WO2004031173A1

WO2004031173A1 - Novel direct black dyes with three heteroaromatic rings

Info

Publication number: WO2004031173A1
Application number: PCT/FR2003/002927
Authority: WO
Inventors: Laurent Vidal
Original assignee: L'oreal
Priority date: 2002-10-04
Filing date: 2003-10-06
Publication date: 2004-04-15
Also published as: FR2845387A1; EP1551825A1; AU2003283499A1; FR2845387B1

Abstract

The invention relates to novel three-ring heteroaromatic direct dyes, dyeing compositions containing said dyes and the method of dyeing keratinous fibres using same. In particular, the invention relates to three-ring heteroaromatic direct dyes comprising a pyridine ring. Said novel dyes can be used to obtain black shades having a good tenacity and a good stability in dyeing compositions.

Description

NEW BLACK DIRECT HETEROAROMATIC TRI-CORE DYES

The subject of the invention is new direct heteroaromatic tri-core dyes, the dye compositions containing these dyes as well as the process for dyeing keratin fibers using them. In particular, the subject of the invention is heteroaromatic tri-core direct dyes comprising a pyridine nucleus.

It is known to dye keratin fibers and in particular human hair, with dye compositions containing direct dyes. The conventional dyes which are used are in particular dyes of the nitrobenzene, anthraquinone, nitropyridine, azo, cationic azo, xanthene, acridine azine, triarylmethane benzene type or natural dyes type.

These dyes which are colored and coloring molecules having an affinity for the fibers are applied to the keratin fibers for a time necessary to obtain the desired coloration, then rinsed.

The resulting colorings are particularly chromatic colors which are however temporary or semi-permanent because the nature of the interactions which bind the direct dyes to the keratin fiber, and their desorption from the surface and / or from the core of the fiber are responsible for their low dye power and their poor resistance to washing or perspiration. These direct dyes are also generally sensitive to light due to the low resistance of the chromophore vis-à-vis photochemical attacks and lead over time to a fading of the coloring of the hair. Patent application EP 1166754 describes a dye composition which comprises cationic azo phenazinium direct dyes. Due to the presence of the azo function, these compounds when they are used in the presence of a reducing agent such as erythorbic acid, metabisulfite or sulfite are unstable which results in destruction of the chromophoric system . The object of the present invention is to provide new direct dyes which do not have the drawbacks of the prior art, in particular direct dyes making it possible to obtain dark shades, black to gray, which are light-stable and resistant. weathering, washing and perspiration, and furthermore stable in a conventional coloring medium. In particular, the object of the present invention is to provide black direct dyes making it possible to dye the hair in shades varying from gray to black, without the need to lighten the hair beforehand, as well as black direct dyes which while fading do not change color, for example by turning after the action of a wash, light or sweat towards shades with blue, purple, red, green reflections, etc. Finally, these black direct dyes must allow the shade obtained during the first application to be retained after several applications.

These objects are achieved with the present invention which relates to a dye composition comprising, in an appropriate medium, a compound of formula (I) below or one of its addition salts:

in which

• R ₃ represents:

- a hydrogen atom,

- a linear or branched C C-10 hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by a oxygen, nitrogen or sulfur atom or by an SO ₂ group; R_ containing no peroxide bond, nor diazo or nitroso radicals,

- NR'ιR ' _2j R'-i and R' ₂ being as defined for R, and R ₂ • i and R ₂ represent independently of each other:

- a hydrogen atom

a linear or branched CC ₁₀ hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which can be replaced by an atom of 'oxygen, nitrogen or sulfur or by an SO ₂ group; Ri and R ₂ not comprising a peroxide bond, nor of diazo or nitroso radicals, and R1 and R2 not being directly connected to the nitrogen atom by an oxygen, sulfur, nitrogen or SO ₂ atom, - an onium radical Z, or R _T and R ₂ form together with the nitrogen atom to which they are attached a cycle of formula (II):

formula (II) in which: R 'represents: - a hydrogen atom;

- a halogen atom such as fluorine, chlorine, bromine;

a CC ₄ alkyl radical optionally substituted by one or more radicals chosen from hydroxy, carboxy, dC ₄ alkoxycarbonyl, alkyl (CC ₄ ) amido (alkyl (CC ₄ ) CONH-), alkyl (CC ₄ ) carbamoyl ( alkyl (CC ₄ ) NHCO-), a (kyl (CC ₄ ) sulfonyl (alkyl (CC ₄ ) SO ₂ -), alkoxy in

CC ₄ , alkyl (C, -C ₄ ) sulfonamido (alkyl (C, -C ₄ ) SO ₂ NH-), alkyl (CC) sulfamoyl (alkyl (CC) NH SO ₂ -), onium Z,

- NR ' ₃ R'₄;

- a carboxy radical; - a C C alkoxycarbonyl radical;

- an amido alkyl radical (CC ₄ ) (alkyl (C _r C ₄ ) CONH-);

- an alkyl radical (CC ₄ ) sulfonyl (alkylSO ₂ -)

- an alkylsulfonamido radical ((C _r C ₄ ) SO ₂ NH - alkyl),

- a hydroxy radical; - a C C alkoxy radical;

- a C ₂ -C hydroxyalkoxy radical;

- a (C1-C4) carbamoyl (C1-C4) NHCO- alkyl radical;

- alkyl (CC ₄ ) sulfamoyl (alkyl (CC ₄ ) -NH-SO ₂ -);

- a C _r C thioether radical; - a sulfonic radical (SO ₃ H) which may be in the form of a salt,

- an onium Z radical, R ' ₃ and R' ₄ , identical or different, represent a hydrogen atom; a CC ₄ alkyl radical optionally substituted by one or more radicals chosen from hydroxy, CrC ₄ alkoxy, amino, mono or di alkylamino, (CC ₄ ) CO- alkyl, (CC ₄ ) NHCO-, alkyl (C _r C ₄ ) SO ₂ -,

- n is an integer between 1 and 8,

- m is an integer between 0 and 3, preferably from 0 to 2,

- Y represents an oxygen atom, a radical CR ', a radical NR' ₅ or a radical NR ' ₆ R' ₇ with

R ' ₅ which represents a hydrogen atom; a linear or branched CrC ₁₀ hydrocarbon chain which may be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group; R's having no peroxide bond, nor diazo or nitroso radicals, and R ' ₅ not being directly linked to the nitrogen atom by an oxygen, sulfur or nitrogen atom, R' ₆ and R ′ ₇ which independently represent a linear or branched CC ₁₀ hydrocarbon chain which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which can be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group; R ' ₆ and R' ₇ not comprising a peroxide bond, nor of diazo or nitroso radicals, and R ' ₆ and R' ₇ not being directly linked to the nitrogen atom by an oxygen atom, of sulfur or nitrogen, i represents an aromatic heterocycle radical chosen from the following radicals

• Zi and Z ₃ , independently of one another, represent a hydroxy radical or

• Z ₂ , Z ₄ , Z ₆ independently of one another represent a nitrogen atom, a radical CR ₁₂ or NRn with the proviso that at least one of them represents a radical CR ₁₂ and that it does not there may be more than 3 contiguous nitrogen atoms,

• Z ₈ represents a nitrogen atom, a radical CR ₁₅ ;

• Re, R ₇ , R ₈ , R ₉ , R10, Ru, R ₁₂ , R ₁₅ independently of one another represent a hydrogen atom;

- a linear or branched Cι-C ₁₀ hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 links, and which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by a oxygen, nitrogen or sulfur atom or by an SO ₂ group; the radicals Rβ to R ₁₂ and R ₁₅ not comprising a peroxide bond, nor of diazo or nitroso radicals and the radical Ru not being connected directly to the nitrogen atom by an oxygen, sulfur or d atom 'nitrogen,

- p can take the values 4 to 8,

- q can take the values 1 to 3, and

- r can take the values 0 to 2, - * indicates the point of attachment of W1 in formula (I).

