FR2857664A1 - New thiazole derivatives and their addition salts used as couplers in hair dye compositions - Google Patents

Abstract

New thiazole derivatives and their addition salts with an acid or a base. The thiazole derivatives are of formula (I). [Image] R1, R2H, phenyl optionally substituted with one or more of halogen or hydroxy or 1-4C alkoxy, carboxy, mono- or dialkyl(1-4C)carboxamido or 1-4C thioether or alkyl(1- 4C)sulfonyl or sulfonic or alkylsulfoxide, alkylsulfonamido or NR13R14 or 1-4C alkyl optionally substituted with one or more hydroxy or 1-4C alkoxy or carboxy or mono- or dialkyl(1-4C)carboxamido or alkyl(1-4C)sulfonyl or sulfonic or alkylsulfoxide or alkylsulfonamido or NR13R14, 1-8C alkyl optionally substituted with one or more hydroxy or 1-2C alkoxy or carboxy or mono- or dialkyl(1-4C)carboxamido or alkyl(1- 4C)sulfonyl or sulfonic or alkylsulfoxide or alkylsulfonamido or NR13R14, together with the nitrogen to which they are attached a 5-8 link heterocycle not comprising a peroxide nor diazo nor nitroso radical of which one or more carbon atoms of the carbon cycle can be replaced by O or N or S or SO2 or substituted with R4; R4halogen, 1-4C alkyl optionally substituted with one or more hydroxy or carboxy or 1-4C alkoxycarbonyl or 1-4C alkoxy or NR5R6, carboxy, mono- or dialkyl(1-4C)carboxamido, alkyl(1-4C)sulfonyl, alkylsulfonamido, hydroxy, 1-4C alkoxy, 2-4C hydroxyalkoxy, aminosulfonyl, 1-4C thioether, alkyl(1-4C)sulfoxide, alkyl(1-4C)sulfonyl, NR7R8; R3R9SO2NH-, R10C(O)NH- ; R9, R10phenyl or 5-6 link aromatic heterocycle optionally substituted with one or more of halogen or hydroxy or 1-4C alkoxy or carboxy or 1-4C alkoxycarbonyl or mono- or dialkyl(1-4C)carboxamido or alkyl(1-4C)sulfonyl or sulfonic or alkyl(1-4C)sulfoxide or 1-4C thioether or alkylsulfonamido or NR11R12 or 1-4C alkyl optionally substituted with one or more hydroxy or 1-4C alkoxy or carboxy or mono- or dialkyl(1-4C)carboxamido or alkyl(1-4C)sulfonyl or sulfonic or alkyl(1-4C)sulfoxide or alkylsulfonamido or NR13R14, 1-8C alkyl optionally substituted with one or more hydroxy or OR15 or carboxy or 1-4C alkoxycarbonyl or mono- or dialkyl(1-4C)carboxamido or alkyl(1-4C)sulfonyl or alkyl(1- 4C)sulfoxide or alkylsulfonamido or NR16R17; R5-R17H, alkyl(1-4C)sulfonyl, alkyl(1-4C)-CO, mono- or dialkylcarboxamido, 1-4C alkyl optionally substituted with one or more hydroxy or 1-4C alkoxy or alkyl(1-4C)sulfonyl or alkyl(1-4C)sulfonamido or carboxy or mono- or dialkylcarboxamido or alkyl(1-4C)sulfoxide or amino or (di)(1-4C)alkylamino or 2-4C (poly)hydroxyalkylamino; and X : H, halogen, 1-4C alkoxy, phenoxy optionally substituted by one or more halogen or hydroxy or 1-4C alkoxy or carboxy or 1-4C alkoxycarbonyl or mono- or dialkyl(1-4C)carboxamido or alkyl(1-4C)sulfonyl or sulfonic or alkylsulfoxide or 1-4C thioether or alkylsulfonamido or NR13R14, 1-4C alkyl, 1-4C thioether optionally substituted with hydroxy or 1-2C alkoxy or carboxy or sulfonic or amino. R7 and R8 may form, together with the nitrogen to which they are attached a 5-8 link heterocycle optionally substituted with one or more halogen, hydroxy, 1-2C alkoxy, alkylsulfonamido, NR13R14, 1-4C alkyl optionally substituted with one or more hydroxy or 1-4C alkoxy or carboxy or mono- or dialkyl(1-4C)carboxamido or NR13R14. Independent claims are included for: (1) a composition for dyeing keratinic fibers comprising, in a medium appropriate for dyeing, one or more oxidation bases and the claimed thiazole derivative; (2) a method of oxidation dyeing of keratinic fibers comprising application of the claimed composition in the presence of an oxidant agent for sufficient time to achieve the desired color; and (3) a device with several compartments, one containing the claimed composition and another and oxidant composition.

Description

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NOVEL THIAZOLE DERIVATIVES AND USE OF THESE DERIVATIVES FOR
STAINING OF KERATIN FIBERS
The invention relates to novel thiazole derivatives useful as couplers for the oxidation dyeing of keratinous fibers.

 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 pyrazolo [1,5-a] pyrimidine derivatives, pyrimidine derivatives, pyridine derivatives, 5,6-dihydroxyindole derivatives, 5,6-dihydroxyindoline derivatives generally referred to as oxidation bases. The precursors of oxidation dyes or oxidation bases are colorless or weakly colored compounds which, combined with oxidizing products, can give rise, by a process of oxidative condensation, to colored and coloring compounds.

 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 meta-phenylenediamines, meta-aminophenols, meta-hydroxyphenols and certain heterocyclic compounds such as, for example, pyrazolo [1,5-b] -1,2,4, -triazole derivatives, pyrazolo [3,2-c] -1,2,4, -triazole derivatives, derivatives thereof; pyrazolo [1,5-a] pyrimidines, pyridine derivatives, pyrazol-5-one derivatives, indoline derivatives and indole derivatives.

 The variety of molecules involved in the oxidation bases and couplers allows a rich palette of colors to be obtained.

 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).

 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. They must also have good chemical stability in the formulations. They must have a good toxicological profile.

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 The object of the present invention is to provide novel couplers which make it possible to obtain an even more varied range of shades as well as tinctorial compositions which have powerful, uniform dyes between the root and the tip of the hair, having a good chromaticity, little selective and particularly resistant, while being able to generate intense colorations in various shades, especially in the fundamental shades.

dans laquelle : # R1, R2 représentent, identiques ou différents, - un atome d'hydrogène ; - un radical phényle éventuellement substitué par un ou plusieurs radicaux choisis parmi les halogènes, les radicaux hydroxy, alcoxy en C1-C4, carboxy,

mono ou di alkyl(CrC4)carboxamido (AlkNHCO- ou (Alk)2NCO), thioéther en CiC4, alkyl(CrC4)sulfonyle (-S02alkyle), sulfonique (-S03H), alkylsulfoxyde (-SOalkyle), alkylsulfonamido (alkyl(Ci-C4)SO2NH-), N13Rl4, alkyle en C-C4 éventuellement substitué parmi un ou plusieurs hydroxy, alcoxy en C1-C4, carboxy, mono ou di alkyl(Ci-C4)carboxamido, alkyl(Ci-C4)Sulfonyle, sulfonique, alkylsulfoxyde, alkylsulfonamido ou NR13R14 ; - un radical alkyle en C1-C8 linéaire ou ramifié, éventuellement substitué par un

ou plusieurs radicaux hydroxy, alcoxy en Croc2, carboxy, mono ou di alkyl(Cr C4)carboxamido, alkyl(C,-C4)sulfonyle, sulfonique, alkylsulfoxyde, alkylsulfonamido ou NR13R14, - R1 et R2 peuvent former avec l'atome d'azote avec lequel ils sont attachés un hétérocycle comportant 5 à 8 chaînons dont un ou plusieurs atomes de carbone du cycle carboné peuvent être remplacés par un atome d'oxygène, d'azote, de soufre ou par un groupement S02, les atomes de carbone du cycle pouvant être This object is achieved with the present invention which relates to a thiazole derivative of formula (I) below as well as its addition salts with an acid or a base:

in which: # R1, R2 represent, identical or different, - a hydrogen atom; a phenyl radical optionally substituted with one or more radicals chosen from halogens, hydroxyl, C 1 -C 4 alkoxy and carboxy radicals,

mono or di (C 1 -C 4) alkylcarboxamido (AlkNHCO- or (Alk) 2NCO), C 1 -C 4 thioether, C 1 -C 4 alkyl (C 1 -C 4) sulfonyl (-SO 2 alkyl), sulfonic (-SO 3 H), alkylsulfoxide (-SOalkyl), alkylsulfonamido (C 1 -C 4 alkyl); C4) SO2NH-), N13R14, C1-C4alkyl optionally substituted with one or more hydroxy, C1-C4alkoxy, carboxy, mono or di (C1-C4) alkylcarboxamido, (C1-C4) alkylsulfonyl, sulphonic, alkylsulfoxide, alkylsulfonamido or NR13R14; a linear or branched C1-C8 alkyl radical, optionally substituted by a

or more than one hydroxyl, Croc2 alkoxy, carboxy, mono or di (C4) alkyl carboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkylsulfoxide, alkylsulphonamido or NR13R14 radicals, R1 and R2 may form with the atom nitrogen with which they are attached a 5- to 8-membered heterocyclic ring of which one or more carbon atoms of the carbon cycle may be replaced by an oxygen, nitrogen, sulfur atom or by a group SO 2, the carbon atoms of the cycle that can be

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radicaux hydroxy, carboxy, alcoxycarbonyle en Ci-C4, alcoxy en Cl-C4, ou NR5R6 ; - un radical carboxy ;

- un radical mono ou di alkyl(Ci-C4)carboxamido ; - un radical alkyl(C1-C4)sulfonyle ; un radical alkylsulfonamido ; - un radical hydroxy ; - un radical alcoxy en C1-C4 ; - un radical hydroxyalcoxy en C2-C4 ; - un radical aminosulfonyle ; - un radical thioéther en C1-C4 ;

