ES2365527T3 - DERIVATIVES OF 4-5-DIAMINO-N, N-DIHIDRO-PIRAZOL-3-ONA USED FOR THE DYING OF KERATIN FIBERS. - Google Patents

Abstract

Dyeing composition of the keratin fibers comprising, in an appropriate dyeing medium, as an oxidation base, at least one derivative of the diamino-N, N-dihydro-pyrazolone of formula (I) or one of its addition salts or solvates : in which: R1, R2, R3 and R4, identical or different, represent: a linear or branched C1-C6 alkyl radical optionally substituted by one or more radicals selected from the group consisting of an OR5 radical, a NR6R7 radical, a carboxy radical, a sulfonic radical, a carboxamide radical CONR6R7, a sulfonamido radical SO2NR6R7, a heteroaryl, an aryl optionally substituted by a (C1-C4) alkyl group, a hydroxy, a C1-C2 alkoxy, an amino, a ( di) (C1-C2) alkyl amino; - an aryl radical optionally substituted by one or more (C1-C4) alkyl, hydroxy, C1-C2 alkoxy, amino, (di) (C1-C2) alkyl amino; - a heteroaryl radical with 5 or 6 links, optionally substituted by one or more radicals selected from (C1-C4) alkyl, (C1-C2) alkoxy; R3 and R4 can also represent a hydrogen atom; R5, R6 and R7, identical or different, represent a hydrogen atom; a linear or branched C1-C4 alkyl radical optionally substituted by one or more radicals selected from the group consisting of a hydroxy, a C1-C2 alkoxy, a CONR8R9 carboxamide, a SO2R8 sulfonyl, an aryl optionally substituted by a (C1- C4) alkyl, a hydroxy, a C1-C2 alkoxy, an amino, a (di) (C1-C2) alkyl; an aryl optionally substituted by a (C1-C4) alkyl, a hydroxy, a C1-C2 alkoxy, an amino, a (di) (C1-C2) alkyl; R6 and R7, identical or different, may also represent a CONR8R9 carboxamide radical; a sulfonyl SO2R8; R8 and R9, identical or different, represent a hydrogen atom; linear or branched C1-C4 alkyl radical optionally substituted by one or more hydroxy, C1-C2 alkoxy; R3 and R4 can form with the nitrogen atom, to which they are attached, a saturated or unsaturated heterocycle, consisting of 5 to 7 links, optionally substituted by one or more radicals selected within the group consisting of halogen atoms, the radicals amino, (di) (C1-C4) alkyl amino, hydroxy, carboxy, carboxamido, (C1-C2) alkoxy, C1-C4 alkyl radicals optionally substituted by one or more hydroxy, amino, (di) alkylamino, alkoxy radicals , carboxy, sulfonyl; R3 and R4 can also form together with the nitrogen atom, to which they are attached, a 5 or 7 link heterocycle whose carbon atoms can be replaced by an optionally substituted oxygen or nitrogen atom.

Description

Background of the invention

The invention relates to a composition for dyeing keratin fibers and, in particular, human keratin fibers such as hair, comprising at least one derivative of diamino-N, N-dihydropyrazzolone or one of its addition salts such as oxidation base and a procedure that applies it. It also refers to derivatives of the amino-N, N-dihydropyrazzolone, as well as derivatives of the diamino-N, N-dihydropyrazzolone or one of its addition salts as such and to its obtaining.

It is usual to dye keratin fibers, and in particular human keratin fibers such as hair, with dyeing compositions comprising 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-dihydroxyindole derivatives generally referred to as bases of oxidation Oxidation dye precursors, or oxidation bases, are colorless or weakly colored compounds that, associated with oxidizing products, can give rise to oxidative condensation to colored or dye compounds.

It is also known that the tones obtained with these oxidation bases can be varied by associating them with couplers or color modifiers, the latter being selected in particular from the meta-phenylenediamines, the meta-aminophenols, the meta-hydroxyphenols and some compounds heterocyclic such as, for example, derivatives of pyrazolo [1,5-b] -triazoles, derivatives of pyrazolo [3,2-c] -1,2,4-triazoles, derivatives of pyrazolo [1,5-a ] pyrimidines, some pyridine derivatives, some pyrazol-5-one derivatives, some indoline derivatives and some indole derivatives.

The variety of molecules involved at the level of oxidation bases and couplers allows obtaining a rich color palette.

The so-called "permanent" coloration obtained by means of these oxidation dyes must, on the other hand, satisfy a certain number of requirements. In this way, this should not present problems in the toxicological plane, it should allow to obtain nuances in the desired intensity, to present a good resistance against external agents such as light, bad weather, washing, permanent, perspiration and friction.

The dyes must also allow gray hair to be covered and be as selective as possible, that is, allow to obtain as little color differences as possible along the same keratin fiber, which may in fact be sensitized differently (p eg damaged) between its tip and its root. They must also have good chemical stability in the formulations. They must have a good toxicological profile.

The use of an oxidation base such as para-phenylenediamine and para-aminophenol derivatives allows a fairly wide range of colors to be obtained with a basic pH without, however, achieving good chromaticity tones, thus giving the hair excellent properties of intensity of color, variety of tones, color uniformity and resistance to external agents.

The use of these bases with neutral pH is also inefficient to reach a range of varied tones, particularly for warm tones.

The use of some diaminopyrazole derivatives, in particular for shades of red to copper red, has already been proposed in DE3843892. However, this proposal does not allow to achieve good chromaticity properties, of resistance to external agents such as washing and light. In addition, the breadth of the tone range is limited.

On the other hand, it is known from the patent application EP 1 250 909 the use of a pyrazole derivative, in particular 3,4-diamino-5-hydroxypyrazole, as an oxidation dye for hair dyeing.

The use of 1-phenyl-3-carboxamido-4-aminopyrazole 5-one as an oxidation base and 1-phenyl-3-methyl-pyrazole-5-one as a coupler is also known from patent application EP 0 873 745 for the coloration of keratin fibers.

However, the applicant has discovered in a completely surprising way that new diamino-N, N-dihydro-pyrazolone compounds of formula (I) are suitable for use as oxidation coloring precursors and allow to obtain a coloration with varying shades, powerful, chromatic, aesthetic, little selective and that resists well the different aggressions that the hair can suffer, such as shampoos, light, sweat and permanent deformations.

The applicant has also surprisingly discovered that the colorations obtained with neutral pH 5 are intense.

The present invention therefore relates to a dyeing composition of the keratin fibers comprising, in an appropriate dyeing medium, as an oxidation base, at least one derivative of the diamino-N, N-dihydropyrazzolone of formula (I ) or one of its addition salts:

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in which:

R1, R2, R3 and R4, identical or different, represent:

- a linear or branched C1-C6 alkyl radical optionally substituted by one or more radicals selected from the group consisting of an OR5 radical, an NR6R7 radical, a carboxy radical, a sulfonic radical, a CONR6R7 carboxamide radical, a SO2NR6R7 sulfonamido radical, a heteroaryl, an aryl

Optionally substituted by a (C1-C4) alkyl group, a hydroxy, a C1-C2 alkoxy, an amino, a (di) (C1-C2) alkyl amino; - an aryl radical optionally substituted by one or more (C1-C4) alkyl, hydroxy, C1-C2 alkoxy, amino, (di) (C1-C2) alkyl amino; - a heteroaryl radical with 5 or 6 links, optionally substituted by one or more radicals selected from (C1-C4) alkyl, (C1-C2) alkoxy;

R3 and R4 can also represent a hydrogen atom;

R5, R6 and R7, identical or different, represent a hydrogen atom; a linear or branched C1-C4 alkyl radical

