EP1064278A1 - Cationic di-benzene dyeing agents, use for oxidation dyeing of keratin fibres, dyeing compositions and dyeing method - Google Patents

Abstract

The invention concerns novel di-benzene dyeing agents comprising at least a cationic group Z, Z being selected among the quaternized aliphatic chains containing at least a saturated quaternized cycle, and aliphatic chains containing at least an unsaturated quaternized cycle. The invention also concerns the use of said dyeing agents as precursors of oxidation dyes for oxidation dyeing of keratin fibres, dyeing compositions containing them, and dyeing methods using them.

Description

CATIONIC DI-BENZENIC DYES, THEIR USE FOR OXIDATION DYEING OF KERATINIC FIBERS, TINCTORIAL COMPOSITIONS AND DYEING PROCESS

The subject of the invention is new di-benzenic dyes comprising at least one cationic group Z, Z being chosen from quaternized aliphatic chains, aliphatic chains comprising at least one quaternized saturated cycle, and aliphatic chains comprising at least one unsaturated cycle quaternized, their use as oxidation dye precursors for the oxidation dyeing of keratin fibers, the dye compositions containing them, as well as the oxidation dyeing processes using them.

It is known to dye keratin fibers and in particular human hair with dye compositions containing oxidation dye precursors, in particular paraphenylenediamines, ortho or paraaminophenols, heterocyclic compounds such as diaminopyrazole derivatives, generally called bases. oxidation. 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.

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 metadiamines, metaaminophenols. metadiphenols and certain heterocyclic compounds such as, for example, indole couplers. The variety of molecules involved in the oxidation bases and couplers, allows obtaining a rich palette of colors.

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 and present good resistance to external agents (light, bad weather, washing, permanent waving, perspiration, friction).

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

Now, the applicant has now discovered, in a completely unexpected and surprising manner, that new cationic di-benzene dyes of formula (I) defined below comprising at least one cationic group Z, Z being chosen from quaternized aliphatic chains, aliphatic chains comprising at least one quaternized saturated ring, and aliphatic chains comprising at least one unsaturated quaternized ring, not only are suitable for use as oxidation dye precursors for the oxidation dyeing of keratin fibers, but also that 'they make it possible to obtain dye compositions leading to powerful colorings, in a wide palette of colors, and having excellent resistance properties to the various treatments which keratin fibers can undergo.

These discoveries are the basis of the present invention. The first object of the invention is therefore new compounds of the following formula (I), and their addition salts with an acid:

in which :

^• B is a linking arm which represents an alkyl chain preferably having from 1 to 14 carbon atoms, linear or branched which can be interrupted by one or more Z groups and / or by one or more heteroatoms such as oxygen atoms , sulfur or nitrogen, and optionally substituted by one or more hydroxyl or C ₆ -C ₆ alkoxy radicals, and which can carry one or more ketone functions;

^• A „A ₂ , and A ₃ , identical or different, represent a group -NR ₇ R ₈ or a hydroxyl radical; one and only one of the groups A. ,, A ₂ and A ₃ may also represent a group R ₃ as defined below;

^• A, A ' ₂ and A' ₃ , identical or different, represent a group -NR ' ₇ R' ₈ or a hydroxyl radical; one and only one of the groups A ' _{1 t} A' ₂ and A ' ₃ can also represent a group R' ₃ as defined below;

^• R. ,, R, R ₂ , R ' ₂ , R ₃ and R' ₃ , which may be identical or different, represent one of the two valences of a link arm B, a hydrogen atom; a halogen atom; a group Z as defined below; an alkyl (CC ₆ ) carbonyl radical; an aminoalkyl radical (C., - C ₆ ) carbonyl; an NZ-aminoalkyl (C _r C ₆ ) carbonyl radical; an N-(C ₁ -C ₆ ) aminoalkyl (C ₁ -C ₆ ) carbonyl radical; an N, N-dialkyl (CC ₆ ) aminoalkyl (C _r C ₆ ) carbonyl radical; an aminoalky radical ^ C _! -

C ₆ ) carbonylalkyl (C _r C ₆ ); an NZ-aminoalkyl (C _r C ₆ ) carbonylalkyl (CC ₆ ) radical; an N-alkyl (C ₁ -C ₆ ) aminoalkyl (C ₁ -C ₆ ) carbonylalkyl (C ₁ -C ₆ ) radical; an N, N-dialkyl (C ₁ -C ₆ ) aminoalkyl (C ₁ -C ₆ ) carbonylalkyl (C ₁ -C ₆ ) radical; a carboxy radical; a carboxy (CC ₆ ) alkyl radical; an alkyl radical (C _r C ₆ ) sulfonyl; an aminosulfonyl radical; an NZ-aminosulfonyl radical; an N-alkyl (CC ₆ ) aminosulfonyl radical; an NN-dialky C ^ C ^ aminosulfonyl radical; an aminosulfonylalkyl radical (C ₁ -C ₆ ); an NZ-aminosulfonylalkyl radical (C ₁ -

C ₆ ); an N-alkyl (C ₁ -C ₆ ) aminosulfonylalkyl (C ₁ -C ₆ ) radical; an N, N-dialkyl (C ₁ -C ₆ ) aminosulfonylalkyl (C ₁ -C ₆ ) radical; a carbamyl radical; an N-alkyl (CC ₆ ) carbamyl radical; an NN-dialky CC ^ carbamyl radical; a carbamylalkyl radical (C _r C ₆ ); an N-alkyl (C ₁ -C ₆₎ alkylcarbamyl (C ₁ - C _6); an N, N-dialkyl (C ₁ -C ₆ ) carbamylalkyl (C ₁ -C ₆ ) radical; an alkyl radical in

CC ₆ ; a CC ₆ monohydroxyalkyl radical; a C ₂ -C ₆ polyhydroxyalkyl radical; alkoxy (CC ₆₎ C _r C _6; a CC ₆ trifluoroalkyl radical; a cyano radical; an ORg, SR ₆ , OR ' ₆ or SR' _{6 group} ; an amino group protected by an alky ^ C ^ C ^ carbonyl, (C, - C ₆ ) carboxy, C ^ C ^ carbonyl, aminoalkyl (C., - C ₆ ) carbonyl radical,

