FR2822690A1 - COMPOSITION FOR OXIDATION DYE CONTAINING AT LEAST ONE 3-AMINO PYRAZOLO [1,5-A] PYRIDINE OXIDATION BASE AND AT LEAST ONE PARTICULAR PYRAZOLOTRIAZOLE COUPLER - Google Patents

Abstract

The invention relates to novel compositions for the oxidation dyeing of keratin fibres comprising at least one 3-amino pyrazolo-[1,5-a]-pyridine as oxidation base and at least one particular pyrazolotriazole coupling agent. The invention also relates to a dyeing method and a device using said composition.

Description

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COMPOSITION FOR OXIDATION DYE CONTAINING AT LEAST ONE 3-AMINO PYRAZOLO- [1,5-A] -PYRIDINE OXIDATION BASE AND AT LEAST ONE
SPECIAL PYRAZOLOTRIAZOLE COUPLER.

 The subject of the invention is new compositions for the oxidation dyeing of keratinous fibers comprising at least one 3-amino pyrazolo [1,5-a] pyridine as oxidation base and at least one particular pyrazolotriazole coupler, a dyeing process and a dyeing device employing this composition.

 It is known to dye keratinous fibers and in particular human hair with dyeing compositions containing oxidation dye precursors, in particular ortho or para-phenylenediamines, ortho or para-aminophenols, heterocyclic compounds such as diaminopyrazole derivatives, called generally oxidation bases. The oxidation dye precursors, called oxidation bases, are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise, by a process of oxidative condensation, to colored and coloring compounds. These compounds have the common point of having an amino group and a hydroxyl group or two amino groups, which gives them their character of oxidation base.

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

 The variety of molecules involved in oxidation bases and couplers, allows to obtain a rich palette of colors.

 The so-called "permanent" coloration obtained with these oxidation dyes must also meet a certain number of requirements. Thus, it must be harmless from the toxicological point of view, it must make it possible to obtain shades in the desired intensity, to have good resistance to external agents (light, bad weather, washing, permanent waving, perspiration, friction).

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 The dyes must also make it possible to cover the white hair, and finally be the least selective possible, that is to say allow to obtain the lowest possible color differences throughout the same keratin fiber, which can be in effect differently sensitized (ie damaged) between its tip and its root.

 Pyridines are already known for the oxidation dyeing of keratin fibers as oxidation bases. For example, GB 1 026 978 and GB 1 153 196 propose to use 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino-3-amino pyridine, 2,3-diamino-6-methoxy pyridine 2- (p-methoxyethyl) amino 3-amino-6-methoxy pyridine, 3,4-diamino pyridine as the oxidation base.

 In addition, it is known to use pyrazolotriazole type couplers for the oxidation dyeing of keratin fibers, for example in patent application FR 2 746 306.

 The object of the invention is to develop new dyeing compositions which make it possible to obtain a new range of colors and which do not have the drawbacks of dyes of the prior art. In particular, the object of the invention is to develop compositions which lead to very powerful colorations, particularly resistant to the various attacks that hair can undergo (light, bad weather, washing, permanent waving, perspiration, friction), which are not very selective and which present good safety.

 To this end, the subject of the invention is a composition for the oxidation dyeing of keratin fibers, comprising in a medium suitable for dyeing, as oxidation base at least one 3-amino pyrazolo [1, 5-a] - pyridine of the following formula (1) and / or one of its addition salts with an acid or with a base:

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dans laquelle : - Ri, Rs, Rs, R4 et R5, identiques ou différents, représentent un atome d'hydrogène ou d'halogène ; un radical -NHSO3H; un radical hydroxyle ; un radical alkyle ; un radical alkoxy ; un radical alkylthio; un radical amino ; un radical monoalkylamino ; un radical dialkylamino dans lequel les deux groupements alkyle peuvent former conjointement avec l'atome d'azote auquel ils sont liés un cycle pouvant être interrompu par un ou plusieurs atomes d'azote, d'oxygène ou de soufre ; un hétérocycle ; un radical nitro ; un radical aryle ; un radical acyle en C1-C4 ; un radical alkoxy(C1-C4)carbonyle ; un radical carboxamido ; un radical cyano ; un radicalCO2H, un radical-S03H ; un radical-PO3H2 ; un radical -PO4H2 ; ou un groupement de formule (11) suivants

dans laquelle X et R représentent indépendamment l'un de l'autre un atome d'oxygène, un groupement NH ou N-alkyle, et Y représente un radical hydroxyle, amino, alkyle, alkoxy, alkylamino, ou dialkylamino, et 'au moins un coupleur pyrazolotriazole de formule (ici) suivante :

in which: R 1, R 5, R 5, R 4 and R 5, which may be identical or different, represent a hydrogen or halogen atom; a radical -NHSO3H; a hydroxyl radical; an alkyl radical; an alkoxy radical; an alkylthio radical; an amino radical; a monoalkylamino radical; a dialkylamino radical in which the two alkyl groups can form together with the nitrogen atom to which they are attached a ring which can be interrupted by one or more nitrogen, oxygen or sulfur atoms; a heterocycle; a nitro radical; an aryl radical; a C1-C4 acyl radical; a (C1-C4) alkoxycarbonyl radical; a carboxamido radical; a cyano radical; a radicalCO2H, a radical-SO3H; a radical-PO3H2; a radical -PO4H2; or a group of formula (11) following

wherein X and R are independently oxygen, NH or N-alkyl, and Y is hydroxyl, amino, alkyl, alkoxy, alkylamino, or dialkylamino, and a pyrazolotriazole coupler of formula (here):

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dans laquelle : - R6 représente un atome d'hydrogène ; un atome d'halogène ; un radical alkyle, un radical aryle ; un hétérocycle à 5 ou 6 chaînons possédant au moins un atome d'azote, d'oxygène ou de soufre, lorsque R6 désigne un radical alkyle, un radical aryle ou un hétérocycle à 5 ou 6

chaînons, il peut être relié à l'atome de carbone du noyau par l'intermédiaire d'un atome d'oxygène, d'azote ou de soufre ; un radical sulfonyl ; un radical sulfinyl ; un radical phosphonyle, - R7 représente un atome d'hydrogène ; un atome d'halogène ; un groupe acétylamido ; un radical alcoxy ; un radical aryloxy ; un radical acyloxy ; un radical arylthio ; un radical alkylthio ; un radical hétéroarylthio ; un radical hétéroaryloxy ; un radical thiocyano ; un radical N, N-diéthyl thiocarbonylthio ; un radical dodécyl-oxythio carbonylthio ; un radical benzènesulfonamido ; un radical N-éthyltoluène sulfonamido ; un radical p-cyanophényluréido, un radical N, N-diéthyl-sulfamoylamino ; un radical pyrazolyl ; un radical imidazolyle ; un radical triazolyl ; un radical tétrazolyle ; un radical benzimidazolyle ; un radical 1-benzyl 5-éthoxy 3-hydantoïnyle ; un radical 1benzyl 3-hydantoïnyle ; un radical 5, 5-diméthyl 2,4-dioxo 3-oxazolidinyle ; un radical 2oxy 1,2-dihydro 1-pyridinyle ; un radical alkylamido ; un radical arylamido ; un radical NRaRb avec Ra et Rb représentant, identiques ou différents, un alkyle, un hydroxyalkyl, un carboxyle, ou un radical alcoxycarboxylique, et - Za, Zb, le représentent, indépendamment l'un de l'autre, un atome d'azote, un atome de carbone portant un radical R8 ou R9 ayant les mêmes significations que celles indiquées pour le radical R6 ; R8 et R9 peuvent également former entre eux un cycle aromatique substitué ou non ; sous réserve que l'un au moins des radicaux Za, Zb et le est différent d'un atome de carbone.

wherein: - R6 represents a hydrogen atom; a halogen atom; an alkyl radical, an aryl radical; a 5- or 6-membered heterocycle having at least one nitrogen, oxygen or sulfur atom, when R 6 denotes an alkyl radical, an aryl radical or a 5- or 6-membered heterocycle

chain, it can be connected to the carbon atom of the ring via an oxygen atom, nitrogen or sulfur; a sulfonyl radical; a sulfinyl radical; a phosphonyl radical; R7 represents a hydrogen atom; a halogen atom; an acetylamido group; an alkoxy radical; an aryloxy radical; an acyloxy radical; an arylthio radical; an alkylthio radical; a heteroarylthio radical; a heteroaryloxy radical; a thiocyano radical; an N, N-diethylthiocarbonylthio radical; a dodecyl-oxythio-carbonylthio radical; a benzenesulphonamido radical; an N-ethyltoluene sulfonamido radical; a p-cyanophenylureido radical, an N, N-diethylsulfamoylamino radical; a pyrazolyl radical; an imidazolyl radical; a triazolyl radical; a tetrazolyl radical; a benzimidazolyl radical; a 1-benzyl 5-ethoxy-3-hydantoinyl radical; a 1-benzyl-3-hydantoinyl radical; a 5,5-dimethyl 2,4-dioxo-3-oxazolidinyl radical; a 2oxy 1,2-dihydro-1-pyridinyl radical; an alkylamido radical; an arylamido radical; a radical NRaRb with Ra and Rb representing, identical or different, an alkyl, a hydroxyalkyl, a carboxyl or an alkoxycarboxylic radical, and - Za, Zb, represent, independently of one another, a nitrogen atom a carbon atom bearing a radical R8 or R9 having the same meanings as those indicated for the radical R6; R8 and R9 may also form between them a substituted or unsubstituted aromatic ring; provided that at least one of the radicals Za, Zb and le is different from a carbon atom.

 In the compounds of formula (1) or (here) that are useful for the present invention, the term alkyl used for the alkyl radicals as well as for the groups comprising an alkyl part, means, unless otherwise indicated, a linear or branched carbon chain comprising from 1 to 30 carbon atoms, which can be

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 interrupted by one or more oxygen, sulfur or nitrogen atoms and may be substituted by one or more groups selected from halogen atoms such as chlorine, bromine, iodine and fluorine; heterocycles; phenyl, hydroxyl, alkyl, amino, acyl, carboxamido, -CO 2 H, -SO 3 H, -PO 3 H 2, -PO 4 H 2, -NHSO 3 H, sulfonamide, monoalkylamino, trialkylammonium or else a dialkylamino radical in which the two alkyl groups can form , together with the nitrogen atom of said dialkyl (C1-C4) amino group to which they are attached, a ring which may be interrupted by one or more nitrogen, oxygen or sulfur atoms.