Optionally substituted by one or more radicals selected from the group consisting of a hydroxy, a C1-C2 alkoxy, a CONR8R9 carboxamide, a SO2R8 sulfonyl, an aryl optionally substituted by a (C1-C4) alkyl, a hydroxy, an alkoxy in C1-C2, an amino, a (di) (C1-C2) alkyl amino; an aryl optionally substituted by a (C1C4) alkyl, a hydroxy, a C1-C2 alkoxy, an amino, a (di) (C1-C2) alkyl;

R6 and R7, identical or different, may also represent a CONR8R9 carboxamide radical; a sulfonyl SO2R8;

R8 and R9, identical or different, represent a hydrogen atom; linear or branched C1-C4 alkyl radical optionally substituted by one or more hydroxy, C1-C2 alkoxy;

R3 and R4 can form with the nitrogen atom, to which they are attached, a saturated or unsaturated heterocycle, consisting of 5 to 7 links, optionally substituted by one or more radicals selected within the group consisting of halogen atoms, amino, (di) (C1-C4) alkyl, amino, hydroxy, carboxy, carboxamido, (C1C2) alkoxy radicals, the C1-C4 alkyl radicals optionally substituted by one or more hydroxy, amino, (di) alkylamino, alkoxy radicals, carboxy, sulfonyl;

R3 and R4 can also form together with the nitrogen atom, to which they are attached, a 5 or 7 link heterocycle whose carbon atoms can be replaced by an optionally substituted oxygen or nitrogen atom.

The present invention makes it possible in particular to obtain a coloration of the keratin fibers that are tenacious, resistant to light and washing.

Another object of the invention is a process of dyeing keratin fibers that applies the composition of the present invention, as well as the use of this composition for dyeing keratin fibers.

A subject of the invention is also novel amino-N-N-dihydropyrazzolone derivatives, as well as diamino-N, N-dihydro-pyrazolone derivatives.

The invention relates, finally, to new methods of synthesis of these (di) amino-N, Ndihydropyrazzolone derivatives of formulas (I ’) and (I’) or their addition salts.

As indicated above, the composition comprises at least one diamino-N derivative, Ndihydro-pyrazolone of formula (I) or one of its addition salts.

More particularly, in formula (I) the radicals R1 and R2, identical or different, are selected from:

- a C1-C4 alkyl radical optionally substituted by a hydroxy, a (C1-C2) alkoxy, a (di) (C1C2) alkyl amino: - a phenyl radical.

Preferably, the radicals R1 and R2, identical or not, are selected from a methyl, ethyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, phenyl radical.

As regards the radicals R3 and R4, the latter, identical or different, are selected more particularly from a hydrogen atom; a linear or branched C1-C4 alkyl radical, optionally substituted by one or more hydroxy, (C1-C2) alkoxy, amino, a (di) (C1-C2) alkyl; a phenyl radical optionally substituted by a hydroxy, amino, (C1-C2) alkoxy radical.

Preferably, the radicals R3 and R4, identical or not, are selected from a hydrogen atom, a methyl, ethyl, isopropyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-carboxyethyl. According to a particular embodiment, the radicals R3 and R4 represent a hydrogen atom.

According to another embodiment, the radicals R3 and R4 form together with the nitrogen atom, to which they are attached, a cycle of 5 or 7 links selected from the heterocycles pyrrolidine, piperidine, homopiperidine, piperazine, homopiperazine; Said cycles may be substituted by one or more hydroxy, amino, (di) (C1-C2) alkyl, carboxy, carboxamido, C1-C4 alkyl radicals, possibly substituted by one or more hydroxy, amino, (di) C1- alkylamino radicals. C2

More particularly, the radicals R3 and R4 form together with the nitrogen atom, to which they are attached, a cycle of 5 or 7 links selected from pyrrolidine, 2,5-dimethylpyrrolidine, pyrrolidine-2-carboxylic acid, 3-hydroxypyrrolidine-2-carboxylic acid, 4-hydroxypyrrolidine-2-carboxylic acid, 2,4-dicarboxypyrrolidine, 3-hydroxy-2-hydroxymethylpyrrolidine, 2-carboxamidopyrrolidine, 3-hydroxy-2-carboxamidopyrrolidine (diethylcarboxamido) pyrrolidine, 2-hydroxymethyl pyrrolidine, 3,4-dihydroxy-2-hydroxymethyl pyrrolidine, 3hydroxypyrrolidine, 3,4-dihydroxy pyrrolidine, 3-amino pyrrolidine, 3-methylamino pyrrolidine, 3dimethylaminopyrrolidine 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-hydroxyipip eridine, 3-hydroxymethylpiperidine, homopiperidine, 2carboxihomopiperidine, 2-carboxamidohomopiperidine, homopiperazine, N-methyl-homopiperazine, N- (2-hydroxyethyl) -homopiperazine.

Preferably, the radicals R3 and R4 together with the nitrogen atom, to which they are attached, a cycle of 5 or 7 links selected from pyrrolidine, 3-hydroxypyrrolidine, 3-aminopyrrolidine, 3-dimethylamino-pyrrolidine, pyrrolidine-2-carboxylic acid, 3-hydroxypyrrolidine-2-carboxylic acid, piperidine, hydroxypiperidine, homopiperidine, diazepan, N-methyl homopiperazine, N β-hydroxyethylhomopiperazine.

According to an even more preferred embodiment of the invention, the radicals R3 and R4 form together with the nitrogen atom, to which they are attached, a cycle of 5 links such as pyrrolidine, 3-hydroxypyrrolidine, 3aminopyrrolidine, the 3-dimethylamino pyrrolidine.

The compounds of formula (I) may eventually be salified by strong mineral acids such as, for example, HCI, HBr, HI, H2SO4, H3PO4, or organic acids such as, for example, acetic, lactic, tartaric, citric or succinic, benzenesulfonic, para-toluenesulfonic, formic or methanesulfonic.

They can also be in the form of solvates, for example, a linear or branched alcohol hydrate or solvate such as ethanol or isopropanol.

As examples of derivatives of formula (I), one can cite the compounds presented below or their addition salts.

4,5-diamino-1,2-dimethyl-1,2-dihydro-pyrazol-3-one 4-amino-5-methylamino-1,2-dimethyl-1,2-dihydro-pyrazol-3-one 4-amino-5-dimethylamino-1,2-dimethyl-1,2-dihydro-pyrazol-3-one 4-amino-5- (2-hydroxyethyl) amino-1,2-dimethyl-1,2-dihydro-pyrazol-3-one

5 4-amino-5- (pyrrolidin-1-yl) -1,2-dimethyl-1,2-dihydro-pyrazol-3-one 4-amino-5- (piperidin-1-yl) -1,2-dimethyl-1,2-dihydro-pyrazol-3-one 4,5-diamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one 4-amino-5-methylamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one 4-amino-5-dimethylamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one

10 4-amino-5- (2-hydroxyethyl) amino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one 4-amino-5- (pyrrolidin-1-yl) -1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one 4-amino-5- (piperidin-1-yl) -1,2-di- (2-hydroxyethyl) - 1,2-dihydro-pyrazol-3-one 4,5-diamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one 4,5-diamino-1,2-phenyl-1,2- dihydro-pyrazol-3-one

4,5-Diamino-1-ethyl-2-methyl-1,2-dihydro-pyrazol-3-one 4,5-diamino-2-ethyl-1-methyl-1,2-dihydro-pyrazol-3- one 4,5-diamino-1-phenyl-2-methyl-1,2-dihydro-pyrazol-3-one 4,5-diamino-1- (2-hydroxyethyl) -2-methyl-1,2-dihydro- pyrazol-3-one 4,5-diamino-2- (2-hydroxyethyl) -1-methyl-1,2-dihydro-pyrazol-3-one

20 4-amino-5-dimethylamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one 4-amino-1,2-diethyl-5-ethylamino-1,2-dihydro-pyrazol-3- one 4-amino-1,2-diethyl-5-isopropylamino-1,2-dihydro-pyrazol-3-one 4-amino-1,2-diethyl-5- (2-hydroxy-ethylamino) -1,2- dihydro-pyrazol-3-one 4-amino-5- (2-dimethylamino-ethylamino) -1,2-diethyl-1,2-dihydro-pyrazol-3-one