NZ-aminoalky C ^ C carbonyl, N-alkyl (C ₁ -C ₆ ) aminoalkyl (C ₁ -C ₆ ) carbonyl, N, N-dialkyl (C ₁ -C ₆ ) aminoalkyl (C ₁ -C ₆ ) carbonyl, alkyl (CC ₆ ) carboxy, carbamyl, N-alkyl (CC ₆ ) carbamyl, N, N-dialkyl (C ₁ -C ₆ ) carbamyl, alkyl (CC ₆ ) sulfonyl, aminosulfonyl, NZ-aminosulfonyl, N-alkyl (CC ₆ ) aminosulfonyl, N, N-dialkyl (CC ₆ ) aminosulfonyl, thiocarbamyl, formyl, or by a group Z as defined below in which the link arm D contains a ketone function directly linked to the nitrogen atom of said amino group; a CC ₆ aminoalkyl radical in which the alkyl is substituted or unsubstituted by one or more hydroxy radicals; an aminoalkyl radical (C ₁ -C ₆ ) in which the alkyl is substituted or unsubstituted by one or more hydroxy radicals and in which the amine is substituted by one or two radicals, identical or different, chosen from alkyl, monohydroxyalkyl C _r C ₆ , polyhydroxyalkyl C ₂ -C ₆ , alkyl (CC ₆ ) carbonyl, carbamyl, N-alkyl (C _r C ₆ ) carbamyl, NN-dialky ^ C _! - C ₆ ) carbamyl, alkyl (C ₁ -C ₆ ) sulfonyl, formyl, trifluoroalky C ^ C ^ carbonyl, alkyl ^ -C ^ carboxy, thiocarbamyl, or among the groups Z as defined below, or which can form together , with the nitrogen atom to which they are attached, a 5 or 6-membered ring, carbon-containing, or containing one or more heteroatoms;

^• R ₆ and R ' ₆ , identical or different, denote one of the two valences of a linking arm B, an alkyl radical in CC ₆ ; a monohydroxyalkyl radical in; a C ₂ -C ₆ polyhydroxyalkyl radical; a group Z as defined below; a CC ₆ alkoxy (C ₁ -C ₆ ) alkyl radical; an aryl radical; a benzyl radical; a CC ₆ carboxyalkyl radical; an alkyl radical (CC ₆₎ carboxyalkyl CC _6; a CC ₆ cyanoalkyl radical; a CC ₆ carbamylalkyl radical; an N-alkyl (C ₁ -C ₆ ) carbamylalkyl radical in ; a radical ; a CC ₆ trifluoroalkyl radical; an aminosulfonylalkyl radical in ; a CC ₆ NZ-aminosulfonylalkyl radical; an N-alkyl (CC ₆ ) aminosulfonylalkyl C _r C ₆ radical; an N, N-dialkyl radical (C

C ₆ ) C _r C ₆ aminosulfonylalkyl; an alkyl (C ₁ -C ₆₎ alkylsulphinyl CC _6; an alkyl radical (CC ₆₎ sulfonylalkyl CC _6; a carbonylalkyl (CC ₆ ) alkyl radical in ; a CC ₆ aminoalkyl radical in which the alkyl is substituted or unsubstituted by one or more hydroxy radicals; a CC ₆ aminoalkyl radical in which the alkyl is substituted or unsubstituted by one or more hydroxy radicals, and in which the amine is substituted by one or two identical or different radicals chosen from the radicals monohydroxyalkyl (C ₁ -C ₆ ), polyhydroxyalkyl (C ₂ -C ₆ ), alkyl (C ₁ -C ₆ ) carbonyl, formyl, trifluoroalky CC ^ carbonyl, alkyl ^ -C ^ carboxy, carbamyl, N-alkyl (C ₁ -C ₆ ) carbamyl, N, N-dialkyl (CC ₆ ) carbamyl, thiocarbamyl, (C ₁ -C ₆ ) alkyl sulfonyl, or among the groups Z as defined below, or being able to form together, with the nitrogen atom to which they are attached, a 5 or 6-membered ring, carbon-containing, or containing one or more heteroatoms;

^• R ₄ , R ' ₄ , R ₅ , R' ₅₎ R ₇ , R ' ₇₎ R ₈ and R' ₈ , identical or different, represent one of the two valences of a link arm B, an atom hydrogen; a group Z as defined below in which the link arm D does not contain a ketone function directly linked to the nitrogen atom of said amino group; a CC ₆ alkyl radical; a CC ₆ monohydroxyalkyl radical; a C ₂ -C ₆ polyhydroxyalkyl radical; alkoxy (CC ₆₎ alkyl, CC _6; an aryl radical; a benzyl radical; a C., - C ₆ cyanoalkyl radical; a C 1 -C ₆ carbamylalkyl radical; an N-alky radical ^ C _! - C ₆ ) CC ₆ carbamylalkyl; an NN-dialkyl ^ -C ^ carbamylalkyl radical in; a C _r C ₆ thiocarbamylalkyl radical; a CC ₆ trifluoroalkyl radical; a CC ₆ sulfoalkyl radical; a (C ₁ -C ₆ ) alkyl carboxyalkyl radical; an alkyl (C ₁ -C ₆₎ alkylsulphinyl C, -C ₆ alkyl; an aminosulfonylalkyl radical in ; an NZ-aminosulfonylalkyl radical in ; a C 6 -C ₆ aminosulfonylalkyl N-alkyl radical CC ₆ ; an N, N-dialkyl (C ₁ -C ₆ ) aminosulfonylalkyl radical CC ₆ ; an alkyl radical (CC ₆₎ carbonylalkyl C _r C _6; a CC ₆ aminoalkyl radical in which the alkyl is substituted or unsubstituted by one or more hydroxy radicals; a CC ₆ aminoalkyl radical in which the alkyl is substituted or unsubstituted by one or more hydroxy radicals and in which the amine is substituted by one or two identical or different radicals chosen from C 1 -C ₆ alkyl, monohydroxyalkyl radicals CC ₆ , C ₂ -C ₆ polyhydroxyalkyl, alkyl (C _r

C ₆ ) carbonyl, carbamyl, N-alkyl (CC ₆ ) carbamyl, N, N-dialkyl (CC ₆ ) carbamyl, (C ₁ -C ₆ ) alkyl sulfonyl, formyl, trifluoroalkyl (C _r C ₆ ) carbonyl, alkyl ( CC ₆ ) carboxy, thiocarbamyl, or by a group Z as defined below, or which can form together, with the nitrogen atom to which they are attached, a 5 or 6-membered ring, carbon-containing, or containing one or several heteroatoms; ^• Z is chosen from the unsaturated cationic groups of formulas (II) and (III) below, and the saturated cationic groups of formula (IV):

in which :