 Likewise, according to the invention, in the formula (1) or (III), the term alkoxy used for the alkoxy radicals as well as for the groups comprising an alkoxy part, means, unless otherwise indicated, an O-alkyl chain, the term alkyl having the meaning indicated above.

 According to the invention, for formulas (1) or (here), the term heterocycle means an aromatic or non-aromatic ring containing 5,6 or 7 vertices, and from 1 to 3 heteroatoms chosen from nitrogen, sulfur and and oxygen. These heterocycles may be fused to other heterocycles or to a phenyl group. They may be substituted by a halogen atom; an alkyl radical; an alkoxy radical; a hydroxyl radical; an amino radical; an alkylamin radical; dialkylamino in which the two alkyl groups can together with the nitrogen atom to which they are attached form a ring which can be interrupted by one or more nitrogen, oxygen or sulfur atoms. These heterocycles may, in addition, be quaternized with an alkyl radical. The terms alkyl and alkoxy have the meanings given above.

 Among these heterocycles, there may be mentioned by way of example the rings: thiadiazole, triazole, isoxazole, oxazole, azaphosphole, thiazole, isothiazole, imidazole, pyrazole, triazine, thiazine, pyrazine, pyridazine, pyrimidine, pyridine, diazepine, oxazepine, benzotriazole, benzoxazole, benzimidazole, benzothiazole, morpholine, piperidine, piperazine, azetidine, pyrrolidine, aziridine, 3- (2hydroxyethyl) benzothiazol-3-ium, and 1- (2-hydroxyethyl) pyridinium.

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Selon l'invention, pour les formules (1) ou (ici), on entend par aryle, un radical aryle pouvant être substitué par un ou plusieurs radicaux alkyle, alcoxy, acyle, cyano, carboxamido,-CO2H,-SO3H,-PO3H2,-P04H2, hydroxyle, amino, monoalkyl (CiC4) amino, ou dialkyl (Ci-C4) amino dans lequel les deux groupements alkyle peuvent former, conjointement avec l'atome d'azote dudit groupement dialkyl (Ci-C4) amino auquel ils sont liés, un cycle pouvant être interrompu par un ou plusieurs atomes d'azote, d'oxygène ou de soufre. De préférence, le groupe aryle est un groupe phényle pouvant être substitué comme indiqué ci dessus.

According to the invention, for the formulas (1) or (here), aryl means an aryl radical which may be substituted by one or more alkyl, alkoxy, acyl, cyano, carboxamido, -CO2H, -SO3H, -PO3H2 radicals. , -P04H2, hydroxyl, amino, monoalkyl (CiC4) amino, or dialkyl (C1-C4) amino in which the two alkyl groups can form, together with the nitrogen atom of said dialkyl (C1-C4) amino group to which they are linked, a cycle that can be interrupted by one or more nitrogen, oxygen or sulfur atoms. Preferably, the aryl group is a phenyl group which may be substituted as indicated above.

 Among the groups of formula (II) above, there may be mentioned acetamide, dimethylurea, O-methylcarbamate, methylcarbonate, Ndimethylcarbamate and esters.

dans laquelle : Ri, R2, R3, identiques ou différents, représentent un atome d'hydrogène ou d'halogène ; un radical-NHSO3H ; un radical hydroxyle ; un radical alkyle ; un radical alkoxy ; un radical alkylthio ; un radical amino ; un radical monoalkylamino ; un radical dialkylamino dans lequel les deux groupements alkyle peuvent conjointement avec l'atome d'azote auquel ils sont liés, former un cycle pouvant être interrompu par un ou plusieurs atomes d'azote, d'oxygène ou de soufre ; un hétérocycle ; un radical acyle ; The composition according to the invention preferably comprises the 3-amino pyrazolo [1,5-a] pyridines corresponding to the following formula (la), as well as their addition salts with an acid or with a base:

in which: R 1, R 2, R 3, which may be identical or different, represent a hydrogen or halogen atom; a radical-NHSO3H; a hydroxyl radical; an alkyl radical; an alkoxy radical; an alkylthio radical; an amino radical; a monoalkylamino radical; a dialkylamino radical in which the two alkyl groups may, together with the nitrogen atom to which they are bonded, form a ring which may be interrupted by one or more nitrogen, oxygen or sulfur atoms; a heterocycle; an acyl radical;

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un radical alkoxycarbonyl ; un radical carboxamido ; ou un groupement de formule (II) suivante

an alkoxycarbonyl radical; a carboxamido radical; or a group of formula (II) below

dans laquelle X et R représentent, indépendamment l'un de l'autre, un atome d'oxygène, un groupement NH ou N (Cl-C4) alkyle, et Y représente un radical hydroxyle, amino, alkyle, alkoxy, alkylamino, ou dialkylamino.

wherein X and R represent, independently of one another, an oxygen atom, an NH or N (C 1 -C 4) alkyl group, and Y represents a hydroxyl, amino, alkyl, alkoxy, alkylamino, or dialkylamino.

Among the 3-amino pyrazolo [1, 5-a] pyridines of formula (1), which are useful as oxidation bases in the dyeing compositions of the invention, mention may be made in particular 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-diamino-pyrazolo [1,5-a] pyridine; pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; pyrazolo [1,5-a] pyridine-3,5-diamine; 5-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 2- [(3-amino-pyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) amino] ethanol; 2- [(3-amino-pyrazolo [1,5-a] pyridin-7-yl) - (2-hydroxyethyl) amino] ethanol; 3-amino-pyrazolo [1,5-a] pyridin-5-ol; 3-amino-pyrazolo [1,5-a] pyridin-4-ol;

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- ta 3-amino-pyrazoio [1, 5-a] pyridine-6-o) ; - la 3-amino-pyrazolo [1, 5-a] pyridine-7-ol ; ainsi que leurs sels d'addition avec un acide ou avec une base.

3-amino-pyrazolo [1,5-a] pyridine-6-o); 3-amino-pyrazolo [1,5-a] pyridin-7-ol; as well as their addition salts with an acid or with a base.

 The 3-amino pyrazolo [1,5-a] pyridines of formula (1) are known compounds, in particular in the pharmaceutical field, and are described in particular in US Pat. No. 5,457,200. These compounds can be prepared according to synthetic methods well known in the literature and as described for example in US Patent 5,457,200.

 The at least 3-amino pyrazolo [1,5-a] pyridines of formula (1) above and / or the acid or base addition salt or salts thereof are preferably from 0.0001 to 10. about% by weight of the total weight of the dye composition, and even more preferably from 0.005 to 6% by weight approximately of this weight.

 In the pyrazolotriazole coupler of formula (III), when R 6 is an aryl group, it is, for example, an optionally substituted phenyl or naphthyl radical.

When R 6 is a 5- or 6-membered heterocycle having at least one nitrogen, oxygen or sulfur atom, it is, for example, a pyridyl, quinolyl, pyrrolyl, morpholyl, uranyl, tetrahydrofuranyl, pyrazolyl, triazolyl or tetrazolyl radical, thiazolyl, oxazolyl, imidazolyl or thiadiazolyl, optionally substituted.

 When the R 6 group of the coupler of formula (here) is substituted, it preferably comprises 1 or 2 substituents.

 According to the particular embodiment in which R 1 denotes an alkyl radical, an aryl radical or a 5- or 6-membered heterocycle connected to the carbon atom of the ring via an oxygen, nitrogen or of sulfur, a group XR1 is obtained with X = O, NH, S.

 Among the radicals R 6 of the formula (here) defined above, the radicals chosen from a hydrogen atom are preferred; an alkyl; phenyl; a phenyl substituted with a halogen atom, an alkyl, an alkoxy, a nitro group, an amino group, a trifluoromethyl group or an alkylamino group; a benzyl radical; a benzyl radical substituted with a halogen atom, an alkyl, an alkoxy, a nitro group, an amino group, a trifluoromethyl group; an alkylamino; a heterocycle selected from

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 thiophene, furan or pyridine; a trifluoromethyl radical; a radical (CH2) pX- (CH2) q-OR 'where p and q are integers, identical or different, between 1 and 3, R' represents H or methyl and X denotes an oxygen atom or a group NR " with R "denoting hydrogen or methyl; hydroxyalkyl; an aminoalkyl; an alkylamin; a dialkylamino; an arylamino; an alkoxy radical selected from methoxy, ethoxy and phenoxy; a halogen selected from fluorine, chlorine and bromine; a carboxyl group; an alkoxycarbonyl; phenyloxycarbonyl; methylthio; ethylthio; phenylthio; methanesulfonyl; cyano.

 Among the radicals R 6 of the formula (here) defined above, hydrogen is more particularly preferred; an alkyl selected from methyl, ethyl, isopropyl, terbutyl; a halogen selected from fluorine and chlorine; phenyl; toluyle; 4-chlorophenyl; 4-methoxyphenyl; 3-methoxyphenyl; 2-methoxyphenyl; benzyl; a heterocycle selected from pyridyl, furyl or thienyl; trifluoromethyl; hydroxymethyl; aminomethyl; methoxy or ethoxy; methylamino or ethylamino or dimethylamino; carboxyl; methoxycarbonyl or ethoxycarbonyl; cyano.