- un radical alkyl(CrC4)sulfoxyde ; - un radical alkyl(C1-C4)sulfonyle ; - un radical NR7Ra ;

#R3 représente un radical R9SO2NH- ou un radical R10C(O)NH- avec Rg et R10 identiques ou différents représentant : - un radical phényle ou un hétérocycle aromatique à 5 ou 6 chaînons, ces radicaux étant éventuellement substitués par un ou plusieurs radicaux choisis parmi les halogènes, les radicaux hydroxy, alcoxy en C1-C4, carboxy,

alcoxycarbonyle en Ci-C4, mono ou di alkyl(C-C4)carboxamido, alkyl(Cr C4)sulfonyle, sulfonique, alkyl(C1-C4)sulfoxyde, thioéther en C1-C4, alkylsulfonamido, NR11R12, alkyle en C1-C4 éventuellement substitué par un ou plusieurs hydroxy, alcoxy en Ci-C4, carboxy, mono ou di alkyl(C1-

C4)carboxamido, alkyl(CrC4)sulfonyle, sulfonique, alkylsulfoxyde, alkylsulfonamido ou NRi3Ri4 - un radical alkyle en Ci-Ce linéaire ou ramifié, éventuellement substitué par un ou plusieurs radicaux hydroxy, OR,5, carboxy, alcoxycarbonyle en C1-C4, mono substituted with an R4 radical and the ring having no peroxide bond, or diazo or nitroso radicals; R4 represents: a halogen atom; a C1-C4 alkyl radical optionally substituted with one or more

hydroxy, carboxy, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkoxy, or NR 5 R 6 radicals; a carboxy radical;

a mono- or di (C 1 -C 4) alkylcarboxamido radical; a (C1-C4) alkylsulphonyl radical; an alkylsulphonamido radical; a hydroxyl radical; a C1-C4 alkoxy radical; a C2-C4 hydroxyalkoxy radical; an aminosulphonyl radical; a C1-C4 thioether radical;

an alkyl (CrC4) sulphoxide radical; a (C1-C4) alkylsulphonyl radical; an NR7Ra radical;

# R3 represents a radical R9SO2NH- or a radical R10C (O) NH- with Rg and R10 identical or different representing: - a phenyl radical or a 5- or 6-membered aromatic heterocycle, these radicals being optionally substituted by one or more radicals chosen among the halogens, hydroxy, C 1 -C 4 alkoxy and carboxy radicals,

C1-C4 alkoxycarbonyl, mono- or di- (C1-C4) alkyl carboxamido, (C1-C4) alkylsulphonyl, sulphonic, (C1-C4) alkylsulfoxide, C1-C4 thioether, alkylsulphonamido, NR11R12, optionally substituted C1-C4 alkyl substituted with one or more hydroxy, C1-C4 alkoxy, carboxy, mono or di (C1-

C4) carboxamido, (C1-C4) alkylsulphonyl, sulphonic acid, alkylsulphoxide, alkylsulphonamido or NRi3R14 - a linear or branched C1-C6 alkyl radical, optionally substituted by one or more hydroxyl, OR, 5, carboxy or C1-C4 alkoxycarbonyl radicals, mono

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ou di alkyl(Cl-C4)carboxamido, alkyl(C1-C4)sulfonyle, sulfonique, alkyl(C1- C4)sulfoxyde, alkylsulfonamido ou NR16R17 ; avec R,5 qui représente un radical alkyle en C1-C4 éventuellement substitué par un ou plusieurs radicaux choisis parmi les radicaux hydroxy, alcoxy en C1-C2,

amino, (di)(Cl-C4)alkylamino, (poly)hydroxyalkylamino en C2-C4 ; - R5, R6, R7, R8e R11, R12, Ris. R,4, R16 et R17 représentent, identiques ou différents, un atome d'hydrogène, un radical alkyl(Ci-C4)sulfonyle, alkyl(Cl-C4)-CO, un radical mono ou di alkyl(CrC4)carboxamido, un radical alkyle en C1-C4 éventuellement substitué par un ou plusieurs hydroxy, alcoxy en Ci-C4, alkyl(Ci-C4)Sulfonyle, alkyl(C,C4)sulfonamido, carboxy, mono ou di alkyl(C-C4)carboxamido, alkyl(C,-C4)sulfoxyde, amino, (di)(Cl-C4)alkylamino, (poly)hydroxyalkylamino en C2-C4 ; - R7 et R8 peuvent également former avec l'atome d'azote qui les porte un cycle de 5 à 8 chaînons éventuellement substitué par un ou plusieurs radicaux choisis parmi les halogènes, les radicaux hydroxy, alcoxy en C1-C2, carboxy, alkylsulfonamido, N13R14, alkyle en C1-C4 éventuellement substitué par un ou plusieurs hydroxy, alcoxy en C1-C4,

carboxy, mono ou di alkyl(C-C4)carboxamido ou NR13R14 ; # X représente un atome d'hydrogène ; un atome d'halogène (tel que fluor, chlore, brome) ; un radical alcoxy en C1-C4 ; un radical phénoxy éventuellement substitué par un ou plusieurs radicaux choisis parmi les halogènes, les radicaux hydroxy, alcoxy en

Croc4, carboxy, alcoxycarbonyle en Ci-C4, mono ou di alkyl(C1-C4)carboxamido, alkyl(CrC4)sulfonyle, sulfonique, alkylsulfoxyde, thioéther en C1-C4, alkylsulfonamido, N13R14, alkyle en C1-C4 ; un radical thioéther en C1-C4 éventuellement substitué par un hydroxy, alcoxy en C1-C2, carboxy, sulfonique, amino.

or di (C1-C4) alkyl carboxamido, (C1-C4) alkylsulfonyl, sulfonic, (C1-C4) alkylsulfoxide, alkylsulfonamido or NR16R17; with R 5, which represents a C 1 -C 4 alkyl radical optionally substituted with one or more radicals chosen from hydroxyl and C 1 -C 2 alkoxy radicals,

amino, (di) (C1-C4) alkylamino, (poly) hydroxyalkylamino C2-C4; - R5, R6, R7, R8e R11, R12, Ris. R, 4, R 16 and R 17 represent, identical or different, a hydrogen atom, a (C 1 -C 4) alkylsulphonyl radical, a (C 1 -C 4) alkyl -CO radical, a mono or di (C 1 -C 4) carboxamido radical, a C1-C4 alkyl radical optionally substituted by one or more hydroxy, C1-C4 alkoxy, (C1-C4) alkylsulfonyl, (C1-C4) alkylsulphonamido, carboxy, mono or di (C1-C4) alkyl carboxamido, alkyl (C 1 -C 4) sulfoxide, amino, (di) (C 1 -C 4) alkylamino, (poly) hydroxyalkylamino C 2 -C 4; R 7 and R 8 may also form, with the nitrogen atom carrying them, a 5 to 8-membered ring optionally substituted with one or more radicals chosen from halogens, hydroxyl, C 1 -C 2 alkoxy, carboxy and alkylsulphonamido radicals, N13R14, C1-C4 alkyl optionally substituted with one or more hydroxy, C1-C4 alkoxy,

carboxy, mono or di (C -C) alkyl carboxamido or NR13R14; # X represents a hydrogen atom; a halogen atom (such as fluorine, chlorine, bromine); a C1-C4 alkoxy radical; a phenoxy radical optionally substituted by one or more radicals chosen from halogens, hydroxyl radicals, alkoxy radicals,

Croc4, carboxy, C1-C4 alkoxycarbonyl, mono- or di (C1-C4) alkyl carboxamido, (C1-C4) alkylsulfonyl, sulfonic, alkylsulfoxide, C1-C4thioether, alkylsulfonamido, N13R14, C1-C4alkyl; a C1-C4 thioether radical optionally substituted with a hydroxy, C1-C2 alkoxy, carboxy, sulfonic or amino.

 The present invention also relates to a dye composition comprising, in a medium suitable for dyeing, - at least one oxidation base - and at least, as a coupler, a thiazole derivative of formula (I) as defined above .

 The invention also relates to dyeing processes using this composition.

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 Another subject of the invention is the use of derivatives of formula (I) for the oxidation dyeing of keratinous fibers, in particular human keratinous fibers such as the hair.

The thiazole derivatives of formulas (I) of the invention are not only suitable for use as a coupler for the oxidation dyeing of keratinous fibers, but also they lead to particularly powerful and low-selective colorations. They also make it possible to obtain dyeing compositions that lead to colorations that are well resistant to the various attacks that the hair can undergo, such as light, bad weather, washing, perspiration. The oxidation dyeing compositions according to the invention also make it possible to achieve shades in a very wide range of colors.
In the radicals defined above bearing alkyl group and unless otherwise indicated, the alkyl radical may be linear or branched, and optionally substituted by a hydroxy, alkoxy or carboxy. In addition, when the molecule contains several radicals of the same denomination, for example NR13R14, these radicals may be identical or different.

