CA2322998A1 - 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-BENZENIUM DYES, THEIR USE FOR DYEING
FOR OXIDATION OF KERATINIOUS FIBERS, TINCTORIAL COMPOSITIONS AND METHOD
DYEING
The subject of the invention is new di-benzene dyes comprising at least at least one cationic group Z, Z being chosen from chains quaternized aliphatics, aliphatic chains comprising at least one saturated quaternized cycle, and aliphatic chains comprising at least one quaternized unsaturated cycle, their use as dye precursors of oxidation for the oxidation dye of keratin fibers, compositions dye containing them, as well as the oxidation dyeing processes implementing.
It is known to dye keratin fibers and in particular the hair humans with dye compositions containing precursors of oxidation dye, in particular paraphenylenediamines, ortho or paraaminophenols, heterocyclic compounds such as derivatives of diaminopyrazole, generally called oxidation bases. The precursors of oxidation dyes, or oxidation bases, are colorless or weakly colored which, combined with oxidizing products, can give birth through a process of oxidative condensation to compounds colored and dyes.
We also know that we can vary the nuances obtained with these oxidation bases by associating them with couplers or modifiers of coloring, the latter being chosen in particular from metadiamines aromatic. metaaminophenols. metadiphenols and certain compounds heterocyclic, such as for example indole couplers.

2 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. So, it must be without toxicological disadvantage, it must make it possible to obtain shades in (desired intensity and show good resistance to agents outdoor (light, weather, washing, permanent waving, sweat, friction).
The dyes should also cover white hair, and Finally, be the least selective possible, that is to say allow to obtain deviations lowest possible coloring throughout a single fiber keratin, which can be sensitized differently (ie damaged) between its tip and its root.
The plaintiff has now just discovered, in a totally unexpected and surprising, that new di-benzene dyes cationic compounds of formula (I) defined below comprising at least one group cationic Z, Z being chosen from quaternized aliphatic chains, aliphatic chains comprising at least one saturated quaternized ring, and aliphatic chains comprising at least one quaternized unsaturated ring, not only suitable for use as dye precursors of oxidation for the oxidation dye of keratin fibers, but in outraged that they make it possible to obtain dye compositions leading to powerful colors, in a wide palette of colors, and presenting excellent resistance properties to different treatments that can undergo keratin fibers.
These discoveries are the basis of the present invention.

WO 00/43386 PC1 '/ FR00 / 00094

3 The first object of the invention is therefore new compounds of formula (I) next, and their addition salts with an acid R4, N ~ R5 R ~ 4.N ~ R ~ 5 R R '~ A' ~
(I) R2 A3 R ~ 2 A ~ 3 in which ~ B is a link arm which represents an alkyl chain comprising preferably from 1 to 14 carbon atoms, linear or branched which may be interrupted by one or more Z groups and / or by one or more heteroatoms such as oxygen, sulfur or nitrogen atoms, and optionally substituted by one or more hydroxyl or alkoxy radicals in C, -C6, and can carry one or more ketone functions;
~ A ,, A2, and A3, identical or different, represent a group -NR, RB
or a hydroxyl radical; one and only one of the groups A ,, A2 and A3 can further represent a group R3 as defined below;
~ A ',, A'2 and A'3, identical or different, represent a group -NR ', R'8 or a hydroxyl radical; one and only one of the groups A ',, A'2 and A'3 can in further represent a group R'3 as defined below;
~ R ,, R ',, R2, R'2, R3 and R'3, which may be the same or different, represent one of the two valences of a link arm B, an atom hydrogen; a halogen atom; a group Z as defined below; a (C 1 -C 6) alkyl carbonyl radical; an aminoalkyl radical (C, -

4 C6) carbonyl; an NZ-aminoalkyl (C, -CB) carbonyl radical; a radical N-alkyl (C, -Cg) aminoalkyl (C, -Cs) carbonyl; an N, N-dialkyl radical (C, -Cs) aminoalkyl (C, -CB) carbonyl; an aminoalkyl radical (C, -C6) carbonylalkyl (C, -Cs); an NZ-aminoalkyl (C, -C6) carbonylalkyl (C, -S C6); an N-alkyl (C, -C6) aminoalkyl (C, -Cs) carbonylalkyl (C, -CB) radical; a N, N-dialkyl (C, -C6) aminoalkyl (C, -Cs) carbonylalkyl (C, -Ce) radical; a radical carboxy; a carboxy (C, -Cs) alkyl radical; a (C, -CB) sulfonyl alkyl radical ;
an aminosulfonyl radical; an NZ-aminosulfonyl radical; a radical N-alkyl (C, -Cs) aminosulfonyl; an N, N-dialkyl (C, -Cs) aminosulfonyl radical;
an aminosulfonyialkyl radical (C, -Ce); an NZ-aminosulfonylalkyl radical (C, an N-alkyl (C, -Cs) aminosulfonylalkyl (C, -C6) radical; a radical N, N-dialkyl (C, -C6) aminosulfonylalkyl (C, -Cs); a carbamyl radical; a N-alkyl (C, -C6) carbamyl radical; an N, N-dialkyl (C, -Cs) carbamyl radical; a carbamylalkyl radical (C, -C6); an N-alkyl (C, -Cs) carbamylalkyl (C, Cs); an N, N-diaikyl (C, -Cg) carbamylalkyl (C, -C6) radical; an alkyl radical in C, -C6; a C, -Cs monohydroxyalkyl radical; a polyhydroxyalkyl radical in C2-Cs; a (C 1 -C 6) alkoxy radical C 1 -C 6 alkyl; a radical trifluoroalkyl C, -C6; a cyano radical; an ORs, SRs, OR'e or SR'g group; a amino group protected by a (C, -C6) alkyl, carbonyl, (C, - alkyl) radical C6) carboxy, trifluoroalkyl (C, -C6) carbonyl, aminoalkyl (C, -C6) carbonyl, NZ-aminoalkyl (C, -C6) carbonyl, N-alkyl (C, -Cs) aminoalkyl (C, -C6) carbonyl, N, N-dialkyl (C, -Cs) aminoalkyl (C, -C6) carbonyl, (C, -Cg) alkyl carboxy, carbamyl, N-alkyl (C, -Cs) carbamyl, N, N-dialkyl (C, -CB) carbamyl, alkyl (C, -Cg) sulfonyl, aminosulfonyl, NZ-aminosulfonyl, N-alkyl (C, -Ce) aminosulfonyle, N, N-dialkyl (C, -Cs) aminosulfonyle, thiocarbamyle, formyle, 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 C 1 -C 6 aminoalkyl radical in which the alkyl is substituted or unsubstituted by one or more hydroxy radicals; a radical aminoalkyl (C, -Cs) in which falkyl 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 radicals, C, -Cs monohydroxyalkyl, CZ-Cs polyhydroxyalkyl, (C, -) alkyl Cs) carbonyl, carbamyl, N-alkyl (C, -Cg) carbamyl, N, N-dialkyl (C, -C6) carbamyl, (C, -Cs) alkyl sulfonyl, formyl, trifluoroalkyl (C, -CB) carbonyl,