4-amino-5- [bis- (2-hydroxy-ethyl) -amino] -1,2-diethyl-1,2-dihydro-pyrazol-3-one 4-amino-1,2-diethyl-5- (3-imidazol-1-yl-propylamino) -1,2-dihydro-pyrazol-3-one 4-amino-5-dimethylamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one 4- amino-1,2-diethyl-5-ethylamino-1,2-dihydro-pyrazol-3-one 4-amino-1,2-diethyl-5-isopropylamino-1,2-dihydro-pyrazol-3-one

30 4-amino-1,2-diethyl-5- (2-hydroxy-ethylamino) -1,2-dihydro-pyrazol-3-one 4-amino-5- (2-dimethylamino-ethylamino) -1,2- diethyl-1,2-dihydro-pyrazol-3-one 4-amino-5- [bis- (2-hydroxy-ethyl) -amino] -1,2-diethyl-1,2-dihydro-pyrazol-3-one 4-amino-1,2-diethyl-5- (3-imidazol-1-yl-propylamino) -1,2-dihydro-pyrazol-3-one 4-amino-1,2-diethyl-5- (3- hydroxy-pyrrolidin-1-yl) -1,2-dihydro-pyrazol-3-one

4-amino-1,2-diethyl-5-pyrrolidin-1-yl-1,2-dihydro-pyrazol-3-one 4-amino-5- (3-dimethylamino-pyrrolidin-1-yl) -1, 2-diethyl-1,2-dihydro-pyrazol-3-one 4-amino-1,2-diethyl-5- (4-methyl-piperazin-1-yl) -pyrazolidin-3-one

some of which are represented below to illustrate the names with their chemical structures: 40

 image 1

4,5-diamino-1,2-dimethyl-1,2-dihydro-pyrazol-3-one

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4,5-diamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one

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4,5-diamino-1,2-diphenyl-1,2-dihydro-pyrazol-3-one

 image 1

4,5-diamino-1-ethyl-2-methyl-1,2-dihydro-pyrazol-3-one

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4,5-diamino-1-phenyl-2-methyl-1,2-dihydro-pyrazol-3-one

4,5-diamino-1- (2-hydroxyethyl) -2-methyl-1,2-dihydro-pyrazol-3-one

 image 1

4,5-diamino-2- (2-hydroxyethyl) -1-methyl-1,2-dihydro-pyrazol-3-one

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Among these compounds, the diamino-N, N-dihydropyrazzolone derivatives of formula (I) or their especially preferred addition salts are: 4,5-diamino-1,2-dimethyl-1,2-dihydro-pyrazol-3 -one, 4,5-diamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one, 4,5-diamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazole -3-one.

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

The dyeing composition of the invention may contain one or more couplers commonly used for dyeing keratin fibers. Among these couplers, mention may be made in particular of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers, heterocyclic couplers and their addition salts.

By way of example, 2-methyl 5-aminophenol, 5-N- (β-hydroxyethyl) amino 2-methyl phenol, 6-chloro-2-methyl-5-aminophenol, 3-amino phenol, 1,3-dihydroxy benzene, 1,3-dihydroxy 2-methyl benzene, 4-chloro 1,3-dihydroxy benzene, 2,4-diamino 1- (β-hydroxyethyloxy) benzene, 2-amino 4- (β-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-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 2-amino- 3-hydroxy pyridine, 6-hydroxy benzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N- (β-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- (β -hydroxyethylamino) toluene and its addition salts with an acid.

In the composition of the present invention, the coupler (s) are each generally present in an amount between about 0.001 and 10% by weight of the total weight of the dye composition, preferably between 0.05 and a 6%

The composition of the present invention may, on the other hand, comprise one or more additional oxidation bases that are routinely used in oxidation dyeing, different from those described above. By way of example, these additional oxidation bases are selected from paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, bis-para-aminophenols, orthoaminophenols, ortho-phenylenediamines, heterocyclic bases other than those derived from formula (I) as defined above and their addition salts.

Para-phenylenediamines include, for example, para-phenylenediamine, paratoluylenediamine, 2-chloro para-phenylenediamine, 2,3-dimethyl para-phenylenediamine, 2,6-dimethyl paraphenylenediamine, 2, 6-diethyl para-phenylenediamine, 2,5-dimethyl para-phenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyl para-phenylenediamine, N, N-dipropyl para-phenylenediamine, 4-amino N , N-diethyl 3-methyl aniline, N, N-bis- (β-hydroxyethyl) para-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino 2-methyl aniline, 4, N, N-bis (β-hydroxyethyl) amino 2-chloro aniline, 2-β-hydroxyethyl para-phenylenediamine, 2-fluoro para-phenylenediamine, 2isopropyl para-phenylenediamine, N- (β-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl para-phenylenediamine, N, N-dimethyl 3-methyl para-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) paraphenylenediamine, N- (β, γ-dihydroxypropyl) para-phenylenediamine, N- (4'-aminophenyl) para-phenylenediamine, N-phenyl p ara-phenylenediamine, 2-β-hydroxyethyloxy para-phenylenediamine, 2-β-acetylaminoethyloxy para-phenylenediamine, N- (β-methoxyethyl) para-phenylenediamine, 4aminophenylpyrrolidine, 2-thienyl para-phenylenediamine, 2- β hydroxyethylamino 5-amino toluene, 3-hydroxy 1- (4'aminophenyl) pyrrolidine and its acid addition salts.

Among the para-phenylenediamines mentioned in the previous paragraph, para-phenylenediamine, paratoluylenediamine, 2-isopropyl para-phenylenediamine, 2-β-hydroxyethyl para-phenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2 , 6-dimethyl para-phenylenediamine, 2,6-diethyl para-phenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (β-hydroxyethyl) para-phenylenediamine, 2-chloro para-phenylenediamine, 2-βacetylaminoethyloxy para-phenylenediamine and its addition salts with an acid are particularly preferred.

Among the bis-phenylalkylenediamines, there may be mentioned, for example, N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'aminophenyl) 1,3-diamino propanol, N, N '-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4aminophenyl) tetramethylene diamine, N, N'-bis- (β-hydroxyethyl) N, N'-bis -) (4'-aminophenyl) tetramethylene diamine, N, N'-bis (4-methyl-aminophenyl) tetramethylene diamine, 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.

Among the para-aminophenols, for example, para-aminophenol, 4-amino 3-methyl phenol, 4amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4-amino 2- methyl phenol, 4-amino 2-hydroxymethyl phenol, 4amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2- (β-hydroxyethyl aminomethyl) phenol, el-4 amino 2fluoro phenol, and its addition salts with an acid.

Among the ortho-aminophenols, there may be mentioned, for example, 2-amino phenol, 2-amino 5-methyl phenol, 2amino 6-methyl phenol, 5-acetamido 2-amino phenol, and their addition salts with an acid.

Among the heterocyclic bases, there may be mentioned, for example, pyridine derivatives, pyrimidine derivatives and pyrazolic derivatives.

Among the pyridinid derivatives, there may be mentioned the compounds described in GB 1 026 978 and GB 1 153 196, such as 2,5 diamino pyridine, 2- (4-methoxyphenyl) amino 3-amino pyridine, 2 , 3-diamino 6-methoxy pyridine, 2- (β-methoxyethyl) amino 3-amino 6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid.