 More particularly, the radicals R 6 chosen from hydrogen are preferred; methyl radicals; ethyl; phenyl; toluyle; 4-chlorophenyl; 4-methoxyphenyl; benzyl; trifluoromethyl; chloro; a methoxy or ethoxy radical; a carboxyl radical; methylamino or dimethylamino; cyano.

un radical phénoxy, 4-méthoxyphénoxy, 4-nitrophénoxy, 4-cyanophénoxy, 4-méthanesulfonamidophénoxy, 4-méthanesulfonylphénoxy, 3-méthylphénoxy, 1naphtyloxy. Lorsque R7 est un radical acyloxy, il peut être un radical acétoxy, propanoyloxy, benzoyloxy, 2, 4-dichlorobenzoyloxy, éthoxyalkyloxy, pyruviloyioxy, cinnamoyloxy, myristoyloxy. Lorsque R7 est un radical arylthio, il est par exemple : phénylthio, 4-carboxy-phénylthio, 2-éthoxy 5-tert-butylphénylthio, 2-carboxyphénylthio, 4-méthane-sulfonyl-phénylthio ; lorsqu'il est un radical alkylthio, il est par exemple : In the pyrazolotriazole coupler of formula (here), when R7 is alkoxy, it is for example a methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy, phenoxyethoxy, 2-cyanoethoxy, phenethyloxy, p-chlorobenzyloxy, methoxyethylcarbamoylmethoxy. When R7 is an aryloxy radical, it is for example

phenoxy, 4-methoxyphenoxy, 4-nitrophenoxy, 4-cyanophenoxy, 4-methanesulfonamidophenoxy, 4-methanesulfonylphenoxy, 3-methylphenoxy, 1-naphthyloxy. When R 7 is an acyloxy radical, it may be an acetoxy, propanoyloxy, benzoyloxy, 2,4-dichlorobenzoyloxy, ethoxyalkyloxy, pyruviloyioxy, cinnamoyloxy or myristoyloxy radical. When R 7 is an arylthio radical, it is for example: phenylthio, 4-carboxy-phenylthio, 2-ethoxy-5-tert-butylphenylthio, 2-carboxyphenylthio, 4-methanesulfonyl-phenylthio; when it is an alkylthio radical, it is for example:

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méthylthio, éthylthio, propylthio, butylthio, 2-cyanoéthylthio, benzylthio, phénéthylthio, 2- (diéthylamino) éthylthio, éthoxyéthylthio, phénoxyéthylthio ; lorsqu'il est un radical hétéroarylthio, il est par exemple 5-phényl 2, 3, 4, 5-tétrazolylthio, 2-benzothiazolylthio. Lorsque R7 est un radical hétéroaryloxy, il est par exemple : 5-phényl 2, 3, 4, 5tétrazolyloxy, 2-benzo-thiazolyloxy.

methylthio, ethylthio, propylthio, butylthio, 2-cyanoethylthio, benzylthio, phenethylthio, 2- (diethylamino) ethylthio, ethoxyethylthio, phenoxyethylthio; when it is a heteroarylthio radical, it is for example 5-phenyl 2,3,4,5-tetrazolylthio, 2-benzothiazolylthio. When R 7 is a heteroaryloxy radical, it is, for example: 5-phenyl 2,3,4,5 tetrazolyloxy, 2-benzothiazolyloxy.

Among the radicals R7 of the formula (here) defined above, the radicals chosen from hydrogen are preferred; an alkoxy; phenoxy; phenoxy substituted with a halogen atom, an alkyl, a carboxyl, a trifluoromethyl group; an acyloxy radical; benzyloxy; alkylthio; phenyithio; phenylthio substituted with halogen, alkyl, carboxyl, trifluoromethyl; an alkylamido; phenylamido; a radical NRaRb with Ra and Rb representing, identical or different, an alkyl, a hydroxyalkyl; a carboxyl; an alkoxycarboxylic radical.

radicaux méthoxy ou éthoxy ; phényloxy ; 4-méthylphényloxy ; acyloxy ; benzyloxy ; méthylthio ou éthylthio ; phénylthio ; 4-méthylphénylthio ; 2-tertio-butylphénylthio ; acétamido ; phénylacétamido ; diméthylamino ; diéthylamino ; éthyl-méthylamino ; (sshydroxyéthyl)-méthylamino. Among the radicals R7 of the formula (III) defined above, the radicals chosen from hydrogen are more particularly preferred; chlorine or bromine; the

methoxy or ethoxy radicals; phenyloxy; 4-methylphenyloxy; acyloxy; benzyloxy; methylthio or ethylthio; phenylthio; 4-methylphenylthio; 2-tert-butylphenylthio; acetamido; phenylacetamido; dimethylamino; diethylamino; ethyl-methylamino; (Sshydroxyéthyl) methylamino.

More particularly, the radicals R7 chosen from hydrogen are preferred; chlorine; ethoxy; phenoxy; benzyloxy; acyloxy; acetamido; dimethylamino.

 Among the radicals R 8 and R 9 of the formula (III) defined above, the radicals chosen from a hydrogen atom are preferred; an alkyl; a trifluoromethyl radical; phenyl; phenyl substituted with one or two groups selected from halogen, alkyl, alkoxy, hydroxy, carboxyl, nitro, alkylthio, methylenedioxy, amino, trifluoromethyl or alkylamino; a benzyl radical; a benzyl radical substituted with a halogen atom, a methyl or isopropyl, methoxy; a hydroxyalkyl; a C1-C4 aminoalkyl; an alkylaminoalkyl; an alkoxy radical selected from methoxy, ethoxy and phenoxy; methylthio; ethylthio; phenylthio; methanesulfonyl; an aromatic cycle

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 substituted or unsubstituted by R8 and R9 such as phenyl, phenyl substituted with sulfonyl, halogen, alkoxy, alkyl, nitro, cyano, amino, alkylamino, trifluoromethyl.

 Among the radicals R 8 and R 9 of the formula (III) defined above, hydrogen is more particularly preferred; an alkyl selected from methyl, ethyl, isopropyl, npropyl, tert-butyl; phenyl; toluyle; 2-, 3- or 4-chlorophenyl; 3- or 4-hydroxyphenyl; 3- or 4-aminophenyl; 3- or 4-methoxyphenyl; 4-trifluoromethylphenyl; benzyl; trifluoromethyl; hydroxymethyl; hydroxyethyl; hydroxyisopropyl; aminomethyl or aminoethyl; methoxy or ethoxy; methylthio or ethylthio; a substituted or unsubstituted aromatic ring with R8 and R9 such as phenyl, toluyl, sulfonylphenyl, chlorophenyl.

l'hydrogène ; les radicaux méthyle ; éthyle ; isopropyl ; phényle ; 4-chlorophényle ; 4méthoxyphényle ; 4-aminophényle ; méthoxy ou éthoxy ; méthylthio ou éthylthio ; un cycle phényle formé par R8 et R9. More particularly, the radicals R 8 and R 9 chosen from

hydrogen; methyl radicals; ethyl; isopropyl; phenyl; 4-chlorophenyl; 4-methoxyphenyl; 4-aminophenyl; methoxy or ethoxy; methylthio or ethylthio; a phenyl ring formed by R8 and R9.

ii) les pyrazolo [3, 2-c] 1,2, 4-triazoles de formule : Among the couplers of formula (III) that are preferred, mention may be made of: i) pyrazolo [1,5-b] 1,2,4-triazoles of formula:

ii) pyrazolo [3,2-c] 1,2,4-triazoles of formula:

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iii) les pyrazolotétrazoles de formule :

iii) pyrazolotetrazoles of formula:

iv) les pyrazolo-[1, 5-a]-imidazoles de formule :

iv) pyrazolo [1,5-a] imidazoles of formula:

v) les pyrazolo-[5, 1-e]-pyrazoles de formule :

v) pyrazolo [5,1-e] pyrazoles of formula:

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vi) les pyrazolo-[5, 1-e]-1, 2, 3-triazoles de formule :

vi) pyrazolo [5,1-e] -1,2,3-triazoles of formula:

dans lesquelles R6, R7, R8 et R9 sont tels que définis précédemment.

wherein R6, R7, R8 and R9 are as previously defined.

 As examples of compounds of formula (IIIa) or (IIIb), there may be mentioned in particular those for which: - R6 denotes hydrogen, methyl, ethylthio, amino, trifluoromethyl, carboxyl, phenyl, ethoxy or cyano, hydroxyalkyl for example hydroxymethyl - R7 means hydrogen or chlorine; - R8 is hydrogen, methyl, ethyl, isopropyl, ss-aminoethyl, ss-hydroxyethyl, phenyl, methylthio or ethoxy.

 Among the compounds of formula (IIIa) above, mention may be made particularly of: 2-methyl pyrazolo [1,5-b] -1,2,4-triazole, 2-ethyl pyrazolo [1,5] 1, 2, 4-triazole, 2-ispropyl pyrazolo [1,5-b] -1,2,4-triazole, 2-phenyl pyrazolo [1,5-b] -1 , 2,4-triazole,

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- le 2, 6-diméthyl pyrazol [1, 5-b]- 1, 2, 4-triazole, - le 6-méthyl-2-éthyl pyrazolo [1, 5-b]-1, 2, 4-triazole, - le 6-méthyl-2-isopropyl pyrazolo [1,5-b]-1, 2, 4-triazole, - - le 6-méthyl-2-phényl pyrazolo [1,5-b]-1, 2, 4-triazole, - le 6-carboxyl-2-méthyl pyrazolo [1,5-b]-1, 2, 4-triazole, - le 6-carboxyl-2-éthyl pyrazolo [1,5-b]-1, 2, 4-triazole, - le 6-carboxyl-2-isopropyl pyrazolo [1,5-b]-1, 2, 4-triazole, - le 6-carboxyl-2-phényl pyrazolo [1,5-b]-1, 2, 4-triazole, - le 6-phényl-2-méthyl pyrazolo [1,5-b]-1, 2, 4-triazole, - le 6-phényl-2-éthyl pyrazolo [1,5-b]-1, 2, 4-triazole, - le 6-phényl-2-isopropyl pyrazolo [1,5-b]-1, 2, 4-triazole,

- le 6-phényl-2-phényl pyrazolo [1, 5-b]-1, 2, 4-triazole, - le 6-amino-2-méthyl pyrazolo [1, 5-b]-1, 2, 4-triazole, - le 6-amino-2-éthyl pyrazolo [1,5-b]-1, 2, 4-triazole, - le 6-amino-2-isopropyl pyrazolo [1, 5-b]-1, 2, 4-triazole, - le 6-amino-2-phényl pyrazolo [1,5-b]-1, 2, 4-triazole, - le 6-éthylthio-2-méthyl pyrazolo [1,5-b]-1, 2, 4-triazole,

- ! e 6-éthy ! thio-2-éthy ! pyrazo ! o [1, 5-b]-1, 2, 4-triazole, - te 6-éthy ! th ! o-2-isopropyt pyrazoio [1, 5-b]-1, 2, 4-triazole, - le 6-éthylthio-2-phényl pyrazolo [1, 5-b]-1, 2, 4-triazole, - le 6-éthoxy-2-méthyl pyrazolo [1,5-b]-1, 2, 4-triazole, - le 6-éthoxy-2-éthyl pyrazolo [1,5-b]-1, 2, 4-triazole, - le 6-éthoxy-2-isopropoyl pyrazolo [1,5-b]-1, 2, 4-triazole, - le 6-éthoxy-2-phényl pyrazolo [1,5-b]-1, 2, 4-triazole, - ! e 6-méthy !-2- (2'-aminoéthyt) pyrazo) o [1, 5-b]-1, 2, 4-triazole, - le 6-carboxy-2- (2'-aminoéthyl) pyrazolo [1, 5-b]-1, 2, 4-triazole, - le 6-phényl-2- (2'-aminoéthyl) pyrazolo [1, 5-b]-1, 2, 4-triazole, - le 6-éthylthio-2-(2'-aminoéthyl) pyrazolo [1,5-b]-1, 2, 4-triazole, - e2-(2'-aminoéthyl) pyrazolo [1,5-b]-1, 2, 4-triazole, - le 2-(2'-hydroxyéthyl) pyrazolo [1,5-b]-1, 2, 4-triazole,