D is a linking arm which represents an alkyl chain preferably having from 1 to 14 carbon atoms, linear or branched which can be interrupted by one or more heteroatoms such as oxygen, sulfur or nitrogen atoms, and which can be substituted by one or more hydroxyl or alkoxy radicals in and can carry one or more ketone functions; the vertices E, G, J, L and M, identical or different, represent a carbon, oxygen, sulfur or nitrogen atom; n is an integer between 0 and 4 inclusive; m is an integer between 0 and 5 inclusive; the radicals R, which are identical or different, represent one of the two valences of a linking arm B, a second group Z identical to or different from the first group Z, a halogen atom, a radical hydroxyl, an alkyl radical in CC ₆ , a monohydroxyalkyl radical in a polyhydroxyalkyl radical in C ₂ -C ₆ , a nitro radical, a cyano radical, a cyanoalkyl radical in a C ₆ -C ₆ alkoxy radical, a radical in CC ₆ , an amido radical, an aldehydo radical, a carboxyl radical, a C ₆ -C ₆ alkylcarbonyl radical, a thio radical, a CC ₆ thioalkyl radical, an alkyl ^ -C ^ thio radical, an amino radical, an amino radical protected by an (O, - C ₆ ) carbonyl, carbamyl or (CC ₆ ) sulfonyl alkyl radical; an NHR "or NR" R "'group in which R" and R'", which may be identical or different, represent a CC ₆ alkyl radical, a CC ₆ monohydroxyalkyl radical or a C ₂ -C ₆ polyhydroxyalkyl radical;

• R ₉ represents one of the two valences of a connecting arm B, an alkyl radical in C, -C ₆ , a monohydroxyalkyl radical in CC ₆ , a polyhydroxyalkyl radical in C ₂ -C ₆ , a cyanoalkyl radical in CC ₆ , a trialkyl (CC ₆ ) silanealkyl radical in CC ₆ , an alkoxy (C ₁ -C ₆ ) alkyl CC ₆ , a carbamylalkyl radical in CC ₆ , a benzyl radical, or a second group Z identical to or different from the first group Z;

• R ₁₀ , R and R ₁₂ , identical or different, represent one of the two valences of a linking arm B, an alkyl radical in a monohydroxyalkyl radical in C ^ Ce, a polyhydroxyalkyl radical in C ₂ -C ₆ , an alkoxy (C ₁ -C ₆ ) alkyl in CC ₆ , a cyanoalkyl radical in C _r C ₆ , an aryl radical, a benzyl radical, an amidoalkyl radical CC _6, a radical trialkyl (CC ₆₎ alkylsilane CC ₆ or an aminoalkyl radical in carbamyl, or alkyl (CC ₆ ) sulfonyl; two of the radicals R ₁₀ , R „and R ₁₂ can also form together, with the nitrogen atom to which they are attached, a saturated 5 or 6-membered carbon ring or containing one or more heteroatoms such as for example a pyrrolidine ring , a cycle piperidine, a piperazine ring or a morpholine ring, which ring may be unsubstituted or substituted by a halogen atom, a hydroxyl radical, an alkyl radical CC ₆ monohydroxyalkyl radical CC _6, a polyhydroxyalkyl radical, C ₂ -C ₆ , a nitro radical, a cyano radical, a cyanoalkyl radical in n alkoxy radical in CC ₆ , a trialkyl (C ₁ -C ₆ ) silanealkyl radical e an amido radical, an aldehydo radical, a carboxyl radical, a ketoalkyl radical in a thio radical, a thioalkyl radical in an amino radical, an amino radical protected by an alkyl ^ -C _f carbonyl, carbamyl or alkyl (CC ₆ ) sulfonyl radical;

one of the radicals R ₁₀ , R 2 and R ₁₂ can also represent a second group Z, identical or different from the first group Z;

• R ₁₃ represents one of the two valences of a linking arm B, a CC ₆ alkyl radical; a CC ₆ monohydroxyalkyl radical; a C ₂ -C ₆ polyhydroxyalkyl radical; an aryl radical; a benzyl radical; a C _r C ₆ aminoalkyl radical, a C ₆ aminoalkyl radical the amine of which is protected by an alkyl (C _r C ₆ ) carbonyl, carbamyl or alkyl (CC ₆ ) sulfonyl radical; a CC ₆ carboxyalkyl radical; a CC ₆ cyanoalkyl radical; a CC ₆ carbamylalkyl radical; a CC ₆ trifluoroalkyl radical; a CC ₆ trialkyl ^ -C ^ silanealkyle radical; a sulfonamidoalkyl radical in ; a radical in ; an alkyl (C ₁ -C ₆₎ sulfιnylalkyle C, -C ₆ alkyl; a (C ₁ -C ₆ ) alkyl sulfonylalkyl radical in ; a radical in

CC ₆ ; a C 6 -C ₆ carbamylalkyl N-alkyl radical CC ₆ ; an N-C ₁ -C ₆ sulfonamidoalkyl radical CC ₆ ;

• a and y are whole numbers equal to 0 or 1; with the following conditions:

- in the unsaturated cationic groups of formula (II): - when a = 0, the link arm D is attached to the nitrogen atom,

- when a = 1, the link arm D is attached to one of the vertices E, G, J or L,

- y can only take the value 1: 1) when the vertices E, G, J and L simultaneously represent a carbon atom, and the radical R ₉ is carried by the nitrogen atom of the unsaturated cycle; or

2) when at least one of the vertices E, G, J and L represents a nitrogen atom on which the radical R ₉ is attached; - in the unsaturated cationic groups of formula (III):

- when a = 0, the link arm D is attached to the nitrogen atom,

- when a = 1, the link arm D is attached to one of the vertices E, G, J, L or M,

- y can only take the value 1 when at least one of the vertices E, G, J, L and M represents a divalent atom, and the radical R ₉ is carried by the nitrogen atom of the unsaturated cycle; - in the cationic groups of formula (IV):

- when a = 0, then the link arm D is attached to the nitrogen atom carrying the radicals R ₁₀ to R ₁₂ , - when a = 1, then two of the radicals R ₁₀ to R ₁₂ form jointly with the nitrogen atom to which they are attached a saturated 5 or 6-membered ring as defined above, and the link arm D is carried by a carbon atom of said saturated ring;

• X ^" represents a monovalent or divalent anion and is preferably chosen from a halogen atom such as chlorine, bromine, fluorine or iodine, a hydroxide, a hydrogenesulfate, or a such as for example a methyl sulphate or an ethyl sulphate;

Being heard that :

- The number of cationic group Z is at least equal to 1. As indicated previously, the colorings obtained with the oxidation dye composition containing the dye (s) of formula (I) according to the invention are powerful and make it possible to achieve a wide palette of colors. They also have excellent resistance properties with regard to the action of various external agents (light, bad weather, washing, permanent waving, perspiration, friction). These properties are particularly remarkable in particular with regard to the resistance of the colorings obtained with respect to the action of light, washing, permanent waving and perspiration.

