FR2994571A1 - New meta-phenylenediamine compounds, useful in a composition for dyeing keratin fibers such as human hair - Google Patents

Abstract

Meta-phenylenediamine compounds (I) or its addition salts and solvates are new. Meta-phenylenediamine compounds of formula (I) or its addition salts and solvates are new. R : H, halo, 1-4C-alkyl, carboxyl or alkoxy(1-4C)carbonyl; R1 : branched 1-10C-alkyl (substituted by cation radical and interrupted by oxygen atoms and/or by NR6 group), where the cation radical is optionally substituted by OH, 1-4C-alkoxy or 1-4C-hydroxyalkyl; R6 : H (preferred) or linear or branched 1-4C-alkyl; and An ->anion or mixture of organic or inorganic anions. An independent claim is included for dyeing keratin fibers comprising applying, to keratin fibers, a composition in the presence of an oxidizing agent for a time sufficient to develop the desired coloring. [Image].

Description

The invention relates to novel o-alkylated derivative compounds of specific cationic metaphenylenediamines, a dyeing composition comprising them, and to a dyeing process using said compounds. . It is known to dye keratinous fibers and in particular human hair with dyeing compositions containing oxidation dye precursors, generally known as oxidation bases, such as ortho or para-phenylenediamines, ortho or para-aminophenols and heterocyclic. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise to colored compounds by a process of oxidative condensation. It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds. such as indole compounds. The variety of molecules involved in oxidation bases and couplers, allows to obtain a rich palette of colors. The so-called "permanent" coloration obtained by virtue of these couplers and oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must be harmless from the toxicological point of view, it must make it possible to obtain shades in the desired intensity and to have good resistance to external agents such as light, bad weather, washing, permanent waves, sweating and friction. The dyes must also make it possible to cover the white hair, and finally be the least selective possible, that is to say, to obtain the lowest possible color differences throughout the same keratin fiber, which is in general differently sensitized (ie damaged) between its tip and its root. It is already known to use couplers of the meta-phenylenediamine type for dyeing keratinous fibers, especially the hair. For example, document FR 2362116 discloses substituted meta-phenylenediamine couplers. These couplers may have the disadvantages of leading to insufficiently intense or chromatic and / or too selective staining. The object of the present invention is to obtain a composition for hair dyeing which has improved dyeing properties in terms of intensity or chromaticity, and / or selectivity and / or resistance to external agents. Surprisingly and advantageously, the applicant has just discovered a new family of couplers consisting of cationic metaphenylenediamines. These couplers lead to a wide colonelle palette in oxidation dyeing. They make it possible in particular to widen the gamut colonel while improving the safety of the oxidation dye couplers. In addition, these cationic meta-phenylenediamines make it possible to obtain colorings with varied, powerful and chromatic shades. The subject of the invention is therefore a meta-phenylenediamine compound of formula (I) below, its addition salts and its solvates: H 2 N NH 2 An-OR 1 (I) in which - R represents a hydrogen atom or halogen; a C1-C4 alkyl radical; a carboxyl radical; a (C1-C4) alkoxycarbonyl radical. - R1 represents a branched C1-C10 alkyl radical substituted with a cationic radical, said alkyl radical being optionally interrupted by one or more oxygen atoms and / or by one or more NR6 groups, said cationic radical being optionally substituted by a or more radicals selected from hydroxy, C1-04 alkoxy or (hydroxy) C1-04 alkyl; - R6 represents a hydrogen atom or a linear or branched C1-C4 alkyl radical. - An- represents an anion or a mixture of anions, organic or inorganic, cosmetically acceptable. The subject of the invention is also a dyeing composition for keratinous fibers comprising, in a suitable dyeing medium, at least one meta-phenylenediamine compound of formula (I) as defined above. The subject of the invention is also a process for dyeing keratinous fibers by applying to said fibers this composition. Another subject of the invention is the use of the composition of the present invention for dyeing keratinous fibers, in particular human keratinous fibers such as the hair. The invention also relates to multi-compartment devices comprising compositions using one or more couplers chosen from the compound of formula (I) or one of its addition salts with an acid.

The invention finally relates to a staining kit comprising firstly a staining composition containing a compound of formula (I) and secondly a composition containing an oxidizing agent. The compounds of the present invention make it possible in particular to obtain keratinous fiber coloring compositions which are suitable for use in oxidation dyeing and make it possible to obtain hair dyeing which has improved dyeing properties in terms of intensity or chromaticity, and / or selectivity and / or resistance to external agents such as shampoos, sweat and permanent deformations and light.

For the purposes of the present invention, and unless a different indication is given: an "alkyl radical" is a C 1 -C 20 hydrocarbon radical, linear or branched, preferably C 1 -C 8; an "alkenylene radical" is a divalent unsaturated hydrocarbon radical as defined above which may contain from 1 to 4 double bonds -C = C-, conjugated or otherwise; particularly the alkenylene group contains 1 or 2 unsaturation (s); the expression "optionally substituted" ascribed to the alkyl radical implies that said alkyl radical may be substituted with one or more radicals chosen from i) hydroxyl radicals, ii) optionally substituted C 1-4 alkoxy, iii) acylamino, iv) amino by one or two identical or different C 1 -C 4 alkyl radicals, said alkyl radicals being able to form, with the nitrogen atom which bears them, a heterocyle comprising from 5 to 7 ring members, optionally comprising another heteroatom different from or different from nitrogen; v) or a quaternary ammonium group -N + R'R "R-, 1 \ / 1- for which R ', R", R-, identical or different, represent a hydrogen atom, or a C1-C6 alkyl group; 04, or else -N + R'R "R" forms a heteroaryl such as imidazolium optionally substituted with a Cl-O 4 alkyl group, and M represents the counter-ion of the organic acid, mineral or the corresponding halide; an "alkoxy radical" is an alkyl-oxy radical for which the alkyl radical is a hydrocarbon radical, linear or branched, at Cl-016, preferably at Cl-08; when the alkoxy group is optionally substituted, this implies that the alkyl group is optionally substituted as defined above; the expression "at least one" is equivalent to "one or more"; and the term "inclusive" for a range of concentrations means that the range terminals fall within the defined range. It should be noted that in what follows, and unless otherwise indicated, the boundaries of a domain of values are included in this area.