5 (C, -C6) alkyl carboxy, thiocarbamyl, or among Z groups such as defined below, or which can form together, with the nitrogen atom to which they are attached, a cycle with 5 or 6 links, carbonaceous, or containing one or several heteroatoms;
'Rs and R'6, identical or different, denote one of the two valences of a linker B, an alkyl radical in C, -Cs; a monohydroxyalkyl radical C, -C6; a C2-Cs polyhydroxyalkyl radical; a group Z such that defined below; a C 1 -C 6 alkyl (C 1 -C 6) alkyl radical; an aryl radical;
a benzyl radical; a C 1 -C 6 carboxyalkyl radical; an alkyl radical (C, -C6) C, -C6 carboxyalkyl; a C 1 -C 6 cyanoalkyl radical; a radical C 1 -C 6 carbamylalkyl; an N-(C, -C6) carbamylalkyl radical in C, -Cs;
an N, N-dialkyl (C, -Cg) carbamylalkyl radical in C, -Cs; a radical C 1 -C 6 trifluoroalkyl; a C 1 -C 6 aminosulfonylalkyl radical; a radical NZ-C 1 -C 6 aminosulfonylalkyl; an N-alkyl radical (C, -C6) C 1 -C 5 aminosulfonylalkyl; an N, N-dialkyl radical (C, -Cs) C 1 -C 5 aminosulfonylalkyl; an alkyl radical (C, -Cs) sulfinylalkyle in C, -C6; a C, -Cs (C, -Cs) sulfonylalkyl radical; an alkyl radical (C, -C6) C 1-6 carbonylalkyl; a C 1 -C 6 aminoalkyl radical in which the alkyl is substituted or unsubstituted by one or more hydroxy radicals; a radical C 1-6 aminoalkyl in which falkyl is substituted or unsubstituted by one or several hydroxy radicals, the amine of which is substituted by one or two identical or different radicals chosen from alkyl radicals (C, -Cg), monohydroxyalkyle (C, -C6), polyhydroxyalkyle (C2 C6), alkyl (C, -C6) carbonyl, formyl, trifluoroalkyl (C, -C6) carbonyl, alkyl (C, -Ce) carboxy, carbamyl, N-alkyl (C, -C6) carbamyl, N, N-dialkyl (C, -Cg) carbamyl, thiocarbamyl, alkyl (C, -C6) sulfonyl, or among the groups Z as defined below, WO 00/4338

6 PCT / FR00 / 00094 or being able to form together, with (nitrogen atom to which they are attached, a cycle with 5 or 6 links, carbonaceous, or containing one or more heteroatoms;
~ R4, R'4, R5, R'S, R ,, R ',, R8 and R'e, identical or different, represent Moon of the two valences of a linking arm B, a hydrogen atom; a group Z as defined below in which the link arm D does not contains no ketone function directly connected to the nitrogen atom of said amino group; a C 1 -C 6 alkyl radical; a monohydroxyalkyl radical in C, -C6; a C2-C6 polyhydroxyalkyl radical; an alkoxy (C, -Cs) alkyl radical C, -C6; an aryl radical; a benzyl radical; a cyanoalkyl radical in C, -C6; a C 1 -C 5 carbamylalkyl radical; an N-alkyl radical (C, -C6) C 1-6 carbamylalkyl; an N, N-dialkyl (C, -C6) carbamylalkyl radical in C, -C6; a C 1 -C 6 thiocarbamylalkyl radical; a trifluoroalkyl radical in C, -C6; a C 1 -C 6 sulfoalkyl radical; a carboxyalkyl (C, -CB) alkyl radical in C, -Cs; a (C 1 -C 6) sulfinyl C 1 -C 6 alkyl radical; a radical C 1-6 aminosulfonylalkyl; an NZ-aminosulfonylalkyl radical in C, -Cg;
an N-alkyl (C, -Cs) aminosulfonylalkyl radical in C, -Cg; a radical N, N-C, -C6 aminosulfonylalkyl (C, -C6) dialkyl; an alkyl radical (C, -Cs) C, -Cs carbonylalkyl; a C, -Cs aminoalkyl radical of which falkyl is substituted or unsubstituted by one or more hydroxy radicals; a radical C 1-6 aminoalkyl in which falkyl is substituted or unsubstituted by one or several hydroxy radicals and the amine of which is substituted by one or two identical or different radicals chosen from C 1 -C 4 alkyl radicals, C, -C6 monohydroxyalkyl, C2-Cs polyhydroxyalkyl, (C, -) alkyl C6) carbonyl, carbamyl, N-alkyl (C, -Cs) carbamyl, N, N-dialkyl (C, -Cg) carbamyl, (C, -C6) alkyl, sulfonyl, formyl, trifluoroalkyl (C, -Ce) carbonyl, (C, -C6) 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 cycle with 5 or 6 links, carbonaceous, or containing one or more heteroatoms;

7 ~ Z is chosen from the unsaturated cationic groups of formulas (II) and (III) below, and the saturated cationic groups of formula (IV) next (R, s) e (~) v (R, s) a (~) y ~ E ~ /
~ E ~
N, - v LJ n M ~ L / J
X-X-(ll) (III) (R ~ a) in Rio DNR »X (IV) Rice in which D is a link arm which represents an alkyl chain comprising preferably from 1 to 14 carbon atoms, linear or branched which can be interrupted by one or more heteroatoms such as atoms oxygen, sulfur or nitrogen, and may be substituted by one or several hydroxyl or C, -Cs alkoxy radicals, which may carry a 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, identical or different, represent one of the two valences of a link arm B, a second identical grouping Z or different from the first group Z, a halogen atom, a radical