In formulas (I), (II), (III) and (IV) above, the alkyl and alkoxy radicals can be linear or branched.

Among the cycles of the unsaturated groups Z of formula (II) above, mention may in particular be made, by way of example, of the pyrrolic, imidazolic, pyrazolic, oxazolic, thiazolic and thazolic cycles.

Among the cycles of the unsaturated groups Z of formula (III) above, mention may in particular be made, by way of example, of the pyridine, pyrimidine, pyrazine, oxazine and triazine cycles.

The compounds of formula (I) above are preferably chosen from:

- 3- [2- (2-amino-4-hydroxy-phenylamino) ethyl] -1- dichloride -1- (4- {3- [2- (2- amino-4-hydroxy-phenylamino) -ethyl] - 3H-imidazol-1-ium} -butyl) -3H-imidazol-1-ium;

- 3- {2 - [(3-amino-4-methylamino-phenyl) -methyl-amino] -ethyl} -1 dichloride -1- [4- (3- {2 - [(3-amino-4-methylamino -phenyl) -methyl-amino] -ethyl} -3H-imidazol-1-ium) -butyl] -3H-imidazol-1-ium;

- 1,3-bis- {2 - [(3-amino-4-methylamino-phenyl) -methyl-amino] - ethyl} -3H-imidazol-1-ium chloride; - 3- {2 - [(3-amino-4-methylamino-phenyl) -methyl-amino] -ethyl} -1-dichloride -1- [3 - ({2 - [(3-amino-4-methylamino-phenyl) ) -methyl-amino] -ethyl} -dimethyl-ammonium) -propyl] -3H-imidazol-1 -ium;

- {2 - [(3-amino-4-methylamino-phenyl) -methyl-amino] -ethyl} - dichloride - [2- ({2 - [(3-amino-4-methylamino-phenyl) -methyl- amino] -ethyl} -dimethylammonium) -ethyl] -dimethylammonium;

- 3- [2- (2,4,5-trihydroxy-phenylamino) -ethyl] -1- dichloride -1- (4- {3- [2- (2,4,5-trihydroxy-phenylamino) -ethyl] - 3H-imidazol-1-ium} -butyl) -3H-imidazol-1-ium; and their addition salts with an acid.

The acid addition salts of the compounds of formula (I) are preferably chosen from hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates and acetates.

The compounds of formula (I) in accordance with the invention can be easily obtained, according to methods well known from the state of the art, by reduction of the corresponding cationic di-benzene nitro compounds.

This reduction step (obtaining a primary aromatic amine) followed or not by salification, is generally, for convenience, the last step of the synthesis.

This reduction can occur earlier in the course of the reactions leading to the preparation of the compounds of formula (I), and according to well known methods it is then necessary to "protect" the primary amine created (for example by an acetylation step, benzenesulfonation, etc.), then make the desired substitution (s) or modification (including quaternization) and finish with the "deprotection" (generally in an acid medium) of the amino function. Likewise, the phenolic function can be protected according to well-known methods by a benzyl radical ("deprotection" by catalytic reduction) or by an acetyl or mesyl radical ("deprotection" in an acid medium).

These cationic di-benzene compounds are obtained by methods well known in the state of the art, for example by:

- condensation of two molecules of a benzene compound carrying a haloalkyl radical on a molecule of a compound carrying two tertiary amine radicals separated by a linker arm B as defined in formula (I) described above, or by

- condensation of two molecules of a benzene compound carrying a tertiary amine radical on a molecule of a compound carrying two halogen radicals separated by a linking arm B as defined in formula (I) described above, or, - (a) condensation of a molecule of a benzene compound carrying a tertiary amine radical on a molecule of a compound carrying two halogen radicals separated by a linking arm B as defined in formula ( I) described above, and (b) condensation of a second benzene compound molecule different from the first and also carrying a tertiary amino radical, or,

- (a) condensation of a molecule of a benzene compound carrying a haloalkyl radical on a molecule of a compound carrying two tertiary amine radicals separated by a linker arm B as defined in formula (I) described above, and (b) condensation of a second molecule of a benzene compound different from the first and also carrying a haloalkyl radical, or else

- Condensation of a molecule of a benzene compound carrying a tertiary amine radical on a molecule of a benzene compound carrying a haloalkyl radical. The halogenoalkyl radicals carried by the intermediate dibenzene compounds can be prepared by methods known from the prior art, in one or more stages, for example by condensation of a dihaloalkyl compound on an amine or a hydroxyl, or by halogenation of a hydroxyalkyl chain.

When the synthesis is complete, the compounds of formula (I) in accordance with the invention can, if necessary, be recovered by methods well known from the state of the art such as crystallization, distillation.

Another subject of the invention is the use of the compounds of formulas (I) in accordance with the invention as an oxidation dye precursor for the oxidation dyeing of keratin fibers, and in particular human keratin fibers such than hair.

A subject of the invention is also a composition for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that it comprises, as oxidation dye precursors, in a medium suitable for dyeing, at least one compound of formula (I) according to the invention.

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 -C 4 alkanols, such as ethanol and isopropanol; glycerol; glycols and ethers of glycols such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and monomethyl ether of diethylene glycol, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, analogues 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 following formula (V):

^R 14 R ₁₆

\ / ¹⁶

N-W-N (V)

^R 15 ^R 17 in which W is a propylene residue optionally substituted by a hydroxyl group or a C _r C ₆ alkyl radical; R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ , identical or different, represent a hydrogen atom, a C _r C ₆ alkyl radical OR hydroxyalkyl in

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

Among the paraphenylenediamines, mention may more particularly be made, for example, of paraphenylenediamine, paratoluylenediamine, 2,6-dimethyl paraphenylenediamine, 2-β-hydroxyethyl paraphenylenediamine, 2-n-propyl paraphenylenediamine, 2-isopropyline paraphenyl , N- (β-hydroxypropyl) paraphenylenediamine, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 4-amino N- (β-methoxyethyl) aniline, the paraphenylenediamines described in French patent application FR 2 630 438, and their addition salts with an acid.