Compound of formula (I) The subject of the invention is therefore a meta-phenylenediamine compound of formula (I) below, its addition salts and its solvates: H 2 N NH 2 An-OR 1 (I) in which - R represents an atom hydrogen or halogen; a C1-C4 alkyl radical; a carboxyl radical; a (C1-C4) alkoxycarbonyl radical. - R1 represents a branched C1-C10 alkyl radical, preferably 0208, substituted by a cationic radical, said alkyl radical being optionally interrupted by one or more oxygen atoms and / or by one or more NR6 groups, said cationic radical; being optionally substituted by one or more radicals selected from hydroxy, C1-04 alkoxy or (hydroxy) C1-04 alkyl; - R6 represents a hydrogen atom or a linear or branched C1-C4 alkyl radical. - An- represents an anion or a mixture of anions, organic or inorganic, cosmetically acceptable, the electroneutrality of the compounds of formula (I) is provided by an anion or a mixture of anions, denoted An-, organic or inorganic, cosmetically acceptable.

An- represents an anion or a mixture of anions, chosen for example from a halide such as chloride, bromide, fluoride or iodide; a hydroxide; sulphate; a hydrogen sulfate; an alkyl sulphate for which the linear or branched alkyl part is C 1 -C 6, such as the methyl sulphate or ethyl sulphate ion; carbonates and hydrogen carbonates; salts of carboxylic acids such as formate, acetate, citrate, tartrate, oxalate; alkylsulphonates for which the linear or branched alkyl part is C 1 -C 6, such as the methylsulphonate ion; arylsulphonates for which the aryl part, preferably phenyl, is optionally substituted by one or more C1-C4 alkyl radicals such as, for example, 4-toluylsulfonate; alkylsulfonyls such as mesylate.

The compounds of general formula (I) may be in free form or in the form of salts, such as the addition salts with a mineral acid, preferably chosen from hydrochloric acid, hydrobromic acid, sulfuric acid and sulphates. , phosphoric acid or with an organic acid such as, for example citric acid, succinic acid, tartaric acid, lactic acid, 4-toluylsulfonic acid, benzenesulphonic acid, and acetic acid, para-toluenesulfonic acid, formic acid, methanesulphonic acid.

The compounds of general formula (I) can also be in the form of solvates, for example a hydrate or a linear or branched alcohol solvate such as ethanol or isopropanol. In the context of the invention, the term "derivative of formula (I)" means any mesomeric or isomeric forms. The compound of formula (I) is a monocationic compound, the radical R 1 being substituted by a single cationic radical. By cationic radical present in the compound of formula (I) is meant in the context of the invention any linear or branched or heterocyclic radical comprising a quaternary ammonium, said quaternary ammonium being of the type - N + RaRbRc, Ra, Rb, Rc identical or different representing a C1-C6 alkyl radical which may be substituted with a hydroxy, a C1-04 alkoxy or a (hydroxy) C1-4 alkyl. Ra and Rb may together form a heterocycle comprising from 5 to 8 members, the radical Rc then being a C 1 -C 6 alkyl radical which may be substituted with a hydroxyl radical, C 1 -C 4 alkoxy radical or a (hydroxy) C 1 -C 4 alkyl radical. 04. Preferably, Ra, Rb, Rc, which may be identical or different, represent a C1-C12 alkyl radical, in particular methyl or ethyl, optionally substituted with a hydroxyl, C1-04 alkoxy or (hydroxy) C1-4 alkyl radical. Preferably, when Ra and Rb together form a heterocycle comprising from 5 to 8 ring members, the radical Rc represents a C1-C12 alkyl radical which may be substituted with a hydroxyl radical, a C1-C4 alkoxy radical or a (hydroxyl) radical. C1-C4 alkyl. Thus, the compounds of formula (I) according to the invention carry a permanent cationic charge which is independent of the pH of the medium in which the compounds are formulated.

By way of example of cationic radicals, mention may be made of the trimethylammonium, triethylammonium, dimethylethylammonium, diethylmethylammonium, diisopropylmethylammonium, diethylpropylammonium, hydroxyethyl diethylammonium, di-hydroxyethylmethylammonium, di-hydroxyethylethylammonium and tri beta hydroxyethylammonium radicals, and their mixtures. The term "cationic heterocycle" means a 5- to 8-membered heterocycle in which one of the chain members is a quaternary ammonium or a non-cationic heterocyclic radical substituted with a cationic radical -N + RaRbRc, Ra, Rb, Rc identical or different, representing a radical. C 1 -C 6 alkyl which may be substituted by a hydroxy, a C 1 -C 4 alkoxy or a C 1 -C 4 (hydroxy) alkyl and preferably chosen from trimethylammonium, triethylammonium, dimethylethylammonium, diethylmethylammonium, diisopropylmethylammonium and diethylpropylammonium radicals; , hydroxyethyl diethylammonium, di beta hydroxyethylmethylammonium, di beta hydroxyethylethylammonium, tri beta hydroxyethylammonium, and mixtures thereof. By way of example of cationic heterocycle, mention may be made of the radicals imidazolium, pyridinium, piperidinium, piperazinium, pyrrolidinium, morpholinium, pyrimidinium, thiazolium, benzimidazolium, benzothiazolium, oxazolium, benzotriazolium, pyrazolium, triazolium, benzoxazolium, these heterocycles. cationic compounds being optionally substituted by one or more identical or different radicals chosen from hydroxyl radical, a C1-04 alkoxy or a (hydroxy) alkyl radical at 01-04, and mixtures thereof. By way of example of a cationic heterocycle, it is possible to also mention the radicals pyrrolidine or piperidine or piperazine, substituted with a cationic radical - N + RaRbRc, Ra, Rb, Rc identical or different representing a C1-C6 alkyl radical which may be substituted by a hydroxy, a C1-04 alkoxy or a (hydroxy) C1-C4-alkyl, and preferably chosen from trimethylammonium, triethylammonium, dimethyl-ethylammonium, diethylmethylammonium radicals; , diisopropylmethylammonium, diethyl-propylammonium, hydroxyethyl diethylammonium, di beta hydroxyethylmethylammonium, tri beta hydroxyethylammonium and in particular the pyrrolidine radical or the piperidine radical, substituted by a trialkyl (C1-C4) ammonium radical, and mixtures thereof. the cationic radicals are chosen from the radicals imidazolium, pyridinium, piperidinium, piperazinium, pyrrolidinium, morpholinium, pyrimidinium, thiazolium, benzimidazolium, benzothiazolium, oxazolium, benzotriazolium, pyrazolium, triazolium, benzoxazolium. Preferably, in formula (I), R represents a hydrogen atom.