 By way of example, mention may be made, for the radicals R 1 and R 2 of formula (I), of hydrogen, a methyl, ethyl, (iso) propyl, 2-hydroxyethyl, 1-hydroxyethyl or 2-carboxyethyl radical. aminoethyl, 2- (dimethylamino) ethyl, 2- (acylamino) ethyl, 2-methoxyethyl, 1,2-dihydroxyethyl, 1-hydroxy-2-aminoethyl, 2-hydroxy-1-aminoethyl, acetyl, or phenyl.

parmi les halogènes, les radicaux hydroxy, alcoxy en Ci-C4, carboxy, alkyl(C- C4) carboxamido, alkyl(C1-C4)sulfonyle, sulfonique, alkylsulfoxyde, thioéther en C1-C4, alkylsulfonamido, N13R14, alkyle en C1-C4 éventuellement substitué parmi un ou

plusieurs hydroxy, alcoxy en Ci-C4, carboxy, alkyl(C-C4)carboxa, alkyl(CrC4)sulfonyle, sulfonique, alkylsulfoxyde, alkylsulfonamido ou NR13R14 ; - un radical alkyle en Ci-Ce linéaire ou ramifié, éventuellement substitué par un ou

plusieurs radicaux hydroxy, alcoxy en C1-C2, carboxy , , alkyl(Ci-C4)carboxamido , alkyl(CrC4)sulfonyle, sulfonique , alkylsulfoxyde , alkylsulfonamido, ou NR13R14
Selon un mode de réalisation préférée, R1 et R2 représentent identiques ou différents, un atome d'hydrogène ; un radical phényle ; un radical alkyle en C1-C4, According to a particular embodiment, R1 and R2, identical or different, represent - a hydrogen atom; a phenyl radical optionally substituted with one or more chosen radicals

among the halogens, hydroxy, C 1 -C 4 alkoxy, carboxy, C 1 -C 4 alkylcarboxamido, C 1 -C 4 alkylsulphonyl, sulfonic, alkylsulphoxide, C 1 -C 4 thioether, alkylsulphonamido, N13R14, C 1 -C 4 alkyl radicals; C4 optionally substituted from one or

several hydroxy, C1-C4 alkoxy, carboxy, (C1-C4) alkyl carboxa, (C1-C4) alkylsulfonyl, sulfonic, alkylsulfoxide, alkylsulfonamido or NR13R14; a linear or branched Ci-Ce alkyl radical, optionally substituted with one or

several hydroxy, C1-C2 alkoxy, carboxy, (C1-C4) alkyl carboxamido, alkyl (CrC4) sulphonyl, sulphonic, alkyl sulphoxide, alkyl sulphonamido, or NR13R14 radicals
According to a preferred embodiment, R1 and R2 represent identical or different, a hydrogen atom; a phenyl radical; a C1-C4 alkyl radical,

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alcoxy en Croc2, amino, di(Cl-C4)alkylamino , carboxy, alkyl(C-C4)carboxamido , alkyl(Ci-C4)sulfonamido , NR13R14 où R13 et R14 représentent, identiques ou différents, un atome d'hydrogène, alkyl(CrC4)-CO, un radical alkyle en C1-C2 éventuellement substitué par un hydroxy ou un alcoxy en C1-C2. linear or branched, optionally substituted by one or more hydroxyl radicals,

Croc2 alkoxy, amino, di (C1-C4) alkylamino, carboxy, (C1-C4) alkyl carboxamido, (C1-C4) alkylsulphonamido, NR13R14 wherein R13 and R14 are, identical or different, hydrogen, alkyl (CrC4) -CO, a C1-C2 alkyl radical optionally substituted by a hydroxy or a C1-C2 alkoxy.

 Preferably, R1 and R2 represent, identical or different, a hydrogen atom, an optionally substituted alkyl radical, for example methyl, 2-hydroxyethyl, 2-carboxyethyl or 1,2-dihydroxyethyl, phenyl.

 According to another embodiment, R1 and R2 form, with the nitrogen atom with which they are attached, a 5- to 8-membered heterocycle chosen from pyrrolidine, piperidine, homopiperidine, piperazine and homopiperazine, said cycles being able to be substituted by a or more radicals R4.

 By way of example of this particular embodiment, R 1 and R 2 together with the nitrogen atom to which they are attached form a heterocycle chosen from pyrrolidine, 2,5-dimethylpyrrolidine, proline, 3-hydroxyproline, 4hydroxyproline, 2,4-dicarboxypyrrolidine, 3-hydroxy-2-hydroxymethylpyrrolidine, 2-carboxamidopyrrolidine, 3-hydroxy-2-carboxamidopyrrolidine, 2- (diethylcarboxamido) pyrrolidine, 2-hydroxymethyl pyrrolidine, 3, 4-dihydroxy-2-hydroxymethyl pyrrolidine, 3-hydroxypyrrolidine, 3,4-dihydroxy pyrrolidine, 3-amino pyrrolidine, 3-methylamino pyrrolidine, 4-amino-3-hydroxy pyrrolidine, 3-hydroxy-4- (2-hydroxyethyl) amino-pyrrolidine, piperidine, 2,6-dimethylpiperidine, 2-carboxypiperidine, 2-carboxamidopiperidine, 2-hydroxymethylpiperidine, 3-hydroxy-2-hydroxymethylpiperidine, 3-hydroxypiperidine, 4-hydroxypiperidine, 3-hydroxymethylpiperidine, homopiperidine, 2-carboxyhomopip ridine, the 2carboxamidohomopipéridine, homopiperazine, N-methyl homopiperazine, N sshydroxyéthylhomopipérazine and their addition salts.

la N (3-hydroxyéthylhomopipérazine et leurs sels d'addition. Preferably, R1 and R2 together with the nitrogen atom to which they are attached form a heterocycle selected from pyrrolidine, 3-hydroxypyrrolidine, 3aminopyrrolidine, proline, 3-hydroxyproline, piperidine, 3-hydroxypiperidine, 4-hydroxypiperidine homopiperidine, homopiperazine, N-methyl homopiperazine,

N (3-hydroxyethylhomopiperazine and their addition salts.

 By way of example, mention may be made, for R 3, of the radicals R 9 SO 2 NH- or a radical R 10 C (O) NH- with R 8 and R 10, which may be identical or different, chosen from a methyl, methyl, ethyl, (iso) propyl, 2-hydroxyethyl, hydroxyethyl, 2-carboxyethyl, 2 aminoethyl, 2- (dimethylamino) ethyl, 2- (acylamino) ethyl, 2-methoxyethyl, phenyl,

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 4-aminophenyl, 4-hydroxyphenyl, 4-diethylaminophenyl, pyrazolyl, thiazolyl, pyridyl or thienyl.

 According to a particular embodiment, when R 3 is an aromatic heterocycle, it is preferably chosen from pyridyl, pyrimidinyl, pyrazolyl, thiazolyl, furyl, imidazolyl and thienyl heterocycles.

un radical R10C(O)NH- ; avec Rg et Rio, identiques ou différents, représentant - un radical phényle ou un hétérocycle aromatique à 5 ou 6 chaînons tel que pyridyle, pyrimidinyle, pyrazolyle, thiazolyle, furyle, imidazolyle, thiènyle, ces radicaux étant éventuellement substitués par un ou plusieurs radicaux choisis parmi les halogènes, les radicaux hydroxy, alcoxy en Ci-C4, carboxy, mono ou di

alkyl(C,-C4)carboxamido, NR11R12, alkyle en C1-C4 éventuellement substitué par un ou plusieurs radicaux hydroxy, alcoxy en C1-C4, carboxy, mono ou di alkyl(Cr C4) carboxamido, ou NR13R14 - un radical alkyle en C1-C8 linéaire ou ramifié, substitué par un ou plusieurs radicaux choisis parmi les radicaux hydroxy, alcoxy en C1-C2, carboxy, mono ou

di alkyl(C,-C4)carboxamido, alkyl(CrC4)sulfonyle, sulfonique, alkyl(C1- C4)sulfoxyde, alkylsulfonamido ou NR16R17 ; - R11, R12, R13, R14, R16 et R17 représentent, identiques ou différents, un atome d'hydrogène, acyle, un carboxamido, un radical alkyle en C1-C4 éventuellement substitué par un ou plusieurs radicaux hydroxy, alcoxy en Ci-C4, alkyl(C1C4)sulfonyle, alkyl(C1-C4)sulfonamido, carboxy, mono ou di alkyl(C1-

C4)carboxamido, alkyl(C1-C4)sulfoxyde, amino, (di)(C,-C4)alkylamino, (poly)hydroxyalkylamino en C2-C4 . According to a preferred embodiment, R3 represents a radical R9SO2NH-,

a radical R10C (O) NH-; with Rg and Rio, identical or different, representing - a phenyl radical or a 5- or 6-membered aromatic heterocycle such as pyridyl, pyrimidinyl, pyrazolyl, thiazolyl, furyl, imidazolyl, thienyl, these radicals being optionally substituted by one or more radicals chosen among the halogens, hydroxy, C 1 -C 4 alkoxy, carboxy, mono or di

alkyl (C 1 -C 4) carboxamido, NR 11 R 12, C 1 -C 4 alkyl optionally substituted with one or more hydroxyl, C 1 -C 4 alkoxy, carboxy, mono or di (C 4 -C 4) carboxamido, or NR 13 R 14 - alkyl radicals; C1-C8 linear or branched, substituted with one or more radicals selected from hydroxyl, C1-C2 alkoxy, carboxy, mono or

di (C 1 -C 4) alkylcarboxamido, (C 1 -C 4) alkylsulphonyl, sulphonic, (C 1 -C 4) alkylsulfoxide, alkylsulphonamido or NR16R17; - R11, R12, R13, R14, R16 and R17 represent, identical or different, a hydrogen atom, acyl, a carboxamido, a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C4 alkoxy radicals; , (C1-C4) alkylsulfonyl, (C1-C4) alkylsulfonamido, carboxy, mono or di (C1-

C4) carboxamido, (C1-C4) alkylsulfoxide, amino, (di) (C1-C4) alkylamino, (poly) hydroxyalkylamino C2-C4.

 According to a particular embodiment, R3 represents a radical R9SO2NH- or a radical R10C (O) NH- with R9 and R10 identical or different selected from an alkyl radical, a phenyl radical, a pyrazolyl radical, a thiazolyl radical, a pyridyl radical; or a thienyl radical, these radicals being preferably substituted, R10 represents a methyl, ethyl, 2-hydroxyethyl, 2-carboxymethyl, phenyl, pyrazolyl, thienyl or pyridyl radical and R8 represents a methyl, phenyl or toluyl radical.

 In formula (I) above, X preferably represents a hydrogen atom, a chlorine atom or an alkoxy radical, for example methoxy.