Mention may more particularly be made, among bis-phenylalkylenediamines, by way of example, of 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-methylaminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) N, N ' -bis- (4'-amino, 3'-methylphenyl) ethylenediamine, and their addition salts with an acid.

Among the para-aminophenols, there may be mentioned more particularly by way of example, 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, and their addition salts with an acid.

Among the ortho-aminophenols, mention may more particularly be made, for 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, non-cationic 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 German patents DE 2,359,399 or Japanese patents JP 88-169,571 and JP 91-10659 or patent application WO 96/15765, such as 2,4, 5,6-tetra-aminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 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 mention may be made of pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; 2,5-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; pyrazolo- [1,5-a] - pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,5-diamine; 3-amino pyrazolo- [1,5-a] -pyrimidin-7-ol; 3-amino pyrazolo- [1,5-a] -pyrimidin-5-ol; 2- (3-amino pyrazolo- [1,5-a] -pyrimidin-7-ylamino) - ethanol, 2- (7-amino pyrazolo- [1, 5-a] -pyrimidin-3-ylamino) -ethanol, 2 - [(3-amino-pyrazolo [1, 5-a3pyrimidin-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-3,7-diamine, 2,6-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 2 , 5, N 7, N 7-tetramethyl pyrazolo- [1,5-a] - pyrimidine-3,7-diamine, and their addition salts and tautomeric forms, when there is a tautomeric equilibrium and their salts 'addition with an acid.

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, 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 py razole, 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 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 and heterocyclic couplers such as, for example, indole derivatives, indolinic derivatives, pyridine derivatives and pyrazolones, and their addition salts with an 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-di hydroxy 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, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N -methyl indole, 6-hydroxy indoline, 2,6-dihydroxy 4-methyl pyridine, 1-H 3-methyl pyrazole 5-one, 1-phenyl 3-methyl pyrazole 5-one, and their salts addition with an acid.

When present, these couplers 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.

In general, the addition salts with an acid which can be used in the context of the invention (compounds of formula (I), oxidation bases and couplers) are in particular chosen from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates and acetates. The dye composition according to 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 , nonionic, 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.

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.

The subject of the invention is also a process for the oxidation dyeing of 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, for a time sufficient to develop the desired coloration, either in air or using an oxidizing agent. The dye composition may optionally contain oxidation catalysts, in order to accelerate the oxidation process.

According to a first embodiment of the process of the invention, the coloring of the fibers can be carried out without the addition of an oxidizing agent, only in contact with the oxygen in the air.

According to a second embodiment of the process of the invention, and in particular when the dye composition according to the invention contains one or more oxidation bases and / or one or more couplers, at least one fiber is applied to the fibers. dye composition as defined above, the color being revealed at acidic, neutral or alkaline pH using an oxidizing agent which is added just at the time of use to the dye composition or which is present in an applied oxidizing composition simultaneously or sequentially separately.

According to this second form of implementation of the dyeing process of the invention, the dye composition described above is preferably mixed with an oxidizing composition containing, in an environment suitable 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 left to stand 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 present in the oxidizing composition as defined above 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 bramates, persalts such as perborates and persulfates and enzymes such as peroxidases, laccases, tyrosynases and oxidoreductases among which may be mentioned in particular pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases, and uricases.

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 mixture to be delivered to the hair. desired, such as the devices described in patent FR-2,586,913 in the name of the applicant.

Claims

Compounds of formula (I) below, and their addition salts with an acid

in which :

^• B is a linking arm which represents an alkyl chain preferably having from 1 to 14 carbon atoms, linear or branched which can be interrupted by one or more Z groups and / or by one or more heteroatoms such as oxygen atoms , sulfur or nitrogen, and optionally substituted by one or more hydroxyl or alkoxy radicals in CC ₆ , and which can carry one or more ketone functions;

^• A _{1 t} A ₂ , and A ₃ , identical or different, represent a group -NR ₇ R ₈ or a hydroxyl radical; one and only one of the groups A ,, A ₂ and A ₃ may also represent a group R ₃ as defined below;

^• A ' _{1 (} A' ₂ and A ' ₃ , identical or different, represent a group -NR' ₇ R ' ₈ or a hydroxyl radical; one and only one of the groups A, A' ₂ and A ' ₃ may also represent a group R ' ₃ as defined below;

^• R. ,, R, R ₂ , R ' ₂ , R ₃ and R' ₃ , which may be identical or different, represent one of the two valences of a link arm B, a hydrogen atom; a halogen atom; a group Z as defined below; an alkyl (CC ₆ ) carbonyl radical; an aminoalkyl (C _r C ₆ ) carbonyl radical; an NZ-aminoalky C CgJcarbonyl radical; an N-(C ₁ -C ₆ ) aminoalkyl (C ₁ -C ₆ ) carbonyl radical; an N, N-dialkyl (C., - radical ; an aminoalkyl (C 1 -C ₆ ) carbonylalkyl radical (CC ₆ ); an NZ-aminoalkyl (C ₁ -C ₆ ) carbonylalkyl (C ₁ -) radical

C ₆ ); an N-alkyl (C ₁ -C ₆ ) aminoalkyl (C ₁ -C ₆ ) carbonylalkyl (C ₁ -C ₆ ) radical; an N, N-dialkyl (C ₁ -C ₆ ) aminoalkyl (C ₁ -C ₆ ) carbonylalkyl (C ₁ -C ₆ ) radical; a carboxy radical; a radical carboxy; an alkyl radical (CC ₆ ) sulfonyl; an aminosulfonyl radical; an NZ-aminosulfonyl radical; an N-alkyl (CC ₆ ) aminosulfonyl radical; an N, N-dialkyl (C ₁ -C ₆ ) aminosulfonyl radical; a radical ; an NZ-aminosulfonylalkyl (C ₁ -C ₆ ) radical; an N-alkyl (C ₁ -C ₆ ) aminosulfonylalkyl (C ₁ -C ₆ ) radical; an N, N-dialkyl (C ₁ -C ₆ ) aminosulfonylalkyl (C ₁ -C ₆ ) radical; a carbamyl radical; a radical ; an N, N-dialkyl (CC ₆ ) carbamyl radical; a carbamylalkyl radical (C ₁ -C ₆ ); an N-alkyl (C ₁ -C ₆ ) carbamylalkyl radical (C ₁ -