According to one embodiment, R 1 represents a branched C 1 -C 10, preferably C 2 -C 8, alkyl radical substituted with a cationic radical, said alkyl radical being optionally interrupted by an oxygen atom and / or by an NH group, Preferably, R 1 is a branched, saturated C 1 -C 8 alkyl radical, preferably a C 2 -C 8 alkyl radical. According to a first embodiment of the invention, the compounds of formula (I) are such that: hydrogen, R1 a saturated alkyl radical branched to 02-08, optionally interrupted by an oxygen atom or an NH group, substituted with a cationic heterocyclic radical of 5 to 8 members selected from imidazolium, pyridinium, piperidinium and piperazinium radicals; , pyrrolidinium, morpholinium, pyrimidinium, thiazolium, benzimidazolium, benzothiazolium, oxazolium, benzotriazolium, pyrazolium, triazolium, benzoxazolium, these cationic heterocycles being optionally substituted by one or more the same or different radicals selected from a hydroxy radical, a C1-04 alkoxy radical or a (C 1 -4) alkyl (hydroxy) alkyl radical, and mixtures thereof.

According to a second embodiment of the invention, the compounds of formula (I) are such that: - R represents a hydrogen atom, - R1 a saturated alkyl radical branched at 02-08, optionally interrupted by an atom of oxygen or an NH group, substituted with a radical -N + RaRbRc, Ra, Rb, Rc identical or different, representing a C1-C6 alkyl radical which may be substituted by a hydroxy, a C1-C4 alkoxy or a (hydroxy) alkyl; C1-04; Ra and Rb may together form a 5- to 8-membered heterocycle, the radical Rc then being a C1-C6 alkyl radical which may be substituted by a hydroxyl radical, a C1-C4 alkoxy radical or a (hydroxy) alkyl radical. in C1-04. - and their mixtures.

Preferably, Ra, Rb, Rc, which are identical or different, represent a C1-C12 alkyl radical, in particular methyl or ethyl, optionally substituted with a hydroxyl radical.

Even more preferably, the radical -N + RaRbRc denotes a trimethylammonium, triethylammonium, dimethyl-ethylammonium, diethylmethylammonium, diisopropylmethylammonium, diethylpropylammonium, hydroxyethyl diethylammonium, di-hydroxyethylmethylammonium, tri beta hydroxyethylammonium.

As cationic phenylenediamines of the general formula (I) according to the invention, mention may be made of the following compounds: ## STR2 ## -CH, CH, N- (N-3- (2,4-diaminophenoxy) -N, N, N-CH3-trimethylbutan-2-aminium, N-3- (2,4-diaminophenoxy) -N-ethyl N, N-dimethylbutan-2-aminium, An-H2N6NH2 3H2N, NH2 CH3H-CH3N-CH3CH3H3H- 2,4-diaminophenoxy) -N, N, N-3- (2,4-diaminophenoxy) -N, N-triethylbutan-2-aminium, N-diethyl-N-methylbutan-2-aminium, An-H2N * 0 H2 (D1-1H2N * H2 (D1-1 + CH2) N- (3- (2,4-diaminophenoxy) -N-ethyl-N, N-bis (2-hydroxyethyl) butan-2-aminium, An- (3- (2,4-diaminophenoxy) -N, N-bis (2-hydroxyethyl) -N-methylbutan-2-yl) Aminium, An-H2N NH2 (311-1 Ô 0 N.) - OH- (OH-3- (2,4-diaminophenoxy) -N, N, N-tris) (2-hydroxyethyl) butan-2-aminium, An-H 2 N NH 2 H 2 N NH 2 I An -An-143- (2,4-diaminophenoxy) butan-2-yl] -IW An-1-methylpiperidinium, An-O-N-R 143 - (2,4-diaminophenoxy) butan-2-yl] -1-methylpyrrolidinium, An-H2N 010 NH2, the H2N NH2 diaminophenoxy) butan-2-yl] - 442- (2,4-diaminophenoxy) ethyl] -4-methyl-1H-imid azol-3-ium, An-methylmorpholin-4-ium, An-H2N i, H2 H2N i H2 +. ## STR13 ## N, N, 2,3-1,1-dimethylpiperazin-1-ium, pentamethylbutan-2-aminium, An-H2N NH2H2NH2O ÔCH2, 44CH2O + Ni + CH An- [CH3,3- (2,4-diaminophenoxy) -N-ethyl-N, N, 2,3-tetramethylbutan-2-aminium, An-An-3- (2,4-diaminophenoxy) -N N, N-diethyl-N, 2,3-trimethylbutan-2-aminium, An-H2N is NH2 O- / OH -N- (2,4-diaminophenoxy) -N- (2-hydroxyethyl) -N, N, 2,3-tetramethylbutan-2-aminium, An-H2Nis NH2 H2N SH2 r. ## STR5 ## wherein N is 1- (2,4-diaminophenoxy) -N, N, N-tris (2-hydroxyethyl) -2,3- dimethylbutan-2-aminium, N-3- (2,4-diaminophenoxy) -N, N-diethyl-N- (2-hydroxyethyl) -2,3-dimethylbutan-2-aminium, An-H2N1, H2H2Ni H2 I + I + O, N-O-An-An-OH 4- [3- (2,4-diaminophenoxy) -2,3-dimethylbutan-2-yl] -1,1-dimethylpiperazine -1-ium, N- [4- (3- (2,4-diaminophenoxy) -2,3-dimethylbutan-2-yl] -1- (2-hydroxyethyl) -1-methylpiperazin-1-ium, An-H2N ## STR5 ## wherein N is 1- [3- (2,4-diaminophenoxy) -2,3-dimethylbutanediol); 2-yl] -3-methyl-1H-imidazol-3-ium, N- [4- (3- (2,4-diaminophenoxy) -2,3-dimethylbutan-2-yl] -4-methylmorpholin-4-ium, An 1H NMR (CDCl3):? N? N? - (2,4-diaminophenoxy) butan-2-yl] - 1- [3- (2,4-diaminophenoxy) -2- 3-dimethylbutan-2-yl] -3- (2-hydroxyethyl) -1H-imidazol-3-ium, N, N, N-trimethylpyrrolidin-3-aminium, N-, OH-, NH2NH2N, NH2 N- [N- [3- (2,4-diaminophenoxy) -2,3-dimethylbutan-2-yl] N, N, N-trimethylpyrrolidin-3-aminium, An-An-OH-443- (2,4-diaminophenoxy) butan-2-yl] -1,1-bis (2-hydroxyethyl) piperazin-1-ium, An- The invention also relates to a keratinous fiber coloring composition comprising, in a suitable medium, at least one compound of formula (I) as defined above. The compound of formula (I) may be present in the composition in an amount of between 0.001 to 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6%.