2,6-dimethyl pyrazol [1,5-b] -1,2,4-triazole; 6-methyl-2-ethyl pyrazolo [1,5-b] -1,2,4-triazole; 6-methyl-2-isopropyl pyrazolo [1,5-b] -1,2,4-triazole, - 6-methyl-2-phenyl pyrazolo [1,5-b] -1,2,4 -triazole, 6-carboxyl-2-methyl pyrazolo [1,5-b] -1,2,4-triazole, 6-carboxyl-2-ethyl pyrazolo [1,5-b] -1,2 , 4-triazole, 6-carboxyl-2-isopropyl pyrazolo [1,5-b] -1,2,4-triazole, 6-carboxyl-2-phenyl pyrazolo [1,5-b] -1 , 2,4-triazole, 6-phenyl-2-methyl pyrazolo [1,5-b] -1,2,4-triazole, 6-phenyl-2-ethyl pyrazolo [1,5-b] -1,2,4-triazole; 6-phenyl-2-isopropyl pyrazolo [1,5-b] -1,2,4-triazole;

6-phenyl-2-phenyl pyrazolo [1,5-b] -1,2,4-triazole; 6-amino-2-methyl pyrazolo [1,5-b] -1,2,4); triazole, 6-amino-2-ethyl pyrazolo [1,5-b] -1,2,4-triazole, 6-amino-2-isopropyl pyrazolo [1,5-b] -1,2, 4-triazole, 6-amino-2-phenyl pyrazolo [1,5-b] -1,2,4-triazole, 6-ethylthio-2-methyl pyrazolo [1,5-b] -1, 2,4-triazole

-! e 6-ethyl! thio-2-ethyl! pyrazo! o [1,5-b] -1,2,4-triazole 6-ethyl! th! o-2-isopropyl pyrazolo [1,5-b] -1,2,4-triazole; 6-ethylthio-2-phenyl pyrazolo [1,5-b] -1,2,4-triazole; 6-ethoxy-2-methyl pyrazolo [1,5-b] -1,2,4-triazole, 6-ethoxy-2-ethyl pyrazolo [1,5-b] -1,2,4-triazole, 6-ethoxy-2-isopropoyl pyrazolo [1,5-b] -1,2,4-triazole; 6-ethoxy-2-phenylpyrazolo [1,5-b] -1,2,4 triazole, -! 6-methyl-2- (2'-aminoethyl) pyrazo) [1,5-b] -1,2,4-triazole, 6-carboxy-2- (2'-aminoethyl) pyrazolo [1] , 5-b] -1,2,4-triazole, 6-phenyl-2- (2'-aminoethyl) pyrazolo [1,5-b] -1,2,4-triazole, 6-ethylthio 2- (2'-aminoethyl) pyrazolo [1,5-b] -1,2,4-triazole-e2- (2'-aminoethyl) pyrazolo [1,5-b] -1,2,4 triazole, 2- (2'-hydroxyethyl) pyrazolo [1,5-b] -1,2,4-triazole,

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- le 6-méthyl-2- (2'-hydroxyéthyl) pyrazolo [1, 5-b]-1, 2, 4-triazole, - le 6-éthylthio-2- (2'-hydroxyéthyl) pyrazolo [1, 5-b]-1, 2, 4-triazole, - le 6-carboxy-2- (2'-hydroxyéthyl) pyrazolo [1, 5-b]-1, 2, 4-triazole, - le 6-phényl-2- (2'-hydroxyéthyl) pyrazolo [1, 5-b]-1, 2, 4-triazole, - le 7-chloro-2,6-diméthylpyrzolo[1,5-b]-1, 2, 4-triazole, - le 7-bromo-2, 6-diméthylpyrazolo [1, 5-b]-1, 2, 4-triazole, et leurs sels d'addition avec un acide.

6-methyl-2- (2'-hydroxyethyl) pyrazolo [1,5-b] -1,2,4-triazole; 6-ethylthio-2- (2'-hydroxyethyl) pyrazolo [1,5 b) -1,2,4-triazole, 6-carboxy-2- (2'-hydroxyethyl) pyrazolo [1,5-b] -1,2,4-triazole, 6-phenyl-2 (2'-hydroxyethyl) pyrazolo [1,5-b] -1,2,4-triazole, 7-chloro-2,6-dimethylpyrzolo [1,5-b] -1,2,4-triazole 7-bromo-2,6-dimethylpyrazolo [1,5-b] -1,2,4-triazole and their addition salts with an acid.

- ! e 3-méthy ! su) finyi-6-phény !-pyrazo ! o [3, 2-c]-1, 2, 4-triazole, - le 3-éthyl pyrazolo[3,2-c]-1, 2, 4-triazole, - ele 3-isopropyl pyrazolo[3,2-c]-1, 2, 4-triazole, - le 3-phényl pyrazolo[3,2-c]-1, 2, 4-triazole, - e 3-(2'-aminoéthyl) pyrazolo[3,2-c]-1, 2, 4-triazole, - le 3-(2'-hydroxyéthyl) pyrazolo[3,2-c]-1, 2, 4-triazole, - le 6-méthyl-3-éthyl pyrazolo[3,2-c]-1, 2, 4-triazole, - le 3, 6-diméthyl- pyrazolo [3, 2-c]-1, 2, 4-triazole, - le 6-méthyl-3-isopropyl-pyrazolo[3,2-c]-1, 2, 4-triazole, - le 6-méthyl-3-phényl-pyrazolo[3,2-c]-1, 2, 4-triazole, - le 6-méthyl-3- (2'-aminoéthyl)- pyrazolo [3, 2-c]-1, 2, 4-triazole, - le 6-méthyl-3- (2'hydroxyéthyl)- pyrazolo [3, 2-c]-1, 2, 4-triazole, - le 6-méthyl-3-méthylthio-pyrazolo [3, 2-c]-1, 2, 4-triazole, - le 6-phényl-3-méthyl-pyrazolo[3,2-c]-1, 2, 4-triazole, - le 6-phényl-3-éthyl-pyrazolo[3,2-c]-1, 2, 4-triazole, - le 6-phényl--3isopropyl-pyrazolo[3,2-c]-1, 2, 4-triazole, - le 6-phényl-3-phényl-pyrazolo[3,2-c]-1, 2, 4-triazole, - le 6-phényl-3-(2'-aminoéthyl)-pyrazolo[3,2-c]-1, 2, 4-triazole, - le 6-phényl-3- (2'-hydroxyéthyl)- pyrazolo [3, 2-c]-1, 2, 4-triazole, - le 6-phényl-3-méthylthio-pyrazolo [3, 2-c]-1, 2, 4-triazole, Among the compounds of formula (IIIb) above, mention may be made especially of: 3-methyl pyrazolo [3,2-c] -1,2,4-triazole,

-! e 3-methyl! su) finyi-6-pheny! -pyrazo! o [3,2-c] -1,2,4-triazole; 3-ethyl pyrazolo [3,2-c] -1,2,4-triazole-3-isopropyl pyrazolo [3,2- c] -1,2,4-triazole; 3-phenylpyrazolo [3,2-c] -1,2,4-triazole; e 3- (2'-aminoethyl) pyrazolo [3,2-c] ] -1,2,4-triazole; 3- (2'-hydroxyethyl) pyrazolo [3,2-c] -1,2,4-triazole; 6-methyl-3-ethyl pyrazolo [3]; 2-c] -1,2,4-triazole, 3,6-dimethyl-pyrazolo [3,2-c] -1,2,4-triazole, 6-methyl-3-isopropyl-pyrazolo [ 3,2-c] -1,2,4-triazole; 6-methyl-3-phenyl-pyrazolo [3,2-c] -1,2,4-triazole; 6-methyl-3- (2'-aminoethyl) -pyrazolo [3,2-c] -1,2,4-triazole, 6-methyl-3- (2-hydroxyethyl) -pyrazolo [3,2-c] -1,2 4-triazole, 6-methyl-3-methylthio-pyrazolo [3,2-c] -1,2,4-triazole, 6-phenyl-3-methyl-pyrazolo [3,2-c] -1,2,4-triazole, 6-phenyl-3-ethyl-pyrazolo [3,2-c] -1,2,4-triazole, 6-phenyl-3-isopropyl-pyrazolo [3,2] 1, 2, 4-triazole, 6-phenyl-3-phenyl-pyrazolo [3,2-c] -1,2,4-triazole, 6-phenyl-3- (2 ') -am inoethyl) -pyrazolo [3,2-c] -1,2,4-triazole, 6-phenyl-3- (2'-hydroxyethyl) -pyrazolo [3,2-c] -1,2,4 triazole, 6-phenyl-3-methylthio-pyrazolo [3,2-c] -1,2,4-triazole,

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- le 6-éthylthio-3-méthyl-pyrazolo [3, 2-c]-1, 2, 4-triazole, - le 6-éthylthio-3-éthyl-pyrazolo [3, 2-c]-1, 2, 4-triazole, - le 6-éthylthio-3-isopropyl-pyrazolo[3,2-c]-1, 2, 4-triazole, - le 6-éthylthio-3-phényl-pyrazolo [3, 2-c]-1, 2, 4-triazole, - le 6-éthylthio-3- (2'-aminoéthyl)- pyrazolo [3, 2-c]-1, 2, 4-triazole, - le 6-éthylthio-3- (2'-hydroxyéthyl)- pyrazolo [3, 2-c]-1, 2, 4-triazole, - le 6-trifluorométhyl-3-méthylthio-pyrazolo [3, 2-c]-1, 2, 4-triazole, - le 6-trifluorométhyl-pyrazolo [3, 2-c]-1, 2, 4-triazole, - le 6-carboxy-3-méthyl-pyrazolo[3,2-c]-1, 2, 4-triazole,

- le 6-carboxy-3-éthyl-pyrazolo [3, 2-c]-1, 2, 4-triazole, - le 6-carboxy-3-isopropyl-pyrazolo [3, 2-c]-1, 2, 4-triazole, - le 6-carboxy-3-phényl-pyrazolo [3, 2-c]-1, 2, 4-triazole, - le 6-carboxy-3- (2'amino-éthyl)- pyrazolo [3, 2-c]-1, 2, 4-triazole, - le 6-carboxy-3- (2'-hydroxyéthyl)- pyrazolo [3, 2-c]-1, 2, 4-triazole, - le 7-chloro-3, 6-diméthylpyrazolo[3, 2-c]-1, 2, 4-triazole, - le 7-méthoxycarbonyl-3,6-diméthylpyrazolo[3,2-c]-1, 2, 4-triazole, - le 3-phényl-6-hyroxyméthylpyrazolo[3,2-c]-1, 2, 4-triazole et leurs sels d'addition avec un acide.