8 hydroxyl, a C 1 -C 6 alkyl radical, a monohydroxyalkyl radical in C, -CB, a C2-CB polyhydroxyalkyl radical, an in vitro radical, a radical cyano, a radical. C, -C6 cyanoalkyl, a C, -C6 alkoxy radical, a trialkyl (C, -Cs) silanealkyl radical in C, -Cg, an amido radical, a radical aldehydo, a carboxyl radical, a C, -Ce alkylcarbonyfe radical, a thio radical, a C, -Ce thioalkyl radical, a thio (C, -C6) alkyl radical, a amino radical, an amino radical protected by an alkyl radical (C, -Cs) carbonyl, carbamyl or (C, -C6) sulfonyl alkyl; an NHR group "
or NR "R"'in which R "and R"', identical or different, represent a C 1 -C 6 alkyl radical, a C 1 -C 6 monohydroxyalkyl radical or a C2-C6 polyhydroxyalkyl radical;
~ R9 represents one of the two valences of a link arm B, a radical C 1 -C 6 alkyl, a C 1 -C 6 monohydroxyalkyl radical, a radical C2-C6 polyhydroxyalkyl, a C, -Cs cyanoalkyl radical, a radical trialkyl (C, -C6) silanealkyle C, -C6, an aicoxy radical (C, -CB) alkyl C, -C6, a carbamylalkyl radical C, -CB, an (C, -Cg) carboxyalkyl alkyl radical in C, -C6, a benzyl radical, or a second identical group Z or different from the first group Z;
R, o, R "and R, 2, identical or different, represent one of the two valences of a linking arm B, a C 1 -C 6 alkyl radical, a radical C, -Cs monohydroxyalkyl, a C2-Cs polyhydroxyalkyl radical, a C, -Cg alkyl (C, -CB) alkyl radical, a C, -Cs cyanoalkyl radical, a aryl radical, a benzyl radical, a C, -Cs amidoalkyl radical, a trialkyl (C, -C6) silanealkyl radical in C, -C6 or an aminoalkyl radical in C, -Cs whose amine is protected by a (C, -C6) carbonyl alkyl radical, carbamyl, or (C, -Cs) sulfonyl alkyl; two of the radicals R, o, R "and R, 2 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 several heteroatoms such as for example a pyrrolidine cycle, a cycle

9 piperidine, a piperazine cycle or a morpholine cycle, said cycle may or may not be substituted by a halogen atom, a radical hydroxyl, a C, -Cs alkyl radical, a monohydroxyalkyl radical in C, -C6, a C2-Cs polyhydroxyalkyl radical, a nitro radical, a radical cyano, a C, -Cs cyanoalkyl radical, a C, -Cs alkoxy radical, a trialkyl radical (C, -C6) silanealk ~ le in C, -C6, an amido radical, a radical aldehydo, a carboxyl radical, a C, -Ce ketoalkyl radical, a radical thio, a C, -Cs thioalkyl radical, a (C, -C6) alkyl radical thio, a radical amino, an amino radical protected by a (C, -Cs) carbonyl alkyl radical, carbamyl or (C 1 -C 6) alkyl sulfonyl;
one of the radicals R, o, R "and R, 2 can also represent a second group Z, identical or different from the first group Z;
~ R, 3 represents one of the two valences of a link arm B, a radical C 1 -C 6 alkyl; a C 1 -C 8 monohydroxyalkyl radical; a radical C2-Cs polyhydroxyalkyl; an aryl radical; a benzyl radical; a C, -Cg aminoalkyl radical, a C, -Cs aminoalkyl radical of which the amine is protected by an alkyl (C, -Cs) carbonyl, carbamyl or (C, -CB) alkyl sulfonyl; a C 1 -C 6 carboxyalkyl radical; a radical C 1-6 cyanoalkyl; a C 1 -C 5 carbamylalkyl radical; a radical C, -Cs trifluoroalkyl; a C, -Cs silanealkyl (C, -C6) trialkyl radical;
a C 6 -C 6 sulfonamidoalkyl radical; a carboxyalkyl (C, -Cs) alkyl radical C, -C6; a C 1 -C 6 sulfinylalkyl alkyl radical; a radical (C, -Cs) alkyl C, -Cs sulfonylalkyl; a (C, -Cs) alkyl ketoalkyl radical in C, -C6; an N-(C 1 -C 6) carbamyl C 1 -C 6 alkyl radical; a radical N-(C, -C6) alkyl C 1-6 sulfonamidoalkyl;
~ a and y are whole numbers equal to 0 or 1; with the conditions following - in the unsaturated cationic groups of formula (II) - when a = 0, the link arm D is attached to (nitrogen atom, - when a = 1, the link arm D is attached to one of the vertices E, G, JouL, - y can only take the value 1 5 1) when the vertices E, G, J and L simultaneously represent a carbon atom, and that the radical R9 is carried by the nitrogen atom from the unsaturated cycle; or 2) when at least one of the vertices E, G, J and L represents an atom nitrogen to which the radical R9 is attached;

10 - 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 that the radical R9 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 (nitrogen atom bear the radicals R, o to R, 2, - when a - 1, then two of the radicals R, o to R, 2 form together with (nitrogen atom to which they are attached a cycle saturated with 5 or 6 links as defined above, and the arm of bond 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 hydrogen sulphate, or an alkyl (C, -CB) sulphate 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.

11 As indicated previously, the colorings obtained with the composition oxidation dye containing the colorant (s) of formula (I) at the invention are powerful and allow a wide range of colors. They also have excellent screw resistance properties at faction screws of the different external agents (light, bad weather, washing, permanent ripple, perspiration, friction). These properties ~ are particularly remarkable especially with regard to the resistance of colorings obtained with regard to the action of light, washes, permanent waving and sweating.
In formulas (1), (II), {III) and {IV) above, the alkyl radicals and alkoxy can be linear or branched.
Among the cycles of the unsaturated groups Z of formula (II) above, there are can in particular to cite as an example the pyrrolic, imidazolic cycles, pyrazolic, oxazolic, thiazolic and triazolic.
Among the cycles of the unsaturated groups Z of formula (ill) above, we find may in particular cite by way of example the pyridine, pyrimidine cycles, pyrazine, oxazine and triazine.
The compounds of formula (I) above are preferably chosen from - 3- [2- (2-amino-4-hydroxy-phenyiamino) ethyl] -1- dichloride (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 [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-phenylrmethyl-amino] chloride] -ethyl} -3H-imidazol-1-ium;