The composition may also comprise at least one oxidation base. These bases may especially be chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases and their addition salts. Among the para-phenylenediamines, para-phenylenediamine, para-toluenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2, may be mentioned by way of example, 6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N -dipropyl-para-phenylenediamine, 4-amino-N, N-diethyl-3-methylaniline, N, N-bis (p-hydroxyethyl) -para-phenylenediamine, 4-N, N-bis-p 1-hydroxyethyl) amino-2-methyl-aniline, 4-N, N-bis (13-hydroxyethyl) amino-2-chloroaniline, 213-hydroxyethyl-para-phenylenediamine, 2-fluoro-para phenylenediamine, 2-isopropyl para-phenylenediamine, N- (13-hydroxypropyl) -para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N , N (éthy1,13-hydroxyethyl) -para-phenyl linediamine, N- (13,7-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) -para-phenylenediamine, N-phenyl-H 2 N H 2 An-OH 4- [3- (2,4-diaminophenoxy)) 2,3-dimethylbutan-2-yl] -1,1-bis (2-hydroxyethyl) piperazin-1-ium, N-para-phenylenediamine, 213-hydroxyethyloxy-para-phenylenediamine, 213-acetylaminoethyloxy-para- phenylenediamine, N- (p-methoxyethyl) -para- phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para-phenylene diamine, hydroxyethylamino-5-amino-toluene, 3-hydroxy-1- (4 ') aminophenyl) pyrrolidine, 6- (4-amino-phenylamino) -hexan-1-ol, N- (4-amino-3-methylphenyl) -N4- (1H-imidazol-1-yl) -propyl] -amine N- (4-aminophenyl) -N [3- (1H-imidazol-1-yl) propyl] amine and their addition salts with an acid. Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-toluenediamine, 2-isopropyl-para-phenylenediamine, 2-13-hydroxyethyl-para-phenylenediamine, 213-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis- (phydroxyethyl) -para-phenylenediamine, 2-chloro- para-phenylenediamine, 2-p-acetylamino-ethyl-para-phenylenediamine, 2 - [{2 - [(4-aminophenyl) amino] ethyl} (2-hydroxyethyl) amino] ethanol and their addition salts with a acid are particularly preferred. Among the bis-phenylalkylenediamines, mention may be made, by way of example, of N, N'-bis- (p-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, N N, N'-bis- (p-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- ( p-hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) N, N ' -bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diamino phenoxy) -3,6-dioxaoctane, and their addition salts with an acid.

Among the para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro-phenol, 4-amino-2-chlorophenol, 4-aminophenol, amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethyl phenol, 4-amino-2- (13-hydroxyethylaminomethyl) phenol, 4-amino-2-fluoro phenol, 4-amino-2,6-dichlorophenol, 4-amino-6R (5'-amino-2-hydroxy-3) [Methyl] phenyl) methyl] -2-methylphenol, bis [(5'-amino-2-hydroxy) phenylmethane and their addition salts with an acid.

Among the ortho-aminophenols, mention may be made, for example, of 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and their addition salts with an acid. Among the heterocyclic bases that may be mentioned by way of example are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives. Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino-3-amino pyridine, 3,4-diamino pyridine, and their addition salts with an acid.