 Among the derivatives of formula (1) in accordance with the invention, mention may be made of the following compounds:

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5-(2-hydroxyéthyl)amino-2-pyridylsulfonylaminothiazole 5-(2-hydroxyéthyl)amino-2-phénacylaminothiazole 5-(2-hydroxyéthyl)amino-2-(pyrid-2-yl)acylaminothiazole 5-(2-hydroxyéthyl)amino-2-(pyrid-3-yl)acylaminothiazole 5-(2-hydroxyéthyl)amino-2-(pyrid-4-yl)acylaminothiazole 5-amino-2-methylsulfonylaminothiazole 5-amino-2-phenylsulfonylaminothiazole 5-amino-2-tolylsulfonylaminothiazole 5-amino-2-thiazolylsulfonylaminothiazole 5-amino-2-pyridylsulfonylaminothiazole 5-amino-2-phenacylaminothiazole 5-amino-2- (pyridin 2-yl) acylaminothiazole 5-amino-2- (pyrid-3-yl) acylaminothiazole 5-amino-2- (pyrid-4-yl) acylaminothiazole 5-amino-2-acetylaminothiazole 5-amino-2-isopropylacylaminothiazole 5- amino-2- (thien-2-yl) acylaminothiazole 5-methylamino-2-methylsulfonylaminothiazole 5-methylamino-2-phenylsulfonylaminothiazole 5-methylamino-2-tolylsulfonylaminothiazole 5-methylamino-2-thiazolylsulfonylaminothiazole 5-methylamino-2-pyridylsulfonylaminothiazole 5-methylamino 2-phenacylaminothiazole 5-methylamino-2- (pyrid-2-yl) acylaminothiazole 5-methylamino-2- (pyrid-3-yl) acylaminothiazole 5-methylamino-2- (pyrid-4-yl) acylaminothiazole 5-methylamino 2-acetylaminothiazole 5-methylamino-2-isopropylacylaminothiazole 5-methylamino-2- (thien-2-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-2-methylsulfonylaminothiazole 5- (2-hydroxyethyl) amino-2-phenylsulfonylaminothiazole 5- (2-hydroxyethyl) amino-2-tolylsulfonylaminothiazole 5- (2-hydroxyethyl) amino-2-thiazolylsulfonylaminothiazole

5- (2-hydroxyethyl) amino-2-pyridylsulfonylaminothiazole 5- (2-hydroxyethyl) amino-2-phenacylaminothiazole 5- (2-hydroxyethyl) amino-2- (pyrid-2-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-2- (pyrid-3-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-2- (pyrid-4-yl) acylaminothiazole

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 5- (2-hydroxyethyl) amino-2-acetylaminothiazole 5- (2-hydroxyethyl) amino-2-isopropylacylaminothiazole 5- (2-hydroxyethyl) amino-2- (thien-2-yl) acylaminothiazole 5-amino-4-chloro 2-methylsulfonylaminothiazole 5-amino-4-chloro-2-phenylsulfonylaminothiazole 5-amino-4-chloro-2-tolylsulfonylaminothiazole 5-amino-4-chloro-2-thiazolylsulfonylaminothiazole 5-amino-4-chloro-2-pyridylsulfonylaminothiazole 5- 4-amino-4-chloro-2-phenacylaminothiazole 5-amino-4-chloro-2- (pyrid-2-yl) acylaminothiazole 5-amino-4-chloro-2- (pyrid-3-yl) acylaminothiazole 5-amino-4 2-chloro-2- (pyrid-4-yl) acylaminothiazole 5-amino-4-chloro-2-acetylaminothiazole 5-amino-4-chloro-2-isopropylacylaminothiazole 5-amino-4-chloro-2- (thien-2-yl) yl) acylaminothiazole 5-methylamino-4-chloro-2-methylsulfonylaminothiazole 5-methylamino-4-chloro-2-phenylsulfonylaminothiazole 5-methylamino-4-chloro-2-tolylsulfonylaminothiazole 5-methylamino-4-chloro-2-thiazolylsulfonylaminothiazole 5-methylamino -4-chloro-2-pyridylsulfonylaminothiaz 5-Methylamino-4-chloro-2-phenacylaminothiazole 5-methylamino-4-chloro-2- (pyrid-2-yl) acylaminothiazole 5-methylamino-4-chloro-2- (pyrid-3-yl) acylaminothiazole 5- Methylamino-4-chloro-2- (pyrid-4-yl) acylaminothiazole 5-methylamino-4-chloro-2-acetylaminothiazole 5-methylamino-4-chloro-2-isopropylacylaminothiazole 5-methylamino-4-chloro-2- (thienate) -2-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2-methylsulfonylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2-phenylsulfonylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro -2-toluylsulfonylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2-thiazolylsulfonylaminothiazole

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5-(pyrrolidin-1 -yl)-2-(pyrid-3-yl)acylaminothiazole 5-(pyrrolidin-1-yl)-2-(pyrid-4-yl)acylaminothiazole 5-(pyrrolidin-1-yl)-2-acétylaminothiazole 5-(pyrrolidin-1-yl)-2-isopropylacylaminothiazole 5-(pyrrolidin-1-yl)-2-(thién-2-yl)acylaminothiazole 5-(pyrrolidin-1-yl)-4-chloro-2-méthylsulfonylaminothiazole

5-(pyrrolidin-1-yl)-4-chloro-2-phénylsulfonylaminothiazole 5-(pyrrolidin-1-yl)-4-chloro-2-toluylsulfonylaminothiazole 5-(pyrrolidin-1-yl)-4-chloro-2-thiazolylesulfonylaminothiazole 5-(pyrrolidin-1-yl)-4-chloro-2-pyridylsulfonylaminothiazole 5-(pyrrolidin-1-yl)-4-chloro-2-phénacylaminothiazole 5-(pyrrolidin-1 -yl)-4-chloro-2-(pyrid-2-yl)acylaminothiazole 5-(pyrrolidin-1-yl)-4-chloro-2-(pyrid-3-yl)acylaminothiazole 5-(pyrrolidin-1-yl)-4-chloro-2-(pyrid-4-yl)acylaminothiazole 5-(pyrrolidin-1-yl)-4-chloro-2-acétylaminothiazole 5-(pyrrolidin-1 -yl)-4-chloro-2-isopropylacylaminothiazole 5-(pyrrolidin-1 -yl)-4-chloro-2-(thién-2-yl)acylaminothiazole ainsi que leurs sels d'addition avec un acide ou une base. 5- (2-hydroxyethyl) amino-4-chloro-2-pyridylsulfonylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2-phenacylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2- (pyridin) 2-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2- (pyrid-3-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2- (pyrid-4-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2-acetylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2-isopropylacylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2-thienate -2-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -2-methylsulfonylaminothiazole 5- (pyrrolidin-1-yl) -2-phenylsulfonylaminothiazole 5- (pyrrolidin-1-yl) -2-tolylsulfonylaminothiazole 5- (pyrrolidin-1-yl) -2-yl) 1-yl) -2-thiazolylsulfonylaminothiazole 5- (pyrrolidin-1-yl) -2-pyridylsulfonylaminothiazole 5- (pyrrolidin-1-yl) -2-phenacylaminothiazole 5- (pyrrolidin-1-yl) -2- (pyrid-2) yl) acylaminothiazole

5- (pyrrolidin-1-yl) -2- (pyrid-3-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -2- (pyrid-4-yl) acylaminothiazole 5- (pyrrolidin-1-yl) - 2-acetylaminothiazole 5- (pyrrolidin-1-yl) -2-isopropylacylaminothiazole 5- (pyrrolidin-1-yl) -2- (thien-2-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro 2-méthylsulfonylaminothiazole

5- (pyrrolidin-1-yl) -4-chloro-2-phenylsulfonylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2-tolylsulfonylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2- thiazolylsulfonylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2-pyridylsulfonylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2-phenacylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2 - (Pyrid-2-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2- (pyrid-3-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2- ( pyrid-4-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2-acetylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2-isopropylacylaminothiazole 5- (pyrrolidin-1-yl) 4-chloro-2- (thien-2-yl) acylaminothiazole and their addition salts with an acid or a base.

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dans laquelle R3 est tel que défini précédemment. According to a particular embodiment, the thiazole derivative corresponds to formula (Ib)

wherein R3 is as defined above.

 A more particularly preferred derivative of formula (I) of the invention is 5- (pyrrolidin-1-yl) -2- (thien-2-yl) acylaminothiazole and its addition salts.

 Another subject of the invention is a dye composition comprising, in a suitable medium, at least one oxidation base and as coupler at least one thiazole derivative of formula (1).

 The composition of the present invention is particularly useful for the oxidation dyeing of keratinous fibers, in particular of human keratinous fibers.