12 - 3- {2 - [(3-amino-4-methylamino-phenyl) -methyl-amino] -ethyl} -1 dichloride [3 - ({2 - [(3-amino-4-methylamino-phenyl) -methyl-amino] -ethyl} -dimethyl-ammonium) -propyl] -3H-imidazol-1-ium;
- {2 - [(3-amino-4-methyiamino-phenyl) -methyl-amino] -ethyl} - dichloride - [2-({2 - [(3-amino-4-methylamino-phenyl) -methyl-amino] -ethyl} -dimethyl-ammonium) -ethyl] -dimethyl-ammonium;
- 3- [2- (2,4,5-trihydroxy-phenylamino ~ ethyl] 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, sulfates, the citrates, succinates, tartrates, lactates and acetates.
The compounds of formula (I) according to (invention can be easily obtained, according to methods well known in 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 salification, is generally, for convenience, the last step in the synthesis.
This reduction may occur earlier in the course of reactions drive 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 a step acetylation; benzenesulfonation, etc.), then do the substitutions or desired modifications (including quaternization) and end with "deprotection" (generally in an acid medium) of the amine function.

13 Likewise, the phenolic function can be protected by well-defined procedures.
known by a benzyl radical ("deprotection" by catalytic reduction) or through an acetyl or mesyl radical ("deprotection" in an acid medium).
These cationic di-benzene compounds are obtained by well-defined methods known from 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 linking arm B as defined in the formula (I) described above, or else 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 link arm B as defined in formula (I) described above, or else, - (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 link arm B as defined in formula (I) described above, and (b) condensation of a second molecule benzene compound different from the first and also carrying a radical tertiary amine, 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 linking arm B as defined in the formula (I) described above, and (b) condensation of a second molecule of a benzene compound different from the first and also carrying a radical haloalkyl, or - condensation of a molecule of a benzene compound carrying a radical tertiary amine on a molecule of a benzene compound carrying a haloalkyl radical.

14 Haloalkyl radicals carried by di-benzene compounds intermediates can be prepared by known methods of (state of the technique, in one or more stages, for example by condensing a dihaloalkyl compound on an amine or hydroxyl, or by halogenation of a hydroxyalkyl chain.
When the synthesis is complete, the compounds of formula (I) in accordance with (invention can, if necessary, be recovered by well-defined methods 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 dye of keratin fibers, and in particular fibers human keratin such as hair.
A subject of the invention is also a composition for dyeing.
oxidation keratin fibers and in particular human keratin fibers such that the hair, characterized by the fact that it comprises by way of precursors oxidation dyes, in a medium suitable for dyeing, at least a compound of formula (I) according to the invention.
The compound (s) of formula (I) in accordance with (invention represent preferably from 0.0005 to 12% by weight approximately of the total weight of the composition dye, and even more preferably from 0.005 to 6% by weight approximately of ~ this weight.
The medium suitable for dyeing (or support) generally consists through water or a mixture of water and at least one organic solvent to solubilize compounds which are not sufficiently soluble in water.
Mention may, for example, be made, as organic solvent, of alkanols.
lower in C, -C4, such as ethanol and fisopropanol; glycerol; glycols and ethers of WO 00/43386 PC "f / FR00 / 00094 glycols such as 2-butoxyethanol, propylene glycol, monomethyl ether propylene glycol, monoethyl ether and monomethyl ether of diethylene glycol, as well as alcohols. aromatics such as (benzyl alcohol or phenoxyethanol, analogues and their mixtures.

The solvents may be present in proportions preferably 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 approx.
The pH of the dye composition in accordance with the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. He can be adjusted to the desired value using acidifying or basifying agents usually used in dyeing keratin fibers.
Among the acidifying agents, there may be mentioned, by way of example, the acids minerals or organic like hydrochloric acid, (orthophosphoric acid, (acid sulfuric, carboxylic acids like acetic acid, (tartaric acid, citric acid, lactic acid, sulfonic acids.
Among the basifying agents, there may be mentioned, by way of example, ammonia, the alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium hydroxides or potassium and the compounds of formula (V) below Rw / Ris NWN (V) Ris R »
in which W is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 5 alkyl radical; R, 4, R, 5, R, g and R ", identical or different, represent a hydrogen atom, an alkyl radical in C, -C6 or hydroxyalkyl in C, -C6.
The dye composition in accordance with the invention may also contain, in more of the compound (s) of formula (I) defined above, at least one base of oxidation which can be chosen from the conventional oxidation bases used in oxidation dyeing and among which there may be mentioned in particular the para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
Among the paraphenylenediamines, there may be mentioned more particularly as for example, paraphenylenediamine, paratoluylenediamine, 2,6-dimethyl paraphenyenediamine, 2-p-hydroxyethyl paraphenylenediamine, 2-n-propyl paraphenylenediamine, ia 2-isopropyl paraphenylenediamine, the N - ((i-hydroxypropyl) paraphenylenediamine, N, N-bis- (~ 3-hydroxyethyl) paraphenylenediamine, 4-amino N- (~ i-methoxyethyl) aniline, para-phenylenediamines described in the French patent application FR 2 630 438, and their addition salts with an acid.
Among the bis-phenylalkylenediamines, mention may be made more particularly of:
title for example, N, N'-bis- (~ i-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, N, N'-bis- (~ i-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis - ((i-hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, la 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 as example, para-aminophenol, 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, ie 4-amino 2-methyl WO 00/43386 PC'T / FR00100094 phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2 - ([i-hydroxyethyl aminomethyl) phenol, and their addition salts with an acid.
Among your ortho-aminophenols, we can more particularly cite as example, quote 2-amino phenol, te 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, there may be more particularly mentioned as for example, pyridine derivatives, non-pyrimidine derivatives cationic and pyrazole derivatives.
Among the pyridine derivatives, mention may be made more particularly of compounds described for example in patents GB 1,026,978 and GB 1,153,196, as the 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino 3-amino pyridine, 2,3-diamino 6-methoxy pyridine, la 2 - ([i-methoxyethyl) amino 3-amino 6-methoxy pyridine, 3,4-diamino pyridine, and their acid addition salts.
Among the pyrimidine derivatives, there may be mentioned more particularly your compounds described for example in German patents DE 2,359,399 or Japanese 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; the 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] -pyrimidtn-7-ol; 3-amino pyrazolo-[1,5-a] -pyrimidin-5-ol; 2- (3-amino pyrazolo- [1,5-a] -pyrimidin-7-ylamino) -ethanol, 2- (7-amino pyrazolo- [1,5-a] -pyrimidin-3-ylamino ~ ethanol, 2 - [(3-amino-pyrazolo [1,5-a] pyrimidin-7-ylr (2-hydroxy-ethyl) -amino] -ethanol, the 2 - [(7-amino-pyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethylramino] -ethanol, the 5,6-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 2,6-dimethyl pyrazolo-[1,5-a] -pyrimidine-3,7-diamine, la 2, 5, N 7, N 7-tetramethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, and their addition salts and their tautomeric forms, when there is a tautomeric equilibrium and their addition salts with a acid.
Among the pyrazole derivatives, mention may be made more particularly of:
compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94108970, FR-A-2 733 749 and DE 195 43 988 like the 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 1 - ([i-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino 1-ethyl 3-methyl pyrazole, 4,5-diamino 1-ethyl 3- (4'-methoxyphenyl) pyrazole, 4,5-diamino 1-ethyl 3-hydroxymethyl pyrazole, 4,5-diamino 3-hydroxymethyl 1-methyl pyrazole, 4,5-diamino 3-hydroxymethyl 1-isopropyl pyrazole, 4,5-diamino 3-methyl 1-isopropyl pyrazole, 4-amino 5- (2'-aminoethyl) amino 1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino 1-methyl 4-methylamino pyrazole, 3,5-diamino 4 - ([i-hydroxyethyl) amino 1-methyl pyrazole, and their addition salts with an acid.
When used, these oxidation bases preferably represent of 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 according to (invention can also contain at least one coupler and / or at least one direct dye, in particular to modify the nuances or to enrich them with reflections.
Couplers usable in oxidation dye compositions according to the invention can be chosen from the couplers used conventional way in oxidation dyeing and among which we can, in particular cite metaphenylenediamines, meta-aminophenols, metadiphenols and heterocyclic couplers such as, for example, indole derivatives, indolinic derivatives, pyridine derivatives and pyrazolones, and their salts addition with an acid.
These couplers are more particularly chosen from 2-methyl 5-amino phenol, 5-N - ((i-hydroxyethyl) amino 2-methyl phenol, 3-amino phenol, 1,3-dihydroxy benzene, 1,3-dihydroxy 2-methyl benzene, 4-chloro 1,3-dihydroxy benzene, 2,4-diamino 1- (~ 3-hydroxyethyloxy) benzene, 2-amino 4 - ((i-hydroxyethylamino) 1-methoxy benzene, 1,3-diamino benzene, 1,3-bis- (2,4-diaminophenoxy) propane, sesamol, a-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.
When present, these couplers preferably represent from 0.0001 to About 10% by weight of the total weight of the dye composition and more more preferably from 0.005 to 5% by weight approximately of this weight.
In general, the acid addition salts usable in the scope of the invention (compounds of formula (I), oxidation bases and couplers) are especially chosen from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates and acetates.