Other pyridinic oxidation bases useful in the present invention are the 3-amino pyrazolo [1,5-a] pyridines oxidation bases or their addition salts described for example in the patent application FR 2801308. By way of example, mention may be made of pyrazolo [1,5-a] pyridin-3-ylamine; 2-acetylamino pyrazolo [1,5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 3-amino-pyrazolo [1,5-a] pyridin-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-a] pyridin-3-ylamino; (3-amino-pyrazolo [1,5-a] pyridine-7-yl) methanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-5-yl) -ethanol; 2- (3-aminopyrazolo [1,5-a] pyridin-7-yl) ethanol; (3-amino-pyrazolo [1,5-a] pyridin-2-yl) methanol; 3,6-diamino-pyrazolo [1,5-a] pyridine; 3,4-diamino-pyrazolo [1,5-a] pyridine; pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-ylpyrazolo [1,5-a] pyridin-3-ylamine; pyrazolo [1,5-a] pyridine-3,5-diamine; 5-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 2 - [(3-Amino-pyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) amino] ethanol; 2 - [(3-Amino-pyrazolo [1,5-a] pyridin-7-yl) - (2-hydroxyethyl) amino] ethanol; 3-amino-pyrazolo [1,5-a] pyridin-5-ol; 3-amino-pyrazolo [1,5-a] pyridin-4-ol; 3-amino-pyrazolo [1,5-a] pyridin-6-ol; 3-amino-pyrazolo [1,5-a] pyridin-7-ol; as well as their addition salts with an acid. Among the pyridine bases which are useful in the present invention, mention may also be made of the compounds described in patent applications EP 1792903 and EP 1792606 as well as their addition salts. Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in DE 2359399; JP 88-169571; JP 05-63124; EP 0770375 or patent application VVO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4 -dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their addition salts and tautomeric forms, when tautomeric equilibrium exists. Among the pyrazolopyrimidine derivatives, mention may be made of the compounds described, for example, in patent applications EP 0847271, EP 0926149 and EP 1147109 and their addition salts. Among the pyrazole derivatives, mention may be made of the compounds described in DE 3843892, DE 4133957 and patent applications VVO 94/08969, VVO 94/08970, FR-A-2 733 749 and DE 195 43 988 as the 4.5 1-diamino-methyl pyrazole, 4,5-diamino-1- (13-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5 -diamino 1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazino pyrazole 1-Benzyl-4,5-diamino-3-methyl-pyrazole, 4,5-diamino-3-tert-butyl-1-methyl-pyrazole, 4,5-diamino-1-tert-butyl-3-methyl-pyrazole, 4, 5-diamino 1- (13-hydroxyethyl) 3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4 5-diamino-1-ethyl-3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl-pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole, 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- (13-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts. As oxidation bases, mention may also be made of the diamino-N, N-dihydro-pyrazolone derivatives of formula (III) or one of their addition salts or solvates: O / NH 2 IR rNI / JNR 3 R 4 In which: R1, R2, R3 and R4, which may be identical or different, represent: a linear or branched C1-C6 alkyl radical optionally substituted with one or more radicals chosen from the group consisting of a radical OR5, a radical NR6R7, a carboxy radical, a sulphonic radical, a carboxamido radical CONR6R7, a sulphonamido radical SO2NR6R7, a heteroaryl, an aryl optionally substituted with a (01-04) alkyl group, a hydroxy, a C1-C12 alkoxy, an amino, a ( Alkyl (01-02) amino; - an aryl radical optionally substituted with one or more (C 1-4) alkyl, hydroxy, C 1-12 alkoxy, amino, (di) alkyl (01-02) amino; - a 5-membered heteroaryl radical; or 6-membered, optionally substituted with one or more radicals selected from (01-04) alkyl, (01-02) alkoxy, R3 and R4 may also represent a hydrogen atom; R5, R6 and R7, which may be identical or different, represent a hydrogen atom; a linear or branched C1-C4 alkyl radical optionally substituted by one or more radicals chosen from the group consisting of a hydroxyl, a C1-C2 alkoxy, a CONR8R9 carboxamido, a SO2R8 sulphonyl, an optionally substituted C1-6 aryl; C4) alkyl, hydroxy, C1-10 alkoxy, amino, (C1-4) alkyl (01-02) amino, aryl optionally substituted with (C1-4) alkyl, hydroxy, C1-C2 alkoxy, amino a (di) alkyl (0102) amino, R6 and R7, which may be identical or different, may also represent a carboxamido radical CONR8R9, a sulfonyl SO2R8, R8 and R9, which may be identical or different, represent a hydrogen atom; Cl-04 linear or branched optionally substituted with one or more hydroxy, alkoxy Cl-02; R1 and R2 on the one hand, and R3 and R4 on the other hand can form with the nitrogen atoms to which they are attached, a saturated or unsaturated 5- to 7-membered heterocycle, optionally substituted by one or more radicals selected from the group consisting of halogen atoms, amino, (alkyl) (01-04) amino, hydroxy, carboxy, carboxamido, (C1-2) alkoxy radicals, C1-C4 alkyl radicals; optionally substituted with one or more hydroxy, amino, (di) alkylamino, alkoxy, carboxy, sulfonyl radicals; R3 and R4 may also together with the nitrogen atom to which they are attached form a 5- or 7-membered heterocycle whose carbon atoms may be replaced by an optionally substituted oxygen or nitrogen atom. These derivatives of diamino-N, N-dihydro-pyrazolone are described in particular in Application FR 2866338, a particularly preferred derivative is 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-dihydro-pyrazolone]. a] pyrazol-1-one dimethanesulfonate. Mention may also be made, by way of oxidation base, of the diaminoN, N-dihydro-pyrazolone derivatives of formula (IV) or one of their addition salts or solvates: in which. z represents independently: a single covalent bond, a divalent radical chosen from an oxygen atom, a radical with R 6 representing a hydrogen atom, a C 1 -C 6 alkyl radical, or R 6 with R 3, together with the nitrogen atom to which they are attached, a 5- to 8-membered, substituted or unsubstituted, saturated or unsaturated heterocycle, aromatic or otherwise, optionally containing one or more other heteroatoms or groups selected from N, O, S , SO2, -00-, the heterocycle being cationic and / or substituted by a cationic radical, - a radical -N + R7R8- with R7 and R8 independently which represent an alkyl radical; the alkyl radical may be substituted with an OH or a -Oalkyl, - R3 represents: - a hydrogen - an optionally substituted C1-C10 alkyl radical, the alkyl radical being interruptable by a heteroatom or a group chosen from 0, N , Si, S, SO, SO2, - a C1-C10 alkyl radical substituted and / or interrupted by a cationic radical, - a halogen, - a SO3H radical, - a 5 to 8-membered ring, substituted or unsubstituted, saturated unsaturated or aromatic, optionally containing one or more heteroatoms or groups selected from N, O, S, SO2, -CO-, the ring being cationic and / or substituted with a cationic radical, R1, R2, which may be identical or different, represent: a linear or branched C1-C6 alkyl radical optionally substituted with one or more radicals chosen from an OR5 radical, an NR9R10 radical, a carboxy radical, a sulphonic radical or a 00NR9R10 carboxamido radical; a sulphonamido radical SO2NR9R10, a heteroaryl, an aryl optionally substituted with a group (01-04) alkyl, hydroxy, C1-C2 alkoxy, amino, (di) alkyl (01-02) amino; an aryl radical optionally substituted with one or more (ClO4) alkyl, hydroxyl, C1-C2 alkoxy, amino, (di) alkyl (01-02) amino; a 5- or 6-membered heteroaryl radical, optionally substituted with one or more radicals chosen from (01-04) mono- or polyalkyl substituted by the radical with an OH or a -Oalkyl, (01-02) alkoxy; R1 and R2 may form, with the nitrogen atoms to which they are attached, a saturated or unsaturated 5- to 7-membered heterocycle, optionally substituted with one or more radicals selected from the group consisting of halogen atoms, amino radicals, , (di) alkyl (01 -04) amino, hydroxy, carboxy, carboxamido, (01-02) alkoxy, C1-C4 alkyl radicals optionally substituted by one or more hydroxy, amino, (di) -alkylamino, alkoxy radicals , carboxy, sulfonyl, An- represents an anion or a group of anions to ensure the electroneutrality of the compounds of formula (IV), provided that at least one of Z and R3 represents a cationic radical. These derivatives of diamino-N, N-dihydro-pyrazolone are described in patent application FR2927078.