 The oxidation bases that can be used in the composition of the present invention are the oxidation bases conventionally used in oxidation dyeing. By way of example, these oxidation bases are chosen from oxidation bases, for example para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts with an acid or a base.

hydroxyéthyl) paraphénylènediamine, la N,N-bis-(p-hydroxyéthyl) 2-méthyl paraphénylènediamine, la N,N-bis-(3-hydroxyéthyl) 2-chloro paraphénylènediamine, la 2-p-hydroxyéthyl paraphénylènediamine, la 2-fluoro paraphénylènediamine,

la 2-isopropyl paraphénylènediamine, la N-(-hydroxypropyl) paraphénylènediamine, la 2-hydroxyméthyl paraphénylènediamine, la N,N-diméthyl 3-méthyl paraphénylènediamine, la N-(éthyl)-N-(j3-hydroxyéthyl) paraphénylènediamine, la N- (p,7-dihydroxypropyl) paraphénylènediamine, la N-(4'-aminophényl) Among the para-phenylenediamines, there may be mentioned, by way of example, para-phenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl paraphenylenediamine, 5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N-dipropyl-para-phenylenediamine, N, N-diethyl-3-methyl-para-phenylenediamine, N, N-bis (ss)

hydroxyethyl) paraphenylenediamine, N, N-bis- (p-hydroxyethyl) 2-methyl-para-phenylenediamine, N, N-bis- (3-hydroxyethyl) -2-chloro-para-phenylenediamine, 2-p-hydroxyethyl-para-phenylenediamine, 2-fluoro phenylenediamine,

2-isopropyl paraphenylenediamine, N - (- hydroxypropyl) paraphenylenediamine, 2-hydroxymethyl paraphenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N- (ethyl) -N- (3-hydroxyethyl) para-phenylenediamine, N - (p, 7-dihydroxypropyl) para-phenylenediamine, N- (4'-aminophenyl)

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 paraphenylenediamine, N-phenyl paraphenylenediamine, 2-p-hydroxyethyloxy para-phenylenediamine, 2-p-acetylaminoethyloxy para-phenylenediamine, N- (p-methoxyethyl) paraphenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl paraphenylenediamine, 2- hydroxyethylamino 5-amino toluene and their addition salts with an acid or a base.

la 2,3-diméthyl paraphénylènediamine, la N,N-bis-((3-hydroxyéthyl} paraphénylènediamine, la 2-chloro paraphénylènediamine, la 2-p-acétylaminoéthyloxy paraphénylènediamine, et leurs sels d'addition avec un acide ou une base sont particulièrement préférées. Of the paraphenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-p-hydroxyethyl paraphenylenediamine, 2-p-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl phenylenediamine,

2,3-dimethyl paraphenylenediamine, N, N-bis - ((3-hydroxyethyl) paraphenylenediamine, 2-chloro-para-phenylenediamine, 2-p-acetylaminoethyloxy-para-phenylenediamine, and their addition salts with an acid or a base are particularly preferred.

aminophényl) tétraméthylènediamine, la N,N'-bis-((3-hydroxyéthyl) N,N'-bis-(4- aminophényl) tétraméthylènediamine, la N,N'-bis-(4-méthyl-aminophényl) tétraméthylènediamine, la N,N'-bis-(éthyl) N,N'-bis- (4'-amino, 3'-méthylphényl) éthylènediamine, le 1,8-bis-(2,5-diamino phénoxy)-3,6-dioxaoctane, et leurs sels d'addition avec un acide ou une base. Among the bis-phenylalkylenediamines, mention may be made, by way of example, of N, N'-bis- (p-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, N N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-

aminophenyl) tetramethylenediamine, N, N'-bis - ((3-hydroxyethyl) N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) N, N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diamino phenoxy) -3,6- dioxaoctane, and their addition salts with an acid or a base.

amino 2-(p-hydroxyéthyl aminométhyl) phénol, le 4-amino 2-fluoro phénol, et leurs sels d'addition avec un acide ou une base. Among the para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro-phenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methyl, may be mentioned by way of example; phenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-

amino 2- (p-hydroxyethylaminomethyl) phenol, 4-amino-2-fluoro phenol, and their addition salts with an acid or a base.

 Among the ortho-aminophenols, mention may be made, for example, of 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and their addition salts with an acid or a base.

 Among the heterocyclic bases that may be mentioned by way of example are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

 Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino

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 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, and their addition salts with an acid or a base.

[1,5-a]-pyrimidin-7-ol ; le 3-amino pyrazolo-[1,5-a]-pyrimidin-5-ol ; le 2-(3-amino pyrazolo-[1,5-a]-pyrimidin-7-ylamino)-éthanol, le 2-(7-amino pyrazolo-[1,5-a]-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 7-tetraméthyl pyrazolo-[1,5-a]pyrimidine-3,7-diamine, la 3-amino-5-méthyl-7-imidazolylpropylamino pyrazolo-[1,5-a]pyrimidine et leurs sels d'addition avec un acide et leurs formes tautomères, lorsqu'il existe un équilibre tautomérique. Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in DE 2 359 399; 88-169,571; 05 163 124; 0 770 375 or patent application WO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in the patent application FR-A-2,750,048 and among which mention may be made of pyrazolone [1,5-a] -pyrimidine-3,7-diamine; 2,5-Dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; pyrazolo [1,5-a] pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-amino pyrazolo

[1,5-a] pyrimidin-7-ol; 3-amino pyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-amino pyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol, 2- (7-amino pyrazolo [1,5-a] pyrimidin-3-ylamino) - ethanol, 2 - [(3-amino-pyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol, 2 - [(7-amino-pyrazolo [1 , 5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol, 5,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5-N, 7-N-7-tetramethylpyrazolo [1,5-a] pyrimidine-3,7- diamine, 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo [1,5-a] pyrimidine and their addition salts with an acid and their tautomeric forms, when tautomeric equilibrium exists.

pyrazole, le 4,5-diamino 1-(P-hydroxyéthyl) pyrazole, le 3,4-diamino pyrazole, le 4,5- diamino 1-(4'-chlorobenzyl) pyrazole, le 4,5-diamino 1,3-diméthyl pyrazole, le 4,5-diamino 3-méthyl 1-phényl pyrazole, le 4,5-diamino 1-méthyl 3-phényl pyrazole, le 4-amino 1,3-diméthyl 5-hydrazino pyrazole, le 1-benzyl 4,5-diamino 3-méthyl pyrazole, le 4,5-diamino 3-tert-butyl 1-méthyl pyrazole, le 4,5-diamino 1-tert-butyl 3-méthyl

pyrazole, le 4,5-diamino 1-{a-hydroxyéthyl) 3-méthyl pyrazole, le 4,5-diamino 1-éthyl 3- méthyl pyrazole, le 4,5-diamino 1-éthyl 3-(4'-méthoxyphényl) pyrazole, le 4,5-diamino 1-éthyl 3-hydroxyméthyl pyrazole, le 4,5-diamino 3-hydroxyméthyl 1-méthyl pyrazole, le 4,5-diamino 3-hydroxyméthyl 1-isopropyl pyrazole, le 4,5-diamino 3-méthyl 1-isopropyl pyrazole, le 4-amino 5-(2'-aminoéthyl)amino 1,3-diméthyl pyrazole, le 3,4,5-triamino pyrazole, le 1-méthyl 3,4,5-triamino pyrazole, le 3,5-diamino 1-méthyl 4-méthylamino Among the pyrazole derivatives, mention may be made 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 as 4,5-diamino-1-methyl

pyrazole, 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-phenyl pyrazole, 4,5-diamino-1-methyl-3-phenyl pyrazole, 4-amino-1,3-dimethyl-5-hydrazino pyrazole, 1-benzyl 4,5-diamino-3-methyl pyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methyl

pyrazole, 4,5-diamino-1- (α-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole, diamino 3-methyl-1-isopropyl pyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl-3,4,5-triamino pyrazole, 3,5-diamino-1-methyl-4-methylamino

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pyrazole, le 3,5-diamino 4-(p-hydroxyéthyl)amino 1-méthyl pyrazole, et leurs sels d'addition avec un acide ou une base.

pyrazole, 3,5-diamino 4- (p-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts with an acid or a base.

 The oxidation base (s) are in general each present in an amount of between 0.001 to 10% by weight approximately of the total weight of the dye composition, preferably between 0.005 and 6%.

 The composition according to the invention may contain one or more additional couplers conventionally used for dyeing keratinous fibers. Among these additional couplers, mention may in particular be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers other than the thiazole derivatives of formula (I) of the invention and their addition salts with an acid. or a base.

dihydroxy benzène, le 2,4-diamino 1-(g-hydroxyéthyloxy) benzène, le 2-amino 4-(R<- 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-f3-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-(ft-hydroxyéthyl)amino-3,4-méthylène dioxybenzène, le 2,6-bis-(f3-hydroxyéthylamino)toluène et leurs sels d'addition avec un acide ou une base. By way of example, mention may be made of 2-methyl-5-aminophenol, 5-N- (s-hydroxyethyl) amino-2-methylphenol, 6-chloro-2-methyl-5-aminophenol and 3-amino phenol. 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-

dihydroxybenzene, 2,4-diamino 1- (g-hydroxyethyloxy) benzene, 2-amino-4- (R <-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-hydroxybenzomorpholine, 3,5-diamino-

2,6-dimethoxypyridine, 1-N- (β-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- (β-hydroxyethylamino) toluene and their addition salts with an acid or a base .

 In the composition of the present invention, the coupler or couplers are each generally present in an amount of between 0.001 and 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6%.

 In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.

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

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 methine. These direct dyes may be nonionic, anionic or cationic in nature.

 The appropriate medium for dyeing also called dyeing medium is generally constituted by water or a mixture of water and at least one organic solvent to solubilize the derivatives that are not sufficiently soluble in water. As organic solvent, there may be mentioned for example lower alkanols C1-C4, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

 The solvents are preferably 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 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.

 The adjuvants above are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the composition.

 Of course, one skilled in the art will take care to choose this or these optional additional compounds such that the advantageous properties intrinsically attached to the oxidation dyeing composition according to the invention are not, or not substantially impaired by the addition or additions envisaged.

 The pH of the dyeing 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 alkalinizing agents usually

<Desc / Clms Page number 16>

 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 C1-C4 ; Ra, Rb, Rc et Rd, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en C1-C4 ou hydroxyalkyle en C1-C4. Among the alkalinizing agents that may be mentioned, for example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula (II):

wherein W is a propylene residue optionally substituted with a hydroxyl group or a C1-C4 alkyl radical; Ra, Rb, Rc and Rd, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.

 The dye composition according to the invention may be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratinous fibers, and especially human hair.

 The process of the present invention is a process in which the composition according to the present invention as defined above is applied to the fibers in the presence of an oxidizing agent for a time sufficient to obtain the desired coloration. The color can be revealed at acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition of the invention just at the time of use or it can be used from an oxidizing composition on containing, applied simultaneously or sequentially to the composition of the invention.

 According to a particular embodiment, the composition according to the present invention is mixed, preferably at the time of use, with a composition containing, in a medium suitable for dyeing, at least one oxidizing agent, this oxidizing agent being present in an amount sufficient to develop a coloration.