6-ethylthio-3-methyl-pyrazolo [3,2-c] -1,2,4-triazole; 6-ethylthio-3-ethyl-pyrazolo [3,2-c] -1,2; 4-triazole, 6-ethylthio-3-isopropyl-pyrazolo [3,2-c] -1,2,4-triazole, 6-ethylthio-3-phenyl-pyrazolo [3,2-c] 1, 2, 4-triazole, 6-ethylthio-3- (2'-aminoethyl) -pyrazolo [3,2-c] -1,2,4-triazole, 6-ethylthio-3- (2) hydroxyethyl) pyrazolo [3,2-c] -1,2,4-triazole; 6-trifluoromethyl-3-methylthio-pyrazolo [3,2-c] -1,2,4-triazole; 6-trifluoromethyl-pyrazolo [3,2-c] -1,2,4-triazole; 6-carboxy-3-methyl-pyrazolo [3,2-c] -1,2,4-triazole;

6-carboxy-3-ethyl-pyrazolo [3,2-c] -1,2,4-triazole, 6-carboxy-3-isopropyl-pyrazolo [3,2-c] -1,2, 4-triazole, 6-carboxy-3-phenyl-pyrazolo [3,2-c] -1,2,4-triazole, 6-carboxy-3- (2'-amino-ethyl) -pyrazolo [3] , 2-c] -1,2,4-triazole; 6-carboxy-3- (2'-hydroxyethyl) -pyrazolo [3,2-c] -1,2,4-triazole; chloro-3,6-dimethylpyrazolo [3,2-c] -1,2,4-triazole; 7-methoxycarbonyl-3,6-dimethylpyrazolo [3,2-c] -1,2,4-triazole; 3-phenyl-6-hyroxymethylpyrazolo [3,2-c] -1,2,4-triazole and their addition salts with an acid.

- le pyrazolo [5, 1-e]-tétrazole, - le 6-méthyl pyrazolo [5, 1-e]-tétrazole, - le 6-phényl pyrazolo [5, 1-e]-tétrazole, - le 6-carboxy pyrazolo [5, 1-e]-tétrazole, - le 7-chloro-6-méthyl pyrazolo[5,1-e]-tétrazole, Examples of compounds of formula (IIIc) that may be mentioned in particular are those for which: R 6 denotes hydrogen, methyl, trifluoromethyl, carboxyl, phenyl, ethoxy or cyano - R 7 denotes hydrogen or chlorine;
Among the compounds of formula (IIIc) above, mention may be made in particular of:

pyrazolo [5,1-e] tetrazole, 6-methyl pyrazolo [5,1-e] tetrazole, 6-phenyl pyrazolo [5,1-e] tetrazole, 6-carboxy pyrazolo [5,1-e] tetrazole, 7-chloro-6-methyl pyrazolo [5,1-e] tetrazole,

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et leurs sels d'addition avec un acide Comme exemples de composés de formule ( ! lid), on peut citer en particulier ceux pour lesquels : - R6 désigne hydrogène, méthyle, trifluorométhyle, amino, carboxyle, phényle, éthoxy ou cyano ; - R7 désigne hydrogène ou chlore ; - R8 et R9 désignent respectivement hydrogène et hydrogène, hydrogène et méthyle, méthyle et hydrogène, hydrogène et amino, hydrogène et phényle ; R8 et R9 forment entre eux un cycle phényle.

Examples of compounds of the formula (1 lid) include, in particular, those for which: R 6 is hydrogen, methyl, trifluoromethyl, amino, carboxyl, phenyl, ethoxy or cyano; R7 denotes hydrogen or chlorine; R8 and R9 respectively denote hydrogen and hydrogen, hydrogen and methyl, methyl and hydrogen, hydrogen and amino, hydrogen and phenyl; R8 and R9 together form a phenyl ring.

Among the compounds of formula (tt! D) above, mention may be made especially of: pyrazolo [1,5-a] imidazole, 2-methyl-pyrazolo [1,5-a] imidazole, 2-phenyl-pyrazolo [1,5-a] imidazole, pyrazolo [1,5-a] benzimidazole, 6-methyl-pyrazolo [1,5-a] imidazole, 2,6-dimethyl- pyrazolo [1,5-a] imidazole; 6-methyl-2-phenyl-pyrazolo [1,5-a] imidazole; 6-methyl-pyrazolo [1,5-a] benzimidazole; phenyl-pyrazolo [1,5-a] imidazole, 6-phenyl-2-methyl-pyrazolo [1,5-a] imidazole, 2,6-diphenyl-pyrazolo [1,5-a] imidazole, 6-phenyl-pyrazolo [1,5-a] benzimidazole, 6-carboxy-pyrazolo [1,5-a] imidazole, 6-carboxy-2-methyl-pyrazolo [1,5-a] imidazole, 6-carboxy-2-phenyl-pyrazolo [1,5-a] imidazole, 6-carboxy-pyrazolo [1,5-a] benzimidazole, 6-ethoxy-pyrazolo [1-5] a] imidazole, 6-ethoxy-2-methyl-pyrazolo [1,5-a] imidazole, 6-ethoxy-2-phenyl-pyrazolo [1,5-a] imidazole,

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- le 6-trifluorométhyl-pyrazolo [1, 5-a] benzimidazole, - le 6-amino-pyrazolo [1, 5-a] imidazole, - le 6-amino-2-méthyl-pyrazolo [1, 5-a] imidazole, - le 6-amino-2-phényl-pyrazolo [1, 5-a] imidazole, - le 6-amino-pyrazolo [1, 5-a] benzimidazole, - le 6-éthylthio-pyrazolo [1, 5-a] imidazole, - le 6-éthylthio-2-méthyl-pyrazolo [1, 5-a] imidazole, - le 6-éthylthio-2-phényl-pyrazolo [1, 5-a] imidazole, - le 7-chloro-6-méthyl-pyrazolo [1, 5-a] imidazole, - le 7-chloro-6-méthyl-pyrazolo [1, 5-a] benzimidazole, et leurs sels d'addition avec un acide.

6-trifluoromethyl-pyrazolo [1,5-a] benzimidazole, 6-amino-pyrazolo [1,5-a] imidazole, 6-amino-2-methyl-pyrazolo [1,5-a] imidazole, 6-amino-2-phenyl-pyrazolo [1,5-a] imidazole, 6-amino-pyrazolo [1,5-a] benzimidazole, 6-ethylthio-pyrazolo [1-5] a] imidazole, 6-ethylthio-2-methyl-pyrazolo [1,5-a] imidazole, 6-ethylthio-2-phenyl-pyrazolo [1,5-a] imidazole, 7-chloro 6-methyl-pyrazolo [1,5-a] imidazole, 7-chloro-6-methyl-pyrazolo [1,5-a] benzimidazole, and their addition salts with an acid.

As examples of compounds of formula (III), there may be mentioned in particular those for which: R 6 denotes hydrogen, methyl, trifluoromethyl, carboxyl, phenyl, ethoxy or cyano; R7 denotes hydrogen or chlorine; R8 and R9 respectively denote hydrogen and methyl, methyl and hydrogen, methyl and methyl, hydrogen and phenyl.

Among the compounds of formula (III) above, mention may be made especially of: - 8-amino-4-methyl-pyrazolo [5,1-e] pyrazole, - 8-amino-5-chloro-4 methyl-pyrazolo [5,1-e] pyrazole, and their addition salts with an acid.

Examples of compounds of formula (IIhf) that may be mentioned in particular are those for which: R 6 denotes hydrogen, methyl, trifluoromethyl, carboxyl, phenyl, ethoxy or cyano; R7 denotes hydrogen or chlorine; - R8 denotes hydrogen or methyl.

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Among the compounds of formula (III) above, mention may be made especially of: 5-methylpyrazolo [5,1-e] -1,2,3-triazole; 5-methyl-6-chloro-pyrazolo [ 5, 1-e] -1,2,3-triazole, 5-phenylpyrazolo [5,1-e] -1,2,3-triazole, and their addition salts with an acid.

 The compounds of the present invention, their synthetic intermediates and their methods of preparation are described in the following patent applications and patents: FR 2,075,583, EP-A-119,860, EP-A-285,274, EP-A- 244,160, EP-A-578,248, GB 1,458,377, US 3,227,554, US 3,419,391, US 3,061,432, US 4,500,630, US 3,725,067, US 3,926,631, US 5,457,210, JP 84/99437, JP 83/42045, JP 84/162548, JP 84/171956, JP 85/33552, JP 85/43659, JP 85/172982, JP 85/190779, as well as in the following publications: Chem. Ber. 32,797 (1899), Chem. Ber. 89, 2550, (1956), J. Chem. Soc. Perkin trans 1, 2047, (1977), J. Prakt. Chem., 320, 533 (1978), J. fur Chem., 326 (5), 829, (1984).

pyrazolo [3, 2-c] 1, 2, 4-triazole, le 4, 6-diéthyl-2H-pyrazolo [3, 2-a] 1, 2, 4-triazole. According to a preferred embodiment, the coupler is 4, 6-dimethyl-2H-

pyrazolo [3,2-c] 1,2,4-triazole, 4,6-diethyl-2H-pyrazolo [3,2-a] 1,2,4-triazole.

 The pyrazolotriazole coupler (s) are preferably present in the triazole composition in an amount of between 0.0001 to 10% by weight approximately of the total weight of the dye composition and even more preferably from 0.005 to 6% by weight approximately of this weight.

comme le 2-butoxyéthanol, le propylèneglycol, le monométhyléther de propylèneglycol, le monoéthyléther et le monométhyléther du diéthylèneglycol, ainsi que les alcools aromatiques comme l'alcool benzylique ou le phénoxyéthanol, les produits analogues et leurs mélanges. The medium suitable for dyeing, also known as dyeing medium, generally consists of water or a mixture of water and at least one organic solvent for solubilizing compounds that are not sufficiently soluble in water. As an organic solvent, there may be mentioned, for example, C1-C4 lower alkanols, 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, the like and mixtures thereof.