Other pyridine oxidation bases useful in the present invention are the 3-amino pyrazolo [1,5-a] -pyridine oxidation bases or their addition salts which are described, for example, in patent application FR 2 801 308. By way of example, the pyrazolo [1,5-a] pyridin-3-ylamine may be cited; 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] pyridine-2-carboxylic acid; 2-methoxy pyrazolo [1,5-a] pyridine-3-ylamino; the (3-amino-pyrazolo [1,5-a] pyridine-7-yl) -methanol; 2- (3-amino-pyrazolo [1,5a] pyridine-5-yl) -ethanol; 2- (3-amino-pyrazolo [1,5-a] pyridine-7-yl) -ethanol; the (3-amino-pyrazolo [1,5-a] pyridine-2-yl-methanol; 3,6-diamino-pyrazollo [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 [1,5a] pyridin-3-ylamine; 2- [3-amino-pyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) -amino] -ethanol; 2 - [(3-amino-pyrazolo [1,5a] pyridin-7-yl) - (2-hydroxyethyl) -amino] ethanol; 3-amino-pyrazolo [1,5-a] pyridine-5-ol; 3-amino-pyrazolo [1,5-a] pyridine-4ol; 3-amino-pyrazolo [1,5-a] pyridine-6-ol; 3-amino-pyrazolo [1,5-a] pyridine-7-ol; as well as its addition salts with an acid or with a base.

Among the pyrimidine derivatives, the compounds described, for example, in DE 23 59 399; JP 88-169571; JP 05-63124; EP 0 770 375 or in patent application WO 96/15765 such as 2,4,5,6-tetraminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4-dihydroxy 5,6diaminopyrimidine, 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4-dihydroxy 5,6diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolo-pyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which there may be mentioned pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; 2,5-dimethylpyrazolo- [1,5-a] -pyrammidine-3,7-diamine; pyrazolo- [1,5-a] -pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo- [1,5a] -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-hydroxy-ethyl) -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-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7diamine, 2, 5, N 7, N 7-tetramethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 3-amino -5-methyl-7-imidazolylpropylamino pyrazolo- [1,5-a] -pyrimidine and its addition salts with an acid and its tautomeric forms, when there is a tautomeric equilibrium.

Among the pyrazole derivatives there may be mentioned the compounds described in patents DE 38 43 892, DE 41 33 957 and in 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 pyrazole, 4,5-diamino 1- (β-hydroxyethyl) pyrazole, 3,4-diamino pyrazol, 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 3phenyl pyrazole, 4-amino 1,3-dimethyl 5-Hydrazino pyrazole, 1-benzyl 4,5-diamino 3-methyl pyrazole, 4,5-diamino 3-tert-butyl 1-methyl pyrazole, 4,5-diamino 1-tert-butyl 3-methyl pyrazole, 4,5-diamino 1- (β-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino 1-ethyl 3-methyl pyrazole, 4,5-diamino 1-ethyl 3- (4'-methoxyphenyl) pyrazole, 4 , 5-diamino 1-ethyl 3-hydroxymethyl pyrazole, 4,5-diamino 3-hydroxymethyl 1-methyl pyrazole, 4,5-diamino 3-hydroxymethyl 1-isopropyl pyrazole, 4,5-diamino 3-methyl 1isopropyl pyrazole, 4-amino 5- (2'-ami noethyl) amino 1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino 1-methyl 4-methylamino pyrazole, 3, 5-diamino 4- (i-hydroxyethyl) amino 1-methyl pyrazole, and its addition salts with an acid.

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

In general, the addition salts of the oxidation bases and of the couplers that can be used in the field of the invention are selected in particular from the addition salts with an acid such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates, and addition salts with a base such as soda, potassium, ammonia, amines or alkanolamines.

The dyeing composition according to the invention may, on the other hand, contain one or more direct dyes that can be selected in particular from the nitrated dyes of the benzene series, the direct azo dyes, the direct methine dyes. These direct dyes can be nonionic, anionic or cationic in nature.

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

The solvents are preferably present in proportions of preference between approximately 1 and 40% by weight with respect to the total weight of the dyeing composition, and even more preferably approximately between 5 and 30% by weight. .

The dyeing composition according to the invention may also contain different additives that are routinely used in hair dyeing compositions, such as anionic, cationic, non-ionic, amphoteric, zwitterionic surfactants or mixtures thereof; anionic, cationic, nonionic, amphoteric, zwitterionic polymers

or their mixtures; mineral or organic thickeners, and in particular the associative thickeners anionic, cationic, non-ionic and amphoteric polymers; antioxidant agents, penetrating agents chelating agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified; film-forming agents, ceramides, preservatives, opacifying agents.

The additives of the preceding paragraph are generally present in amounts comprised for each of them between 0.01 and 20% by weight with respect to the weight of the dyeing composition.

Obviously, the person skilled in the art will be concerned with selecting that or those complementary compounds in such a way that the advantageous properties intrinsically linked to the oxidation dyeing composition according to the invention are not altered, or at least do not substantial form, by the addition (s) considered.

The pH of the dyeing composition according to the invention is generally between approximately 3 and 12, and preferably between approximately 5 and 11. It can be adjusted to the desired value by means of acidifying or alkalizing agents that are routinely used in the dyeing of keratin fibers or even by means of usual buffer systems.

Among the acidifying agents, there may be mentioned, for example, mineral or organic acids, such as hydrochloric acid, orthophosphoric acid or sulfuric acid, carboxylic acids, such as acetic acid, tartaric acid,

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

citric acid, lactic acid or sulfonic acids.

Among the alkalizing agents, for example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines, as well as their derivatives, sodium or potassium hydroxides and the compounds of the following may be mentioned. formula (II):

image 1

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

The dyeing composition according to the invention can be presented in different forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing the keratin fibers, and in particular human hair.

The process of the present invention is a process in which the composition according to the present invention is applied on the fibers as defined above, and the color is revealed by means of an oxidizing agent. The color can be developed with acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition of the invention at the same time of its use or it can be applied by means of an oxidizing composition containing it, applied simultaneously or sequential 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 an appropriate medium for dyeing, at least one oxidizing agent, this oxidizing agent being present in an amount sufficient to reveal a dye. The mixture obtained is then applied to the keratin fibers. After an exposure time of about 3 to 50 minutes, preferably about 5 to 30 minutes, the keratin fibers are rinsed, washed with shampoo, rinsed again and then dried.

The oxidizing agents that are routinely used for oxidation dyeing of keratin fibers are, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persales such as perborates and persulfates, peracids and the oxidases enzymes among which peroxidases, oxido-reductases with 2 electrons, such as uricases, and oxygenases with 4 electrons, such as lacases can be mentioned. Hydrogen peroxide is particularly preferred.

The oxidizing composition may also contain different additives that are routinely used in hair dyeing compositions 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 that is applied to the keratin fibers varies preferably between approximately 3 and 12, and even more preferably between 5 and 11. It can be adjusted to the desired value by means of acidifying or alkalizing agents that are routinely used in the dyeing of keratin fibers and as defined above.

The ready-to-use composition that is finally applied to the keratin fibers can be presented in different forms, such as in the form of liquids, creams, gels, or in any other appropriate form for dyeing the keratin fibers, and in particular of human hair

A subject of the invention is also a device with several compartments or "dyeing kit" in which a first compartment contains the dyeing composition of the present invention that has been defined above and a second compartment contains an oxidizing composition. This device may be equipped with a means that allows the desired mixture to be applied to the hair, such as the devices described in FR-2 586 913 in the name of the applicant.

By means of this device, the keratin fibers can be dyed by means of a process comprising mixing a dyeing composition, comprising at least one oxidation base of formula (I), with an oxidizing agent, and the application of the mixture obtained on the keratin fibers for sufficient time to reveal the desired coloration.

The present invention also aims at the use for oxidation dyeing of keratin fibers, and in particular of human keratin fibers such as hair, of a diamino-N derivative, N-dihydropyrazzolone of formula (I) or one of its addition salts as defined above.