The mixture obtained is then applied to the keratinous fibers. After a time of

<Desc / Clms Page number 17>

 The keratinous fibers are rinsed, washed with shampoo, rinsed again and then dried, for about 3 to 50 minutes, preferably for about 5 to 30 minutes.

 The oxidizing agents conventionally used for the oxidation dyeing of keratin fibers are, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes. among which there may be mentioned peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred.

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

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

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

 The invention also relates to a multi-compartment device or "kit" of dyeing in which a first compartment contains the dye composition of the present invention defined above and a second compartment contains an oxidizing agent. 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.

 From this device, it is possible to dye the keratinous fibers from a process which comprises mixing a dye composition comprising at least one oxidation base of formula (1) with an oxidizing agent, and application of the mixture obtained on the keratin fibers for a time sufficient to develop the desired coloration.

 The derivatives of formula (1) can be obtained according to synthetic methods known in the field of heterocycle synthesis. For example, publications EP1256578, US61143665, WO97 / 47299, EP402716,

<Desc / Clms Page number 18>

 DE3842970, DE3518520, Khimico Farmaberticheskii Zhurnal 1983, 17 (11), 1340-2, J. Org.Chem., 1975, 40 (9), 1275-8.

 The derivatives of the present invention are obtained for example from nitro radical substituted thiazole reagents which are reduced by conventional reduction methods.

chlorure d'acyle Rlo-COCI ou un anhydride (R,p-CO)2-0 dans des solvants aprotiques de point d'ébullition compris entre 45 C et 180 C pour conduire aux composés de formules 4. Le groupe nitro est ensuite réduit par action d'un métal tel que du fer, de l'étain ou du zinc et en présence catalytique d'acide tel que des acides protiques comme HCI, HBr ou NH4CI, pour conduire aux 5-amino-4-chloro-2-acylaminothiazole 5. Celui-ci est ensuite soumis à une réaction d'alkylation classique (se référer par exemple au Advanced Organic Chemistry, 3eme édition, J. March , Willey Interscience.) par des halogénures d'alkyle ou des O-sulfonates d'alkyle pour conduire aux composés désirés 6. One method is to treat 2,4-dichlorothiazole with nitric acid to yield 5-nitro-2,4-dichlorothiazole 2, which reacts at temperatures between 0 ° C and 130 ° C in a polar solvent, with primary, secondary or tertiary amines, and in particular with ammonia, to give the compounds 2-amino-4-chloro-5-nitrothiazole 3. The acylation reaction of the amine in position 2 is carried out according to the methods classics (see, for example, Advanced Organic Chemistry, 3rd Edition, J. March, Willey Interscience.) by a

acyl chloride Rlo-COCI or an anhydride (R, p-CO) 2-0 in aprotic solvents of boiling point between 45 C and 180 C to yield the compounds of formulas 4. The nitro group is then reduced by action of a metal such as iron, tin or zinc and in the catalytic presence of acid such as protic acids such as HCl, HBr or NH4Cl, to give 5-amino-4-chloro-2- acylaminothiazole 5. This is then subjected to a conventional alkylation reaction (see for example Advanced Organic Chemistry, 3rd edition, J. March, Willey Interscience.) by alkyl halides or O-sulfonates. alkyl to yield the desired compounds 6.

 The compounds of formula 7 are obtained by reaction of alkyl halide or aryl sulphonyls on amine 3 in aprotic solvents with a boiling point of between 45 ° C. and 180 ° C. Reduction reactions of the nitrothiazole group 7, then The alkylation of the thus obtained amine 8 is carried out as specified above.

<Desc / Clms Page number 19>

Compounds 10 (respectively 12) are obtained by heterogeneous catalytic hydrogenation of compounds 4 (respectively 7), the catalyst being for example palladium on carbon, Raney nickel, palladium dihydroxide, in a polar point solvent. boiling range between 60 C and 180 C. The 5-amino-thiazoles derivatives 10 and 12 are then reacted with nucleofuges (halides, O-sulfonates, ...) to yield the desired compounds 11 and 13.

 A second method is to react the commercial 2-amino-5-bromo-thiazole 14 with nitric acid in the presence of tetrafluoroboric acid and copper to yield the nitro derivative 15. The bromine becomes labile and is put into reaction with amines NHR1R2 in polar solvents of boiling points between 65 C and 180 C to yield derivatives 2-nitro-5-aminothiazole 16. The reduction of the nitro group by conventional methods (Reduction in organic Chemistry, M Hudlicky, Ellis Horwood series Chemical Science), for example by catalytic hydrogenation

<Desc / Clms Page number 20>

 heterogeneous by Pd (O) or Pd (ll) on charcoal, leads to the di-amino compounds 17. The acylation reaction of the amine in position 2 is carried out according to conventional methods (refer for example to Advanced Organic Chemistry , 3rd edition, J.

March, Willey Interscience.) With an acyl chloride R10-COCI or an anhydride (R10CO) 2-0 in aprotic solvents with a boiling point of between 45 ° C. and 180 ° C. to give compounds of formula 18. The compounds of formula 21 ~ are obtained by reaction of alkyl halides or aryl sulfonyl on amine 17 in aprotic solvents boiling point between 45 C and 180 C.

The introduction of a halogen atom at the 4-position of thiazole derivatives 18 and 21 is carried out by the action of N-chlorosuccinimide or N-bromosuccinimide according to conventional methods and provides access to compounds 19 and 22.

The introduction of an alkoxy, aryloxy or alkylthio group is carried out by substitution of the halogen with the corresponding alkanol or thiolate anion and makes it possible to obtain compounds 20 and 23.

 The examples which follow serve to illustrate the invention without, however, being limiting in nature.

EXAMPLES
To 10 ml of a hydroalcolic solution (80: 20 ethanol: water), containing 10% of protic acid such as hydrochloric acid, ammonium chloride, acetic acid or sulfuric acid, and 0, 5 g of zinc in powder form are added 1 mmol of

<Desc / Clms Page number 21>

 derivative 5-nitro-2- (thien-2-yl) acylaminothiazole at a temperature of 80 C. After total consumption of the nitrated starting material, the reaction mixture is concentrated until precipitation of a solid which is drained, washed with diisopropyl ether and dried under vacuum to constant weight.

There is thus obtained 5-amino-2- (thien-2-yl) acylaminothiazole (C8H7N3OS2): Yield 95%.

Examples of dyeing Example 1 The following compositions were made from the above compound:

Alkyl en C8-Cl5POlYglucoside vendu en 5,3g solution à 60% sous la dénomination ORAMIXCG110 par la société SEPPIC Alcool benzylique 1,8g Polyethylène glycol à 8 moles d'OE 2,7g <Tb>
<tb> 5-amino-2- (thien-2-yl) acylaminothiazole <SEP> 4.10-4 <SEP> mole
<tb> 3,7-diamino-5-methyl-pyrazolo [1,5-a] pyrimidine <SEP> 4.10-4 <SEP> mole
<tb> Support <SEP> of <SEP> tincture <SEP> (1) <SEP> (*)
<tb> Demineralized water <SEP><SEP> qsp <SEP> 100g
<Tb>
(*) Dyeing medium (1) pH 9.5
DMSO 0.18g
Ethyl alcohol 96.3g
Methyl alcohol 39.7g
Acetic acid 4,4g
Sodium metabisulfite 0.204g
Pentasodium salt of diethylene 1,1 g triamino pentaacetic acid in 40% aqueous solution

Alkyl C8-Cl5POlYglucoside sold in 5.3 g 60% solution under the name ORAMIXCG110 by the company SEPPIC benzyl alcohol 1,8g Polyethylene glycol 8 moles of EO 2.7g

<Desc / Clms Page number 22>

PH 9.5 NH4Cl / Ammonia buffer at 31, Og
20% of NH3
At the time of use, the composition is mixed with one third of its weight of hydrogen peroxide at 20 volumes (6% by weight).

 The resulting mixture is applied to a lock of gray hair at 90% white. After 30 minutes of laying, the lock is rinsed, washed with a standard shampoo, rinsed again and then dried.

 The shade obtained is dark purple.

EXAMPLE 2 The following compositions were prepared from the above compound:

<Tb>
<tb> 5-amino-2- (thien-2-yl) acylaminothiazole <SEP> 4.10-4 <SEP> mole
<tb> 3,7-diamino-5-methyl-pyrazolo [1,5-a] pyrimidine <SEP> 4.10-4 <SEP> mole
<tb> Support <SEP> of <SEP> tincture <SEP> (2) <SEP> (*)
<tb> Demineralized <SEP> Water <SEP> q. <SEP> sp <SEP> 100g
<Tb>
(*) Dye support (2) pH 7
DMSO 0.18g
Ethyl alcohol 96.3g
Methyl alcohol 39.7g
Acetic acid 4,4g
Sodium metabisulfite 0.204g
Pentasodium salt of diethylene 1,1g triamino pentaacetic acid in 40% aqueous solution
C8-C15polyglucoside alkyl sold in 5.3 g 60% solution under the name
ORAMIXCG110 by the company SEPPIC
Benzyl alcohol 1,8g
Polyethylene glycol with 8 moles of EO 2.7g
0.5M ammonium chloride buffer pH 7 31, Og

<Desc / Clms Page number 23>

At the time of use, the composition is mixed with one third of its weight of hydrogen peroxide at 20 volumes (6% by weight).

 The resulting mixture is applied to a lock of gray hair at 90% white. After 30 minutes of laying, the lock is rinsed, washed with a standard shampoo, rinsed again and then dried.

 The shade obtained is dark purple.