According to a particular embodiment, the dye composition according to the present invention comprises, in a suitable medium, a compound of formula (I) below or one of its addition salts:

in which

• R ₃ represents:

- a hydrogen atom, - a linear or branched C1-C10 hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, including one or more carbon atoms of the carbon chain can be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group, and whose carbon atoms can be, independently of each other, substituted by one or more halogen atoms or hydroxy, amino, carboxy, sulfonic or thiol radicals; R ₃ having no peroxide bond, nor diazo or nitroso radicals,

- NR ^ R's, R '., And R' ₂ being as defined for Ri and R ₂

• Ri and R ₂ represent independently of each other:

- a hydrogen atom - a linear or branched CC ₁₀ hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 links, and which can be saturated or unsaturated, of which one or more carbon atoms of the carbon chain can be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group, and whose carbon atoms can be, independently of one another, substituted by one or more halogen atoms or hydroxy radicals, amino, carboxy, sulfonic or thiol; R ^ and R ₂ not comprising a peroxide bond, nor of diazo or nitroso radicals, and R1 and R2 not being directly linked to the nitrogen atom by an oxygen, sulfur, nitrogen or SO ₂ , - an onium radical Z, or

• Ri and R ₂ together with the nitrogen atom to which they are attached form a cycle of formula (11):

formula (II) in which:

• R 'represents:

- a hydrogen atom;

- a halogen atom such as fluorine, chlorine, bromine;

- a C C alkyl radical optionally substituted by one or more radicals chosen from hydroxy, carboxy, alkoxycarbonyl radicals

CC ₄ , alkyl (CrC ₄ ) amido (alkyl (C _r C ₄ ) CONH-), alkyl (CC) carbamoyl (alkyl (CC ₄ ) NHCO-), alkyl (CC ₄ ) sulfonyl (alkyl (CC ₄ ) SO ₂ -), alkoxy in CC ₄ , alkyl (CC) sulfonamido (alkyl (CC) SO ₂ NH-), alkyl (CC ₄ ) sulfamoyl (alkyl (CC ₄ ) NH SO ₂ -), onium Z,

- NR ' ₃ R'₄;

- a carboxy radical; - a C 1 alkoxycarbonyl radical;

- an alkyl (C _r C ₄ ) amido radical (alkyl (CC ₄ ) CONH-);

- an alkyl radical (CC ₄ ) sulfonyl (alkylSO ₂ -)

- an alkylsulfonamido radical (alkyl (CC ₄ ) SO ₂ NH -),

- a hydroxy radical; - a C C alkoxy radical;

- a C ₂ -C hydroxyalkoxy radical;

- a (C1-C4) carbamoyl (C1-C4) NHCO- alkyl radical;

- alkyl (CC ₄ ) sulfamoyl (alkyl (CC ₄ ) -NH-SO ₂ -);

- a thioether radical in CC ₄ ; - a sulfonic radical (SO ₃ H) which may be in the form of a salt,

- an onium Z radical,

R ' ₃ and R' ₄ , identical or different, represent a hydrogen atom; a CC ₄ alkyl radical optionally substituted by one or more radicals chosen from hydroxy, CC alkoxy, amino, mono or di alkylamino, alkyl (CC ₄ ) CO-, alkyl (C _r C ₄ ) NHCO-, alkyl ( CC ₄ ) SO ₂ -,

- n is an integer between 1 and 8,

- m is an integer between 0 and 3, preferably from 0 to 2,

- Y represents an oxygen atom, a radical CR ', a radical NR' ₅ or a radical NR ' ₆ R' ₇ with R ' ₅ which represents a hydrogen atom; a linear or branched CC ₁₀ hydrocarbon chain, which may be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, carboxy, sulfonic or thiol radicals; R ′ ₅ not comprising a peroxide bond, nor of diazo or nitroso radicals, and R ′ ₅ not being directly connected to the nitrogen atom by an oxygen, sulfur or nitrogen atom, R ' ₆ and R' ₇ which independently represent a linear or branched Cι-C ₁₀ hydrocarbon chain, which may be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen atom, d nitrogen or sulfur or with an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, carboxy, sulphonic or thiol radicals; R ' ₆ and R' ₇ not comprising a peroxide bond, nor of diazo or nitroso radicals, and R ' ₆ and R' ₇ not being directly linked to the nitrogen atom by an oxygen atom, of sulfur or nitrogen, Wi represents an aromatic heterocycle radical chosen from the following radicals

• ^ and Z ₃ , independently of one another, represent a hydroxy or NRnR ₁₂ radical;

• Z ₂ , Z ₄ , Z ₆ independently of one another represent a nitrogen atom, a radical CR ₁₂ or NR-H provided that at least one of them represents a radical CR ₁₂ and that there cannot be more than 3 contiguous nitrogen atoms,

• Z ₈ represents a nitrogen atom, a radical CR ₁₅ ; • Re, R7, Rs, R9, R10. Ru, R1 ₂ , R ₁₅ represent independently of each other

- a hydrogen atom; .

- a linear or branched CC o hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 links, and which can be saturated or unsaturated, of which one or more carbon atoms of the carbon chain can be replaced by one atom oxygen, nitrogen or sulfur or by an SO ₂ group, and whose carbon atoms can be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, carboxy, sulfonic or thiol radicals; the radicals R ₆ to R ₁₂ and R ₁₅ not comprising a peroxide bond, nor of diazo or nitroso radicals and the radical Ru not being connected directly to the nitrogen atom by an oxygen, sulfur or nitrogen,

- p can take the values 4 to 8,

-, q can take the values 1 to 3, and

- r can take the values 0 to 2,

- * indicates the point of attachment of W1 in formula (I). According to another particular embodiment, the dye composition according to the present invention comprises, in a suitable medium, a compound of the following formula (I) or one of its addition salts:

in which

• R ₃ represents:

- a hydrogen atom,

- a linear or branched CrC ₁₀ hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, of which one or more carbon atoms of the carbon chain can be replaced by an atom d oxygen, nitrogen or sulfur or with an SO ₂ group, and whose carbon atoms may be, independently of each other, substituted by one or more halogen atoms or hydroxy, amino, (di) alkylamino radicals in

CrCa, C ₂ -C ₂ alkoxy, carboxy, sulfonic or thiol; R ₃ having no peroxide bond, nor diazo or nitroso radicals,

- NR'ιR ' ₂ , R and R' ₂ being as defined for R, and R ₂

• R _t and R ₂ represent independently of each other: - a hydrogen atom

- a linear or branched C Cι ₀ hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 links, and which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group, and whose carbon atoms may be, independently each other, substituted by one or more halogen atoms or hydroxy, amino, (di) alkylamino radicals

C-rCz, ^ -0 ₂ alkoxy, carboxy, sulfonic or thiol; R ₁ and R ₂ not comprising a peroxide bond, nor of diazo or nitroso radicals, and R1 and R2 not being directly linked to the nitrogen atom by an oxygen, sulfur, nitrogen atom or SO ₂ , - an onium radical Z, or R- _\ and R ₂ together with the nitrogen atom to which they are attached form a cycle of formula (II):

formula (II) in which: R 'represents:

- a hydrogen atom;

- a halogen atom such as fluorine, chlorine, bromine;

a CC ₄ alkyl radical optionally substituted by one or more radicals chosen from hydroxy, carboxy, alkoxycarbonyl radicals

CC ₄ , alkyl (C _r C ₄ ) amido (alkyl (CC ₄ ) CONH-), alkyl (C Ç) carbamoyl (alkyl (CC ₄ ) NHCO-), alkyl (CC ₄ ) sulfonyl (alkyl (CC ₄ ) SO ₂ -), C _r C ₄ alkoxy, alkyl (CC ₄ ) sulfonamido (alkyl (CrC ₄ ) SO ₂ NH-), alkyl (CC ₄ ) sulfamoyl (alkyl (CC) NH SO ₂ -), onium Z, - NR ' ₃ R'₄;

- a carboxy radical;

- a Cι-C ₄ alkoxycarbonyl radical;

- an alkyl (CC ₄ ) amido radical (alkyl (CC ₄ ) CONH-);

- an alkyl (CC ₄ ) sulfonyl radical (alky! SO ₂ -) - an alkylsulfonamido radical (alkyl (CC ₄ ) SO ₂ NH -),

- a hydroxy radical;

- a CC alkoxy radical; - a C ₂ -C ₄ hydroxyalkoxy radical;

- a (C1-C4) carbamoyl (C1-C4) NHCO- alkyl radical;

- alkyl (CC ₄ ) sulfamoyl (alkyl (CC ₄ ) -NH-SO ₂ -);

- a thioether radical in Cι-C; - a sulfonic radical (SO ₃ H) which may be in the form of a salt,

- an onium Z radical,

R ' ₃ and R' ₄ , identical or different, represent a hydrogen atom; a CC ₄ alkyl radical optionally substituted by one or more radicals chosen from hydroxy, CC ₄ alkoxy, amino, mono or di aikylamino, alkyl (CC ₄ ) CO-, alkyl (CC ₄ ) NHCO-, alkyl (CrC) radicals ₄ ) SO ₂ -,

- n is an integer between 1 and 8,

- m is an integer between 0 and 3, preferably from 0 to 2,

- Y represents an oxygen atom, a radical CR ', a radical NR' ₅ or a radical NR ' ₆ R' ₇ with R ' ₅ which represents a hydrogen atom; a linear or branched C Cιo hydrocarbon chain, which may be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group ₎ and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, carboxy, sulfonic or thiol radicals; R ' ₅ not comprising a peroxide bond, nor of diazo or nitroso radicals, and R' ₅ not being directly connected to the nitrogen atom by an oxygen, sulfur or nitrogen atom, R ' ₆ and R ' ₇ which independently represent a linear or branched CC ₁₀ hydrocarbon chain, which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which can be replaced by an oxygen, nitrogen or sulfur or with an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, carboxy, sulfonic or thiol radicals; R ' ₆ and R' ₇ not comprising a peroxide bond, nor of diazo or nitroso radicals, and R ' ₆ and R' ₇ not being directly linked to the nitrogen atom by an oxygen atom, of sulfur or nitrogen,, represents an aromatic heterocycle radical chosen from the following radicals

• Zi and Z ₃ , independently of one another, represent a hydroxy radical or

• Z ₂ , Z, Z ₆ independently of one another represent a nitrogen atom, a radical CR ₁₂ or NR-n with the proviso that at least one of them represents a radical CR ₁₂ and that it cannot be more than 3 contiguous nitrogen atoms,

• Z ₈ represents a nitrogen atom, a ^" CR ₁₅ radical;

• RQ, R ₇ , Rβ, Rg, R ₁ 0, R ₁₁ , Ri ₂ , R ₁₅ represent independently of each other - a hydrogen atom;

a linear or branched CC ₁₀ hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which can be replaced by an atom of oxygen, nitrogen or sulfur or with an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, carboxy, sulphonic or thiol; the radicals Rβ to R ₁₂ and R ₁₅ not comprising a peroxide bond, nor of diazo or nitroso radicals and the radical Ru not being connected directly to the nitrogen atom by an oxygen, sulfur or d atom 'nitrogen,

- p can take the values 4 to 8,

- q can take the values 1 to 3, and

- r can take the values 0 to 2,

- - ^* indicates the point of attachment of W1 in formula (I). When in the definition of Z ₂ , Z _A , Z ₆ which independently represent one another a nitrogen atom, a radical CR12 or NR ^, it is specified that it does not can have more than 3 contiguous nitrogen atoms, this means that it is not possible for example to obtain the following structure ^"

The present invention also relates to a dye composition containing in a suitable medium at least one direct dye of the present invention. The composition of the present invention is particularly useful for dyeing keratin fibers, in particular human keratin fibers.

In the context of the present invention, the compounds of formula (I) are are not only those described by formula (I) but any other tautomeric form such as for example the following tautomeric form:

In the examples which are given in the following description, only one of these tautomeric forms will be indicated.

In formula (I), R ₃ is preferably chosen from a hydrogen atom or a CC alkyl radical optionally substituted by one or more radicals chosen from hydroxy, CC ₂ alkoxy, amino, (mono) - or (di) C-ι-C ₂ alkylamino, 2-hydroxyethyl, 2-aminoethyl. For example, R ₃ represents a hydrogen atom, a methyl, ethyl, 2-hydroxyethyl radical, even more preferable: a hydrogen atom or a methyl radical. The radicals R, and R ₂ are preferably separately chosen from a hydrogen atom, an Oι-C ₆ alkyl radical optionally substituted by a hydroxy, alkoxy, amino, (mono) - or (di) alkylamino in CC ₄ . By way of example, R and R ₂ are chosen from a hydrogen atom, a methyl, ethyl, hydroxyethyl, propyl, etc. radical. When R, and R ₂ , form with the nitrogen atom to which they are attached a heterocycle of 5 to 8 members, this heterocycle is preferably chosen from the heterocycles pyrrolidine, piperidine, homopiperidine, piperazine, homopiperazine, diazepane optionally substituted. By way of example, the heterocycle is chosen from the pyrrolidine, 3-hydroxypyrrolidine, 3-aminopyrrolidine, 3-NN- dimethylaminopyrrolidine, 3-acetamidopyrrolidine, 3- (methylsulfonylamino) - pyrrolidine, proline, 3-hydroxyproline, piperidine, hydroxypiperidine, ' homopiperidine, diazepane, N-methyl homopiperazine, N β-hydroxyethylhomopiperazine and their addition salts. Preferably, Ri and R ₂ form, with the nitrogen atom to which they are attached, an optionally substituted pyrrolidine ring.

According to a particular embodiment, the compound of formula (I) is a cationic compound substituted with at least one onium Z radical, that is to say a cationic radical of the quaternary ammonium type.

