atom in which the radical R5 is fixed; in the unsaturated cationic groups of formula (III): when a = 0, the linking arm D is attached to the nitrogen atom, when a = 1, the connecting arm D is attached to one of the links E, G, J , L or M, and can not take the value 1 more than when at least one of the links E, G, J, L and M represents a divalent atom, and when the radical R5 is supported by the nitrogen atom of the unsaturated cycle; - in the cationic groups of formula (IV): when a = 0, then the linking arm D is attached to the nitrogen atom bearing the radicals R6 to Rs, when a = 1, then two of the radicals R6 to Rd form together with the nitrogen atom to which a 5 or 6-membered saturated cycle is attached as defined above, and the linking arm D is supported by a carbon atom of said saturated cycle; • X "represents a monovalent or divalent anion, it being understood that the number of cationic groups Z is at least equal to 1.
2. 2. Compounds according to claim 1, characterized in that the cycles of the unsaturated groups Z of formula (II) are chosen from the pyrrole, imidazole, pyrazole, oxazole, thiazole and triazole rings.
3. 3. Compounds according to claim 1, characterized in that the cycles of the unsaturated groups Z of formula (III) are chosen from the pyridine, pyrimidine, pyrazine, oxazine and triazine rings.
4. 4. Compounds according to any one of the preceding claims, characterized in that two of the radicals R6, R7 and Re form a pyrrolidine ring, a piperidine ring, a piperazine ring or a morpholine ring.
5. 5. Compounds according to any one of the preceding claims, characterized in that X ~ is chosen from a halogen atom, a hydroxide, a hydrogen sulfate, or an alkyl (C? ~ D) sulfate.
6. 6. Compounds according to any one of the preceding claims, characterized in that they are chosen from: [3- (4-amino-2, 5-dimethyl-2H-pyrazol-3-ylamino) -propyl] - chloride trimethylammonium; [3- (4-amino-2,5-dimethyl-2H-pyrazol-3-ylamino) -propyl] - (2-hydroxy-ethyl) -dimethyl-ammonium chloride; - 3- [3- (4-amino-2,5-dimethyl-2H-pyrazol-3-ylamino) -propyl] -1- (2-hydroxy-ethyl) -3H-imidazol-1-yl chloride; 3- [(4-amino-2H-pyrazol-3-ylcarbamoyl) -methyl] -1-methyl-3H-imidazol-1-yl chloride; - 3- [2- (4,5-diamino-3-methyl-pyrazol-1-yl) -ethyl] -l-methyl-3H-imidazol-1-yl chloride; 3- [2- (4,5-diamino-pyrazol-1-yl) -ethyl] -1-methyl-3H-imidazol-1-yl chloride; - [2- (4,5-diamino-3-methyl-pyrazol-1-yl) -ethyl] -trimethyl-ammonium chloride; - [2- (4,5-diamino-pyrazol-1-yl) -ethyl] -trimethyl-ammonium chloride; - [2- (4-amino-5-hydroxy-pyrazol-1-yl) -ethyl] -trimethyl-ammonium chloride; - [2- (4-amino-5-hydroxy-3-methyl-pyrazol-1-yl) -ethyl] -trimethyl-ammonium chloride; - 3- [2- (4-amino-5-hydroxy-3-methyl-pyrazol-1-yl) -ethyl] -l-methyl-3H-imidazol-1-yl chloride; - 3- [2- (4-amino-5-hydroxy-pyrazol-1-yl) -ethyl] -l-methyl-3H-imidazol-1-yl chloride; - 3- [2- (4,5-diamino-1-methyl-1H-pyrazol-3-yl) -ethyl] -l-methyl-3H-imidazol-1-yl chloride, and its addition salts with an acid or a base, and its possible tautomeric forms.