Claims (26)

1. Thiazole derivative of the following formula (I) and its addition salts with an acid or a base:

 in which: # R1, R2 represent, identical or different, - a hydrogen atom; a phenyl radical optionally substituted with one or more radicals chosen from halogens, hydroxyl, C 1 -C 4 alkoxy and carboxy radicals,

 mono or di (C1-C4) alkyl carboxamido, C1-C4 thioether, (C1-C4) alkylsulphonyl, sulphonic, alkylsulfoxide, alkylsulphonamido, N13R14, C1-C4 alkyl optionally substituted by one or more hydroxy, C1-C4 alkoxy,

 carboxy, mono or di (C 1 -C 4) carboxamido, C 1 -C 4 alkyl sulphonyl, sulphonic, alkyl sulphoxide, alkyl sulphonamido or NR 13 R 14; a linear or branched C1-C8 alkyl radical, optionally substituted with one or more hydroxyl, C1-C2 alkoxy, carboxy, mono or di (C1-C4) alkyl carboxamido, alkyl (CrC4) sulphonyl, sulphonic or alkyl sulphoxide radicals, alkylsulphonamido or NR13R14, -R1 and R2 may form with the nitrogen atom with which they are attached a 5- to 8-membered heterocycle of which one or more carbon atoms of the carbon ring may be replaced by an oxygen atom, a nitrogen, sulfur or a group SO2, the ring carbon atoms being able to be substituted by an R4 radical and the ring having no peroxide bond, or diazo or nitroso radicals; R4 represents: a halogen atom; a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, carboxy, C1-C4 alkoxycarbonyl, C1-C4 alkoxy or NR5R6 radicals; <Desc / Clms Page number 25>  amino, (di) (C 1 -C 4) alkylamino, (poly) hydroxyalkylamino C 2 -C 4; - R5, Re, R7, R8, R11. R12, R13, R14, R16 and R17 represent, identical or different, a hydrogen atom, a (C1-C4) alkylsulfonyl radical, a (C1-C4) alkyl radical, a mono- or di-alkyl radical ( C, -C4) carboxamido, a radical

 or di (C 1 -C 4) carboxamido, C 1 -C 4 alkylsulfonyl, sulfonic, C 1 -C 4 alkylsulfoxide, alkylsulfonamido or NR16R17; with R 15 which represents a C 1 -C 4 alkyl radical optionally substituted with one or more radicals chosen from hydroxyl and C 1 -C 2 alkoxy radicals,

 C1-C4 alkoxycarbonyl. mono or di (C 1 -C 4) alkyl carboxamido, C 1 -C 4 alkylsulphonyl, sulfonic, C 1 -C 4 alkylsulfoxide, C 1 -C 4 thioether, alkylsulfonamido, NR 11 R 12, C 1 -C 4 alkyl optionally substituted with one or more hydroxy, C1-C4 alkoxy, carboxy, mono or di (C1C4) alkyl carboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkylsulphoxide, alkylsulphonamido or NR1-3R14 - a linear or branched C1-C8 alkyl radical, optionally substituted by a or more hydroxy, OR, 5, carboxy, C1-C4 alkoxycarbonyl, mono radicals

 # R3 represents a radical R9SO2NH- or a radical R10C (O) NH- with Rg and R10 identical or different representing: - a phenyl radical or a 5- or 6-membered aromatic heterocycle, these radicals being optionally substituted by one or more radicals chosen among the halogens, hydroxy, C 1 -C 4 alkoxy and carboxy radicals,

 an alkyl (CrC4) sulphoxide radical; an alkyl (CrC4) sulphonyl radical; an NR7R8 radical;

 a carboxy radical; a mono- or di (C 1 -C 4) alkylcarboxamido radical; an alkyl (CrC4) sulphonyl radical; an alkylsulphonamido radical; a hydroxyl radical; a C1-C4 alkoxy radical; a C2-C4 hydroxyalkoxy radical; an aminosulphonyl radical; a C1-C4 thioether radical; <Desc / Clms Page number 26>  CrC4, (C1-C4) alkylsulphonyl, (C1-C4) alkylsulphonamido, carboxy, mono- or di (C1-C4) alkyl carboxamido, (C1-C4) alkylsulfoxide, amino, (di) (C1-C4) alkylamino, (poly ) C2-C4 hydroxyalkylamino; R 7 and R 8 may also form, with the nitrogen atom carrying them, a 5 to 8-membered ring optionally substituted with one or more radicals chosen from halogens, hydroxyl, C 1 -C 2 alkoxy, carboxy and alkylsulphonamido radicals, N13R14, C1-C4alkyl optionally substituted with one or more hydroxy, C1-C4alkoxy, carboxy, mono or di (C1-C4) alkylcarboxamido or NR13R14; # X represents a hydrogen atom; a halogen atom; a C1-C4 alkoxy radical; a phenoxy radical optionally substituted with one or more radicals chosen from halogens, hydroxyl, C 1 -C 4 alkoxy, carboxy, C 1 -C 4 alkoxycarbonyl, mono or di (C 1 -C 4) carboxamido, C 1 -C 4 alkylsulphonyl or sulphonic radicals, alkylsulfoxide, C1-C4 thioether, alkylsulfonamido, N13R14, C1-C4 alkyl; a C1-C4 thioether radical optionally substituted with a hydroxy, C1-C2 alkoxy, carboxy, sulfonic or amino.

 C1-C4 alkyl optionally substituted by one or more hydroxy, alkoxy  2. Derivative according to claim 1 wherein R1 and R2 represent independently of each other - a hydrogen atom; a phenyl radical optionally substituted with one or more chosen radicals

 among the halogens, hydroxy, C 1 -C 4 alkoxy, carboxy, C 1 -C 4 alkylcarboxamido, C 1 -C 4 alkylsulphonyl, sulphonic, alkylsulphoxide, C 1 -C 4 thioether, alkylsulphonamido, N 13 R 14, optionally C 1 -C 4 alkyl radicals; substituted with one or more hydroxy, C 1 -C 4 alkoxy, carboxy, C 1 -C 4 alkylcarboxa, C 1 -C 4 alkylsulfonyl, sulfonic, alkylsulfoxide, alkylsulphonamido or NR13R14; a linear or branched C1-C6 alkyl radical, optionally substituted with one or more hydroxyl, C1-C2 alkoxy, carboxy or C1-C4 alkoxycarbonyl radicals,

 (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkylsulfoxide, alkylsulphonamido, or NR13R14.  3. Derivative according to claim 2 wherein R1 and R2 represent, identical or different, a hydrogen atom; a phenyl radical; a linear or branched C1-C4 alkyl radical optionally substituted with one or more radicals <Desc / Clms Page number 27>  hydroxy, C 1 -C 2 alkoxy, amino, di (C 1 -C 4) alkylamino, carboxy, C 1 -C 4 alkylcarboxamido, C 1 -C 4 alkylsulphonamido, NR 13 R 14 where R 13 and R 14 represent, identical or different, an atom of hydrogen, a (C 1 -C 4) alkyl radical -CO, a C 1 -C 2 alkyl radical optionally substituted with a hydroxy or a C 1 -C 2 alkoxy.

 4. Derivative according to claim 3 wherein R1 and R2 represent, identical or different, a hydrogen atom, methyl, 2-hydroxyethyl, 2carboxyethyl, 1,2-dihydroxyethyl, phenyl.  5. Derivative according to claim 1 wherein R1 and R2 form with the nitrogen atom with which they are attached a 5- to 8-membered heterocycle selected from pyrrolidine, piperidine, homopiperidine, piperazine, homopiperazine, said cycles may be substituted by one or more radicals R4.  6. Derivative according to claim 5 wherein R1 and R2 together with the nitrogen atom to which they are attached a heterocycle selected from pyrrolidine, 2,5-dimethylpyrrolidine, proline, 3-hydroxyproline, 4hydroxyproline, 2,4-dicarboxypyrrolidine, 3-hydroxy-2-hydroxymethylpyrrolidine, 2-carboxamidopyrrolidine, 3-hydroxy-2-carboxamidopyrrolidine, 2- (diethylcarboxamido) pyrrolidine, 2-hydroxymethyl pyrrolidine, 3,4-dihydroxy 2-Hydroxymethyl pyrrolidine, 3-hydroxypyrrolidine, 3,4-dihydroxy pyrrolidine, 3-amino pyrrolidine, 3-methylamino pyrrolidine, 4-amino-3-hydroxy pyrrolidine, 3-hydroxy-4- (2-hydroxyethyl) amino-pyrrolidine , piperidine, 2,6-dimethylpiperidine, 2-carboxypiperidine, 2-carboxamidopiperidine, 2-hydroxymethylpiperidine, 3-hydroxy-2-hydroxymethylpiperidine, 3-hydroxypiperidine, 4-hydroxypiperidine, 3-hydroxymethylpiperidine, homopiperidine, 2-carboxyhomopiperidine, 2carboxamidohomopiperidine, homopiperazine, N-methyl homopiperazine, N p-hydroxyethylhomopiperazine and their addition salts.  7. Derivative according to claim 5 or 6 wherein R1 and R2 together with the nitrogen atom to which they are attached a heterocycle selected from pyrrolidine, 3-hydroxypyrrolidine, 3-aminopyrrolidine, praline, 3hydroxyproline, piperidine, 3-hydroxypiperidine, 4-hydroxypiperidine homopiperidine, homopiperazine, N-methyl homopiperazine, N-hydroxyethylhomopiperazine and their addition salts.  8. Derivative according to any one of claims 1 to 7 wherein R3 represents an aromatic heterocycle pyridyl, pyrimidinyl, pyrazolyl, thiazolyl, furyl, imidazolyl, thienyl. <Desc / Clms Page number 28>  9. Derivative according to claim 1 to 8 wherein R3 represents a radical

 R9SO2NH-, a radical R1OC (O) NH-; with R9 and Rio, identical or different, representing - a phenyl radical or a 5- or 6-membered aromatic heterocycle such as pyridyl, pyrimidinyl, pyrazolyl, thiazolyl, furyl, imidazolyl, thienyl, these radicals being optionally substituted by one or more radicals chosen among the halogens, the radicals hydroxy, C1-C4 alkoxy, carboxy, mono or di