The onium radical Z can be represented by the following formula (III)

in which • D is a covalent bond or a linear or branched C-rC alkylene chain which may contain one or more heteroatoms chosen from oxygen, sulfur or nitrogen, SO ₂ , one or more ketone functions, the chain may be substituted by one or more hydroxyl, CC ₆ alkoxy or amino, (mono) - or (di) alkylamino radicals CC; • R ₁₆ , R ₁₇ and R, 8, taken separately, represent a C ₁ -C ₁₅ 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 CC ₆ amidoalkyl radical; a trialkyl radical (CC ₆₎ alkylsilane C _r C _6; a _t -C ₆ aminoalkyl radical; a CC ₆ aminoalkyl radical in which the amine is mono- or di-substituted by a CC ₄ alkyl, alkyl (GrC ₆ ) carbo yl, amido or (CC ₆ ) sulfonyl alkyl radical; a C 1 -C ₆ carbamylalkyl radical; an alkyl (C _r _C6) carboxyaIkyle C _r C _6; a carbonylalkyl (C _r C ₆ ) alkyl radical in G, -

C ₆ ; an N-alkyl ^ -C ^ carpamylalkyl C _r C ₆ radical; '

• R, ₆ , R ₁₇ and R, ₈ together, two by two, form, with the nitrogen atom to which they are attached, a saturated carbonaceous cycle with 4, 5, 6 or 7 links which may contain one or more heteroatoms , the cation cycle can be substituted by a halogen atom, a hydroxyl radical, a C1-C6 alkyl radical, a CC ₆ monohydroxyalkyl radical, a C ₂ -C ₆ polyhydroxyalkyl radical, a CC ₆ alkoxy radical, a trialkyl (CrC ₆₎ radical ) silanealkyle in C _r C ₆ , an amido radical, a carboxyl radical, a (C -C ₆ ) carbonyl alkyl radical, a thio radical, a Cι-C ₆ thioalkyl radical, a thio (Cι-C ₆ ) alkyl radical , an amino radical, an amino radical mono- or di-substituted by an alkyl (CC ₆ ), alkyl (CrCe) carbonyl, amido or alkyl (CC ₆ ) sulfonyl radical;

• R ₉ represents an alkyl radical in CrC ₆ ; a C C ₆ monohydroxyalkyl radical; a C ₂ -C ₆ polyhydroxyalkyl radical; an aryl radical; a benzyl radical; a CC ₆ aminoalkyl radical; a CC ₆ aminoalkyl radical in which the amine is mono- or di-substituted by an alkyl radical (C ₁ -C ₆ ), alkyl (CrC ₆ ) carbonyl, amido or alkyl (C ₁ -C ₆ ) sulfonyl; a Cι-C ₆ carboxyalkyl radical; a CC ₆ carbamylalkyl radical; a CrC ₆ trifluoroalkyl radical; a trialkyl (Cι-C ₆ ) silanealkyl radical in CC ₆ ; a CC ₆ sulfonamidoalkyl radical; a CC ₆ carboxyalkyl (Cι-C ₆ ) alkyl radical; an alkyl radical (CC ₆ ) C ₁ -C ₆ sulfinylalkyl; an aIkyl (Cι-C ₆ ) sulfonylalkyl radical CC ₆ ; a Cι-C ₆ alkyl (CC ₆ ) carbonylalkyl radical; an N-alkyl (Cι-C ₆ ) carbamylalkyl radical in CC ₆ ; an N-alkyl (CrC ₆ ) sulfonamidoalkyl Cι-C ₆ radical;

• x is 0 or i, - when x = 0, then the link arm D is attached to the nitrogen atom carrying the radicals R ₆ to Rι ₈ ,

- when x = 1, then two of the radicals R ₆ to Rι ₈ form jointly with the nitrogen atom to which they are attached a saturated cycle with 5, 6 or 7 members and the link arm D is connected to an atom of saturated cycle carbon;

• T is a counter ion.

According to a first variant of formula (III) when x is equal to 0, and R ₁₆ ,

R z and Rι ₈ separately are preferably chosen from an alkyl radical in CC ₆ , a monohydroxyalkyl radical in CrC ₄ , a polyhydroxyalkyl radical in C ₂ -C ₄ , an alkoxy radical (CC ₆ ) alkyl in C, -C, a amidoalkyl radical in C, -C ₆ , a trialkyl radical (C, -

C ₆ ) silanealkyle in C _r C ₆ .

According to a second variant of formula (III), when x is equal to 0 and Rι ₆ with R _n together form a cycle azetidine, pyrrolidine, piperidine, homopiperidine, piperazine, homopiperazine, morpholine, Rι ₈ is then chosen from an alkyl radical in Cι-C ₆ ; a C _r C ₆ monohydroxyalkyl radical; a C ₂ -C ₆ polyhydroxyalkyl radical; a Cι-C ₆ aminoalkyl radical, an aminoalkyl radical in which the amine is mono- or disubstituted by an alkyl (CC ₄ ), alkyl (CC ₆ ) carbonyl, amido or alkyl (CC ₆ ) sulfonyl radical; a CC ₆ carbamylalkyl radical; a trialkyl radical _(Cι-C6) alkylsilane Cι-C _6; a CC ₆ carboxyalkyl (C _r C ₆ ) alkyl radical; an alkyl radical (CC ₆₎ carbonylalkyl CC _6; an N-alkyl (CrC ₆ ) carbamylalkyl C _r C ₆ radical.

In formula (III), when x is equal to 1, R, ₉ is preferably chosen from a CC ₆ alkyl radical; a monohydroxyalkyl radical in CrC ₆ ; a C ₂ -C ₆ polyhydroxyalkyl radical; a Cι-C ₆ aminoalkyl radical, a CC ₆ aminoalkyl radical in which the amine is mono or disubstituted by an alkyl (CrC ₆ ), alkyl (O | - C ₆ ) carbonyl, amido or alkyl (CrC ₆ ) sulfonyl radical ; a Cι-C ₆ carbamylalkyl radical; a CC ₆ trialkyl (CrC ₆ ) silanealkyl radical; an alkyl radical (CC ₆₎ carboxyalkyl -C Ce; alkyl (CC ₆₎ alkoxycarbonyl C _r C _6; an N-alkyl (Cι-C ₆ ) carbamylalkyl radical in CC ₆ ; Rie with R ₁ together form a cycle azetidine, pyrrolidine, piperidine, ^* homopiperidine, piperazine, homopiperazine, morpholine, and Rι ₈ is then chosen from an alkyl radical CC ₆ ; a CC ₆ monohydroxyalkyl radical; a C ₂ -C ₆ polyhydroxyalkyl radical; an aminoalkyl radical -C ₆ aminoalkyl, C What the amine is mono- or disubstituted with an alkyl (Ci-C ₄₎ alkyl (Cr C ₆₎ alkylcarbonyl, amido or alkyl (Ci-C ₆₎ alkylsulphonyl radical; a CC ₆ carbamylalkyl radical; a thalkyl (CrC ₆ ) silanealkyl radical in CrC ₆ ; an alkyl radical (CC ₆₎ carboxyalkyl Cr C _6; a CC ₆ alkyl (CrC ₆ ) carbonylalkyl radical; an N-alkyl (CC ₆ ) carbamylalkyl radical at CC _Q.

According to a preferred embodiment, x is equal to 0 and Rι ₆ Rι ₇ and R ₁₈ are alkyl radicals.

In formula (III), D is preferably a covalent bond or a CC ₆ alkylene chain which can be substituted.