7. 7. Compounds according to claim 6, characterized in that they are chosen from: - [3- (4-amino-2,5-dimethyl-2H-pyrazol-3-ylamino) -propyl] -trimethyl- chloride ammonium; [3- (4-amino-2,5-dimethyl-2H-pyrazol-3-ylamino) -propyl] - (2-hydroxy-ethyl) -dimethyl-ammonium chloride; 3- [3- (4-amino-2, 5-dimethyl-2H-pyrazol-3-ylamino) -propyl] -1- (2-hydroxy-ethyl) -3H-imidazol-1-yl chloride; - 3- [(4-amino-2H-pyrazol-3-ylcarbamoyl) methyl) -l-methyl-3H-imidazol-1-yl chloride; 3- [2- (4,5-diamino-3-methyl-pyrazol-1-yl) -ethyl] -1-methyl-3H-imidazol-1-yl chloride; - 3- [2- (4,5-diamino-l-methyl-lH-pyrazol-3-yl) -ethyl] -l-methyl-3H-imidazol-1-yl chloride; and their addition salts with an acid or a base, and their possible tautomeric forms.
8. 8. Compounds according to any one of the preceding claims, characterized in that the addition salts with an acid are chosen from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates and acetates and because addition salts with a base are chosen from those obtained with soda, potash, ammonia or amines.
9. 9. Use of the compounds of formula (I) as defined in any one of claims 1 to 8, as oxidation base for the oxidation dyeing of keratin fibers.
10. 10. Composition for oxidation dyeing of keratin fibers, characterized in that it comprises, as a base for oxidation, in a medium suitable for dyeing, at least one compound of formula (I) as defined in Any one of claims 1 to 8.
11. The composition according to claim 10, characterized in that the compound (s) of formula (I) represent from 0.0005 to 12% by weight of the total weight of the dyeing composition.
12. 12. Composition according to claim 11, characterized in that the compound (s) of formula (I) represent from 0.005 to 6% by weight of the total weight of the dyeing composition.
13. Composition according to any one of Claims 10 to 12, characterized in that it includes at least one additional oxidation base selected from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases. different from the compounds of formula (I).
14. Composition according to claim 13, characterized in that the additional oxidation base (s) represent 0.0005 to 12% by weight of the total weight of the dyeing composition.
15. Composition according to any one of claims 10 to 14, characterized in that it includes at least one copulator and / or at least one direct dye.
16. Composition according to Claim 15, characterized in that the coupler or couplers are chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic couplers, and their addition salts with an acid.
17. 17. The composition according to claim 16, characterized in that the coupler (s) are chosen from 2-methyl-5-aminophenol, 5-N- (β-hydroxyethyl) amino-2-methylphenol, 3-aminophenol. , 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1- (β-hydroxyethyl-oxy) benzene, 2-amino -4- (ß-hydroxyethylamino) -1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis- (2, -diaminophenoxy) propane, sesamol, a-naphthol, 6-hydroxyindole, -hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, l-H3-methylpyrazol-5-one, l-phenyl-3-methylpyrazole-5- ona, and its addition salts with an acid.
18. Composition according to any one of Claims 15 to 17, characterized in that the coupler (s) represent from 0.0001 to 10% by weight of the total weight of the dyeing composition.
19. Composition according to any one of Claims 10 to 18, characterized in that the addition salts with an acid are chosen from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates and acetates.
20. 20. Method of dyeing keratin fibers and in particular human keratin fibers such as hair characterized in that at least one dyeing composition as defined in any one of claims 10 to 19 is applied to these fibers. , and because the color is revealed at an acidic, neutral or alkaline pH with the aid of an oxidizing agent which is added at the time of use to the dye composition or which is present in an oxidizing composition applied simultaneously or sequentially in a separated.
21. 21. Process according to claim 20, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates and enzymes.
22. 22. Multi-compartment device or dyeing "equipment" of several compartments, of which the first compartment includes a dye composition as defined in any one of claims 10 to 19 and a second compartment includes an oxidizing composition. NEW CATIONIC OXIDATION BASES, ITS USE FOR THE OXIDATION TISSUE OF KERATINIC FIBERS, TINTORIAL COMPOSITIONS AND DYEING PROCEDURES SUMMARY OF THE INVENTION The invention relates to novel pyrazole derivatives comprising at least one cationic group Z, Z being selected from quaternized aliphatic chains. aliphatic chains comprising at least one quaternized saturated cycle, and aliphatic chains comprising at least one unsaturated quaternized cycle, its use as an oxidation base for the oxidation dyeing of the keratin fibers, the dye compositions containing them, as well as the oxidation dyeing procedures that use them.