Generally the concentration of the oxidation base (s) ranges from 0.0001 to 20%, preferably from 0.005 to 6% by weight relative to the total weight of the composition.

Couplers The coloring composition according to the invention may contain and preferably contains one or more additional oxidation couplers, different from the compounds of general formula (1), conventionally used for dyeing keratinous fibers. Among these couplers, mention may in particular be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. By way of example of a coupler, mention may be made of 2-methyl-5-aminophenol, 5-N- (11-hydroxyethyl) amino-2-methylphenol, 6-chloro-2-methyl-5-aminophenol, 3 amino phenol, 2,4-dichloro-3-aminophenol, 5-amino-4-chloro-o-cresol, 1,3-dihydroxy benzene, 1,3-dihydroxy-2-methyl benzene, 4- chloro 1,3-dihydroxybenzene, 2,4-diamino 1- (11-hydroxyethyloxy) benzene, 2-amino 4- (11-hydroxyethylamino) -1-methoxybenzene, 1,3-diamino benzene, 1,3 bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol, 1-11-hydroxyethylamino-3,4-methylenedioxybenzene, naphthol, 2-methyl-1-naphthol, 1,5-dihydroxy naphthalene, 2,7-naphthalenediol, 1-acetoxy-2-methylnaphthalene, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methyl indole, 2-amino-3-hydroxy pyridine, 6-hydroxybenzomorpholine 3,5-diamino-2,6-dimethoxypyridine, 2,6-dihydroxy-3-4-dimethylpyridine, 3-amine ino-2-methylamino-6-methoxypyridine, 1-N- (11-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- (11-hydroxyethylamino) toluene, 3-methyl-1- phenyl-5-pyrazolone and their addition salts with an acid. In the dye composition of the present invention, the coupler (s), if present, is generally from about 0.001 to about 10% by weight of the total weight of the composition, preferably from about 0.005 to about 6%. The dyeing composition in accordance with the invention may also contain one or more direct dyes which may be chosen in particular from nitro dyes of the benzene series, azo direct dyes and methine direct dyes. These direct dyes may be nonionic, anionic or cationic in nature. The medium suitable for dyeing, also known as a dyeing medium, generally comprises water or a mixture of water and one or more solvents, for example the lower alkanols at Cl-O 4, such as ethanol and isopropanol. polyols such as propylene glycol, dipropylene glycol or glycerol, and polyol ethers such as dipropylene glycol monomethyl ether. The solvent or solvents are generally present in proportions which may be between 1 and 40% by weight approximately with respect to total weight of the coloring composition, and even more preferably between 3 and 30% by weight. The coloring composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants, or mixtures thereof, anionic polymers. , cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.

The adjuvants above are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the composition. Of course, one skilled in the art will take care to choose this or these optional additional compounds such that the advantageous properties intrinsically attached to the oxidation dyeing composition according to the invention are not, or not substantially impaired by the addition or additions envisaged. The pH of the dyeing composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used for dyeing keratin fibers or else using conventional buffer systems. Acidifying agents include, for example, inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid and the like. , citric acid, lactic acid, sulphonic acids. Among the alkalinizing agents that may be mentioned, by way of example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and the compounds of the following formula (III): (III) in which VV is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 4 alkyl radical; Ra, Rb, Rc and Rd, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl or C1-C4 hydroxyalkyl radical. The composition according to the invention may comprise one or more oxidizing agents. The oxidizing agents are those conventionally used for the oxidation dyeing of keratin fibers, for example hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and the like. oxidase enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred. The coloring composition with or without an oxidizing agent according to the invention may be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratinous fibers, and including human hair. It can result from mixing at the time of use of several compositions. In particular, it results from the mixture of at least two compositions, one comprising at least one compound of formula (I), optionally one or more R a \ b N -W-N ReRd oxidation bases, optionally one or several additional couplers different from the compounds of formula (I) or their salts, and a second composition comprising one or more oxidizing agents as described above. The composition of the invention is therefore applied to the hair for dyeing keratinous fibers either as such or in the presence of one or more oxidizing agents, for dyeing keratinous fibers. The process of the present invention is a process in which the composition according to the present invention as defined above, is applied to the fibers either alone or in the presence of an oxidizing agent for a time sufficient to develop the desired coloration. The color can be revealed at acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition of the invention just at the time of use or it can be used from an oxidizing composition containing it applied simultaneously or sequentially to the composition of the invention.

According to one particular embodiment, the composition is oxidant-free and is mixed, preferably at the time of use, with a composition containing, in a medium suitable for dyeing, one or more oxidizing agents, these oxidizing agents being present in an amount sufficient to develop a coloration. The mixture obtained is then applied to the keratinous fibers.