The dye composition in accordance (invention may also include various adjuvants conventionally used in compositions for dyeing hair, such as. anionic, cationic, non-surface active agents ionic, amphoteric, zwitterionic or mixtures thereof, polymers 5 anionic, cationic, nonionic, amphoteric, zwitterionic or their mixtures, mineral or organic thickening agents, agents antioxidants, penetrating agents, sequestering agents, perfumes, tampons, dispersing agents, conditioning agents such as for example silicones, fifmogens, agents 10 preservatives, opacifying agents.
Of course, the person skilled in the art will take care to choose this or these possible compounds complementary in such a way that the advantageous properties attached intrinsically to the oxidation dye composition in accordance with the invention

15 are not, or is not substantially, altered by the addition (s) considered.
The dye composition according to (invention can be in forms various, such as liquids, creams, gels, or any 20 another suitable form for dyeing keratin fibers, and especially human hair.
The invention also relates to a process for dyeing fibers.
keratin and in particular human keratin fibers such as hair using the dye composition as defined previously.
The invention also relates to a process for dyeing oxidation of fibers keratin and in particular human keratin fibers such as hair using the dye composition as defined previously.

According to this process, at least one composition is applied to the fibers dye as defined above, for a time sufficient to develop the desired coloration, either in air or using an agent oxidant. The dye composition may optionally contain catalysts oxidation, to speed up the oxidation process.
According to a first form of implementation of the method of (invention, the fiber coloring can be carried out without the addition of an oxidizing agent, only contact with oxygen in the air.
According to a second form of implementation of the method of (invention, and especially when the dye composition in accordance with (invention includes one or more oxidation bases and / or one or more couplers, we applies to the fibers at least one dye composition as defined previously, 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 composition dye 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 composition is preferably mixed, at the time of use, dye described above with an oxidizing composition containing, in a medium suitable for dyeing, at least one oxidizing agent present in one enough to develop a color. 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 one rinses, one wash with shampoo, rinse again and dry.
The oxidizing agent present in the oxidizing composition as defined above above can be chosen from the oxidizing agents conventionally used for the oxidation dye of keratin fibers, and among which we can cite the hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates and enzymes such as peroxidases, lacca $ es, tyrosynases and oxidoreductases among which can in particular be mentioned pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases, and uricases.
The pH of the oxidizing composition containing (oxidizing agent as defined above is such that after mixing with the dye composition, the pH of the resulting composition applied to keratin fibers varies from preference between 3 and 12 approximately, and even more preferably between 5 and 11. It is adjusted to the desired value using acidifying or basifying agents usually used in dyeing keratin fibers and such as defined previously.
The oxidizing composition as defined above can also contain various adjuvants conventionally used in dyeing compositions hair and as defined above.
The composition which is finally applied to the keratin fibers can is present in various forms, such as in the form of liquids, creams, gels, or any other suitable form to achieve a dyeing of keratin fibers, and in particular human hair.
Another object of the invention is a device with several compartments or "kit"
dye or any other multi-pack system compartments of which a first compartment contains the composition dye as defined above and a second compartment contains the oxidizing composition as defined above. These devices can be equipped with a means for delivering the mixture to the hair desired, such as the devices described in patent FR-2,586,913 in the name of the plaintiff.