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The solvents may be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.

The pH of the dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents usually used for dyeing 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.

dans laquelle W est un reste propylène éventuellement substitué par un groupement hydroxyle ou un radical alkyle en Ci-C4 ; R6, R7, R8 et Rg, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en Ci-C4 ou hydroxyalkyl en Ci-C4. Among the alkalinizing agents, mention may be made, for example, of ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula (IV):

wherein W is a propylene residue optionally substituted with a hydroxyl group or a C1-C4 alkyl radical; R6, R7, R8 and Rg, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.

 The composition according to the invention may contain, in addition to the pyrazolotriazole coupler, additional couplers conventionally used for dyeing keratinous fibers. Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers and heterocyclic couplers.

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A titre d'exemple, on peut citer le 2-méthyl 5-aminophéno !, ! e 5-N- ( (- hydroxyéthyl) amino 2-méthyl phénol, le le 6-chloro-2-méthyl--aminophénol, le 3-amino phénol, le 1, 3-dihydroxy benzène, le 1,3-dihydroxy 2-méthyl benzène, le 4-chloro 1,3dihydroxy benzène, le 2,4-diamino 1- (ss-hydroxyéthyloxy) benzène, le 2-amino 4- (ss- hydroxyéthylamino) 1-méthoxybenzène, le 1,3-diamino benzène, le 1, 3-bis- (2, 4diaminophénoxy) propane, la 3-uréido aniline, le 3-uréido 1-diméthylamino benzène, le

sésamol, le 1-ss-hydroxyéthylamino-3, 4-méthylènedioxybenzène, l'a-naphtol, le 2 méthyl-1-naphtol, le 6-hydroxy indole, le 4-hydroxy indole, le 4-hydroxy N-méthyl indole, la 2-amino-3-hydroxy pyridine, la 6-hydroxy benzomorpholine, la 3,5-diamino- 2, 6-diméthoxypyridine, le 1-N- (ss-hydroxyéthyl) amino-3, 4-méthylène dioxybenzène, le 2, 6-bis- (ss-hydroxyéthylamino) toluène et leurs sels d'addition.

By way of example, mention may be made of 2-methyl-5-aminophenol. 5-N- ((-hydroxyethyl) amino-2-methylphenol, 6-chloro-2-methyl-aminophenol, 3-amino phenol, 1,3-dihydroxybenzene, 1,3-dihydroxy 2 methyl benzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1- (ss-hydroxyethyloxy) benzene, 2-amino-4- (ss-hydroxyethylamino) -1-methoxybenzene, 1,3-diamino benzene , 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido-1-dimethylamino benzene,

sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy N-methylindole, 2-amino-3-hydroxy pyridine, 6-hydroxy benzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N- (ss-hydroxyethyl) amino-3,4-methylene dioxybenzene, , 6-bis (ss-hydroxyethylamino) toluene and their addition salts.

 When present, the additional coupler (s) 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 6% by weight approximately of this weight.

 The dyeing composition in accordance with the invention may also contain at least one additional oxidation base, and which may be chosen from oxidation bases conventionally used in oxidation dyeing, among which may especially be mentioned paraphenylenediamines, bis phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases other than the amino pyrazolo [1,5-a] pyridines of formula (1) used in accordance with the invention.

d'exemple, la paraphénylènediamine, la paratoluylènediamine, la 2-chloro paraphénylènediamine, la 2, 3-diméthyl paraphénylènediamine, la 2, 6-diméthyl paraphénylènediamine, la 2, 6-diéthyl paraphénylènediamine, la2, 5-dimethyl paraphénylènediamine, la N, N-diméthyl paraphénylènediamine, la N, N-diéthyl paraphénylènediamine, la N, N-dipropyl paraphénylènediamine, la 4-amino N, N-diéthyl 3-méthyl aniline, la N, N-bis- (ss-hydroxyéthyl) paraphénylènediamine, la4-N, N-bis- (sshydroxyéthyl) amino 2-méthyl aniline, la 4-N, N-bis- (j3-hydroxyéthyt) amino 2-chloro aniline, la 2-ss-hydroxyéthyl paraphénylènediamine, la 2-fluoro paraphénylènediamine, Among the para-phenylenediamines, mention may be made more particularly of

for example, paraphenylenediamine, paratoluylenediamine, 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 paraphenylenediamine, N, N-diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl-3-methylaniline, N, N-bis (ss-hydroxyethyl) paraphenylenediamine, la4 N, N-bis- (s-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- (3-hydroxyethyl) amino-2-chloroaniline, 2-ss-hydroxyethyl para-phenylenediamine, 2-fluoro-para-phenylenediamine,

<Desc / Clms Page number 22>

) a 2-isopropy) paraphényiènediamine,) a N- ( (3-hydroxypropyt) paraphénytènediamine, ! a 2-hydroxyméthyl Iparaphénylènediamine, la N, N-diméthyl 3-méthyl paraphénylènediamine, la N, N- (éthyl, ss-hydroxyéthyl) paraphénylènediamine, la N- (ss, ydihydroxypropyl) paraphénylènediamine, la N- (4'-aminophényl) paraphénylènediamine, la N-phényl paraphénylènediamine, la 2-ss-hydroxyéthyloxy paraphénylènediamine, la 2- ss-acétylaminoéthyloxy paraphénylènediamine, la N-(ss-méthoxyéthyl) paraphénylènediamine, la 4 aminophenyl pyrrolidine, le 2 thiényl paraphénylène dianine, le 2-ss hydroxyéthylamino 5-amino toluène et leurs sels d'addition avec un acide.

2-isopropyl) paraphenylenediamine) N- ((3-hydroxypropyl) paraphenylenediamine, 2-hydroxymethyl-1-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, ss-hydroxyethyl) paraphenylenediamine, N- (ss, ydihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-ss-hydroxyethyloxy para-phenylenediamine, 2-ss-acetylaminoethyloxy para-phenylenediamine, N- (ss methoxyethyl) paraphenylenediamine, 4 aminophenyl pyrrolidine, 2 thienyl paraphenylene dianine, 2-ss hydroxyethylamino 5-amino toluene and their addition salts with an acid.

particulièrement la paraphénylènediamine, la paratoluylènediamine, la 2-isopropyl paraphénylènediamine, la 2-ss-hydroxyéthyl paraphénylènediamine, la 2-ss-hydroxyéthyloxy paraphénylènediamine, la 2, 6-diméthyl paraphénylènediamine, la 2, 6-diéthyl paraphénylènediamine, la 2, 3-diméthyl paraphénylènediamine, la N, N-bis- (ss-hydroxyéthyl) paraphénylènediamine, la 2-chloro paraphénylènediamine, la 2-ss-acétylaminoéthyloxy paraphénylènediamine, et leurs sels d'addition avec un acide.

Of the paraphenylenediamines mentioned above, all

especially paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-ss-hydroxyethyl paraphenylenediamine, 2-ss-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,3-diethylenediamine, dimethyl paraphenylenediamine, N, N-bis (ss-hydroxyethyl) paraphenylenediamine, 2-chloro-para-phenylenediamine, 2-ss-acetylaminoethyloxy-para-phenylenediamine, and their addition salts with an acid.

Among the bis-phenylalkylenediamines, N, N'-bis- (p-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol may be mentioned more particularly by way of example; N, N'-bis- (p-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N. bis- (p-hydroxyethyl) N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) N N, N'-bis (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diamino phenoxy) -3,5-dioxaoctane, and their 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-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino

<Desc / Clms Page number 23>

2-aminométhyl phénol, le 4-amino 2- (p-hydroxyéthyt aminométhy)) phénot, te 4-amino 2-fluoro phénol, et leurs sels d'addition avec un acide.

2-aminomethyl phenol, 4-amino 2- (p-hydroxyethylaminomethyl) phenot, 4-amino-2-fluoro phenol, and their addition salts with an acid.

 Among the ortho-aminophenols, 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-amino phenol may be mentioned by way of example, and their addition salts with an acid.

 Among the heterocyclic bases, there may be mentioned more particularly by way of example, the pyridine derivatives different from the compounds of formula (1) in accordance with the invention, pyrimidine derivatives and pyrazole derivatives.

 Among the different pyridine derivatives of the compounds of formula (1) in accordance with the invention, mention may be made more particularly of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2- (4-methoxyphenyl) amino-3-amino pyridine, 2,3-diamino-6-methoxy pyridine, 2- (p-methoxyethyl) amino-3-amino-6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid.

2- (3-amino pyrazolo-[1, 5-a]-pyrimidin- 7-ylamino)-éthanol, le 2- (7-amino pyrazolo-[1, 5a]-pyrimidin-3-ylamino)-éthanol, le 2- [ (3-amino-pyrazolo [1, 5-a] pyrimidin-7-yl)- (2-hydroxy-éthyl)-amino ]-éthanol, le 2-[ (7-amino-pyrazolo[1, 5-a]pyrimidin-3-yl)- (2-hydroxy-éthyl)-amino]-éthanol, la 5, 6-diméthyl pyrazolo-[1, 5-a]-pyrimidine- 3, 7-diamine, la 2, 6-diméthyl pyrazolo-[1, 5-a]-pyrimidine-3, 7-diamine, la 2, 5, N 7, N 7tetraméthyl pyrazolo-[1, 5-a]-pyrimidine-3, 7-diamine, la 3-amino-5-méthyl-7- Among the pyrimidine derivatives, there may be mentioned more particularly the compounds described for example in DE 2,359,399; JP 88-169,571; JP 05 163 124; EP 0 770 375 or patent application WO 96/15765 such as 2,4,5,6tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6triaminopyrimidine 2,4 dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2750 048 and among which mention may be made of pyrazolo [1,5] -a] -pyrimidine-3, 7diamine; 2,5-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; pyrazolo [1,5-a] pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-amino pyrazolo [1,5-a] pyrimidin-7-ol; 3-amino pyrazolo [1,5-a] pyrimidin-5-ol; the

2- (3-Amino-pyrazolo [1,5-a] pyrimidin-7-ylamino) -ethanol, 2- (7-Amino-pyrazolo [1,5a] -pyrimidin-3-ylamino) -ethanol, 2- [(3-amino-pyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol, 2 - [(7-aminopyrazolo [1,5 a) pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol, 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine, 2, 6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5-N, 7-N-tetramethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 3-amino-5-methyl-7-

<Desc / Clms Page number 24>

 imidazolylpropylamino pyrazolo [1,5-a] pyrimidine and their addition salts with an acid and their tautomeric forms, when tautomeric equilibrium exists.