C ₆ ); an N, N-dialkyl (C ₁ -C ₆ ) carbamylalkyl (C ₁ -C ₆ ) radical; a CC ₆ alkyl radical; a CC ₆ monohydroxyalkyl radical; a C ₂ -C ₆ polyhydroxyalkyl radical; an alkoxy radical (C Cg) alkyl in ; a CC ₆ trifluoroalkyl radical; a cyano radical; an ORg, SR ₆ , OR ' ₆ or SR' _{6 group} ; an amino group protected by an alkyl (CC ₆ ) carbonyl, alkyl (C

C ₆ ) carboxy, trifluoroalky C ^ C _f carbonyl, aminoalkyl (CC ₆ ) carbonyl, NZ-aminoalky C.-CgJcarbonyl, N-alkyl (C ₁ -Cg) aminoalkyl (C ₁ -C ₆ ) carbonyl, N, N- dialkyl (C ₁ -C ₆ ) aminoalkyl (C ₁ -C ₆ ) carbonyl, alkyl (CC ₆ ) carboxy, carbamyl, N-alkyl (C ₁ -C ₆ ) carbamyl, N, N-dialkyl (C, -C ₆ ) carbamyl, (C _r C ₆ ) alkyl sulfonyl, aminosulfonyl, NZ-aminosulfonyl, N-alkyl (C

C ₆ ) aminosulfonyl, NN-dialky C CgJaminosulfonyl, thiocarbamyl, formyl, or by a group Z as defined below in which the linking arm D contains a ketone function directly linked to the nitrogen atom of said amino group; a CC ₆ aminoalkyl radical in which the alkyl is substituted or unsubstituted by one or more hydroxy radicals; an aminoalkyl radical (CC ₆ ) in which the alkyl is substituted or unsubstituted by one or several hydroxy radicals and the amine of which is substituted by one or two radicals, identical or different, chosen from alkyl, monohydroxyalkyl radicals, polyhydroxy C ₂ -C ₆ alkyl (CC ₆₎ alkylcarbonyl, carbamyl, N-alky ^ C ^ C ^ alkylcarbamoyl, N, N-dialkyl C _i - C ₆₎ carbamyl, (C ₁ -C ₆₎ alkylsulphonyl, formyl, trifluoroalkyl (C ₁ -Cg) carbonyl, thiocarbamyl, or among the Z groups as defined below, or which can form, together with the nitrogen atom to which they are attached, a 5 or 6-membered ring, carbon-containing, or containing one or more heteroatoms;

^• R ₆ and R ' ₆ , identical or different, denote one of the two valences of a link arm B, an alkyl radical in ; a CC ₆ monohydroxyalkyl radical; a C ₂ -C ₆ polyhydroxyalkyl radical; a group Z as defined below; alkoxy (CC ₆₎ alkyl, CC _6; an aryl radical; a benzyl radical; a CC ₆ carboxyalkyl radical; an alkyl radical ^ C, -

C ₆ ) CC ₆ carboxyalkyl; a cyanoalkyl radical in ; a carbamylalkyl radical in ; a radical in CC ₆ ; an N, N-dialkyl (C ₁ -C ₆ ) carbamylalkyl radical in ; a CC ₆ trifluoroalkyl radical; a CC ₆ aminosulfonylalkyl radical; an NZ-aminosulfonylalkyl radical in C _r C ₆ ; an N-alkyl radical (C

C ₆ ) C _r C ₆ aminosulfonylalkyl; an N, N-dialkyl (CC ₆ ) aminosulfonylalkyl radical in CC ₆ ; a radical in CC ₆ ; an alkyl (C ₁ -C ₆₎ sulfonyl, C ₁ -C ₆ alkyl; a (C 1 -C ₆ ) carbonylalkyl alkyl radical in ; a CC ₆ aminoalkyl radical in which the alkyl is substituted or unsubstituted by one or more hydroxy radicals; a C ₁ -C ₆ aminoalkyl radical in which the alkyl is substituted or unsubstituted by one or more hydroxy radicals, and in which the amine is substituted by one or two identical or different radicals chosen from alkyl radicals (CC ₆ ), monohydroxyalkyle ^ -Cg), polyhydroxyalkyle (C ₂ -C ₆ ), formyl, thfluoroalkyl (C ₁ -C ₆ ) carbonyl, carbamyl,

N-alkyl (C., - C ₆ ) carbamyl, thiocarbamyl, (C ₁ -C ₆ ) alkyl, sulfonyl, or among the Z groups as defined below, or which can form together, with the nitrogen atom to which they are attached, a 5 or 6-membered, carbon-containing ring, or containing one or more heteroatoms;

^• R ₄ , R ' ₄ , R ₅ , R' ₅ , R ₇ , R ' ₇ , R ₈ and R' ₈ , identical or different, represent one of the two valences of a link arm B, an atom hydrogen; a group Z as defined below in which the link arm D does not contain a ketone function directly linked to the nitrogen atom of said amino group; a C 1 -C ₆ alkyl radical; a monohydroxyalkyl radical in

CC ₆ ; a C ₂ -C ₆ polyhydroxyalkyl radical; a CC ₆ alkoxy (C ₁ -C ₆ ) alkyl radical; an aryl radical; a benzyl radical; a CC ₆ cyanoalkyl radical; a CC ₆ carbamylalkyl radical; an N-alkyl (CC ₆ ) carbamylalkyl radical in ; an N, N-dialkyl (C ₁ -C ₆₎ carbamyl C _ï C₆ alkyl; a CC ₆ thiocarbamylalkyl radical; a trifluoroalkyl radical in

CC ₆ ; a CC ₆ sulfoalkyl radical; a CC ₆ -C ₁ -C ₆ carboxyalkyl alkyl radical; a C ₁ -C ₆ sulfinylalkyl alkyl radical; a CC ₆ aminosulfonylalkyl radical; an O, -Cg NZ-aminosulfonylalkyl radical; an N-alkyl radical (C ₁ -C ₆ ) aminosulfonylalkyl CC ₆ ; an N, N-dialkyl (CC ₆ ) aminosulfonylalkyl C _r C ₆ radical; an alkyl radical (C

