EP1341507A1 - Oxidation dyeing composition based on 1-(4-aminophenyl) pyrrolidines substituted in positions 2 and 5 - Google Patents

Abstract

The invention concerns a composition for oxidation dyeing of keratinous fibres, and in particular human keratinous fibres such as hair, comprising as oxidation base a 1-(4-aminophenyl) pyrrolodine substituted in positions 2 and 5. The invention also concerns the method dyeing keratinous fibres using said compositions.

Description

OXIDATION DYE COMPOSITION BASED ON 1- (4-AMINOPHENYL) PYRROLIDINES SUBSTITUTED IN POSITIONS 2 AND 5

5 The subject of the invention is a composition for the oxidation dyeing of keratin fibers, and in particular human keratin fibers such as the hair, comprising as oxidation base a 1- (4-aminophenyl) pyrrolidine substituted for less in positions 2 and 5.

It is known to dye keratin fibers and in particular human hair with dye 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,

15,6-dihydroxyindole derivatives, 5,6-dihydroxyindoline derivatives generally called oxidation bases. The precursors of oxidation dyes, or oxidation bases, are colorless or weakly colored compounds which, associated with oxidizing products, can give rise, through an oxidative condensation process, to colored and coloring compounds. 0

It is also known that the shades obtained with these oxidation bases can be varied by associating them with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta- hydroxyphenols and certain heterocyclic compounds such as, for example, pyrazolo derivatives [1, 5-b] -1, 2,4, -triazoles, pyrazolo derivatives [3,2-cJ-1, 2,4, -triazoles ,. pyrazolo derivatives [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, 0 allows a rich palette of colors to be obtained.

The so-called "permanent" coloration obtained thanks to these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must be without drawbacks from the toxicological point of view, it must make it possible to obtain nuances 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 white hair, and finally be the least selective possible, that is to say allow to obtain the smallest possible color differences throughout the same keratin fiber, which can be in differently sensitized effect (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.

In the field of hair coloring, para-phenylenediamine and paratoluene diamine are widely used oxidation bases. They make it possible to obtain various nuances with oxidation couplers.

However, there is a need to discover new oxidation bases having a better toxicological profile than para-phenylenediamine and paratoluene diamine, while making it possible to give the hair excellent properties of color intensity, variety of shades. , color uniformity and tenacity to external agents

It has already been proposed, in particular in patent application GB 2 239 265, to use 2- (β-hydroxyethyl) para-phenylenediamine or else N, N-bis- (β-hydroxyethyl) para-phenylenediamine as substitutes potentials of paraphenylenediamine and paratoluylenediamine. The same is true for 2- (hydroxyalkoxy) paraphenylenediamines (see in particular US Pat. No. 5,538,516).

However, NN-bis- (β-hydroxyethyl) paraphenylenediamine and 2- (β-hydroxyethyl) paraphenylenediamine have the disadvantage of leading to a less wide variety of shades and of imparting less color intensity, less uniformity. to hair than para-phenylenediamine and 4-amino-2-methylaniline. It is the same for 2- (hydroxyalkoxy) -paraphenylene diamine which give the hair colors which evolve and change over time.

Furthermore, it is known in the literature (RL Bent et al., JACS 73, 3100, 1951) that 4-paraphenylenediamine derivatives in which one of the nitrogen atoms is included in a non-aromatic 6 or 7-membered carbon ring or heterocyclic compounds are less oxidizable than the derivatives of 4-paraphenylenediamines in which one of the nitrogen atoms is substituted by two asymmetric substituents, which are themselves less oxidizable than the derivatives in paraphenylenediamine in which one of the nitrogen atoms is substituted by two symmetrical substituents . It is also mentioned in the same article that the paraphenylenediamine derivative, one of the nitrogen atoms of which is included in a nonaromatic 5-carbon chain ring is more oxidizable than each of the derivatives mentioned above. This particular class of N- (4-aminophenyl) -pyrrolidine derivatives therefore makes it possible to obtain condensation reactions with couplers in an oxidizing medium whose kinetics is found to be accelerated compared to the para-phenylenediamine derivatives mentioned above.