 Among the pyrazole derivatives, mention may be made more particularly of the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43. 988 such as 4,5-diamino-1-methyl pyrazol, 4,5-diamino 1- (p-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-phenylpyrazole, 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 pyrazol, 4,5-diamino 1- (p-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methyl-pyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-ethyl-3-hydroxymethyl-pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl-pyrazol, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole 4,5-diamino-3-methyl-1-isopropyl pyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethyl-pyrazole, 3,4,5-triamino-pyrazole, 1-methyl-3-yl , 4,5-triamino pyrazole, 3,5-diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino 4- (p-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts with a acid.

 When they are used, the additional oxidation base (s) preferably represent from 0.0001 to 10% by weight approximately of the total weight of the dye composition, and still more preferably from 0.005 to 6% by weight approximately of this weight. .

 In general, the addition salts with an acid that can be used in the context of the dyeing compositions of the invention (oxidation bases and couplers) are chosen in particular from hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, phosphates and acetates. The addition salts with a base which can be used in the context of the dyeing compositions of the invention are in particular those obtained with soda, potassium hydroxide, ammonia or amines.

<Desc / Clms Page number 25>

 The dye composition in accordance with the invention may also contain one or more direct dyes that may be chosen in particular from nitro dyes of the benzene series, cationic direct dyes, in particular azo or methine dyes.

 The dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or their mixtures, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.

 These compounds may be present in an amount of between 0.01 and 20% by weight of the total 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 oxidation dyeing composition according to the invention are not or not substantially impaired by the or the proposed additions.

 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 especially human hair.

 The invention also relates to a process for dyeing keratinous fibers and in particular human keratinous fibers such as the hair using the dye composition as defined above.

<Desc / Clms Page number 26>

 According to this method, at least one dye composition as defined above is applied to the fibers, the color being revealed using an oxidizing agent. The color can be revealed at acidic, neutral or alkaline pH and the oxidizing agent can be added just at the time of use to the dye composition or in an oxidizing composition applied simultaneously or sequentially.

 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 a composition containing, in a medium which is suitable for dyeing, at minus an oxidizing agent present in an amount sufficient to develop a coloration. The mixture obtained is then applied to the keratinous fibers. After a residence time of about 3 to 50 minutes, preferably about 5 to 30 minutes, the keratinous fibers are rinsed, washed with shampoo, rinsed again and then dried.

 The oxidizing agent may be chosen from the oxidizing agents conventionally used for the oxidation dyeing of keratin fibers, and among which mention may be made of hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as: Perborates and persulfates, peracids and enzymes among which we may mention peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred.

 The pH of the oxidizing composition containing the oxidizing agent is such that, after mixing with the dyeing composition, the pH of the resulting composition applied to the keratinous fibers preferably varies between 3 and 12 approximately, and even more preferably between 5 and 11. It can be adjusted to the desired value by means of acidifying or basifying agents usually used for dyeing keratin fibers and as defined above.

 The oxidizing composition as defined above may also contain various adjuvants conventionally used in compositions for dyeing hair and as defined above.

<Desc / Clms Page number 27>

 The composition which is finally applied to the keratinous fibers may be in various forms, such as in the form of liquids, creams, gels, or in any other form that is suitable for dyeing keratinous fibers, and in particular human hair. .

 Another object of the invention is a multi-compartment device or "kit" of dyeing in which a first compartment contains the dye composition defined above and a second compartment contains the oxidizing composition. This device may be equipped with means for delivering the desired mixture to the hair, such as the devices described in patent FR-2 586 913 in the name of the applicant.

 The invention finally relates to the colored product obtainable by reaction of a base of formula (1) as defined above and a coupler of formula (III) as defined above. This colored product can be used in cosmetics for example make-up.

 The following examples are intended to illustrate the invention.

On prépare la composition tinctoriale suivante :

EXAMPLES OF DYEING Example 1. Staining at basic pH

The following dye composition is prepared:

<Tb>
<tb> Pyrazolo [1,5-a] pyridin-3-ylaminomonochlorhydrate <SEP> 0. <SEP> 508 <SEP> g
<tb> 4, <SEP> 6-dimethyl-2H-pyrazolo <SEP> [3, <SEP> 2-c] <SEP> [1, <SEP> 2, <SEP> 4] triazole <SEP> 0, <SEP> 408 <SEP> g
<tb> Alcohol <SEP> Benzyl <SEP> 2g
<tb> Polyethylene <SEP> Glycol <SEP> 8 <SEP> OE <SEP> 3 <SEP> g
<tb> Ethanol <SEP> 18g
<tb> Alkyl <SEP> (C8-C10) <SEP> polyglucoside <SEP> in <SEP> solution <SEP> aqueous <SEP> to <SEP> 60% <SEP> of <SEP> material <SEP> 5 <SEP> g <SEP> in <SEP> state
SEP <SEQ ID><SEQID><SEQID><SEP> by <SEP><SEP> Ammonium <SEP><SEP><SEP><SEP><SEP>
<tb> denomination <SEP> ORAMIX <SEP> CG110 <SEP> by <SEP> SEPPIC
<tb> Ammonia <SEP> to <SEP> 20% <SEP> of <SEP> NH310g
<tb> Metabisulfite <SEP> of <SEP> sodium <SEP> 0, <SEP> 205 <SEP> g
<tb> Sequestering <SEP> q. <SEP> s.
<Tb>

Demineralized water <SEP> q. <SEP> s. <SEP> p. <SEP> 100 <SEP> g
<Tb>

<Desc / Clms Page number 28>

The coloring composition is mixed, weight for weight, at the time of use with hydrogen peroxide at 20 V. The mixture is applied to gray hair with 90% white, permed or not, at 10g for 1g hair. After 30 min. laying, the hair is rinsed, washed with a standard shampoo, rinsed and dried. The hair is colored with a slightly coppery golden reflection.

Example 2. Staining at pH = 7
The following dye composition is prepared:

<Tb>
<tb> Pyrazolo [1,5-a] pyridin-3-ylaminomonochlorhydrate <SEP> 0. <SEP> 0,508 <SEP> g
<tb> 4,6-dimethyl-2H-pyrazolo [3,2-c] [1,2,4] triazole <SEP> 0.408 <SEP> g
<tb> Alcohol <SEP> Benzyl <SEP> 2g
<tb> Polyethylene <SEP> glycol <SEP> 8 <SEP> OE <SEP> 3 <SEP> 9
<tb> Ethanol <SEP> 18 <SEP> g
<tb> Alkyl <SEP> (C8-C10) <SEP> polyglucoside <SEP> in <SEP> solution <SEP> aqueous <SEP> to <SEP> 60% <SEP> of <SEP> material <SEP> 5 <SEP> g <SEP> in <SEP> state
SEP <SEQ ID><SEQID><SEQID><SEP> by <SEP><SEP> Ammonium <SEP><SEP><SEP><SEP><SEP>
<tb> denomination <SEP> ORAMIX <SEP> CG110 <SEP> by <SEP> SEPPIC
<tb> Buffer <SEP> phosphate <SEP> (K2HP04 <SEP> 1. <SEP> 5M / KH2PO4 <SEP> 1M) <SEP> 10
<tb> Metabisulfite <SEP> of <SEP> sodium <SEP> 0, <SEP> 205 <SEP> g
<tb> Sequestering <SEP> q. <SEP> s.
<Tb>

Demineralized water <SEP> q. <SEP> s. <SEP> p. <SEP> 100 <SEP> g
<Tb>

After mixing with the oxidizing agent and application to the locks according to the procedure of Example 1, the hair is tinted with a slightly coppery golden reflection.

EXAMPLE 3 Staining at pH 7 with the O2 / Laccase Revelation System The following dye composition is prepared:

<Tb>
<tb> hydroxyethyl <SEP> cellulose <SEP> (PM <SEP>: <SEP> 1 <SEP> 300 <SEP> 000) <SEP> 1, <SEP> 5 <SEP> g
<tb> carboxymethyl <SEP> chitosan <SEP> 2 <SEP> g
<tb> monooleate <SEP> of <SEP> polyglycerol <SEP> 1 <SEP> g
<tb> N-acetyl-L-cysteine <SEP> 0, <SEP> 05 <SEP> g
<tb> Agent <SEP> of <SEP> pH <SEP> q. <SEP> s. <SEP> p. <SEP> pH <SEP> 7
<tb> Pyrazolo <SEP> [1, <SEP> 5-a] <SEP> pyridin-3-ylamine <SEP> monochlorhydrate <SEP> 0.509 <SEP> g
<tb> 4, <SEP> 6-dimethyl-2H-pyrazolo [3, <SEP> 2-c] [1, <SEP> 2, <SEP> 4] <SEP> triazole0, <SEP> 408
<tb> laccase <SEP> 5g
<tb> water <SEP> distilled <SEP> ee <SEP> q. <SEP> s. <SEP> p. <SEP> 100g
<Tb>

<Desc / Clms Page number 29>

This mixture is applied to natural gray hair that is 90% white.

After 30 minutes, the hair is rinsed, washed with shampoo, rinsed again and dried. The hair is dyed with a golden reflection.