Another object of the present invention is also the amino-N, N-dihydro-pyrazolone derivatives of the following formula (I ’), and their addition salts:

image2

in which:

R’1 and R’2, identical or different, represent: 15

- a linear or branched C1-C6 alkyl radical optionally substituted by one or more radicals selected from the group consisting of an OR'5 radical, an NR'6R'7 radical, a carboxy radical, a sulfonic radical, a CONR carboxamide radical '6R'7, a sulfonamido radical SO2NR'6R'7, a heteroaryl, an aryl optionally substituted by a (C1-C4) alkyl group, a hydroxy, a C1-C2 alkoxy, an amino, a

20 (di) (C1-C2) alkyl amino; - a heteroaryl radical with 5 or 6 links optionally substituted by one or more radicals selected from (C1-C4) alkyl, (C1-C2) alkoxy;

R’3 and R’4 identical or different, represent: 25

- a linear or branched C1-C6 alkyl radical optionally substituted by one or more radicals selected from the group consisting of an OR'5 radical, an NR6R'7 radical, a carboxy radical, a sulfonic radical, a CONR'6R carboxamide radical '7, a sulfonamido radical SO2NR'6R'7, a heteroaryl, an aryl optionally substituted by a (C1-C4) alkyl group, a hydroxy, a C1-C2 alkoxy, an amino, a

30 (di) (C1-C2) alkyl amino; - an aryl radical optionally substituted by one or more (C1-C4) alkyl, hydroxy, C1-C2 alkoxy, amino, (di) (C1-C2) alkyl amino; - a heteroaryl radical with 5 or 6 links, optionally substituted by one or more radicals selected from (C1-C4) alkyl, (C1-C2) alkoxy; 35 R’3 and R’4 can also represent a hydrogen atom;

R’3 and R’4 can form with the nitrogen atom, to which they are attached, a saturated or unsaturated heterocycle, consisting of 5 to 7 links, eventually substituted by one or more radicals selected within the group

40 formed by halogen atoms, the amino, (di) alkyl (C1-C4) amino, hydroxy, carboxy, carboxamido, (C1C2) alkoxy radicals, the C1-C4 alkyl radicals optionally substituted by one or more hydroxy radicals, amino, (di) alkylamino, alkoxy, carboxy, sulfonyl;

R’3 and R’4 can also form together with the nitrogen atom, to which they are attached, a heterocycle of 5 or 7 links whose carbon atoms can be substituted by an oxygen or nitrogen atom eventually substituted;

R’5, R’6 and R’7, identical or different, represent a hydrogen atom; a linear or branched C1C4 alkyl radical optionally substituted by one or more radicals selected from the group consisting of a hydroxy, a

50 C1-C2 alkoxy, a CONR'6R'9 carboxamido, a sulfonyl SO2R'8, an aryl optionally substituted by a (C1-C4) alkyl, a hydroxy, a C1-C2 alkoxy, an amino, a (di ) (C1-C2) alkyl amino; an aryl optionally substituted by a (C1-C4) alkyl, a hydroxy; a C1-C2 alkoxy, an amino, a (di) (C1-C2) alkyl amino;

R’6 and R'7, identical or different, may also represent a CONR’8R’9 carboxamide radical; a sulfonyl SO2R’8; R’8 and R’9, identical or different, represent a hydrogen atom; linear or branched C1-C4 alkyl radical optionally substituted by one or more hydroxy, C1-C2 alkoxy;

R'13 represents a nitro, nitroso or arylazo group AR-N = N-, the aryl radical Ar being optionally substituted by a C1-C4 alkyl radical, amino, (di) (C1-C4) alkyl amino C1 alkoxy -C2, sulfonic, carboxy or halogen.

on condition that

10 • R’1 and R’2 do not simultaneously represent a methyl radical when R’3 and R’4 represent a hydrogen atom and

• R’13 does not represent an Ar-N = N-group when R’3 and R’4 simultaneously represent a hydrogen atom.

Another object of the present invention is also the diamino-N, N-dihydropyrazzolone derivatives of the following formula (I ’), and their addition salts:

image 1

20 in which:

R’’1 and R’’2, identical or different, represent:

- a linear or branched C1-C6 alkyl radical optionally substituted by one or more radicals

25 selected from the group consisting of an OR''5 radical, an NR''6R''7 radical, a carboxy radical, a sulfonic radical, a carboxamide radical CONR''6R''7, a sulfonamido radical SO2NR''6R '7, a heteroaryl, an aryl optionally substituted by a (C1-C4) alkyl group, a hydroxy, a C1-C2 alkoxy, an amino, a (di) (C1-C2) alkyl;

- a heteroaryl radical with 5 or 6 links optionally substituted by one or more radicals selected from (C1-C4) alkyl, (C1-C2) alkoxy;

R’’3 and R’’4, identical or different, represent:

- a linear or branched C1-C6 alkyl radical optionally substituted by one or more radicals

35 selected from the group consisting of an OR''5 radical, an NR''5R''7 radical, a carboxy radical, a sulfonic radical, a carboxamide radical CONR''6R''7, a sulfonamido radical SO2NR''6R '7, a heteroaryl, an aryl optionally substituted by a (C1-C4) alkyl group, a hydroxy, a C1-C2 alkoxy, an amino, a (di) (C1-C2) alkyl;

- an aryl radical optionally substituted by one or more (C1-C4) alkyl, hydroxy, C1-C2 alkoxy, amino, (di) (C1-C4) alkyl amino; - a heteroaryl radical with 5 or 6 links, optionally substituted by one or more radicals selected from (C1-C4) alkyl, (C1-C2) alkoxy;

R’’3 and R’’4 can also represent a hydrogen atom;

45 R’’5, R’’6 and R’’7, identical or different, represent a hydrogen atom; a linear or branched C1-C4 alkyl radical optionally substituted by one or more radicals selected from the group consisting of a hydroxy, a C1-C2 alkoxy, a CONR''8R''9 carboxamido, a SO2R''8 sulfonyl, an aryl optionally substituted by a (C1-C4) alkyl, a hydroxy, a C1-C2 alkoxy, an amino, a (di) (C1-C2) alkyl; an aryl eventually substituted by a

50 (C1-C4) alkyl, a hydroxy, a C1-C2 alkoxy, an amino, a (di) (C1-C2) alkyl;

R’9 and R’7, identical or different, may also represent a CONR’’8R’’9 carboxyamide radical; a sulfonyl SO2R’’6; R’8 and R’9, identical or different, represent a hydrogen atom, linear or branched C1-C4 alkyl radical optionally substituted by one or more hydroxy, C1-C2 alkoxy;

R’’3 and R’’4 can form with the nitrogen atom, to which they are attached, a heterocycle, saturated or unsaturated, that

5 consists of 5 to 7 links, optionally substituted by one or more radicals selected from the group consisting of halogen atoms, the amino, (di) alkyl (C1-C4) amino, hydroxy, carboxy, carboxyamide, (C1C2) radicals alkoxy; C1-C4 alkyl radicals optionally substituted by one or more hydroxy, amino, (di) alkylamino, alkoxy, carboxy, sulfonyl radicals;

10 R’’3 and R’’4 can also form together with the nitrogen atom, to which they are attached, a heterocycle with 5 or 7 links whose carbon atoms can be replaced by an oxygen or nitrogen atom eventually substituted;

provided that R’’1 and R’’2 do not simultaneously represent a methyl radical when R’’3 and R’’4 represent a hydrogen atom.

The amino-N, N-dihydropyrazzolone and diamino-N, N-dihydropyrazzolone derivatives according to the invention and whose radicals R'3 and R'4, on the one hand, and R''3 and R''4, on the other hand, they represent a hydrogen atom can be obtained from intermediaries and synthetic pathways that have been described in different publications and in

20 particular in the following references: J. Het. Chem., 2001, 38 (3), 613-616, Helvetica Chimica Acta, 1950, 33, 1183-1194, J. Org. Chem., 23, 2029 (1958), J. Am. Chem. Soc., 73, 3240 (1951), J. Am. Chem. Soc., 84, 590 (1962), Justus Liebig Ann. Chem., 686, 134 (1965), Tetrahedron. Lett., 31, 2859-2862 (1973), US 4128425 and US 2841584 and references cited.