The onium radical Z can also be represented by the formula (IV)

(IV) in which

• D is as defined above, • the vertices E, G, J, L, identical or different, represent a carbon, oxygen, sulfur or nitrogen atom to form a pyrazolic, imidazolic, triazolic, oxazolic, isooxazolic, thiazolic, isothiazolic ring,

• a is an integer between 0 and 3 inclusive; • b is an integer between 0 and 1 inclusive;

• a + b is an integer between 2 and 4;

• R, which are identical or different, represent a hydrogen or halogen atom, a hydroxyl radical, an alkyl radical -C ₆ monohydroxyalkyl radical -C ₆ polyhydroxyalkyl radical a C ₂ -C ₆ alkoxy CC ₆ , a trialkyl (CrC ₆ ) silanealkyl radical in CrC ₆ , an amido radical, a carboxyl radical, an alkylcarbonyl radical in CrC ₆ , a thio radical, a thioalkyl radical in CrC ₆ , an alkyl (CrCe) thio radical, a amino radical, an amino radical mono or di substituted by an alkyl (Cι-C ₆ ), alkyl (CrC ₆ ) carbonyl, amido, alkyl (CrC ₆ ) sulfonyl radical; monohydroxyalkyl radical -C ₆ polyhydroxyalkyl radical or a C ₂ -C _6; a benzyl radical; a phenyl radical optionally substituted by one or more radicals chosen from methyl, hydroxy, amino and methoxy radicals; it being understood that the radicals R are carried by a carbon atom;

• R ₂₀ represents an alkyl radical in C Ce, a monohydroxyalkyl radical in CC ₆ , a polyhydroxyalkyl radical in C ₂ -C ₆ , a trialkyl (CrC ₆ ) silanealkyl radical in CrC ₆ , an alkoxy radical (G | -C ₆ ) alkyl -C _6, a carbamyl radical -C Ce, an alkyl (CrC ₆₎ carboxyalkyIe CC _6, a benzyl radical; it being understood that the radical R ₂₀ is carried by a nitrogen atom,

• R ₉ is as defined above, • x is equal to 0 or 1

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

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

• T is a counterion. Preferably, the vertices E, G, J and L form an imidazolic, pyrazolic, oxazolic, thiazolic and triazolic cycle.

According to a particular embodiment of formula (III), x is equal to 0 and D is a covalent bond or a CC ₄ alkylene chain which can be substituted.

The onium radical Z can be represented by the formula (V) ( ^R 1S)) χ _

N G

( ^R ) _d

Mr.

(V) in which:

• D, R, Rig are as defined above,

The vertices E, G, J, L and M which are identical or different, represent a carbon or nitrogen atom and form a cycle chosen from the pyridine, pyrimidine, pyrazine, triazine and pyridine cycles,

• d is an integer between 3 and 5 inclusive;

• x is 0 or 1

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

L or M, when E, G, J, L or M represents a carbon atom,

• T represents a counter ion.

Preferably, the vertices E, G, J, L and M with the nitrogen of the cycle form a cycle chosen from the pyridine, pyrimidine, pyridine and pyrazine cycles.

According to a variant of formula (V), x is 0 and R is chosen from a hydroxyl radical, an alkyl radical -C ₆ monohydroxyalkyl radical -C ₆ polyhydroxyalkyl radical a C ₂ -C ₆ radical alkoxy -C ₆ trialkyl radical (Cr C ₆₎ alkylsilane -C _6, an amido radical, an alkylcarbonyl C _r C ₆ radical, an amino radical, an amino radical mono- or di-substituted by alkyl (Ci-C ₆ ), alkyl (Cι-C ₆ ) carbonyl, amido or alkyl (CrC ₆ ) sulfonyl; monohydroxyalkyl radical -C ₆ polyhydroxyalkyl radical or a C ₂ -C _6; it being understood that the radicals R are carried by a carbon atom.

According to another variant of the formula (V), x is equal to 1, R ₁₉ is chosen from a CC ₆ alkyl radical; a CC ₆ monohydroxyalkyl radical; a C ₂ -C ₆ polyhydroxyalkyl radical; an aminoalkyl radical -C ₆ aminoalkyl radical in C _r C ₆ whose amine is mono- or disubstituted by a radical a! kyl (Ci-C ₆₎ alkyl (CC ₆₎ alkylcarbonyl, amido radical or a radical alkyl (CC ₆ ) sulfonyl; a carbamylalkyl radical in CrC ₆ ; a trialkyl (CrC ₆ ) silanealkyl radical in CrC ₆ ; a radical alkyl (CrC ₆ ) carbonylalkyl in CrC ₆ ; an N-aikyl (CrC ₆ ) carbamylalkyl radical CC ₆ ; R is chosen from a hydroxyl radical, an alkyl radical in CrC ₆ , a monohydroxyalkyl radical in CrC ₆ , a polyhydroxyalkyl radical in C ₂ -C ₆ , an alkoxy radical in Cι- ₆ , a trialkyl radical (C -C ₆ ) silanealkyle in CrC ₆ , an amido radical, an alkylcarbonyl radical in CrC ₆ , an amino radical, an amino radical mono- or di-substituted by an alkyl (CrC ₆ ), alkyl (CrC ₆ ) carbonyl, amido or alkyl (Cι) radical -C ₆ ) sulfonyl.

In a preferred embodiment, Rig is an alkyl radical in O, -0, which can be substituted and R, a hydrogen atom, an alkyl radical in CC _{4 which} can be substituted. When the compound of formula (I) is a cationic compound substituted by a radical Z, preferably at least one of the radicals Ri and R ₂ represents an onium radical Z. According to a particular embodiment, Ri and R ₂ form a ring of formula (II) in which R 'is an onium radical Z, preferably with Y equal to NR' ₆ R ' ₇ .

In formula (I), W1 represents in particular the 5-aminopyrazole,, 5-hydroxypyrazole, pyrazolo- [1, 5-b] -pyridine, pyrazolp- [1 _, 5-a] - pyrimidine, pyrazolo radicals [3 , 2-c]. triazole, pyrazp, lo [1., 5-p] trjazole, aminopyrimidines, triaminopyrimidine, hydroxyaminopyrimidines, 2-aminopyridine, indoline and indole. •

According to a particular embodiment ,. VV1 is chosen from 5-aminopyrazole, 5-hydroxypyrazole radicals. of formula (R1). • In this case, W1 is chosen from. preferably from the 5-aminopyrazole and 5-hydroxypyrazoIe radicals in which R6 and R1.1, which are identical or different, are chosen from one. hydrogen atom,;. a hydrocarbon chain; in linear or branched form, which can form one or more carbon rings comprising from 4 to 8 links, and which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which can be replaced by, an oxygen atom , nitrogen or sulfur or by a grouping sp. ₂ , and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy radicals. amino, carboxy, sulfonic or thiol; the radicals R ₆ to R ₁₂ not comprising Ijajson. peroxide, nor of .diazo or nitroso radicals and the radical R11, not being. not. linked directly to the atom _, nitrogen by an oxygen, sulfur or nitrogen atom. ,

According to a particularly preferred embodiment of (R1), R6 and R11 are independently chosen from a hydrogen atom or a linear or branched CrC ₄ hydrocarbon chain, can form one or more carbon rings comprising from .5 to 6 members , and can be saturated or unsaturated, the carbon atoms can be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino radicals.

According to another particular embodiment, W1 represents

R6, R7, R8, R9 and Z8 being such that ns pr c emmen.

In this particular case, W1 can be a pyrazolo- [1, 5-b] - pyridine radical in which R ₆ , R ₇ , R ₈ , R ₉ and R ₁₅ , identical or different, are chosen from

• a hydrogen atom,

• a linear or branched C -C ₀ hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by a oxygen, nitrogen or sulfur atom or by an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, carboxy radicals, sulfonic or thiol; radicals not comprising a peroxide bond, nor of diazo or nitroso radicals,

• hydroxy or amino radicals, the amine can be substituted by a linear or branched CC ₄ hydrocarbon chain, which can form one or more carbon rings comprising from 5 to 6 members, and which can be saturated or unsaturated, carbon atoms can be, independently of each other, substituted by one or more halogen atoms or hydroxy, amino radicals.