 C 1 -C 4 alkyl, carboxamido, NR 11 R 12, C 1 -C 4 alkyl optionally substituted with one or more hydroxy, C 1 -C 4 alkoxy, carboxy, mono or di (C 1 -C 4) alkyl carboxamido, or NR 13 R 14 -C 1-6 alkyl radical; Linear or branched C8, substituted with one or more radicals selected from hydroxy, C1-C2 alkoxy, carboxy, mono or

 di (C 1 -C 4) alkylcarboxamido, (C 1 -C 4) alkylsulphonyl, sulphonic, alkyl (C 1 -C 4) alkyl, C4) sulfoxide, alkylsulfonamido or NR16R17; - R11, R12, R13, R14, R16 and R17 represent, identical or different, a hydrogen atom, acyl, a carboxamido, a C1-C4 alkyl radical optionally substituted with one or more hydroxyl radicals, C1-C4 alkoxy radicals; , (C1-C4) alkylsulphonyl,

 (C1-C4) alkylsulphonamido, carboxy, mono or di (C1-C4) alkyl carboxamido, (C1-C4) alkylsulfoxide, amino, (di) (C1-C4) alkylamino, (poly) hydroxyalkylamino C2-C4.  10. Derivative according to claim 9 wherein R3 represents a radical R9SO2NH- or a radical R10C (O) NH- with Rg and R10 identical or different selected from an alkyl radical, a phenyl radical, a pyrazolyl radical, a thiazolyl radical, a pyridyl radical or a thienyl radical, these radicals being substitutable.  11. Derivative according to claim 10 wherein R3 represents a radical R10C (O) NH0- where R10 represents a methyl, ethyl, 2-hydroxyethyl, 2carboxyethyl, phenyl, pyrazolyl, thienyl or pyridyl radical and Rg represents a methyl, phenyl or toluyl.  12. Derivative according to any one of claims 1 to 11 wherein X represents a hydrogen atom, chlorine or an alkoxy radical.  13. Derivative according to any one of claims 1 to 12, selected from the following compounds and their addition salts with an acid or a base: 5-amino-2-methylsulfonylaminothiazole 5-amino-2-phenylsulfonylaminothiazole <Desc / Clms Page number 29>  5-amino-2-tolylsulfonylaminothiazole 5-amino-2-thiazolylsulfonylaminothiazole 5-amino-2-pyridylsulfonylaminothiazole 5-amino-2-phenacylaminothiazole 5-amino-2- (pyrid-2-yl) acylaminothiazole 5-amino-2- (pyridinyl) 3-yl) acylaminothiazole 5-amino-2- (pyrid-4-yl) acylaminothiazole 5-amino-2-acetylaminothiazole 5-amino-2-isopropylacylaminothiazole 5-amino-2- (thien-2-yl) acylaminothiazole 5- methylamino-2-methylsulfonylaminothiazole 5-methylamino-2-phenylsulfonylaminothiazole 5-methylamino-2-tolylsulfonylaminothiazole 5-methylamino-2-thiazolylsulfonylaminothiazole 5-methylamino-2-pyridylsulfonylaminothiazole 5-methylamino-2-phenacylaminothiazole 5-methylamino-2- (pyrid-2 -yl) acylaminothiazole 5-methylamino-2- (pyrid-3-yl) acylaminothiazole 5-methylamino-2- (pyrid-4-yl) acylaminothiazole 5-methylamino-2-acetylaminothiazole 5-methylamino-2-isopropylacylaminothiazole 5-methylamino 2- (thien-2-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-2-methylsulfonylaminothiazole 5- (2-hydroxyethyl) am Ino-2-phenylsulfonylaminothiazole 5- (2-hydroxyethyl) amino-2-tolylsulfonylaminothiazole 5- (2-hydroxyethyl) amino-2-thiazolylsulfonylaminothiazole 5- (2-hydroxyethyl) amino-2-pyridylsulfonylaminothiazole 5- (2-hydroxyethyl) amino 2-phenacylaminothiazole 5- (2-hydroxyethyl) amino-2- (pyrid-2-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-2- (pyrid-3-yl) acylaminothiazole 5- (2-hydroxyethyl) amino- 2- (Pyrid-4-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-2-acetylaminothiazole 5- (2-hydroxyethyl) amino-2-isopropylacylaminothiazole <Desc / Clms Page number 30>  5- (2-hydroxyethyl) amino-2- (thien-2-yl) acylaminothiazole 5-amino-4-chloro-2-methylsulfonylaminothiazole 5-amino-4-chloro-2-phenylsulfonylaminothiazole 5-amino-4-chloro-2 5-amino-4-chloro-2-thiazolylsulfonylaminothiazole-5-amino-4-chloro-2-thiazolylsulfonylaminothiazole 5-amino-4-chloro-2-phenacylaminothiazole 5-amino-4-chloro-2- (pyrid-2-) -toluylsulfonylaminothiazole yl) acylaminothiazole 5-amino-4-chloro-2- (pyrid-3-yl) acylaminothiazole 5-amino-4-chloro-2- (pyrid-4-yl) acylaminothiazole 5-amino-4-chloro-2-acetylaminothiazole 5-amino-4-chloro-2-isopropylacylaminothiazole 5-amino-4-chloro-2- (thien-2-yl) acylaminothiazole 5-methylamino-4-chloro-2-methylsulfonylaminothiazole 5-methylamino-4-chloro-2- phenylsulfonylaminothiazole 5-methylamino-4-chloro-2-tolylsulfonylaminothiazole 5-methylamino-4-chloro-2-thiazolylsulfonylaminothiazole 5-methylamino-4-chloro-2-pyridylsulfonylaminothiazole 5-methylamino-4-chloro-2-phenacylaminothiazole 5-methylamino-4 -chloro-2- (pyrid-2-yl) acylaminoth 5-Methylamino-4-chloro-2- (pyrid-3-yl) acylaminothiazole 5-methylamino-4-chloro-2- (pyrid-4-yl) acylaminothiazole 5-methylamino-4-chloro-2-acetylaminothiazole methylamino-4-chloro-2-isopropylacylaminothiazole 5-methylamino-4-chloro-2- (thien-2-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2-methylsulfonylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2-phenylsulfonylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2-tolylsulfonylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2-thiazolylsulfonylaminothiazole 5- (2-hydroxyethyl) amino 4-chloro-2-pyridylsulfonylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2-phenacylaminothiazole <Desc / Clms Page number 31>  5- (pyrrolidin-1-yl) -4-chloro-2-isopropylacylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2- (thien-2-yl) acylaminothiazole, and their addition salts with a acid or base.

 5- (pyrrolidin-1-yl) -4-chloro-2-thiazolylsulfonylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2-pyridylsulfonylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2- phenacylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2- (pyrid-2-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2- (pyrid-3-yl) acylaminothiazole - (Pyrrolidin-1-yl) -4-chloro-2- (pyrid-4-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2-acetylaminothiazole

 5- (pyrrolidin-1-yl) -4-chloro-2-methylsulfonylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2-phenylsulfonylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2- toluylsulfonylaminothiazole

 5- (pyrrolidin-1-yl) -2- (pyrid-2-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -2- (pyrid-3-yl) acylaminothiazole 5- (pyrrolidin-1-yl) - 2- (pyrid-4-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -2-acetylaminothiazole 5- (pyrrolidin-1-yl) -2-isopropylacylaminothiazole 5- (pyrrolidin-1-yl) -2- (thien) -2-yl) acylaminothiazole

 5- (pyrrolidin-1-yl) -2-thiazolylsulfonylaminothiazole 5- (pyrrolidin-1-yl) -2-pyridylsulfonylaminothiazole 5- (pyrrolidin-1-yl) -2-phenacylaminothiazole

 5- (2-hydroxyethyl) amino-4-chloro-2- (pyrid-2-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2- (pyrid-3-yl) acylaminothiazole 5- (2-hydroxyethyl) hydroxyethyl) amino-4-chloro-2- (pyrid-4-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2-acetylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2- isopropylacylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2- (thien-2-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -2-methylsulfonylaminothiazole 5- (pyrrolidin-1-yl) -2-phenylsulfonylaminothiazole 5- (pyrrolidin-1-yl) -2-toluylsulfonylaminothiazole  14. Derivative according to any one of claims 1 to 12 of formula (II) <Desc / Clms Page number 32>  wherein R3 is as defined above in claims 1 to 13.

 15. Derivative according to any one of claims 1 to 14 selected from 5- (pyrrolidin-1-yl) -2- (thien-2-yl) acylaminothiazole and its addition salts.  16. A dyeing composition for keratin fibers, comprising, in a suitable dyeing medium: at least one oxidation base, and at least one thiazole derivative of formula (I) as defined in any one of claims 1. to 15 as a coupler.  17. A composition according to claim 16 wherein the one or more oxidation bases are chosen from para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.  18. Composition according to any one of claims 17, wherein the one or more oxidation bases are each present in an amount of 0.001 and 10% by weight of the total weight of the dyeing composition.  19. Composition according to any one of claims 16 to 18 comprising one or more additional couplers chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers and heterocyclic couplers other than those of formula (I) and their salts. addition.  20. Composition according to any one of claims 15 to 19, wherein the coupler or couplers are each present in an amount of between 0.001 and 10% by weight of the total weight of the dye composition.  21. Process for the oxidation dyeing of keratinous fibers, characterized in that a composition as defined in any one of Claims 16 to 20 is applied to the fibers in the presence of an oxidizing agent for a time sufficient to reveal the desired color.  22. The method of claim 21, wherein the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes. <Desc / Clms Page number 33>  23. The method of claim 22 wherein the oxidizing agent is mixed at the time of use in the composition as defined in any one of claims 16 to 19.  24. The method of claim 23 wherein the oxidizing agent is applied to the fibers simultaneously or sequentially to the composition as defined in any one of claims 16 to 19 in the form of an oxidizing composition.  25. Multi-compartment device in which a first dye compartment contains a composition as defined in any one of claims 16 to 19 and a second compartment contains an oxidizing agent.  26. Use of at least one thiazole derivative as defined according to any one of claims 1 to 15 for the oxidation dyeing of keratinous fibers.