Claims (25)

24 1. Compounds of the following formula (I), and their addition salts with an acid:
in which:
~ B is a linker which represents an alkyl chain comprising preferably 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, sulfur or nitrogen atoms, and optionally substituted by one or more hydroxyl or alkoxy radicals in C1-C6, and which can bear one or more ketone functions;
~ A1, A2, and A3, identical or different, represent a -NR7R8 group Where a hydroxyl radical; one and only one of the groups A1, A2 and A3 can in addition to representing an R3 group as defined below;
~ A'1, A'2 and A'3, identical or different, represent a group -NR'7R'8 or a hydroxyl radical; one and only one of the groups A'1, A'2 and A'3 can in in addition to representing an R′3 group as defined below;
R1, R'1, R2, R'2, R3 and R'3, which may be identical or different, represent one of the two valences of a bonding arm B, an atom hydrogen; a halogen atom; a group Z as defined below; a (C1-C6) alkyl carbonyl radical; an amino(C1-)alkyl radical C6)carbonyl; an NZ-aminoalkyl(C1-C6)carbonyl radical; a radical N-alkyl(C1-C6)aminoalkyl(C1-C6)carbonyl; an N,N-dialkyl radical (C1-C6)aminoalkyl(C1-C6)carbonyl; an amino(C1-)alkyl radical C6)carbonyl(C1-C6)alkyl; an NZ-aminoalkyl(C1-C6)carbonylalkyl(C1-C6); an N-alkyl(C1-C6)aminoalkyl(C1-C6)carbonylalkyl(C1-C6) radical; a N,N-dialkyl(C1-C6)aminoalkyl(C1-C6)carbonylalkyl(C1-C6) radical; a radical carboxy; an alkyl (C1-C6) carboxy radical; an alkyl (C1-C6) sulfonyl radical ;
an aminosulfonyl radical; an NZ-aminosulfonyl radical; a radical N-alkyl (C1-C6) aminosulfonyl; an N,N-dialkyl(C1-C6)aminosulphonyl radical;
an aminosulfonyl(C1-C6)alkyl radical; an NZ-aminosulphonyl(C1-)alkyl radical C6); an N-alkyl(C1-C6)aminosulfonylalkyl(C1-C6) radical; a radical N,N-dialkyl(C1-C6)aminosulfonylalkyl(C1-C6); a carbamyl radical; a N-alkyl(C1-C6)carbamyl radical; an N,N-dialkyl(C1-C6)carbamyl radical; a carbamyl(C1-C6)alkyl radical; an N-alkyl(C1-C6)carbamylalkyl(C1-) radical C6); an N,N-dialkyl(C1-C6)carbamylalkyl(C1-C6) radical; an alkyl radical in C1-C6; a C1-C6 monohydroxyalkyl radical; a polyhydroxyalkyl radical in C2-C6; a (C1-C6)alkoxy(C1-C6)alkyl radical; a radical trifluoroalkyl in C1-C6; a cyano radical; an OR6, SR6, OR'6 or SR'6 group; a amino group protected by an alkyl(C1-C6)carbonyl radical, alkyl(C1-C6)carboxy, trifluoroalkyl(C1-C6)carbonyl, aminoalkyl(C1-C6)carbonyl, NZ-aminoalkyl(C1-C6)carbonyl, N-alkyl(C1-C6)aminoalkyl(C1-C6)carbonyl, N,N-dialkyl(C1-C6)aminoalkyl(C1-C6)carbonyl, alkyl(C1-C6)carboxy, carbamyl, N-alkyl(C1-C6)carbamyl, N,N-dialkyl(C1-C6)carbamyl, alkyl(C1-C6)sulfonyl, aminosulfonyl, NZ-aminosulfonyl, N-alkyl(C1-C6)aminosulfonyl, N,N-dialkyl(C1-C6)aminosulfonyl, thiocarbamyl, formyl, or by a group Z as defined below in which the connecting arm D contains a ketone function directly linked to the nitrogen atom of said amino group; a C1-C6 aminoalkyl radical in which the alkyl is substituted or unsubstituted by one or more hydroxy radicals; a radical amino(C1-C6)alkyl whose alkyl is substituted or unsubstituted by one or several hydroxy radicals and whose amine is substituted by one or two radicals, identical or different, chosen from alkyl radicals, C1-C6 monohydroxyalkyl, C2-C6 polyhydroxyalkyl, (C1-C6)carbonyl, carbamyl, N-alkyl(C1-C6)carbamyl, N,N-dialkyl(C1-C6)carbamyl, alkyl(C1-C6)sulfonyl, formyl, trifluoroalkyl(C1-C6)carbonyl, (C1-C6)alkylcarboxy, thiocarbamyl, or from the groups Z such as defined below, or which can form together, with the nitrogen atom to which they are attached, a 5 or 6 membered ring, carbonaceous, or containing one or several heteroatoms;
~ R6 and R'6, identical or different, designate one of the two valences of a connecting arm B, a C1-C6 alkyl radical; a monohydroxyalkyl radical in C1-C6; a C2-C6 polyhydroxyalkyl radical; a group Z such that defined below; a (C1-C6)alkoxy(C1-C6)alkyl radical; an aryl radical;
a benzyl radical; a C1-C6 carboxyalkyl radical; an alkyl radical (C1-C6) C1-C6 carboxyalkyl; a C1-C6 cyanoalkyl radical; a radical C1-C6 carbamylalkyl; an N-alkyl(C1-C6)carbamylalkyl C1-C6 radical;
an N,N-dialkyl(C1-C6)carbamylalkyl C1-C6 radical; a radical C1-C6 trifluoroalkyl; a C1-C6 aminosulfonylalkyl radical; a radical NZ-aminosulfonyl-C1-C6 alkyl; an N-alkyl radical (C1-C6)aminosulfonyl-C1-C6 alkyl; an N,N-dialkyl radical (C1-C6)aminosulfonyl-C1-C6 alkyl; an alkyl(C1-C6)sulfinylalkyl radical in C1-C6; a (C1-C6)alkylsulphonyl(C1-C6)alkyl radical; an alkyl radical (C1-C6)carbonyl-C1-C6 alkyl; a C1-C6 aminoalkyl radical whose alkyl is substituted or unsubstituted by one or more hydroxy radicals; a radical C1-C6 aminoalkyl in which the alkyl is substituted or unsubstituted by one or several hydroxy radicals, and whose amine is substituted by one or two identical or different radicals chosen from (C1-C6) alkyl radicals, monohydroxyalkyl(C1-C6), polyhydroxyalkyl(C2-C6), alkyl(C1-C6)carbonyl, formyl, trifluoroalkyl(C1-C6)carbonyl, alkyl(C1-C6)carboxy, carbamyl, N-alkyl(C1-C6)carbamyl, N,N-dialkyl(C1-C6)carbamyl, thiocarbamyl, (C1-C6)alkylsulphonyl, or from 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, carbonaceous, or containing one or more heteroatoms;