However, the oxidation bases which are too oxidizable and which react with couplers according to accelerated reaction rates, generally lead to the formation of dyes outside the keratin fiber. The intensities, tenacity and uniformity of the colorings thus obtained on the hair are generally insufficient.

However, US Patent 5,851,237 proposes the use of 1- (4-aminophenyl) pyrrolidine derivatives optionally substituted on the benzene ring in order to replace paraphenylenediamine. As such, the same patent very preferably proposes the use of 1- (4-aminophenyl) pyrrolidine as a substitute for paraphenylenediamine.

However, it is known in the literature that 1- (4-aminophenyl) pyrrolidine has a highly allergenic activity (R.L. Bent et al., J.A.C.S. 73, 3100, 1951).

US Patent 5,993,491 proposes the use of N- (4-aminophenyl) -2-hydroxymethylpyrrolidine derivatives optionally substituted on the benzene ring and on the pyrrolidinin heterocycle in position 4 with a hydroxy radical in order to replace paraphenylenediamine. As preferred compounds, said patent proposes N- (4-aminophenyl) -2- (hydroxymethyl) -pyrrolidine substituted by a hydrogen atom or a methyl radical in position 3. However, it is clearly established that these compounds do not allow to give the hair a coloration of quality equivalent to that obtained with para-phenylenediamine or with paratoluenediamine due to a lack of intensity and uniformity of color.

Patent application JP 11158048 proposes hair coloring compositions offering good spreading properties, ease of application and resistance to shampoo. These compositions contain at least one compound selected from derivatives of 4-aminoaniline optionally substituted on the benzene ring and one of whose nitrogen atoms is included in a 5- to _7-membered carbon ring, or at least a compound chosen from 4-aminoaniline derivatives optionally substituted on the benzene ring and one of the nitrogen atoms of which is substituted by a radical Zi and a radical Z ₂ , Zi being an alkyl, aryl or heterocycle group, and Z ₂ being a radical - (CH ₂ - CH ₂ -O) -Z ₃ where Z ₃ represents a hydrogen atom, an alkyl, aryl or heterocycle group.

In terms of coloring power, ease of application, uniformity of color and resistance to shampooing, this patent application demonstrates that the preferred derivatives N- (3-isopropyloxy-4-aminophenyl) -2.5- dimethylpyrrolidine, 1- (3-methyl 4-Amino-phenyl) 2,5- dihydroxyethyl-pyrrolidine, N- (3-methyl-4-aminophenyl) -3- (2-hydroxyethyloxy) pyrrolidine, and N- (3-methyl -4-aminophenyl) -2-methyl-4-hydroxypyrrolidine behave like oxidation bases equivalent to paraphenylenediamine derivatives, the nitrogen atom of which is included in a functionalized piperidine 6-membered ring.

However, it is known that when one of the nitrogen atoms of the para-phenylenediamine derivatives is included in a 6-membered ring, in particular piperidine, the activation energy to lead to the corresponding oxidized quinonimine form is among the highest from the series of para-phenylenediamines N, N-disubstituted. Consequently, the oxidative condensation reactions of such bases with or without couplers are kinetically and energetically disadvantaged and the dye compositions containing such oxidation bases give the hair insufficient properties in terms of intensity and uniformity of the color. color compared to those containing para-phenylenediamine or paratoluenediamine.

It follows that the compositions containing derivatives of paraphenylenediamine having a nitrogen atom included in a functionalized pyrrolidine cycle as described in patent application JP 11158048 do not make it possible to confer on the hair dyeing results equivalent to those obtained with para -phenylenediamine or paratoluenediamine.

It is therefore clear that there is a real need to discover new oxidation bases having both a good toxicological profile and properties such as the compositions containing them make it possible to confer excellent properties of color intensity on the hair. , variety of shades, uniformity of color and tenacity with regard to the different external aggressions that the hair can undergo. The aim of the present invention is to develop new dye compositions which do not have the drawbacks of the oxidation bases of the prior art.