According to these references, the compounds of formula (I) having the radicals R3 and R4 equal to hydrogen atoms can be obtained by means of the synthesis route that is represented below in Scheme A:

image 1

30

Scheme A

The compounds according to the invention and whose radicals R1 and R2 simultaneously represent a methyl group and the radicals R3 and R4 hydrogen atoms can be obtained by being inspired by the method described in Justus Lieb. Ann. Chem., 686, 134 (1965) (scheme B):

image 1

Scheme B

The compounds according to the invention and whose radical R1 represents a methyl group R2, a phenyl radical, and the radicals R3 and R4 hydrogen atoms can be obtained by being inspired by the method described in J. Org. Chem., 23, 2029 (1958), J. Am. Chem. Soc., 73, 3240 (1951) (scheme C):

image 1

10

Scheme C

According to a new procedure, the compounds of the formula (I) can be obtained according to the

synthesis illustrated in scheme E:

fifteen

image 1

Scheme E

In accordance with this new procedure, the following steps apply: a) step 1: a compound is reacted to R1HN-NHR2 a

25

with a compound b:

image 1

to obtain a 5-amino-1,2-dihydro-pyrazol-3-one c compound:

image3

image4 b) step 2: the derivative c obtained in this way is reacted with an aryldiazonium salt (Ar-NH2,

image 1

c) step 3: a functionalization step of the primary amine group of the azo compound which gives f is obtained to obtain the following compound g:

image5

d) step 4: a reduction reaction of the azo compound f or g is carried out to obtain, respectively, a compound e or h aminated:

image6

The eventual stage of functionalization of the primary amine group in position 5 in secondary and tertiary amine NR3R4,

to obtain the compounds g, it is carried out in accordance with the usual methods of organic synthesis (alkyl halide, alkyl O-sulphonate, alkyl trialkylammonium, reductive amination, etc., see for example, Advanced Organic Chemistry, 3rd edition , 1985, J. March, Willey Interscience).

The reduction of the azo group leads to compounds e and h according to the invention.

The reduction step is carried out in the usual manner, for example by carrying out a hydrogenation reaction by heterogeneous catalysis in the presence of Pd / C, Pd (II) / C, Ni / Ra, etc., or even carrying out a reduction reaction by a metal, for example by zinc, iron, tin, etc. (see Advanced documents

10 organic Chemistry, 3rd edition, J. March, 1985, Willey Interscience and Reduction in organic Chemistry, M. Hudlicky, 1983, Ellis Horwood Series Chemical Science),

Claims (30)

1. Dye composition of keratin fibers comprising, in an appropriate dyeing medium, as an oxidation base, at least one derivative of the diamino-N, N-dihydro-pyrazolone of formula (I) or one of its addition salts or solvates: image 1 in which: 10 R1, R2, R3 and R4, identical or different, represent: - a linear or branched C1-C6 alkyl radical optionally substituted by one or more radicals selected from the group consisting of an OR5 radical, an NR6R7 radical, a carboxy radical, a radical 15 sulfonic, a carboxamide radical CONR6R7, a sulfonamido radical SO2NR6R7, a heteroaryl, an aryl optionally substituted by a (C1-C4) alkyl group, a hydroxy, a C1-C2 alkoxy, an amino, a (di) (C1) alkyl -C2) amino; - an aryl radical optionally substituted by one or more (C1-C4) alkyl, hydroxy, C1-C2 alkoxy, amino, (di) (C1-C2) alkyl amino; 20 - a heteroaryl radical with 5 or 6 links, optionally substituted by one or more radicals selected from (C1-C4) alkyl, (C1-C2) alkoxy; R3 and R4 can also represent a hydrogen atom; R5, R6 and R7, identical or different, represent a hydrogen atom; a linear or branched C1-C4 alkyl radical optionally substituted by one or more radicals selected from the group consisting of a hydroxy, a C1-C2 alkoxy, a CONR8R9 carboxamide, a SO2R8 sulfonyl, an aryl optionally substituted by a (C1- C4) alkyl, a hydroxy, a C1-C2 alkoxy, an amino, a (di) (C1-C2) alkyl; an aryl optionally substituted by a (C1C4) alkyl, a hydroxy, a C1-C2 alkoxy, an amino, a (di) (C1-C2) alkyl; R6 and R7, identical or different, may also represent a CONR8R9 carboxamide radical; a sulfonyl SO2R8; R8 and R9, identical or different, represent a hydrogen atom; linear or branched C1-C4 alkyl radical optionally substituted by one or more hydroxy, C1-C2 alkoxy; R3 and R4 can form with the nitrogen atom, to which they are attached, a saturated or unsaturated heterocycle, consisting of 5 to 7 links, optionally substituted by one or more radicals selected within the group consisting of halogen atoms, amino, (di) (C1-C4) alkyl, amino, hydroxy, carboxy, carboxamido, (C1C2) alkoxy radicals, the C1-C4 alkyl radicals optionally substituted by one or more hydroxy, amino radicals, 40 (di) alkylamino, alkoxy, carboxy, sulfonyl; R3 and R4 can also form together with the nitrogen atom, to which they are attached, a 5 or 7 link heterocycle whose carbon atoms can be replaced by an optionally substituted oxygen or nitrogen atom. Four. Five 2. Composition according to claim 1 wherein R1 and R2 are selected from a C1-C4 alkyl radical optionally substituted by a hydroxy, a (C1-C2) alkoxy, an amino, a (di) (C1-) alkyl C2) amino or a phenyl radical. 3. Composition according to claim 2 wherein R1 and R2 are selected from a methyl, ethyl, 250 hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl or phenyl radical.

Four.

 Composition according to any one of the preceding claims wherein R3 and R4 are selected from a hydrogen atom; a linear or branched C1-C4 alkyl radical optionally substituted by one or more hydroxy, (C1-C2) alkoxy, amino, a (di) (C1-C2) alkyl; a phenyl radical eventually substituted by a

hydroxy radical, amino, (C1-C2) alkoxy.

5.

Composition according to any one of claims 1 to 4, wherein R3 and R4 are selected from a hydrogen atom, a methyl, ethyl, isopropyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-carboxy-ethyl radical.

6.

Composition according to claim 5 wherein R3 and R4 represent a hydrogen atom.

7.

Composition according to any one of claims 1 to 3, wherein R3 and R4 form together with the nitrogen atom to which a cycle with 5 or 7 links selected is selected from the heterocycles pyrrolidine, piperidine, homopiperidine, piperazine, homopiperazine ; said cycles may be substituted by one or more hydroxy, amino, (di) (C1-C2) alkyl, carboxy, carboxamido, C1-C4 alkyl radicals, possibly substituted by one or more hydroxy, amino, (di) C1- alkylamino radicals. C2

8.

Composition according to any one of claims 1 to 3, wherein R3 and R4 form together with the nitrogen atom, to which they are attached, a cycle of 5 or 7 links selected from pyrrolidine, 2,5-dimethylpyrrolidine, the Pyrrolidine-2-carboxylic acid, 3-hydroxypyrrolidine-2-carboxylic acid, 4hydroxypyrrolidine-2-carboxylic acid, 2,4-dicarboxypyrrolidine, 3-hydroxy-2-hydroxymethylpyrrolidine, 2-carboxyamidopyrrolidine, 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, 3-dimethylaminopyrrolidine, 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-hydroxymethylpiperi dyna, 3-hydroxypiperidine, 4-hydroxypiperidine, 3hydroxymethylpiperidine, homopiperidine, 2-carboxythiomopiperidine, 2-carboxamidohomopiperidine, homopiperazine, N-methyl-homopiperazine-Nie (2) (2) (2)

9.