~ R4, R'4, R5, R'5, R7, R'7, R8 and R'8, identical or different, represent moon of the two valences of a connecting arm B, a hydrogen atom; a group Z as defined below in which the connecting arm D does not does not contain a ketone function directly linked to the nitrogen atom of said amino group; a C1-C6 alkyl radical; a monohydroxyalkyl radical in C1-C6; a C2-C6 polyhydroxyalkyl radical; an alkoxy(C1-C6)alkyl radical in C1-C6; an aryl radical; a benzyl radical; a cyanoalkyl radical C1-C6; a C1-C6 carbamylalkyl radical; an N-alkyl radical (C1-C6) carbamyl-C1-C6 alkyl; an N,N-dialkyl(C1-C6)carbamylalkyl radical C1-C6; a C1-C6 thiocarbamylalkyl radical; a trifluoroalkyl radical in C1-C6; a C1-C6 sulfoalkyl radical; a (C1-C6)alkylcarboxyalkyl radical in C1-C6; a (C1-C6)alkylsulfinyl(C1-C6)alkyl radical; a radical C1-C6 aminosulfonylalkyl; a C1-C6 NZ-aminosulfonylalkyl radical;
an N-alkyl(C1-C6)aminosulfonylalkyl C1-C6 radical; a radical N,N-dialkyl (C1-C6)aminosulfonylalkyl C1-C6; a radical (C1-C6)alkylcarbonylC1-C6 alkyl; a C1-C6 aminoalkyl radical of which alkyl is substituted or unsubstituted by one or more hydroxy radicals; a radical C1-C6 aminoalkyl in which the alkyl is substituted or unsubstituted by one or several hydroxy radicals and whose amine is substituted by one or two identical or different radicals chosen from C1-C6 alkyl radicals, C1-C6 monohydroxyalkyl, C2-C6 polyhydroxyalkyl, alkyl(C1-C6)carbonyl, carbamyl, N-alkyl(C1-C6)carbamyl, N,N-dialkyl(C1-C6)carbamyl, alkyl(C1-C6)sulfonyl, formyl, trifluoroalkyl(C1-C6)carbonyl, (C1-C6)alkylcarboxy, thiocarbamyl, or by a group Z as defined below, or which may form together, with the nitrogen atom to which they are attached, a 5 or 6 membered ring, carbonaceous, or containing one or more heteroatoms;
~ Z is chosen from unsaturated cationic groups of formulas (II) and (III) below, and the saturated cationic groups of formula (IV) next in which ~ D is a connecting arm which represents an alkyl chain comprising preferably from 1 to 14 carbon atoms, linear or branched which can be interrupted by one or more heteroatoms such as atoms of oxygen, sulfur or nitrogen, and which may be substituted by one or several hydroxyl or C1-C6 alkoxy radicals, and which may carry a 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, identical or different, represent one of the two valences of a linker arm B, a second identical group Z or different from the first group Z, a halogen atom, a radical hydroxyl, a C1-C6 alkyl radical, a monohydroxyalkyl radical in C1-C6, a C2-C6 polyhydroxyalkyl radical, a nitro radical, a radical cyano, a C1-C6 cyanoalkyl radical, a C1-C6 alkoxy radical, a C1-C6 trialkyl(C1-C6)silanealkyl radical, an amido radical, a aldehyde, a carboxyl radical, a C1-C6 alkylcarbonyl radical, a thio radical, a C1-C6 thioalkyl radical, a (C1-C6)alkylthio radical, a amino radical, an amino radical protected by an alkyl radical (C1-C6)carbonyl, carbamyl or (C1-C6)alkylsulfonyl; an NHR group"
or NR"R"' in which R" and R"', identical or different, represent a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical or a C2-C6 polyhydroxyalkyl radical;
~ R9 represents one of the two valences of a linker arm B, a radical C1-C6 alkyl, a C1-C6 monohydroxyalkyl radical, a radical C2-C6 polyhydroxyalkyl, a C1-C6 cyanoalkyl radical, a radical trialkyl(C1-C6)silanealkyl-C1-C6, an alkoxy(C1-C6)alkyl-C1- radical C6, a C1-C6 carbamylalkyl radical, a (C1-C6)alkylcarboxyalkyl radical C1-C6, a benzyl radical, or a second identical Z group or different from the first group Z;
~ R10, R11 and R12, identical or different, represent one of the two valences of a connecting arm B, a C1-C6 alkyl radical, a radical C1-C6 monohydroxyalkyl, a C2-C6 polyhydroxyalkyl radical, a (C1-C6)alkoxy(C1-C6)alkyl radical, a C1-C6 cyanoalkyl radical, a aryl radical, a benzyl radical, a C1-C6 amidoalkyl radical, a trialkyl(C1-C6)silane-C1-C6alkyl radical or an amino(C1-C6)alkyl radical C1-C6 whose amine is protected by an alkyl(C1-C6)carbonyl radical, carbamyl, or (C1-C6)alkylsulfonyl; two of the radicals R10, R11 and R12 can also form together, with the nitrogen atom to which they are attached, a saturated ring with 5 or 6 carbon members or containing one or several heteroatoms, said ring possibly being or not substituted by a halogen atom, a hydroxyl radical, a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C1-C6 polyhydroxyalkyl radical C2-C6, a vitro radical, a cyano radical, a C1-C6 cyanoalkyl radical, a C1-C6 alkoxy radical, a trialkyl(C1-C6)silanealkyl C1-C6 radical, an amido radical, an aldehyde radical, a carboxyl radical, a radical C1-C6 ketoalkyl, a thio radical, a C1-C6 thioalkyl radical, a (C1-C6)alkylthio radical, an amino radical, an amino radical protected by a (C1-C6)alkylcarbonyl, carbamyl or (C1-C6)alkylsulfonyl radical;
one of the radicals R10, R11 and R12 can also represent a second group Z, identical to or different from the first group Z;
~ R13 represents one of the two valences of a bonding arm B, a radical C1-C6 alkyl; a C1-C6 monohydroxyalkyl radical; a radical C2-C6 polyhydroxyalkyl; an aryl radical; a benzyl radical; a C1-C6 aminoalkyl radical, a C1-C6 aminoalkyl radical of which the amine is protected by an alkyl(C1-C6)carbonyl, carbamyl or (C1-C6)alkylsulfonyl; a C1-C6 carboxyalkyl radical; a radical C1-C6 cyanoalkyl; a C1-C6 carbamylalkyl radical; a radical C1-C6 trifluoroalkyl; a trialkyl(C1-C6)silanealkyl C1-C6 radical;
a C1-C6 sulfonamidoalkyl radical; a (C1-C6)alkylcarboxyalkyl radical in C1-C6; a (C1-C6)alkylsulfinyl(C1-C6)alkyl radical; a radical (C1-C6)alkylsulfonylC1-C6 alkyl; an alkyl (C1-C6) ketoalkyl radical C1-C6; an N-alkyl(C1-C6)carbamylalkyl C1-C6 radical; a radical N-alkyl (C1-C6)sulfonamidoalkyl C1-C6;