In this particular case, W1 can also be a pyrazolo- [1, 5-b] - pyridine radical in which R_, R ₇ , R ₈ , R _g and R ₅ , identical or different, are chosen from

• a hydrogen atom,

• a linear or branched CrCι ₀ hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 links, and which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which can be replaced by an atom d oxygen, nitrogen or sulfur or by an SO ₂ group, and whose carbon atoms may be, independently of each other, substituted by one or more atoms halogen or hydroxy, amino, carboxy, sulfonic or thiol radicals; radicals not comprising a peroxide bond, nor of diazo or nitroso radicals,

• hydroxy or amino radicals; the amine can be substituted by a linear or branched dC hydrocarbon chain, which can form one or more carbon rings comprising 6 members, and which can be saturated or unsaturated, the carbon atoms can be, independently of each other, substituted by a or more halogen atoms or hydroxy, amino radicals. In this particular case, W1 can also be a pyrazolo- [1, 5-b] - pyridine radical in which Re, R ₇ , Rg, R ₉ and R ₁₅ , identical or different, are chosen from

• a hydrogen atom,

• a linear or branched C1-C ₁₀ hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, and whose carbon atoms can be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, mono or disubstituted amino, C1-C4 alkoxy, C1-C4 thioether, carboxy, sulfonic or thiol;

• hydroxy or amino radicals, the amine can be substituted by a linear or branched CC ₄ hydrocarbon chain, which can form one or more - carbon rings comprising from 5 to 6 members, and which can be saturated or unsaturated, the carbon atoms can be, independently of each other, substituted by one or more halogen atoms or hydroxy, amino radicals.

When W1 is a pyrazolo- [1,5-b] -pyridine radical, the radicals Re, R ₇ , R ₈ , R ₉ and R ₁₅ are preferably chosen from a hydrogen atom, a linear CC hydrocarbon chain or branched and possibly saturated or unsaturated, the carbon atoms can be, independently of each other, substituted by one or more halogen atoms or hydroxy or amino radicals.

W1 can also be a pyrazolo- [1,5-a] -pyrimidine radical in which R7 and R9 are chosen from a hydrogen atom, a linear or branched C _r C ₆ alkyl radical; a CC ₆ monohydroxyalkyl radical; a C ₂ -C ₆ polyhydroxyalkyl radical; an aminoalkyl radical -C ₆ aminoalkyl -C ₆ whose amine is mono- or di- substituted with an alkyl radical (C _r -C ₆₎ alkyl (Ci-C ₆₎ alkoxycarbonyl; a hydroxy or amino radical, the amino being able to be substituted by a linear or branched C Cιo hydrocarbon chain, being able to form one or more carbon rings having 5 to 6 members, and being able to be saturated or unsaturated, the carbon atoms can be, independently of each other, substituted by one or more halogen atoms or hydroxy, amino radicals; R6 and R8 are chosen from a hydrogen atom, an alkyl radical -C ₆ linear or branched; a monohydroxyalkyl radical in CrC ₆ ; a C ₂ -C ₆ polyhydroxyalkyl radical; a C ₁ -C ₆ aminoalkyl radical, a C ₁ -C ₆ aminoalkyl radical in which the amine is mono- or disubstituted by an alkyl (CrC ₆ ), alkyl (CrC ₆ ) carbonyl radical. In this case, R7 and R9 are preferably chosen from a hydrogen atom; a linear or branched CC ₄ alkyl radical; a CC monohydroxyalkyl radical; a C ₂ -C ₄ polyhydroxyalkyl radical; an aminoalkyl radical -C ₄ aminoalkyl DC ₄ whose amine is mono- or di- substituted with an alkyl (Ci-C _2); a hydroxy or amino radical, the amino being able to be substituted by a linear or branched CrC hydrocarbon chain, the carbon atoms can be, independently of one another, substituted by one or more hydroxy, amino, and R6 and R8 radicals are preferably chosen from a hydrogen atom, a linear or branched CC ₄ alkyl radical; a CC monohydroxyalkyl radical; a C ₂ -C polyhydroxyalkyl radical; an aminoalkyl radical -C ₄ aminoalkyl radical whose amine CC ₄ is mono- or di- substituted with an alkyl (Ci-C _2); a C 1 -C ₂ alkoxy radical. According to a particularly preferred embodiment, W1 is a pyrazolopyridine or pyrazolopyrimidine derivative in which R6, R7, R8 and R9 are preferably chosen from a hydrogen atom; a C1-C4 alkyl radical; an amino radical; a mono or di C1-C4 alkylamino radical; a C1-C4 hydroxyalkyl radical; a G, -C ₂ alkoxy radical. The compound of formula (I) can be represented by the following formula

in which R1, R2, R6 are as defined above.

As an example, the compounds of formula (I) can be cited

The composition of the invention preferably contains an amount of compound of formula (I) of between 0.01 and 10% by weight, preferably from 0.1 to 5%. The dye composition in accordance with the invention may also contain direct dyes different from the compounds of formula (I). These direct dyes which are useful according to the invention are, for example, chosen from neutral, acidic or cationic benzene nitro direct dyes, neutral azo acidic or cationic direct dyes, quinone direct dyes and in particular neutral, acidic or cationic anthraquinone dyes, direct dyes azines, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

Among the benzene direct dyes, the following compounds may be mentioned without limitation: -1, 4-diamino-2-nitrobenzene

-1-amino-2 nitro-4-β- hydroxyethylaminobenzene -1-amino-2 nitro-4-bis (β-hydroxyethyl) -aminobenzene -1,4-Bis (β-hydroxyethylamino) -2-nitrobenzene -1-β-hydroxyethylamino-2-nitro-4-bis- (β-hydroxyethylamino) -benzene

-1-β-hydroxyethylamino-2-nitro-4-aminobenzene

-1-β-hydroxyethylamino-2-nitro-4- (ethyl) (β-hydroxyethyl) -aminobenzene

-1-amino-3-methyl-4-β-hydroxyethylamino-6-nitrobenzene -1-amino-2-nitro-4-β-hydroxyethylamino-5-chlorobenzene

-1, 2-Diamino-4-nitrobenzene

-1-amino-2-β-hydroxyethylamino-5-nitrobenzene

-1,2-Bis- (β-hydroxyethylamino) -4-nitrobenzene

-1-amino-2-tris- (hydroxymethyl) -methylamino-5-nitrobenzene -1-Hydroxy-2-amino-5-nitrobenzene

-1-Hydroxy-2-amino-4-nitrobenzene

-1-Hydroxy-3-nitro-4-aminobenzene

-1-Hydroxy-2-amino-4,6-dinitrobenzene

-1-β-hydroxyethyloxy-2-β-hydroxyethylamino-5-nitrobenzene -1-Methoxy-2-β-hydroxyethylamino-5-nitrόbenzene

-1-β-hydroxyethyloxy-3-methylamino-4-nitrobenzene

-1-β, γ-dihydroxypropyloxy-3-methylamino-4-nitrobenzene

-1-β-hydroxyethylamino-4-β, γ-dihydroxypropyloxy-2-nitrobenzene

-1 -β, γ-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene -1 -β-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene

-1-β-hydroxyethylamino-3-methyl-2-nitrobenzene

-1-β-aminoethylamino-5-methoxy-2-nitrobenzene

-1-Hydroxy-2-chloro-6-ethylamino-4-nitrobenzene

-1-Hydroxy-2-chloro-6-amino-4-nitrobenzene -1-Hydroxy-6-bis- (β-hydroxyethyl) -amino-3-nitrobenzene

- 1 -β-hyd roxyethylam i no-2-nitrobenzene

-1-Hydroxy-4-β-hydroxyethylamino-3-nitrobenzene.