C ₆ ) CC ₆ carbonylalkyl; an aminoalkyl radical in the alkyl of which is substituted or unsubstituted by one or more hydroxy radicals; a CC ₆ aminoalkyl radical in which the alkyl is substituted or unsubstituted by one or more hydroxy radicals and in which the amine is substituted by one or two identical or different radicals chosen from CC ₆ alkyl radicals, monohydroxyalkyl in C ₆ ) carbonyl, carbamyl, N, N-dialkyl (CC ₆ ) carbamyl, (C ₁ -C ₆ ) alkyl sulfonyl, formyl, trifluoroalkyl (C ₁ -C ₆ ) carbonyl, (CC ₆ ) alkyl carboxy, thiocarbamyl, or by a group Z as defined below, or which can form together, with the nitrogen atom to which they are attached, a 5 or 6-membered ring, carbon-containing, or containing one or more heteroatoms;

^• Z is chosen from the unsaturated cationic groups of formulas (II) and (III) below, and the saturated cationic groups of formula (IV):

in which :

D is a linking arm which represents an alkyl chain preferably having from 1 to 14 carbon atoms, linear or branched which can be interrupted by one or more heteroatoms such as oxygen, sulfur or nitrogen atoms, and may be substituted by one or more hydroxyl or alkoxy radicals in and can carry one or more ketone functions;

• the vertices E, G, J, L and M, identical or different, represent a carbon, oxygen, sulfur or nitrogen atom;

• n is an integer between 0 and 4 inclusive; • m is an integer between 0 and 5 inclusive;

The radicals R, which are identical or different, represent one of the two valences of a linking arm B, a second group Z identical or different from the first group Z, a halogen atom, a hydroxyl radical, an alkyl radical in a monohydroxyalkyl radical in

C, -C ₆ , a C ₂ -C ₆ polyhydroxyalkyl radical, a nitro radical, a cyano radical, a C, -C ₆ cyanoalkyl radical, an alkoxy radical in a trialkyl (C ₁ -C ₆ ) silanealkyl radical in CC ₆ , an amido radical, an aldehydo radical, a carboxyl radical, a C ₁ -C ₆ alkylcarbonyl radical, a thio radical, a thioalkyl radical in an alkyl radical (CC ₆ ) thio, an amino radical, an amino radical protected by an alkyl radical (C ₆ -C ₆ ) carbonyl, carbamyl or ; an NHR "or NR" R "'group in which R" and R'", which may be identical or different, represent a C 6 alkyl radical, a CC ₆ monohydroxyalkyl radical or a C ₂ -C ₆ polyhydroxyalkyl radical;

• R ₉ represents one of the two valences of a linking arm B, an alkyl radical in C Cg, a monohydroxyalkyl radical in a C ₂ -C ₆ polyhydroxyalkyl radical, a C ₁ -C ₆ cyanoalkyl radical, a silanealkyl trialkyl (CC ₆ ) radical a C ₁ -C ₆ alkoxy radical

C ₆ , a carbamylalkyl radical C Cg, a radical in Ci-Cg, a benzyl radical, or a second group Z identical or different from the first group Z;

• R ₁₀ , Ru and R ₁₂ , identical or different, represent one of the two valences of a linking arm B, a C ₁ -C ₆ alkyl radical, a CC ₆ monohydroxyalkyl radical, a C ₆ polyhydroxyalkyl radical ₂ -C ₆ , an alkoxy radical (CC ₆ ) alkyl in a cyanoalkyl radical at 0, -Cg, an aryl radical, a benzyl radical, an amidoalkyl radical at a trialkyl (C _r C ₆ ) silanealkyl radical in CC ₆ or an aminoalkyl radical in

C, -C ₆ , the amine of which is protected by an alkyl (CC ₆ ) carbonyl radical, carbamyl, or alkyl (CC ₆ ) sulfonyl; two of the radicals R ₁₀ , R „and R ₁₂ can also form together, with the nitrogen atom to which they are attached, a saturated 5 or 6-membered ring carbon-containing or containing one or more heteroatoms, said cycle possibly being or not substituted by a halogen atom, a hydroxyl radical, a C _r C ₆ alkyl radical, a CC ₆ monohydroxyalkyl radical, a C ₂ -C ₆ polyhydroxyalkyl radical, a nitro radical, a cyano radical, a cyanoalkyl radical in an alkoxy radical in a tri (C ₁ -C ₆₎ alkylsilane C, -C ₆ alkyl, an amido radical, an aldehydo radical, a carboxyl radical, a keto in a thio radical, a C _r C ₆ thioalkyl radical, an alkyl radical (CC ₆ ) thio, an amino radical, an amino radical protected by an alkyl radical (CC ₆ ) carbonyl, carbamyl or alkyl (C ₁ -C ₆ ) sulfonyl;

one of the radicals R ₁₀ , R and R ₁₂ can also represent a second group Z, identical or different from the first group Z;

R ₁₃ represents one of the two valences of a link arm B, an alkyl radical in ; a monohydroxyalkyl radical in ; a C ₂ -C ₆ polyhydroxyalkyl radical; an aryl radical; a benzyl radical; an aminoalkyl radical at 0, -Cg, an aminoalkyl radical at whose amine is protected by a radical carbamyl or (CC ₆ ) sulfonyl alkyl; a CC ₆ carboxyalkyl radical; a cyanoalkyl radical in; a carbamylalkyl radical in ; a trifluoroalkyl radical in ; a radical in C _r C ₆ ; an O, -Cg sulfonamidoalkyl radical; a carboxyalkyl (CC ₆ ) alkyl radical in ; an alky radical CgJsulfinylalkyle Ci-C _r C _6; a radical in C _r C ₆ ; a CC ₆ alkyl (C _r C ₆ ) ketoalkyl radical; an N-alkyl (CC ₆ ) carbamylalkyl C ₁ -C ₆ radical; an N-(C ₁ -C ₆ ) sulfonamidoalkyl radical in; • a and y are whole numbers equal to 0 or 1; with the following conditions:

- in the unsaturated cationic groups of formula (II):

- when a = 0, the link arm D is attached to the nitrogen atom, - when a = 1, the link arm D is attached to one of the vertices E,

G, J or L,

- y can only take the value 1 if:

1) when the vertices E, G, J and L simultaneously represent a carbon atom, and the radical R ₉ is carried by the nitrogen atom of the unsaturated cycle; or

2) when at least one of the vertices E, G, J and L represents a nitrogen atom on which the radical R ₉ is attached;

- in the unsaturated cationic groups of formula (III):

- when a = 0, the link arm D is attached to the nitrogen atom, - when a = 1, the link arm D is attached to one of the vertices E,

G, J, L or M,

- y can only take the value 1 when at least one of the vertices E, G, J, L and M represents a divalent atom, and the radical R ₉ is carried by the nitrogen atom of the unsaturated cycle; - in the cationic groups of formula (IV):

- when a = 0, then the link arm D is attached to the nitrogen atom carrying the radicals R ₁₀ to R ₁₂ ,

- when a = 1, then two of the radicals R ₁₀ to R ₁₂ form, together with the nitrogen atom to which they are attached, a saturated 5 or 6-membered ring as defined above, and the link arm D is carried by a carbon atom of said saturated ring;

• X ^" represents a monovalent or divalent anion;

Being heard that :

- The number of cationic group Z is at least equal to 1.