This object is achieved with the present invention which relates to a composition for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, comprising, in a medium suitable for dyeing, - at least one base oxidation chosen from the compounds of formula (I) below, and / or their addition salts with an acid

in which: - Ri represents a halogen atom; a C-ι-C ₇ carbon chain, saturated or which may contain one or more double bonds and / or one or more triple bonds, linear or branched, which may be in the form of a ring having 3 to 6 members, one or more atoms of carbon of the chain which can be replaced by an oxygen, nitrogen or sulfur atom, by an SO ₂ group or by a halogen atom, the radical Ri not comprising a peroxide bond, nor of diazo or nitro radicals or nitroso;

- R ₂ and R ₃ represent, independently of one another, a carbon chain of CrC ₄ , saturated or unsaturated; a C-ι-C alkyl radical substituted by a Cι-C ₄ alkoxy radical, acetoxy, amino, carboxyl, carbamoyl, (mono or dialkyl) (CC ₄ ) carbamoyl, alkoxy (Cι-C ₄ ) carbonyl, monohydroxyalkoxy CrC ₆ or by a C ₂ -C ₆ polyhydroxyalkoxy group; a CC ₄ monohydroxyalkyl radical; a C-ι-C ₆ polyhydroxyalkyl radical; a CC aminoalkyl radical in which the amine is mono or disubstituted by a CC ₄ alkyl, acetyl, CC ₄ monohydroxyalkyl or C ₂ -C ₆ polyhydroxyalkyl radical; a C ₂ -C ₄ polyaminoalkyl radical; a C ₂ alkyl radical - C ₄ substituted with at least one amino group and at least one hydroxy group; a carboxyl radical; a carbamoyl radical; a carbamoyl (mono or dialkyl) (CC ₄ ) radical; an alkoxy (CC ₄ ) carbonyl radical; a (C1-C4) carbonyl alkyl radical

-n is between 0 and 2, it being understood that when n is equal to 2 then the radicals i can be identical or different, with the exception of compound 1 - (3-isopropyloxy 4-Amino-phenyl) 2,5- dimethyl-pyrrolidine and compound 1- (3-methyl 4-Amino-phenyl) 2,5-dihydroxymethyl-pyrrolidine.

Totally unexpectedly and surprisingly, the 1- (4-aminophenyl) - pyrrolidine derivatives of formula (I) substituted at least in positions 2 and 5 of the pyrrolidine ring can be used as oxidation dye precursors, and in addition allow to obtain dye compositions which lead to powerful coloring of keratin fibers and which exhibit good resistance to external agents (light, bad weather, washing, permanent waving, perspiration, friction). Finally, these compounds appear to be easily synthesizable and are chemically stable.

Unless otherwise indicated, the radicals, groups, or carbon chains defined above in formula (I) may be linear or branched.

According to the invention, when it is indicated that one or more of the carbon atoms of the radical Ri may be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group, and / or that said radical R < _\ may contain one or more double bonds and / or one or more triple bonds, this means that the following transformations can be made, for example:

-CH— H can become '- O-H

In formula (I), the radical R ₁ is preferably chosen from a chlorine or bromine atom, a methyl, ethyl, isopropyl, vinyl, allyl, methoxymethyl radical, hydroxymethyl,, 1-carboxymethyl, 1-aminomethyl, 2-carboxyethyl, 2-hydroxyethyl, 3-hydroxypropyl, 1, 2-dihydroxyethyl, 1-hydroxy-2-aminoethyl, 1-amino-2-hydroxyethyl, 1, 2-diaminoethyl , methoxy, ethoxy, allyloxy, 2-hydroxyethyloxy. According to a particular embodiment, R 1 is chosen from a methyl, hydroxymethyl, 2-hydroxyethyl, 1, 2-dihydroxyethyl, methoxy, 2-hydroxyethoxy radical, and preferably a methyl, hydroxymethyl or 1, 2-dihydroxyethyl radical.

According to a particular embodiment, n is equal to 0 or 1. When n is equal to 1, then R is preferably in position 3 of the benzene ring.

The radicals R ₂ and R ₃ of formula (I) are preferably chosen from the hydroxymethyl radical, the aminomethyl radical, the carboxyl radical, the carbamoyl radical, the 2-hydroxyethyloxymethyl radical, the 2-hydroxyethylaminomethyl radical, methoxymethyl.