After a residence time of about 3 to 50 minutes, preferably about 5 to 30 minutes, the keratinous fibers are rinsed, washed with shampoo, rinsed again and then dried. The oxidizing agents are those indicated above. The oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing hair and as defined above. The pH of the oxidizing composition containing the oxidizing agent is such that, after mixing with the dye composition, the pH of the resulting composition applied to the keratinous fibers preferably varies between 3 and 12 approximately, and even more preferably between 5 and 12. 11. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used in dyeing keratinous fibers and as defined above. The ready-to-use composition which is finally applied to the keratin fibers may be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratinous fibers, and including human hair. The invention also relates to a multi-compartment device or dye "kit" in which a first compartment contains the non-oxidant coloring composition of the present invention defined above comprising one or more oxidation bases selected from the compound of formula (I) or its addition salts with an acid and a second compartment contains one or more oxidizing agents. These devices may be equipped with means for delivering the desired mixture onto the hair, such as the devices described in patent FR-2 586 913 in the name of the applicant. Preparation of the compound of formula (I) The synthesis of the compounds of formula (I) can be carried out, for example, according to the following procedures: General procedure 1 X = halogen or methoxy NO2 substitution NO2 Ri OH Reduction H2 General procedure 2 As a matter of course for example, when R 1 represents a C 1 -C 10 alkyl radical substituted with a cationic radical, said alkyl radical being interrupted by one or more heteroatoms chosen from NR 2 or O, then the synthesis method used may be the following: NO 2 NH 2 substitution reduction substitution NO2 R 1 OH OH R 1 X = halogen or methoxy Pg: protecting group Deprotection NH2 24 R1 NO2 HOAOH substitution -NO2 A = alkyl XX = halogen or methoxy Pg: precursor group Pg NH HNPg Substitution NO2 0 A-OH OSO2B Substitution 02 Pg'NH NO2 A, 0 An-, N Ra I Rb R c deprotection A, 0, Ra NRb ationization Reduction NO2 A, 0 An- Ra I Rb R c (I) A, 0 'An- Ra I Rb R c NH NO2 2 NO2 26 substitution NO2 A = alkyl XX = halogen or methoxy Pg: protective group Pg HN HOAOH HN.Pg HN, Pg NO2 0 A-O-X-NRaRb NO2 A-OS 02B Pg'NH OH A.0 cationization i`n-12 HN Reduction reduction .Pg HN NH2 0, 0, a Rc Rb An- NH2 0, 0, a Rc Rb An- NO2 0, A 0, A '' R a RcRb An- Deprotection NO2 H2N-A'NRaRb NO2 o A-OSO2B Pg._NH A..0 OH, LPg HN HN..Pg NO2 0 A-NH-A'-NRaRb 1. cationization NO2 HOA OH NO2 XX = halogen or methoxy Pg: protecting group substitution A = alkyl Reduction Deprotection HN NH 2 O, A HN, A 'to RcRb An-HN..Pg NO 2 O, A HN. The substitution reaction is carried out in a dipolar solvent such as acetonitrile, THF or in DMF or NMP, or in an alcohol such as ethanol for example, in the presence of a base such as triethylamine, ethyldiisopropylamine, sodium hydroxide or potassium hydroxide for example and 1 to several HOAZ1H for 1 to 24 hours at a temperature of 20 ° C at the reflux temperature of the solvent.

The hydroxyl function thus introduced is then substituted with a halide (mesyl or tosyl halide, for example) in a solvent such as acetonitrile, THF or in an alcohol such as ethanol, for example, in the presence of a base. such as triethylamine, ethyldiisopropylamine, sodium hydroxide or potassium hydroxide for example, for 1 to 24 hours at a temperature of 20 ° C at the reflux temperature of the solvent. The substitution of the leaving group introduced in the preceding step is carried out either by reaction with an aromatic tertiary amine such as methylimidazole to lead directly to the cationic compounds or by reaction with a particular primary or secondary amine such as, for example, N, N-dimethylethylenediamine, 2-piperidin-1-ylethanamine to yield compounds which are alkylated with at least one equivalent of alkyl halide or methyl sulfate in a solvent such as TH F or acetonitrile or dioxane or ethyl acetate for 15 minutes to 24 hours at a temperature ranging from 15 ° C to the reflux temperature of the solvent to give the cationic nitro compounds. The reduction of the nitro group of these compounds is carried out under standard conditions, for example by carrying out a hydrogenation reaction by heterogeneous catalysis in the presence of Pd / C, Pd (II) / C, Ni / Ra, etc. by carrying out a reduction reaction by a metal, for example by zinc, iron, tin, etc. (See Advanced Organic Chemistry, 3rd Edition, J. March, 1985, VVilley Interscience and Reduction in Organic Chemistry, M. Hudlicky, 1983, Ellis Horwood Chemical Science Series).

Claims (13)