2. Compounds according to claim 1, characterized in that the cycles of the unsaturated groups Z of formula (II) are chosen from the pyrrolic, imidazolic, pyrazolic, oxazolic, thiazolic and triazolic cycles.

3. Compounds according to claim 1, characterized in that the rings of the unsaturated groups Z of formula (III) are chosen from pyridine, pyrimidine, pyrazine, oxazine and triazine rings.

4. Compounds according to any one of the preceding claims, characterized in that two of the radicals R ₁₀ , R and R ₁₂ form a pyrrolidine cycle, a piperidine cycle, a piperazine cycle or a morphoiine cycle, said cycle possibly or not substituted by a halogen atom, a hydroxyl radical, a 0, -Cg alkyl radical, a 0, -Cg monohydroxyalkyl radical, a C ₂ -C ₆ polyhydroxyalkyl radical, a nitro radical, a cyano radical, a radical cyanoalkyl, C, -C ₆ alkoxy, C, -C ₆ alkyl radical, a tri (C -, - C ₆₎ alkylsilane an amido radical, an aldehydo radical, a carboxyl radical, a C ₁ -C ₆ ketoalkyl radical, a thio radical, a CC ₆ thioalkyl radical, a (CC ₆ ) thio alkyl radical, an amino radical, a protected amino radical by a (C, -C ₆ ) alkyl carbonyl, carbamyl or (CC ₆ ) sulfonyl alkyl radical.

5. Compounds according to any one of the preceding claims, characterized in that X ^" represents a halogen atom, a hydroxide, a hydrogenesulfate, or an alkyl (CC ₆ ) sulfate.

6. Compounds according to any one of the preceding claims, characterized in that they are chosen from:

- 3- [2- (2-amino-4-hydroxy-phenylamino) ethyl] -1- dichloride -1- (4- {3- [2- (2- amino-4-hydroxy-phenylamino) -ethyl] - 3H-imidazol-1-ium} -butyl) -3H-imidazol-1-ium; - 3- {2 - [(3-amino-4-methylamino-phenyl) -methyl-amino] -ethyl} -1 dichloride -1- [4- (3- {2 - [(3-amino-4-methylamino -phenyl) -methyl-amino] -ethyl} -3H-imidazol-1-ium) -butyl] -3H-imidazol-1-ium;

- 1,3-bis- {2 - [(3-amino-4-methylamino-phenyl) -methyl-amino] - ethyl} -3H-imidazol-1-ium chloride;

- 3- {2 - [(3-amino-4-methylamino-phenyl) -methyl-amino] -ethyl} -1-dichloride -1- [3 - ({2 - [(3-amino-4-methylamino-phenyl) ) -methyl-amino] -ethyl} -dimethyl-ammonium) -propyl] -3H-imidazol-1 -ium;

- {2 - [(3-amino-4-methylamino-phenyl) -methyl-amino] -ethyl} - dichloride - [2- ({2 - [(3-amino-4-methylamino-phenyl) -methyl- amino] -ethyl} -dimethylammonium) -ethyl] -dimethylammonium;

- 3- [2- (2,4,5-trihydroxy-phenylamino) ethyl] -1- dichloride -1- (4- {3- [2- (2,4,5-trihydroxy-phenylamino) -ethyl] - 3H-imidazol-1 -ium} -butyl) -3H-imidazol-1 -ium; and their addition salts with an acid.

7. Compounds according to any one of the preceding claims, 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.

8. Use of the compounds of formula (I) as defined in any one of claims 1 to 7, as an oxidation dye precursor for the oxidation dyeing of keratin fibers.

9. Composition for the oxidation dyeing of keratinous fibers, characterized in that it comprises, in a medium suitable for dyeing, at least one compound of formula (I) as defined in any one of claims 1 to 7.

10. Composition according to Claim 9, 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.

11. Composition according to claim 10, characterized in that the compound or compounds of formula (I) represent from 0.005 to 6% by weight of the total weight of the dye composition.

12. Composition according to any one of claims 9 to 11, characterized in that it contains one or more oxidation bases chosen from paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.

13. Composition according to claim 12, characterized in that the heterocyclic bases are chosen from pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

14. Composition according to claim 12 or 13, characterized in that the oxidation base or bases represent from 0.0005 to 12% by weight of the total weight of the dye composition.

15. Composition according to any one of claims 9 to 14, characterized in that it contains one or more couplers chosen from metaphenylenediamines, meta-aminophenols, metadiphenols and heterocyclic couplers, and / or one or more dyes direct.

16. Composition according to Claim 15, characterized in that the couplers are 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-di hydroxy 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, 6 -hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 6-hydroxy indoline, 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.

17. Composition according to claim 15 or 16, characterized in that the coupler (s) represent from 0.0001 to 10% by weight approximately of the total weight of the dye composition.

18. Composition according to any one of claims 9 to 17, characterized in that the addition salts with an acid are chosen from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates and acetates.

19. Process for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that at least one dye composition as defined in any one of claims 9 is applied to the fibers at 18, for a time sufficient to develop the desired coloration, either in air or using an oxidizing agent.

20. The method of claim 19, characterized in that the coloring of the fibers can be carried out without the addition of an oxidizing agent, only in contact with the oxygen in the air.

21. The method of claim 19, characterized in that the color is revealed at acidic, neutral or alkaline pH using an oxidizing agent which is added just at the time of use to the dye composition or which is present in an oxidizing composition applied simultaneously or sequentially separately.

22. The method of claim 21, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts and enzymes.

23. The method of claim 22, characterized in that the enzymes are chosen from peroxidases, laccases, tyrosynases and oxidoreductases.

24. The method of claim 23, characterized in that the oxidoreductases are chosen from pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases, and uricases.

25. Multi-compartment device, or “kit” for dyeing with several compartments, a first compartment of which contains a dye composition as defined in any one of claims 9 to 18 and a second compartment of which contains an oxidizing composition.