In formula (I), the asymmetric carbons substituted by the radicals R ₂ and R ₃ may be independently of each other of configuration (R) and / or (S).

Among the compounds of formula (I) useful for the present invention, there may be mentioned in particular:

and their addition salts with an acid.

The addition salts with an acid of the compounds of formula (I) according to the invention are preferably chosen from inorganic or organic salts such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates , lactates and acetates. The hydrochlorides are particularly preferred.

Paraphenylenediamine derivatives with pyrrolidinyl group of formula (I), as well as their methods of synthesis are known, see in particular patent application DE 4 241 532 (AGFA).

The compound (s) of formula (I) according to the invention preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition, and even more preferably from 0.005 to 6% by weight approximately of this weight .

The medium suitable for dyeing (or support) generally consists of water or a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water. As organic solvent, mention may, for example, be made of lower C 1 alkanols, such as ethanol and isopropanol; polyols or polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, analogous products and mixtures thereof.

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

The pH of the dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers. Among the acidifying agents, there may be mentioned, by way of example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.

Among the basifying agents, there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of formula (II) below:

in which W is a propylene residue optionally substituted by a hydroxyl group or a CC ₆ alkyl radical; R, R _5, Rβ and R _7, identical or different, represent a hydrogen atom, alkyl or hydroxyalkyl ₆ CC CC _6.

The dye composition in accordance with the invention may also contain, in addition to the compound or compounds of formula (I) defined above, at least one additional oxidation base which can be chosen from the oxidation bases conventionally used in dyeing oxidation and among which there may be mentioned paraphenylenediamines different from the compounds of formula (I), bis-phenylalkylenediamines, paraaminophenols, ortho-aminophenols and heterocyclic bases.

Among the paraphenylenediamines, mention may more particularly be made, for example, of paraphenylenediamine, paratoluylenediamine, 2-chloro paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine , 2,5-dimethyl paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl 3-methyl aniline, N, N-bis- (β- hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino 2-methyl aniline, 4-N, N-bis- (β-hydroxyethyl) amino 2-chloro aniline , 2-β-hydroxyethyl paraphenylenediamine, 2-fluoro paraphenylenediamine, 2-isopropyl paraphenylenediamine, N- (β-hydroxypropyl) paraphenylenediamine, 2-hydroxymethyl paraphenylenediamine, N, N-dimethyl 3-methyl paraphenylen , N- (ethyl, β- hydroxyethyl) paraphenylenediamine, the N- (β, γ-dihydroxypropyl) paraphenylenediamine, the N- (4'-aminophenyl) para-phenylenediamine, N-phenyl para-phenylenediamine, 2-β-hydroxyethyloxy para-phenylenediamine, 2-β-acetylaminoethyloxy para-phenylenediamine, N- (β-methoxyethyl) para-phenylenediamine, and their salts, and their acid.

Among the para-phenylenediamines mentioned above, very particularly preferred are para-phenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-β-hydroxyethyl para-phenylenediamine, 2-β-hydroxyethyloxy para-phenylenediamine, 2,6-dimethyl , 6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 2-chloro paraphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine, and their addition salts with a acid.

Among the bis-phenylalkylenediamines that may be mentioned more particularly by way of 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- (4-aminophenyl) tetramethylenediamine, N, N'-bis - (β-hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methyl-aminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) N, N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1, 8-bis- (2,5-diamino phenoxy) -3,5-dioxaoctane, and their addition salts with an acid.

Among the para-aminophenols, mention may more particularly be made, for example, of para-aminophenol, 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4-amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2- (β-hydroxyethyl aminomethyl) phenol, 4-amino 2-fluoro phenol, and their addition salts with an acid.

Among the ortho-aminophenols, mention may more particularly be made, by way of example, of 2-amino phenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol, 5-acetamido 2-amino phenol, and their addition salts with an acid.

Among the heterocyclic bases that may be mentioned more particularly by way of example, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives. Among the pyridine derivatives, mention may more particularly be made of the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino 3-amino 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.