Composition according to any one of claims 1 to 3 and 7 to 8, wherein R3 and R4 form together with the nitrogen atom, to which they are attached, a cycle of 5 or 7 links selected from pyrrolidine, 3-hydroxypyrrolidine , 3-aminopyrrolidine, 3-dimethylamino-pyrrolidine, pyrrolidine-2-carboxylic acid, 3hydroxypyrrolidine-2-carboxylic acid, piperidine, hydroxypiperidine, homopiperidine, diazephan, Nmethylhomopiperazine, lamethylpiperazine.

10.

Composition according to any one of claims 1 to 3 and 7 to 9, wherein R3 and R4 form together with the nitrogen atom, to which they are attached, a cycle with 5 links such as pyrrolidine, 3-hydroxypyrrolidine, 3-aminopyrrolidine, 3-dimethylamino-pyrrolidine.

eleven.

 Composition according to any one of the preceding claims wherein the compound of formula (I) or one of its addition salts is selected from 4,5-diamino-1,2-dimethyl-1,2-dihydro-pyrazole- 3-one; 4-amino-5-methylamino-1,2-dimethyl-1,2-dihydropyrazol-3-one; 4-amino-5-dimethylamino-1,2-dimethyl-1,2-dihydro-pyrazol-3one; 4-amino-5- (2-hydroxyethyl) amino-1,2-dimethyl-1,2-dihydro-pyrazol-3-one; 4-amino-5- (pyrrolidin-1-yl) -1,2-dimethyl-1,2-dihydro-pyrazol-3-one; 4-amino-5- (piperidin-1-yl) -1,2-dimethyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-1,2-di- (2-hydroxyethyl) 1,2-dihydro-pyrazol-3-one; 4-amino-5-methylamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one; 4-amino-5-dimethylamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one; 4-amino-5- (2-hydroxyethyl) amino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one; 4-amino-5- (pyrrolidin-1-yl) -1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one; 4-amino-5- (piperidin-1yl) -1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one; 4,5-diamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-1,2phenyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-1-ethyl-2-methyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-2-ethyl-1-methyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-1-phenyl-2-methyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-1- (2-hydroxyethyl) -2-methyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-2- (2-hydroxyethyl) -1-methyl-1,2-dihydro-pyrazol-3-one.

12.

 Composition according to claims 1 to 11, wherein the compound of formula (I) or one of its addition salts is selected from 4,5-diamino-1,2-dimethyl-1,2-dihydro-pyrazole- 3-one, 4,5-diamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one, 4,5-diamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro- pyrazole-3-one.

13.

 Composition according to any one of the preceding claims further comprising a coupler selected from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers, heterocyclic couplers and their addition salts, as well as mixtures thereof.

14.

Composition according to claim 13 wherein the amount of each of the couplers is between 0.001 and 10% by weight of the total weight of the dye composition.

fifteen.

Composition according to any one of the preceding claims comprising an additional oxidation base selected from para-phenylenediamines, bis-phenylalkylenediamines, paraaminophenols, bis-para-aminophenols, ortho-aminophenols, ortho-phenylenediamines, heterocyclic bases other than derivatives of formula (I) as defined in any one of claims 1 to 12 and

their addition salts, as well as their mixtures.

16.

 Composition according to claim 15 wherein the amount of each of the oxidation bases

it is comprised between 0.001 and 10% by weight of the total weight of the dye composition. 5 17. Procedure for dyeing keratin fibers, characterized in that a composition as defined in any one of claims 1 to 16 is applied to the keratin fibers in the presence of an oxidizing agent for a time sufficient to reveal the desired coloration A method according to claim 17, wherein the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidases enzymes. 19. Multi-compartment device in which a first compartment contains a dyeing composition such and 15 as defined in any one of claims 1 to 16 and a second compartment contains an oxidizing agent. 20. Use for oxidation dyeing of keratin fibers of a composition as defined in a any one of claims 1 to 16. 20 21. Amino-N, N-dihydro-pyrazolone derivatives of formula (I ’) or their addition salts: image 1 25 in which: R’1 and R’2, identical or different, represent: - a linear or branched C1-C6 alkyl radical optionally substituted by one or more radicals 30 selected from the group consisting of an OR'5 radical, an NR'6R'7 radical, a carboxy radical, a sulfonic radical, a carboxamido radical CONR'6R'7, a sulfonamido radical SO2NR'6R'7, a heteroaryl, an aryl optionally substituted by a (C1-C4) alkyl group, a hydroxy, a C1-C2 alkoxy, an amino, a (di) (C1-C2) alkyl amino; - a heteroaryl radical with 5 or 6 links optionally substituted by one or more radicals selected from (C1-C4) alkyl, (C1-C2) alkoxy; R’3 and R’4 identical or different, represent: - a linear or branched C1-C6 alkyl radical optionally substituted by one or more radicals 40 selected from the group consisting of an OR'5 radical, an NR6R'7 radical, a carboxy radical, a sulfonic radical, a carboxamide radical CONR'6R'7, a sulfonamido radical SO2NR'6R'7, a heteroaryl, an aryl optionally substituted by a (C1-C4) alkyl group, a hydroxy, a C1-C2 alkoxy, an amino, a (di) (C1-C2) alkyl; - an aryl radical optionally substituted by one or more (C1-C4) alkyl, hydroxy, C1-C2 alkoxy, amino, (di) (C1-C2) alkyl amino; - a heteroaryl radical with 5 or 6 links, optionally substituted by one or more radicals selected from (C1-C4) alkyl, (C1-C2) alkoxy; R’3 and R’4 can also represent a hydrogen atom; R'3 and R'4 can form with the nitrogen atom, to which they are attached, a saturated or unsaturated heterocycle, consisting of 5 to 7 links, optionally substituted by one or more radicals selected within the group formed by atoms halogen, the amino, (di) (C1-C4) alkyl, amino, hydroxy, carboxy, carboxyamido, (C1C2) alkoxy radicals, the C1-C4 alkyl radicals optionally substituted by one or more hydroxy, amino, (di) radicals alkylamino, alkoxy, carboxy, sulfonyl; R’3 and R’4 can also form together with the nitrogen atom, to which they are attached, a 5 or 7 link heterocycle whose carbon atoms can be substituted by an optionally substituted oxygen or nitrogen atom; R’5, R’6 and R’7, identical or different, represent a hydrogen atom; a linear or branched C1C4 alkyl radical optionally substituted by one or more radicals selected from the group consisting of a hydroxy, a C1-C2 alkoxy, a CONR'6R'9 carboxamide, a SO2R'8 sulfonyl, an aryl optionally substituted by a (C1-C4) Alkyl, a hydroxy, a C1-C2 alkoxy, an amino, a (di) (C1-C2) alkyl amino; an aryl optionally substituted by a (C1-C4) alkyl, a hydroxy; a C1-C2 alkoxy, an amino, a (di) (C1-C2) alkyl amino; R’6 and R'7, identical or different, may also represent a CONR’8R’9 carboxamide radical; a sulfonyl SO2R’8; 15 R’8 and R’9, identical or different, represent a hydrogen atom; linear or branched C1-C4 alkyl radical optionally substituted by one or more hydroxy, C1-C2 alkoxy; R'13 represents a nitro, nitroso or arylazo group AR-N = N-, the aryl radical Ar being optionally substituted by a C1-C4 alkyl radical, amino, (di) (C1-C4) alkyl amino C1- alkoxy C2, sulfonic, carboxy or halogen. 20 on condition that • R’1 and R’2 do not simultaneously represent a methyl radical when R’3 and R’4 represent a hydrogen atom and 25 • R’13 does not represent an Ar-N = N-group when R’3 and R’4 simultaneously represent a hydrogen atom. 22. Derivatives of the diamino-N, N-dihydro-pyrazolone of formula (I ’) or its addition salts: image2 in which: R’’1 and R’’2, identical or different, represent: 35 - a linear or branched C1-C6 alkyl radical optionally substituted by one or more radicals selected from the group consisting of an OR''5 radical, a NR''6R''7 radical, a carboxy radical, a sulfonic radical, a carboxamido radical CONR''6R''7, a sulfonamido radical SO2NR''6R''7, a heteroaryl, an aryl optionally substituted by a (C1-C4) alkyl group, a hydroxy, a C1-C2 alkoxy, an amino , a 40 (di) (C1-C2) alkyl amino; - a heteroaryl radical with 5 or 6 links optionally substituted by one or more radicals selected from (C1-C4) alkyl, (C1-C2) alkoxy; R’’3 and R’’4, identical or different, represent: 45 - a linear or branched C1-C6 alkyl radical optionally substituted by one or more radicals selected from the group consisting of an OR''5 radical, a NR''5R''7 radical, a carboxy radical, a sulfonic radical, a carboxamido radical CONR''6R''7, a sulfonamido radical SO2NR''6R''7, a heteroaryl, an aryl optionally substituted by a (C1-C4) alkyl group, a hydroxy, a C1-C2 alkoxy, an amino , a 50 (di) (C1-C2) alkyl amino; - an aryl radical optionally substituted by one or more (C1-C4) alkyl, hydroxy, C1-C2 alkoxy, amino, (di) (C1-C4) alkyl amino; - a heteroaryl radical with 5 or 6 links, optionally substituted by one or more radicals selected from (C1-C4) alkyl, (C1-C2) alkoxy; R’’3 and R’’4 can also represent a hydrogen atom; R’’5, R’’6 and R’’7, identical or different, represent a hydrogen atom; a linear or branched C1-C4 alkyl radical optionally substituted by one or more radicals selected from the group consisting of a hydroxy, a C1-C2 alkoxy, a CONR''8R''9 carboxamido, a SO2R''8 sulfonyl, an aryl optionally substituted by a (C1-C4) alkyl, a hydroxy, a C1-C2 alkoxy, an amino, a (di) (C1-C2) alkyl; an aryl optionally substituted by a (C1-C4) alkyl, a hydroxy, a C1-C2 alkoxy, an amino, a (di) (C1-C2) alkyl; R’9 and R’7, identical or different, may also represent a CONR’’8R’’9 carboxyamide radical; a sulfonyl SO2R’’6; R’8 and R’9, identical or different, represent a hydrogen atom, linear or branched C1-C4 alkyl radical optionally substituted by one or more hydroxy, C1-C2 alkoxy; R''3 and R''4 can form with the nitrogen atom, to which they are attached, a heterocycle, saturated or unsaturated, consisting of 5 to 7 links, possibly substituted by one or more radicals selected within the group formed by halogen atoms, amino radicals, (di) C1-C4 alkyl, amino, hydroxy, carboxy, carboxyamido, (C1C2) alkoxy; C1-C4 alkyl radicals optionally substituted by one or more hydroxy, amino, (di) alkylamino, alkoxy, carboxy, sulfonyl radicals; R’’3 and R’’4 can also form together with the nitrogen atom, to which they are attached, a heterocycle with 5 or 7 links whose carbon atoms can be replaced by an oxygen or nitrogen atom eventually substituted; provided that R’’1 and R’’2 do not simultaneously represent a methyl radical when R’’3 and R’’4 represent a hydrogen atom.