Among the azo direct dyes, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO-95/01772 and EP-714954, the content of which forms an integral part of the invention.

Among these compounds, the following dyes can be particularly mentioned:

-1,3-dimethyl-2 chloride - [[4- (dimethylamino) phenyl] azo] -1 H-lmidazolium,

-1,3-dimethyl-2 chloride - [(4-aminophenyl) azo] -1 H-lmidazolium, - 1-methyl-4-methyl sulfate - [(methylphenylhydrazono) methyl] -pyridinium.

One can also cite among the azo direct dyes the following dyes, described in the COLOR INDEX INTERNATIONAL 3 ^rd edition:

-Disperse Red 17 -Acid Yellow 9

-Acid Black 1

-Basic Red 22

-Basic Red 76

-Basic Yellow 57 -Basic Brown 16

-Acid Yellow 36

-Acid Orange 7

-Acid Red 33

-Acid Red 35 -Basic Brown 17

-Acid Yellow 23

-Acid Orange 24

-Disperse Black 9.

Mention may also be made of 1- (4'-aminodiphenylazo) -2-methyl-4bis- (β-hydroxyethyl) aminobenzene and 4-hydroxy-3- (2-methoxyphenylazo) -1-naphthalene sulfonic acid.

Among the quinone direct dyes, mention may be made of the following dyes:

-Disperse Red 15 -Solvent Violet 13

-Acid Violet 43

-Disperse Violet 1

-Disperse Violet 4

-Disperse Blue 1 -Disperse Blue 1

-Disperse Blue 3

-Disperse Red 11

-Acid Blue 62

-Disperse Blue 7 -Basic Blue 22 -Disperse Violet 15

-Basic Blue 99 as well as the following compounds:

-1-N-methylmorpholiniumpropylamino-4-hydroxyanthràquinone -1-Aminopropylamino-4-methylaminoanthraquinone

-1-Aminopropylaminoanthraquinone

-5-β-hydroxyethyl-1,4-diaminoanthraquinone

-2-Aminoéthylaminoanthraquinone

-1,4-Bis- (β, γ-dihydroxypropylamino) anthraquinone. Among the azine dyes, mention may be made of the following compounds:

-Basic Blue 17

-Basic Red 2.

Among the triarylmethane dyes, mention may be made of the following compounds: -Basic Green 1

-Acid blue 9

-Basic Violet 3

-Basic Violet 14

-Basic Blue 7 -Acid Violet 49

-Basic Blue 26

-Acid Blue 7

Among the indoamine dyes, mention may be made of the following compounds:

-2-β-hydroxyethlyamino-5- [bis- (β-4'-hydroxyethyl) amino] anilino-1,4-benzoquinone -2-β-hydroxyethylamino-5- (2'-methoxy-4'-amino) anilino -1,4-benzoquinone

-3-N (2'-Chloro-4'-hydroxy) phenyl-acetylamino-6-methoxy-1,4-benzoquinone imine

-3-N (3'-Chloro-4'-methylamino) phenyl-ureido-6-methyl-1,4-benzoquinone imine

-3- [4'-N- (Ethyl, carbamylmethyl) -amino] -phenyl-ureido-6-methyl-1,4-benzoquinone imine Among the natural direct dyes which can be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurine, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine. One can also use extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna. The direct dye (s) preferably represent from 0.001 to 20% by weight approximately of the total weight of the ready-to-use composition and even more preferably from 0.005 to 10% by weight approximately.

The composition of the present invention may also contain oxidation bases and couplers conventionally used for coloring by oxidation.

By way of example, mention may be made of para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.

The couplers are, for example, meta-phenylenediamine couplers, meta-aminophenol couplers, meta-diphenol couplers, naphthalene couplers, heterocyclic couplers and their addition salts.

When they are present, the bases and the couplers are each generally present in an amount of between 0.001 and 10% by weight approximately of the total weight of the dye composition, preferably between 0.005 and 6%. The medium suitable for dyeing, also called dye support, generally consists of water or of a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water. As organic solvent, mention may, for example, be made of lower C 1 alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

For dyeing human keratin fibers, the dyeing medium is an appropriate cosmetic medium. 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 dye composition in accordance with the invention may also contain various adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic polymers , cationic, non-ionic, amphoteric, zwitterionic or mixtures thereof, mineral or organic thickening agents, and in particular associative thickeners anionic, cationic, nonionic and amphoteric, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.

These adjuvants above are generally present in an amount for each of them of between 0.01 and 20% by weight relative to the weight of the composition.

Of course, those skilled in the art will take care to choose this or these possible complementary compounds in a way. such 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 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 or even using conventional buffer systems.

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 the following formula (III):

^R 6 \ _/ ^R 8

NWN ^/ (III)

R ₇ R _g in which W is a propylene residue optionally substituted by a hydroxyl group or a CC alkyl radical; Re, R ₇ , Rβ and R ₉ , identical or different, represent a hydrogen atom, an alkyl radical in CC ₄ or hydroxyalkyl in CrC ₄ . ^"

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 direct dyeing process which comprises the application of a dye composition containing a dye of formula (I) as defined above on keratin fibers. After a pause, the keratin fibers are rinsed leaving colored fibers to appear. The pause time is generally between 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately.

When the dye composition comprises an oxidation base and / or a coupler, the dye composition may then contain an oxidizing agent. The oxidizing agents conventionally used for the oxidation dyeing of keratin fibers are for example hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes among which there may be mentioned peroxidases, oxidoreductases with 2 electrons such as uricases and oxygenases with 4 electrons such as laccases. Hydrogen peroxide is particularly preferred. The oxidizing agent can be added to the composition of the invention just at the time of use or it can be used from an oxidizing composition containing it, applied simultaneously or sequentially to the composition of the invention. The oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.

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

The compounds of the invention of formula (I) can be prepared in the following way:

CAN, NaOH

2 equivalents of + 1 equivalent of coupler * - gray direct dye of H, O, CH ₃ CN tri-core oxidation base type. The term “oxidation base” is intended to mean the heterocyclic oxidation bases conventionally used in coloring which, after reaction with the coupler formed, a radical W1. The coupler used is a 2,3 diaminopyridine coupler substituted in position 6 by a leaving group such as an alkoxy, a halogen atom, an aryloxy, - OSO ₂ R, a radical -OCOR, a trifluoroalkoxy radical in CC ₃ , with R representing an alkyl radical.

Mention may be made, as heterocyclic oxidation base, of pyridine derivatives, pyrimidine derivatives and pyrazole derivatives. According to a particular embodiment, the base and the coupler are mixed with a solvent, for example acetonitrile. A base, for example, sodium hydroxide and CAN, is added to this mixture. After a (period) of stirring, water is added to the reaction medium. The aqueous phase is extracted for example with ethyl acetate. The organic phase is eliminated. The aqueous phase is again extracted, for example with butanol. The butanolic phase is subsequently dried, filtered and then concentrated, then purified.

The examples which follow serve to illustrate the invention without, however, being limiting in nature.

EXAMPLES

Example 1: preparation of a compound of formula:

G

3-amino-7-diethylaminopyrazolopyrimidine (A: 0.440 g), 2-pyrrolidino-3-amino-6-methoxypyridine (B: 0.386 g), ethanol / water ((60/40), 40 g), H2O2 ( 20 vol, 50 g) and a buffer at pH 7 (10 g of buffer: H2KPO4 13.6 g; HK2PO426.1g and Water qs 100 ml) are mixed and stirred at room temperature for 1 hour. The reaction mixture is then precipitated and the dye obtained (C) is purified by column chromatography.