Among the pyrimidine derivatives, mention may be made more particularly of the compounds described, for example, in patents DE 2,359,399; JP 88-169,571; JP 05 163 124; EP 0 770 375 or patent application WO 96/15765 such as 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy 2,5,6-thaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4-dihydroxy 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolo-pyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which may be mentioned pyrazolo - [1,5-a] -pyrimidine-3J-diamine; 2,5-dimethyl pyrazolo- [1,5-a] - pyrimidine-3J-diamine; pyrazolo- [1,5-a] -pyrimidine-3,5-diamine; 2J-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-hydroxy-ethyl) -amino] -ethanol, 2 - [(7-amino- pyrazolo [1,5-a] -pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol, 5,6-dimethyl pyrazolo- [1,5-a] -pyrimidine-3J-diamine, 2,6-dimethyl pyrazolo- [1, 5-a] -pyrimidine-3J-diamine, 2, 5, N 7, N 7-tetramethyl pyrazolo- [1,5-a] -pyrimidine-3J-diamine, 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo- [1,5-a] -pyrimidine and their acid addition salts and their tautomeric forms, when there is a tautomeric equilibrium.

Among the pyrazole derivatives, mention may more particularly 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 such as 4,5-diamino 1-methyl pyrazole, 4,5-diamino l- (β-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-methyl pyrazole, 4,5-diamino 1-tert-butyl 3- methyl pyrazole, 4,5-diamino l- (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 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 pyrazole, 3,5-diamino 4- (β-hydroxyethyl) amino 1-methyl pyrazole, and their addition salts with an acid.

When used, these additional oxidation bases preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition, and even more preferably from 0.005 to 6% by weight approximately of this weight.

The oxidation dye compositions in accordance with the invention may also contain at least one coupler and / or at least one direct dye, in particular for modifying the nuances or enriching them with reflections.

The couplers which can be used in the oxidation dye compositions in accordance with the invention can be chosen from the couplers conventionally used in oxidation dyeing and among which there may be mentioned in particular metaphenylenediamines, meta-aminophenols, metadiphenols, naphthols and heterocyclic couplers such as, for example, indole derivatives, indoline derivatives, pyridine derivatives, indazole derivatives, pyrazolo derivatives [1, 5-b] -1, 2,4-triazole, pyrazolo derivatives [ 3,2-c] -1, 2,4-triazole, benzimidazole derivatives, benzothiazole derivatives, benzoxazole derivatives, 1,3-benzodioxole derivatives and pyrazolones, and their addition salts with a acid.

These couplers are more particularly chosen from 2-methyl 5-amino phenol, 5-N- (β-hydroxyethyl) amino 2-methyl phenol, 3-amino phenol, 1, 3-dihydroxy benzene, 1,3 -dihydroxy 2-methyl benzene, 4-chloro 1, 3-dihydroxy benzene, 2,4-diamino l- (β-hydroxyethyloxy) benzene, 2-amino 4- (β-hydroxyethylamino) 1 -methoxy benzene, 1,3-diamino benzene, 1,3-bis- (2,4-diaminophenoxy) propane, sesamol, α-naphthol, 2-methyl-1-naphthol, 6-hydroxy indole, 4- hydroxy indole, 4-hydroxy N-methyl indole, 6-hydroxy indoline, 6-hydroxybenzomorpholine, 3,5 diamino 2,6dimethoxy pyridine, 1-N β hydroxyethylamine 3,4 methylenedioxy benzene, 2,6 bis (β hydroxyethylamino) toluene, 2,6-dihydroxy 4-methyl pyridine, 1-H 3-methyl pyrazole 5-one, 1-phenyl 3-methyl pyrazole 5-one, and their addition salts with an acid .

When they are present, the coupler (s) preferably represent from 0.0001 to 10% by weight approximately of the total weight of the dye composition and even more preferably from 0.005 to 5% by weight approximately of this weight. The dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic polymers , non-ionic, amphoteric, zwitterionic or their mixtures, mineral or organic thickening agents, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example silicones, film-forming agents, preserving agents, opacifying agents.

Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the oxidation dye composition according to the invention are not, or not substantially, altered. by the addition (s) envisaged. The dye composition according to the invention can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair.