2. 3.

Derivatives according to any one of claims 21 or 22, for which R''1, R''2, R'1 and R'2, independently of each other, are selected from an alkyl radical in C1-C4 optionally substituted by a hydroxy, a (C1-C2) alkoxy, an amino, a (di) (C1-C2) alkyl amino.

24.

Derivatives according to claim 23, for which R''1, R''2, R'1 and R'2, independently of each other, are selected from a methyl, ethyl, 2-hydroxyethyl radical , 3-hydroxypropyl, 2-hydroxypropyl.

25.

Derivatives according to any one of claims 21 to 24, for which R''3, R''4, R'3 and R'4, independently of each other, are selected from a hydrogen atom ; a linear or branched C1-C4 alkyl radical optionally substituted by one or more hydroxy, (C1-C2) alkoxy, amino, a (di) (C1-C2) alkyl; a phenyl radical optionally substituted by a hydroxy, amino, (C1-C2) alkoxy radical.

26.

Derivatives according to any one of claims 21 to 25, for which R''3, R''4, R'3 and R'4, independently of each other, are selected from a hydrogen atom , a methyl, ethyl, isopropyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-carboxyethyl.

27.

 Derivatives according to any one of claims 21 to 26, for which R''3, R''4, on the one hand, R'3 and R'4, on the other hand, together with the nitrogen atom, to which they are attached, a cycle with 5 or 7 links selected from the pyrrolidine heterocycles; piperidine; homopiperidine; piperazine; homopiperazine; said cycles may be substituted by one or more hydroxy radicals; Not me; (di) (C1-C2) alkyl amino; carboxy; carboxamide; C1-C4 alkyl optionally substituted by one or more hydroxy, amino, (di) C1-C2 alkylamino.

28.

Derivatives according to any one of claims 21 to 24 and 27, for which R''3, R''4, on the one hand, R'3 and R'4, on the other hand, form together with the atom of nitrogen, to which they are attached, a cycle of 5 or 7 links selected from pyrrolidine, 2,5-dimethylprirrolidine, pyrrolidine-2-carboxylic acid, 3-hydroxypyrrolidine-2-carboxylic acid, 4-hydroxypyrrolidine-2- acid carboxylic, 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, 3-dimethylamino pyrrolidine, 4-amino-3-hydroxy pyrrolidine, 3-hydroxy-4 - (2-hydroxyethyl) amino pyrrolidine, piperidine, 2,6-dimethylpiperidine, 2-carboxypiperidine, 2-carboxamidopiperid ina, 2-hydroxymethylpiperidine, 3-hydroxy-2-hydroxymethylpiperidine, 3-hydroxypiperidine, 4-hydroxypiperidine, 3-hydroxymethylpiperidine, homopiperidine, 2-carboxythiomopiperidine, 2-carboxamido-homopripene, homopripene-homopripene N- (2-hydroxyethyl) -homopiperazine.

29.

Derivatives according to any one of claims 21 to 24 and 27 to 28, for which R''3, R''4, on the one hand, R'3 and R'4, on the other hand, form together with the Nitrogen atom, to which they are attached, a cycle with 5 or 7 links selected from pyrrolidine, 3-hydroxypyrrolidine, 3-amino pyrrolidine, 3-dimethylamino-pyrrolidine, pyrrolidine-2-carboxylic acid, 3-acid 2-carboxylic hydroxypyrrolidine, piperidine, hydroxypiperidine,

5 homopiperidine, diazepán, N-methyl homopiperazine, N β-hydroxyethylhomopiperazine. 30. Derivatives according to any one of claims 21 to 24 and 27 to 29, for which R''3, R''4, on the one hand, R'3 and R'4, on the other hand, together form with the nitrogen atom, to which they are attached, a cycle with 5 links such as pyrrolidine, 3-hydroxypyrrolidine, 3-aminopyrrolidine, 3-dimethylamino-pyrrolidine. 10 31. Method of preparing a compound of formula (I) as defined in the compositions according to any one of claims 1 to 12, characterized in that the following steps apply: 15 a) step 1: a compound is reacted at R1HN-NHR2 a with a compound b: 20 image 1 to obtain a 5-amino-1,2-dihydro-pyrazol-3-one c compound: image3 b) step 2: the derivative c which is obtained in this way is reacted with an aryldiazonium salt (Ar-NH2 + Y-) to obtain an azo compound f: image2 c) step 3: a functionalization step of the primary amine group of the azo compound which gives f is obtained to obtain the following compound g: image 1 d) step 4: a reduction reaction of the azo compound f or g is carried out to obtain, respectively, a compound e or h aminated: image 1