Claims (18)

 in which: R 1, R 2, R 3, R 4 and R 5, which may be identical or different, represent a hydrogen or halogen atom; a radical-NHSO3H; a hydroxyl radical; an alkyl radical; an alkoxy radical; an alkylthio radical; an amino radical; a monoalkylamino radical; a dialkylamino radical in which the two alkyl groups can form together with the nitrogen atom to which they are attached a ring which can be interrupted by one or more nitrogen, oxygen or sulfur atoms; a heterocycle; a nitro radical; an aryl radical; a C1-C4 acyl radical; a (C 1 -C 4) alkoxycarbonyl radical; a carboxamido radical; a cyano radical; a radical-CO2H, a radical-SO3H; a radical -PO3H2; a radical-PO4H2; or a group of formula (II) below:

 1. A composition for the oxidation dyeing of keratinous fibers, characterized in that it comprises, in a medium suitable for dyeing, as oxidation base at least one 3-amino pyrazolo- [1, 5 -a] - pyridine of formula (1) and / or one of its addition salts with an acid or with a base: <Desc / Clms Page number 31>  chain, it can be connected to the carbon atom of the ring via an oxygen atom, nitrogen or sulfur; a sulfonyl radical; a sulfinyl radical; a phosphonyl radical; R7 represents a hydrogen atom; a halogen atom; an acetylamido group; an alkoxy radical; an aryloxy radical; an acyloxy radical; an arylthio radical; an alkylthio radical; a heteroarylthio radical; a heteroaryloxy radical; a thiocyano radical; an N, N-diethylthiocarbonylthio radical; a dodecyl-oxythio-carbonylthio radical; a benzenesulphonamido radical; an N-ethyltoluene sulfonamido radical; a p-cyanophenylureido radical, an N, N-diethylsulfamoylamino radical; a pyrazolyl radical; an imidazolyl radical; a triazolyl radical; a tetrazolyl radical; a benzimidazolyl radical; a 1-benzyl 5-ethoxy-3-hydantoinyl radical; a 1-benzyl-3-hydantoinyl radical; a 5,5-dimethyl 2,4-dioxo-3-oxazolidinyl radical; a 2oxy 1,2-dihydro-1-pyridinyl radical; a 1-alkylamido radical; an arylamido radical; a radical NRaRb with Ra and Rb representing, identical or different, an alkyl, a hydroxyalkyl, a carboxyl, or an alkoxycarboxylic radical,

 wherein: - R6 represents a hydrogen atom; a halogen atom; an alkyl radical, an aryl radical; a 5- or 6-membered heterocycle having at least one nitrogen, oxygen or sulfur atom, when R 6 denotes an alkyl radical, an aryl radical or a 5- or 6-membered heterocycle

 wherein X and R are independently oxygen, NH or N-alkyl, and Y is hydroxyl, amino, alkyl, alkoxy, alkylamino, or dialkylamino, and a pyrazolotriazole coupler of formula (here): <Desc / Clms Page number 32>  - Za, Zb, represent, independently of one another, a nitrogen atom, a carbon atom carrying a radical R8 or R9 having the same meanings as those indicated for the radical R6; R8 and R9 may also form between them a substituted or unsubstituted aromatic ring; provided that at least one of the radicals Za, Zb and Ze is different from a carbon atom.  2. Composition according to claim 1, characterized in that the compounds of formula (1) are chosen from compounds of formula (Ia) below, and

 their addition salts with an acid or with a base:

 in which: R 1, R 2, R 3, which may be identical or different, represent a hydrogen or halogen atom; a radical-NHS03H; a hydroxyl radical; an alkyl radical; an alkoxy radical; an alkylthio radical; an amino radical, a monoalkylamin radical; a dialkylamino radical in which the two alkyl groups may, together with the nitrogen atom to which they are bonded, form a ring which may be interrupted by one or more nitrogen, oxygen or sulfur atoms; a heterocycle; an acyl radical; an alkoxycarbonyl radical; a carboxamido radical; or a group of formula (II) below

<Desc / Clms Page number 33>  wherein X and R are, independently of one another, an oxygen atom, an NH or N (C 1 -C 4) alkyl group, and Y represents a hydroxyl, amino, alkyl, alkoxy, alkylamino or dialkylamin radical.

3. Composition according to claim 1 or 2 wherein the 3-amino pyrazolo [1,5-a] pyridines of formula (1) are chosen from: - pyrazolo [1,5-a] pyridin-3-ylamine ; 2-acetylamino-pyrazolo [1,5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 3-amino-pyrazolo [1,5-a] pyridin-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-a] pyridin-3-ylamino; (3-Amino-pyrazolo [1,5-a] pyridin-7-yl) -methanol-2- (3-aminopyrazolo [1,5-a] pyridin-5-yl) -ethanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-7-yl) -ethanol; (3-amino-pyrazolo [1,5-a] pyridin-2-yl) -methanol; 3,6-diamino-pyrazolo [1,5-a] pyridine; 3,4-diamino-pyrazolo [1,5-a] pyridine; pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; pyrazolo [1,5-a] pyridine-3,5-diamine; 5-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; -! e 2 - [(3-amino-pyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) -am! no] -ethano); 2- [(3-amino-pyrazolo [1,5-a] pyridin-7-yl) - (2-hydroxyethyl) amino] ethanol; 3-amino-pyrazolo [1,5-a] pyridine-5-ot; 3-amino-pyrazolo [1,5-a] pyridin-4-ol - 3-amino-pyrazolo [1,5-a] pyridin-6-ol; 3-amino-pyrazolo [1,5-a] pyridin-7-ol; and their addition with an acid or with a base. 4. Composition according to any one of the preceding claims, characterized in that the or 3-amino pyrazolo [1, 5-a] -pyridines of formula (1) and / or <Desc / Clms Page number 34>  the or their addition salts with an acid or a base represent from 0.0001 to 10% by weight of the total weight of the dyeing composition.  5. Composition according to any one of claims 1 to 4 wherein the coupler of formula (here) is such that R6 represents a hydrogen atom; an alkyl; phenyl; a phenyl substituted with a halogen atom, an alkyl, an alkoxy, a nitro group, an amino group, a trifluoromethyl group or an alkylamino group; a benzyl radical; a benzyl radical substituted with a halogen atom, an alkyl, an alkoxy, a nitro group, an amino group, a trifluoromethyl group; an alkylamin; a heterocycle selected from thiophene, furan or pyridine; a trifluoromethyl radical; a radical (CH 2) pX- (CH 2) q -OR 'where p and q are integers, identical or different, between 1 and 3, R' represents H or methyl and X denotes an oxygen atom or a group NR " with R "denoting hydrogen or methyl; a hydroxyalkyl; an aminoalkyl; an alkylamin; a dialkylamino; an arylamino; an alkoxy radical selected from methoxy, ethoxy and phenoxy; a halogen selected from fluorine, chlorine and bromine; a carboxyl group; an alkoxycarbonyl; phenyloxycarbonyl; methylthio; ethylthio; phenylthio; methanesulfonyl; cyano.  6. Composition according to any one of claims 1 to 5 wherein the coupler of formula (here) is such that R6 represents hydrogen; an alkyl selected from methyl, ethyl, isopropyl, tert-butyl; a halogen selected from fluorine and chlorine; phenyl; toluyle; 4-chlorophenyl; 4-methoxyphenyl; 3-methoxyphenyl; 2-methoxyphenyl; benzyl; a heterocycle selected from pyridyl, furyl or thienyl; trifluoromethyl; hydroxymethyl; aminomethyl; methoxy or ethoxy; methylamino or ethylamino or dimethylamino; carboxyl; methoxycarbonyl or ethoxycarbonyl; cyano.  7. Composition according to any one of claims 1 to 6 wherein the coupler of formula (here) is such that R6 represents hydrogen; methyl; ethyl; phenyl; toluyle; 4-chlorophenyl; 4-methoxyphenyl; benzyl; trifluoromethyl; chloro; a methoxy or ethoxy radical; a carboxyl radical; methylamino or dimethylamino; cyano. <Desc / Clms Page number 35>

8. Composition according to any one of claims 1 to 7 wherein the coupler of formula (here) is such that R7 represents a hydrogen atom; an alkoxy; phenoxy; phenoxy substituted with a halogen atom, an alkyl, a carboxyl, a trifluoromethyl group; an acyloxy radical; benzyloxy; alkylthio; phenylthio; phenylthio substituted with halogen, alkyl, carboxyl, trifluoromethyl; an alkylamido; phenylamido; a radical NRaRb with Ra and Rb representing, identical or different, an alkyl, a hydroxyalkyl; a carboxyl; an alkoxycarboxylic radical.  9. Composition according to any one of claims 1 to 8 wherein the coupler of formula (here) is such that R7 represents hydrogen; chlorine or bromine; methoxy or ethoxy; phenyloxy; 4-methylphenyloxy; acyloxy; benzyloxy;

 methylthio or ethylthio; phenylthio; 4-methylphenylthio; 2-tert-butylphenylthio; acetamido; phenylacetamido; dimethylamino; diethylamino; ethyl-methylamino; (ss-hydroxyethyl) methylamino.  10. Composition according to any one of claims 1 to 9 wherein the coupler of formula (III), (IV) or (V) is chosen from: i) pyrazolo [1,5-b] 1,2, 4-triazoles of formula:

 ii) pyrazolo [3,2-c] 1,2,4-triazoles of formula: <Desc / Clms Page number 36>

 iii) pyrazolotetrazoles of formula:

 iv) pyrazolo [1,5-a] imidazoles of formula:

 v) pyrazolo [5,1-e] pyrazoles of formula:

<Desc / Clms Page number 37>

 vi) pyrazolo [5,1-e] -1,2,3-triazoles of formula:

 in which R6, R7, Rs and Rg are as defined in claims 1 to 9.

 11. Composition according to any one of the preceding claims, characterized in that the coupler (s) of formula (hot) are present in an amount of between 0.0001 to 10% by weight approximately of the total weight of the dyeing composition.  12. Composition according to any one of the preceding claims,

 further comprising at least one additional oxidation base selected from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases other than 3-amino pyrazol- [1,5-a] -pyridines of formula (1) as defined in claim 1.  13. Composition according to any one of the preceding claims, further comprising one or more additional couplers chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers and heterocyclic couplers. <Desc / Clms Page number 38>  indole, 6-hydroxy benzomorpho! ine,! e 1-N- (3-hydroxyethyl) amino-3,4-methyl dioxybenzene, 2,6-bis (ss-hydroxyethylamino) toluene and their addition salts.

 14. Composition according to Claim 9, characterized in that the additional couplers are chosen from 2-methyl-5-aminophenol, 5-N- (ss-hydroxyethyl) amino-2-methylphenol and 6-chloro-2-methyl. 5-aminophenol, 3-amino phenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1- (S- hydroxyethyloxy) benzene, 2-amino-4- (ss-hydroxyethylamino) -1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol, 1-ss-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxy indole, 4-hydroxy N-methyl  15. Process for the oxidation dyeing of keratin fibers, characterized in that at least one dye composition as defined in any one of Claims 1 to 14 is applied to the fibers, and the color in color is revealed. presence of an oxidizing agent.  16. The method of claim 15, characterized in that the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids, and enzymes.  17. A multi-compartment device comprising a first compartment which contains a dye composition as defined in any one of claims 1 to 14 and a second compartment which contains a composition containing an oxidizing agent.  18. Colored product obtainable by reaction of an oxidation base of formula (1) and a coupler of formula (III) from the composition according to any one of claims 1 to 14.