Another subject of the invention is the use of the compositions of the invention for the oxidation dyeing of keratin fibers, and in particular human fibers such as the hair.

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

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

According to a preferred embodiment of the dyeing process of the invention, the dye composition described above is preferably mixed with an oxidizing composition containing, in a suitable medium for dyeing, at the time of use. at least one oxidizing agent present in an amount sufficient to develop coloring. The mixture obtained is then applied to the keratin fibers and is left lay for 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, after which it is rinsed, washed with shampoo, rinsed again and dried.

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

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

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

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

Another object of the invention is a device with several compartments or "kit" for dyeing or any other packaging system with several compartments, a first compartment of which contains the dye composition as defined above and a second compartment of which contains the oxidizing composition. as defined above. These devices can be equipped with a means enabling the desired mixture to be delivered to the hair, by any means known to a person skilled in the art, for example the devices described in patent FR-2,586,913 in the name of the applicant.

Finally, the subject of the invention is also the colored product resulting from the oxidation of at least one compound of formula (I) as defined above in the presence of at least one oxidizing agent, and optionally in the presence of at least one coupler and / or at least one additional oxidation base.

These colored products can also be in the form of pigments and be used as direct dyes for the direct dyeing of hair or even be incorporated in cosmetic products such as for example in makeup products.

The examples which follow are intended to illustrate the invention without however limiting its scope.

EXAMPLES EXAMPLE 1: [1- (4-Amino-phenyl) -5-hydroxymethyl-pyrrolidin-2-yl] -methanol (6)

- synthesis of compound (2): 70 ml (1.36 mole) of bromine are added dropwise to a solution of 125 g (0.68 mole) of adipoyl chloride in 600 ml of chloroform. The solution obtained is heated for 14 h at reflux. After returning to ambient temperature, the mixture obtained is added dropwise to 500 ml of ethanol cooled by an ice bath, taking care that the temperature does not exceed 50 ° C. After addition, the mixture is stirred overnight at room temperature and then poured into 21 of cold water. The organic phase is collected, washed with 500 ml of a 2% sodium bisulfite solution and then twice with a 3% solution of sodium carbonate. After drying over magnesium sulfate and filtration, the organic phase is concentrated in vacuo. 164 g (67%) of compound (2) are thus obtained, which is in the form of white crystals.

-Synthesis of compound (3):

A mixture consisting of 120 g (0.333 mole) of compound (2), 36.4 ml (0.333 mole) of benzylamine, 115 g (0.872 mole) of potassium carbonate, 300 ml of toluene and 100 ml of water is heated 12 hours at reflux. After decantation, the aqueous phase is extracted by

2x200 ml of ethyl ether. The organic phases are combined, dried (magnesium sulfate), filtered and then concentrated in vacuo. 57 g (56%) of compound are thus obtained

(3) in the form of a yellow oil.

-Synthesis of compound (4): 21 g (55.3 moles) of LiAIH4 are added in small fractions in a solution of 50 g (0.164 mole) of compound (3) in 400 ml of anhydrous THF, cooled by a bath of ice cream.

The mixture obtained is brought to reflux for 3 hours, cooled and then poured slowly onto ice. After filtration, the solvents are removed under vacuum. 12.8 g are thus obtained.

(84%) of compound (4) in the form of a colorless oil.

-Synthesis of compound (5):

25 g (0.113 mole) of compound 4, 8.6 g of palladium dihydroxide and 250 ml of methanol are placed in a reactor. Hydrogen is introduced at atmospheric pressure and stirred for 24 hours at room temperature. The mixture obtained is filtered and the filtrate concentrated in vacuo. 12 g (80%) of compound (5) are thus obtained in the form of a colorless oil.

-Synthesis of compound (6): A mixture consisting of 10 g (mole) of compound 5, of 16 g (0.1 14 mole) of p-nitro fluorobenzene, of 15.6 g (0.111 mole) of potassium carbonate and 150 ml of DMF at 65 ° C. The DMF is then evaporated under vacuum and the residue taken up in 120 ml of water. After extraction with ethyl acetate (2x200 ml), drying over magnesium sulfate of the organic phase, filtration and concentration in vacuo, a yellow solid is obtained. This product is chromatographed on silica gel using a 4/1 chloroform / ethyl acetate mixture as eluent. 12 g (62%) decomposed 6 are thus obtained in the form of yellow crystals.