~ a and y are integers equal to 0 or 1; with the conditions following:
- in the unsaturated cationic groups of formula (II):
- when a = 0, the connecting arm D is attached to the nitrogen atom, - when a = 1, the connecting 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 R9 radical 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 an atom nitrogen to which the R9 radical is fixed;
- in the unsaturated cationic groups of formula (III):
- when a = 0, the connecting arm D is attached to the nitrogen atom, - when a = 1, the connecting arm D is attached to one of the vertices E, G, Y, L or M, - y can only take the value 1 when at least one of the vertices E, G, J, L and M represent a divalent atom, and the radical R9 is carried by the nitrogen atom of the unsaturated ring;
- in the cationic groups of formula (IV):
- when a = 0, then the connecting arm D is attached to the nitrogen atom bearing the radicals R10 to R12, - when a - 1, then two of the radicals R10 to R12 form together with the nitrogen atom to which they are attached a ring saturated with 5 or 6 members as previously defined, and the arm of bond 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 groups Z is at least equal to 1. 2. Compounds according to claim 1, characterized in that the cycles unsaturated groups Z of formula (II) are chosen from the cycles pyrrolic, imidazolic, pyrazolic, oxazolic, thiazolic and triazolic. 3. Compounds according to claim 1, characterized in that the cycles unsaturated groups Z of formula (III) are chosen from the cycles pyridine, pyrimidine, pyrazinic, oxazinic and triazinic. 4. Compounds according to any one of the preceding claims, characterized in that two of the radicals R10, R11 and R12 form a cycle pyrrolidine, a piperidine ring, a piperazine ring or a morpholine ring, said ring which may or may not be substituted by a halogen atom, a radical hydroxyl, a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a nitro radical, a cyano radical, a radical C1-C6 cyanoalkyl, a C1-C6 alkoxy radical, a trialkyl radical (C1-C6)silaneC1-C6alkyl, an amido radical, an aldehyde radical, a carboxyl, a C1-C6 ketoalkyl radical, a thio radical, a radical thioalkyl in C1-C6, an alkyl(C1-C6)thio radical, an amino radical, a protected amino radical by a (C1-C6)alkylcarbonyl, carbamyl or (C1-C6)alkylsulphonyl radical. 5. Compounds according to any one of the preceding claims, characterized in that X - represents a halogen atom, a hydroxide, a hydrogen sulphate, or an alkyl (C1-C6) sulphate. 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-(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 [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]- chloride ethyl}-3H-imidazol-1-ium;
- 3-{2-[{3-amino-4-methylamino-phenyl)-methyl-amino]-ethyl}-1-dichloride [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}-[2-dichloride ({2-[(3-amino-4-methylamino-phenyl)-methyl-amino]-ethyl}-dimethyl-ammonium)-ethyl]-dimethyl-ammonium;
- 3-[2-(2,4,5-trihydroxy-phenylamino)-ethyl]-1-{4-{3-[2-dichloride (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 (1) are chosen from hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates and acetates. 8. Use of the compounds of formula (I) as defined in one any of claims 1 to 7, as dye precursor dye for the oxidation dyeing of keratin fibres. 9. Composition for the oxidation dyeing of keratin fibres, characterized by the fact that it comprises, in an environment suitable for the dye, at least one compound of formula (I) as defined in any of claims 1 to 7. 10. Composition according to claim 9, characterized in that the or the compounds of formula (I) represent from 0.0005 to 12% by weight of the weight total dye composition. 11. Composition according to claim 10, characterized in that the or the compounds of formula (I) represent from 0.005 to 6% by weight of the weight total 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 para-phenylenediamines, 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, derivatives pyrimidines 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 weight total dye composition. 15. Composition according to any one of claims 9 to 14, characterized in that it contains one or more selected couplers among meta-phenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic couplers, and/or one or more direct dyes. 16. Composition according to claim 15, characterized in that the couplers are chosen from 2-methyl 5-amino phenol, 5-N-(.beta.-hydroxyethyl)amino 2-methyl phenol, 3-amino phenol, 1,3-dihydroxy benzene, 1,3-dihydroxy 2-methyl benzene, 4-chloro 1,3-dihydroxy benzene, 2,4-diamino 1-(.beta.-hydroxyethyloxy) benzene, 2-amino 4-(.beta.-hydroxyethylamino) 1-methoxy benzene, 1,3-diamino benzene, 1,3-bis-(2,4-diaminophenoxy) propane, sesamol, .alpha.-naphthol, the 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 pyrazol 5-one, and their addition salts with a acid. 17. Composition according to claim 15 or 16, characterized in that the coupler or couplers represent from 0.0001 to 10% by weight approximately of the weight total dye composition. 18. Composition according to any one of claims 9 to 17, characterized in that the addition salts with an acid are chosen among hydrochlorides, hydrobromides, sulphates, citrates, succinates, the tartrates, lactates and acetates. 19. Oxidation dyeing process for keratin fibers and in particular human keratin fibers such as hair, characterized by the do that at least one dye composition such as defined in any one of claims 9 to 18, for a time enough to develop the desired coloration, either completely or with the help of of one oxidizing agent. 20. Method according to claim 19, characterized in that the coloring of the fibers can be carried out without addition of an oxidizing agent, only contact with the oxygen in the air. 21. Process according to claim 19, characterized in that the color 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 separate way. 22. Process according to claim 21, characterized in that the agent oxidant is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts and enzymes. 23. Method according to claim 22, characterized in that the enzymes are chosen from peroxidases, laccases, tyrosynases and oxido-reductases. 24. Method according to 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 multi-dye "kit"
compartments, of which a first compartment contains a composition dye as defined in any one of claims 9 to 18 and a second compartment contains an oxidizing composition.