REVENDICATIONS1. Meta-phenylenediamine compound of formula (I) below, its addition salts and its solvates: H 2 N NH 2 An-OR 1 (I) in which - R represents a hydrogen or halogen atom; a C1-C4 alkyl radical; a carboxyl radical; a (C1-C4) alkoxycarbonyl radical; R1 represents a C1-C10 branched alkyl radical substituted with a cationic radical, said alkyl radical being optionally interrupted by one or more oxygen atoms and / or by one or more groups; NR6, said cationic radical being optionally substituted with one or more radicals selected from hydroxy, C1-C4 alkoxy or (hydroxy) C1-C4 alkyl; - R6 represents a hydrogen atom or a linear or branched C1-C4 alkyl radical. - An- represents an anion or a mixture of anions, organic or inorganic, cosmetically acceptable. 2. Compound according to claim 1, in which the cationic radical is a linear or branched or heterocyclic radical comprising a quaternary ammonium, this quaternary ammonium being of the type -N + RaRbRc, Ra, Rb, Rc identical or different representing an alkyl radical. C1-C6 may be substituted with hydroxy; Ra and Rb, which can together form a heterocycle comprising 5 to 8 members, the radical Rc then being a C 1 -C 6 alkyl radical, preferably a C 1 -C 2 radical, which may be substituted by a hydroxyl radical or a C 1 -C 4 alkoxy radical; C4 or (C1-C4) hydroxyalkyl radical. 3. Compound according to claim 2, characterized in that Ra, Rb, Rc identical or different, represent a C1-C2 alkyl radical, in particular methyl, ethyl, optionally substituted with a hydroxyl radical. 4. Compound according to one of the preceding claims, characterized in that the cationic radical is chosen from trimethylammonium, triethylammonium, dimethyl-ethylammonium, diethylmethylammonium, diisopropylmethylammonium, diethylpropylammonium, hydroxyethyl diethylammonium, di beta hydroxyethylmethylammonium, di beta hydroxyethylethylammonium, tri beta hydroxyethylammonium, imidazolium, pyridinium, piperidinium, piperazinium, pyrrolidinium, morpholinium, pyrimidinium, thiazolium, benzimidazolium, benzothiazolium, and mixtures thereof. 5. Compound according to one of the preceding claims, wherein R represents a hydrogen atom. 6. R1 represents a branched C1-C10, preferably C2-C8, alkyl radical substituted by a cationic radical, said alkyl radical optionally being interrupted by an oxygen atom and / or by an NH group, 7. Compound according to one of the preceding claims, wherein R1 represents a branched saturated alkyl radical C1-C8, preferably C2-C8. 8. Compound according to one of the preceding claims, wherein R1 is a branched C2-C8 saturated alkyl radical, optionally interrupted by an oxygen atom or an NH group, substituted with a cationic heterocyclic radical of 5 to 8 selected members. among the radicals imidazolium, pyridinium, piperidinium, piperazinium, pyrrolidinium, morpholinium, pyrimidinium, thiazolium, benzimidazolium, benzothiazolium, oxazolium, benzotriazolium, pyrazolium, triazolium, benzoxazolium, these cationic heterocycles being optionally substituted with one or more identical or different radicals chosen; among hydroxy radical, a C1-C4 alkoxy radical or a (C1-C4) hydroxyalkyl radical, and mixtures thereof. 9. Compound according to one of claims 1 to 7, wherein R1 is a branched C2-C8 saturated alkyl radical, optionally interrupted by an oxygen atom or an NH group, substituted with a radical -N + RaRbRc, Ra , Rb, Rc identical or different representing a C1-C6 alkyl radical which may be substituted by a hydroxy, Ra and Rb, may together form a heterocycle comprising from 5 to 8 members, the radical Rc then being a C1-C6 alkyl radical; which may be substituted with a hydroxy radical, a C1-C4 alkoxy radical or a (C1-C4) hydroxyalkyl radical. 10. Compound according to the preceding claim, wherein R1 the radical - N + RaR bRc denotes a trimethylammonium, triethylammonium, dimethyl-ethylammonium, diethylmethylammonium, diisopropylmethylammonium, diethylpropylammonium, hydroxyethyl diethylammonium, di-hydroxyethylmethylammonium, tri beta hydroxyethylammonium. 11. Compound according to one of the preceding claims, characterized in that it is chosen from the following compounds: 3- (2,4-diaminophenoxy) -N, N, N-trimethylbutan-2-aminium, An-, 3- (2,4-diaminophenoxy) -N-ethyl-N, N-dimethylbutan-2-aminium, N-, 3- (2,4-diaminophenoxy) -N, N-diethyl-N-methylbutan-2-aminium , N-, 3- (2,4-diaminophenoxy) -N, N, N-triethylbutan-2-aminium, N-, 3- (2,4-diaminophenoxy) -N, N-bis (2-hydroxyethyl) - N-methylbutan-2-aminium, N-3- (2,4-diaminophenoxy) -N-ethyl-N, N-bis (2-hydroxyethyl) butan-2-aminium, N-3- (2,4-diaminophenoxy) N, N, N-tris (2-hydroxyethyl) butan-2-aminium, N-, N- (14- (2,4-diaminophenoxy) butan-2-yl] -1-methylpiperidinium, An-, 442- (2H); 4-diaminophenoxy) ethyl] -4-methylmorpholin-4-ium, N-, O- (2,4-diaminophenoxy) butan-2-yl] -3-methyl-1H-imidazol-3-ium, An-, 443- (2,4-diaminophenoxy) butan-2-yl] -1,1-dimethylpiperazin-1-ium, An-, 3- (2,4-diaminophenoxy) -N, N, N, 2,3-pentamethylbutan -2-Aminium, N- (3- (2,4-diaminophenoxy) -N-ethyl-N, N, 2,3-tetramethylbutan-2-aminium, An-, 3 - (2,4-diaminophenoxy) -N, N-diethyl-N, 2,3-trimethylbutan-2-aminium, N- (3- (2,4-diaminophenoxy) -N- (2-hydroxyethyl) -N, N, 2,3-tetramethylbutan-2-aminium, An-, 3- (2,4-diaminophenoxy) -N, N-diethyl-N- (2-hydroxyethyl) -2,3-dimethylbutan-2-aminium, An 3- (2,4-diaminophenoxy) -N, N, N-tris (2-hydroxyethyl) -2,3-dimethylbutan-2-aminium, An-, 443- (2,4-diaminophenoxy) -2, 3-dimethylbutan-2-yl] -1,1-dimethylpiperazin-1-ium, N-, 443- (2,4-diaminophenoxy) -2,3-dimethylbutan-2-yl] -1- (2-hydroxyethyl) 1-methylpiperazin-1-ium, N-, 443- (2,4-diaminophenoxy) -2,3-dimethylbutan-2-yl] -4-methylmorpholin-4-ium, An-143- (2,4- diaminophenoxy) -2,3-dimethylbutan-2-yl] -3-methyl-1H-imidazol-3-ium, An, 143- (2,4-diaminophenoxy) -2,3-dimethylbutan-2-yl] -3 (- (2-hydroxyethyl) -1H-imidazol-3-ium, N-, O- (2,4-diaminophenoxy) butan-2-yl] -N, N, N-trimethylpyrrolidin-3-aminium, An-, 143 - (2,4-Diaminophenoxy) -2,3-dimethylbutan-2-yl] -N, N, N-trimethylpyrrolidin-3-aminium, N-, 443- (2,4-diaminophenoxy) butan-2-yl] -1,1-bis (2-hydroxyethyl) piper azin-1-ium, An-443- (2,4-diaminophenoxy) -2,3-dimethylbutan-2-yl] -1,1-bis (2-hydroxyethyl) piperazin-1-ium, An-, and their mixtures. 12. Coloring composition of keratinous fibers comprising, in a medium suitable for dyeing keratinous fibers, at least one compound according to one of claims 1 to 11. 13. A process for dyeing keratinous fibers, wherein a composition according to claim 12 is applied to the fibers, either alone or in the presence of an oxidizing agent, for a time sufficient to develop the desired coloration.