-synthesis of compound (7): [1- (4-Amino-phenyl) -5-hydroxymethyl-pyrrolidin-2-yl] - methanol:

12 g (47.6 moles) of nitro derivative 6, 400 ml of absolute ethanol and 4 g of 5% Pd / C are placed in an autoclave. A hydrogen pressure of the order of 10 bars is introduced into the apparatus and the mixture is stirred at room temperature for 7 hours. After a nitrogen purge, the catalyst is filtered and the filtrate concentrated in vacuo. 6.5 g (73%) of compound (7) are thus obtained in the form of brown crystals.

- 1 H-NMR (DMSO d6, 500 MHz)

1.88-1.97 (m, 4H), 3.44-3.63 (m, 6H), 6.68 (m, 4H)

• Mass spectrum: spectrum in agreement with the structure

EXAMPLE 2: Dye compositions

The following dye compositions in accordance with the invention were prepared:

(*) Common dye support: - Polyglycerolated oleic alcohol with 2 moles of glycerol 4.0

- Polyglycerolated oleic alcohol with 4 moles of glycerol, 78% active ingredient (M .A.) 5.69 g M.A

- Oleic acid 3.0 g

- Oleic amine containing 2 moles of ethylene oxide sold under the trade name ETHOMEEN 012 ® by the company AKZO 7.0 g

- Laurylamino diethylaminopropyl succinamate, sodium salt at 55% of M.A. 3.0 g M.A

- Oleic alcohol 5.0 g

- Oleic acid diethanolamide 12.0 g - Propylene glycol 3.5 g

- Ethyl alcohol 7.0 g

- Dipropylene glycol 0.5 g

- Propylene glycol monomethyl ether 9.0 g

- Sodium metabisulfite in aqueous solution, at 35% of MA. 0.455 g M.A - Ammonium acetate 0.8 g

- Antioxidant, sequestering q.s.

- Perfume, preservative q.s.

- Ammonia at 20% NH ₃ 10.0 g At the time of use, each dye composition is mixed with an equal amount of an oxidizing composition consisting of a solution of hydrogen peroxide at 20 volumes (6% by weight) and having a pH of approximately 3.

Each mixture obtained has a pH of approximately 9.5 and is applied for 30 minutes to locks of natural gray hair containing 90% white hairs.

After rinsing, washing with shampoo, rinsing and drying, each lock is evaluated before and after dyeing in the L * a * b * system, using a CM 2002 MINOLTA® spectrophotometer (Illuminant D65).

In the L * a * b * system, the three parameters designate respectively the intensity (L *), the hue (a *) and the saturation (b ^* ). According to this system, the higher the value of L, the lighter or less intense the color. Conversely, the lower the value of L, the darker or very intense the color, a ^* and b ^* indicate two color axes, a ^* indicates the green / red color axis and b ^* the blue color axis /yellow. The results are reported in the following table

Claims

1. Composition for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, comprising, in a medium suitable for dyeing, - at least one oxidation base chosen from the compounds of formula (I) below, and / or their addition salts with an acid in which : - Ri represents a halogen atom; a carbon chain of CrC ₇ , saturated or which may contain one or more double bonds and / or one or more triple bonds, linear or branched, which may be in the form of a ring having 3 to 6 members, one or more carbon atoms of the chain may be replaced by an oxygen, nitrogen or sulfur atom, by an SO ₂ group or by a halogen atom, the radical Ri not comprising a peroxide bond, nor of diazo, nitro or nitroso radicals; - R ₂ and R ₃ represent, independently of one another, a carbon chain C-ι-C ₄ , saturated or unsaturated; an alkyl radical in Cι-C substituted by an alkoxy radical in CrC ₄ , acetoxy, amino, carboxyl, carbamoyl, (mono or dialkyl) (CC ₄ ) carbamoyl, alkoxy (CC ₄ ) carbonyl, monohydroxyalkoxy in CC ₆ or by a group C ₂ -C ₆ polyhydroxyalkoxy; a C _r C monohydroxyalkyl radical; a CC ₆ polyhydroxyalkyl radical; a Cι-C ₄ aminoalkyl radical, the amine of which is mono or disubstituted by a CC ₄ alkyl, acetyl, monohydroxyalkyl C ₄ -C or polyhydroxyalkyl C ₂ -C ₆ radical; a C ₂ -C ₄ polyaminoalkyl radical; a C ₂ -C ₄ alkyl radical substituted by at least one amino group and at least one hydroxy group; a radical carboxyl; a carbamoyie radical; a (mono or dialkyl) (C _r C ₄ ) carbamoyl radical; an alkoxy (CC ₄ ) carbonyl radical; a (C1-C4) carbonyl alkyl radical -n is between 0 and 2, it being understood that when n is equal to 2 then the radicals Ri can be identical or different, with the exception of the compound 1- (3-isopropyloxy 4-Amino-phenyl) 2,5- dimethyl-pyrrolidine and of compound 1 - (3-methyl 4-Amino-phenyl) 2,5-dihydroxymethyl-pyrrolidine. 2. Composition according to Claim 1, in which the radical R 1 of formula (I) is chosen from a chlorine or bromine atom, a methyl, ethyl, isopropyl, vinyl, allyl, methoxymethyl, hydroxymethyl, 1-carboxymethyl radical. , 1- aminomethyl, 2-carboxyethyl, 2-hydroxyethyl, 3-hydroxypropyl, 1,2-dihydroxy ethyl, 1-hydroxy-2-aminoethyl, 1-amino-2-hydroxyethyl, 1, 2-diaminoethyl, methoxy, ethoxy, allyloxy, 2-hydroxyethyloxy. 3. Composition according to claim 1 or 2, in which the radicals R ₂ and R ₃ are chosen from the hydroxymethyl radical, the aminomethyl radical, the carboxyl radical, the carbamoyie radical, the 2-hydroxyethyloxymethyl radical, the 2-hydroxyethylaminomethyl radical, methoxymethyl. 4. Composition according to any one of claims 1 to 3 in which n is 0 or 1. 5. Composition according to any one of claims 1 to 4, in which the compound of formula (I) is chosen from the group consisting of: 6. Composition according to any one of claims 1 to 5, characterized in that the compound or compounds of formula (I) represent from 0.0005 to 12% by weight of the total weight of the dye composition. 7. Composition according to any one of claims 1 to 6, characterized in that it contains, in addition to the compound or compounds of formula (I), at least one additional oxidation base chosen from paraphenylenediamines different from the compounds of formula (I), bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases. 8. Composition according to any one of claims 1 to 7, characterized in that the additional oxidation base (s) represent from 0.0005 to 12% by weight of the total weight of the dye composition. 9. Composition according to any one of claims 1 to 8, characterized in that it contains at least one coupler and / or at least one direct dye. 10. Composition according to claim 9, characterized in that the couplers are chosen from metaphenylenediamines, meta-aminophenols, metadiphenols, naphthols and heterocyclic couplers. 11. Composition according to any one of claims 9 and 10, characterized in that the coupler (s) represent from 0.0001 to 10% by weight of the total weight of the dye composition. 12. Composition according to any one of claims 1 to 11, characterized in that the addition salts with an acid of the compounds of formula (I) are chosen from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates and acetates. 13. Use of the composition according to any one of claims 1 to 12 for the oxidation dyeing of keratin fibers, and in particular human fibers such as the hair. 14. Process for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that the composition as defined in any one of claims 1 to 12 is applied to the fibers, and an oxidizing agent, the oxidizing agent being added at the time of use to the composition or applied to the fibers separately, simultaneously or sequentially. 15. The method of claim 14, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids, and enzymes. 16. Device with several compartments comprising a first compartment containing a composition as defined in any one of claims 1 to 12 and a second compartment containing an oxidizing composition. 17. A colored product capable of being obtained by reaction of the composition as defined according to any one of claims 1 to 12 with an oxidizing agent.