NMR (H CD ₃ OD, 400 MHz), 3.18 ppm (s, 12H); 3.97 ppm (s, 4H); 6.21 ppm (s, 1 H); 6.27 ppm (s, 1 H); 6.62 ppm (d, 1 H), 6.71 ppm (d, 1 H); 7.95 ppm (s, 1 H); 8.39 ppm (d, 1H); 8.41 ppm (d, 1H); 8.83 ppm (s, 1 H)

ESI + / MS M = 511 (2 exchangeable protons) S / MS m / z = 485 [M + H-HCN] ⁺ ; m / z = 350 [M + HC ₈ H ₁₀ N ₄ ] + and m / z = 323 [M + H- HCN-C ₈ H ₁₀ N ₄ ] + and m / z == 176 [^ ₅ ^ -1-1] +

Example 2: preparation of a compound of formula

0.327 g of 3-amino-7-diethylaminopyrazolopyrimidine (A: 1.31 mmol; 2 eq.) And 0.138 g of 2,3-diamino-6-methoxypyridine (B: 0.65) are dissolved in 80 ml of absolute ethanol. mmoles; 1 eq.). 8 ml of 6% hydrogen peroxide are then added, and stirring is continued at room temperature. After one week, the mixture is filtered and the black dye (C) is recovered.

NMR ( ¹ H, DMSO-d6, 400 MHz): 3.14 ppm (s, 6H); 3.20 ppm (s, 6H); 6.34 ppm, (s, 1H); 6.70-6.66 (2d, 2H); 8.13 ppm (s, 1H); 8.68-8.63 ppm (2d, 2H); 9.11 (s, 1H); 10.21 (s extended, 1H exchangeable).

Mass (ES +): m / z: 458 (MH ⁺ )

Example 3: preparation of a compound of formula

0.222 g of 3-aminopyrazolopyridine (A: 1.31 mmol; 2 eq.) And 0.138 g of 2,3-diamino-6-methoxypyridine (B: 0.65 mmol; 1) are dissolved in 80 ml of absolute ethanol. eq.). 8 ml of 6% hydrogen peroxide are then added, and stirring is continued at room temperature. After one week, the mixture is filtered and the coloring solid (C) is recovered

NMR ^(1H, DMSO-d6, 400 MHz): 5.98 ppm (s, 1H); 7.12-7.04 (2dd, 2H); 7.37 ppm (dd, 1H); 7.52-7.49 ppm (dd, 1H); 7.70-7.68 ppm (d, 1H); 8.29 ppm (s, 1H); 8.52-8.50 ppm (d, 1H); 8.80-8.75 ppm (2dd, 2H), 9.22 ppm (s, 1H), 9.54 ppm (s expanded, 2H exchangeable); 10.66 (s extended, 1H exchangeable).

Mass (ES +): m / z: 370 (MH ⁺ ) Example 4: preparation of a compound of formula:

0.097 g of A (0.45 mmol; 2 eq.) And 0.050 g of B (0.22 mmol; 1 eq.) Are introduced into 10 ml of acetonitrile. 338 mg of 35% sodium hydroxide diluted in 10 ml of water are then added, then 499 mg of CAN immediately. The solution takes a blue-gray tint in a few minutes. After 4 hours of stirring, 100 ml of water are added. The aqueous phase is extracted with ethyl acetate. The organic phase is eliminated. The aqueous phase is again extracted with butanol. The butanolic phase is subsequently dried over sodium sulfate, filtered and then concentrated. The product is taken up in ethanol (2 ml) then precipitated again in diisopropyl ether. A black powder is obtained (C: m = 0.081 g).

Mass (ES +): m / z: 428 (MH ⁺ )

Example 5: preparation of a compound of formula:

0.169 g of A (0.45 mmol; 2 eq.) And 0.050 g of B (0.22 mmol; 1 eq.) Are introduced into 10 ml of acetonitrile. 338 mg of 35% sodium hydroxide diluted in 10 ml of water are then added, then immediately 499 mg of CAN (Cerium (IV) Ammonium. Nitrate: (NH ₄ ) ₂ Ce (N0 ₃ ) ₆ ). The solution takes a gray tint in a few minutes. After 4 hours of stirring, 100 ml of water are added. The aqueous phase is extracted with ethyl acetate. The organic phase is eliminated. The aqueous phase is again extracted with butanol. The butanolic phase is subsequently dried over sodium sulfate, filtered and then concentrated. The product is taken up in ethanol (2 ml) and then precipitated again in diisopropyl ether. A black powder is obtained (C).

Mass (ES +): m / z: 414 (MH ⁺ )

Example 6: preparation of a compound of formula:

VS

0.238 g of A (0.45 mmol; 2 eq.) And 0.050 g of B (0.22 mmol; 1 eq.) Are introduced into 10 ml of acetonitrile. 338 mg of 35% sodium hydroxide diluted in 10 ml of water are then added, then 499 mg of CAN immediately. The solution takes a gray tint in a few minutes. After 4 hours of stirring, 100 ml of water are added. The aqueous phase is extracted with ethyl acetate. The organic phase is eliminated. The aqueous phase is again extracted with butanol. The butanolic phase is subsequently dried over sodium sulfate, filtered and then concentrated. The product is taken up in ethanol (2 ml) and then precipitated again in diisopropyl ether. A black powder is obtained (C).

Mass (ES +): m / z: 384 (MH ⁺ ) Example 7: preparation of a compound of formula:

_N NH ₂

0.097 g of A (0.45 mmol; 2 eq.) And 0.050 g of B (0.22 mmol; 1 eq.) Are introduced into 10 ml of acetonitrile. 338 mg of 35% sodium hydroxide diluted in 10 ml of water are then added, then 499 mg of CAN immediately. The solution takes a blue-gray tint in a few minutes. After 4 hours of stirring, 100 ml of water are added. The aqueous phase is extracted with ethyl acetate. The organic phase is eliminated. The aqueous phase is again extracted with butanol. The butanolic phase is subsequently dried over sodium sulfate, filtered and then concentrated. The product is taken up in ethanol (2 ml) and then precipitated again in diisopropyl ether. A black powder is obtained (C),

Mass (ES +): m / z: 384 (MH ⁺ )

Example 8: preparation of a compound of formula:

0.097 g of A (0.45 mmol; 2 eq.) And 0.058 g of B (0.22 mmol; 1 eq.) Are introduced into 10 ml of acetonitrile. 338 mg of 35% sodium hydroxide diluted in 10 ml of water are then added, then 499 mg of CAN immediately. The solution takes a blue-gray tint in a few minutes. After 4 hours of stirring, 100 ml of water are added. The sentence aqueous is extracted with ethyl acetate. The organic phase is eliminated. The aqueous phase is again extracted with butanol. The butanolic phase is subsequently dried over sodium sulfate, filtered and then concentrated. The product is taken up in ethanol (2 ml) and then precipitated again in diisopropyl ether. A black powder is obtained (C)

Mass (ES +): m / z: 438 (MH ⁺ )

By following the synthesis process described above, the following compounds can be obtained according to the synthetic scheme indicated:

Evaluation in coloring of keratin fibers

Each of the dyes of the preceding examples is mixed in the following medium to form a dye composition (dye 0.5% by weight). Keratin fibers are then added to the composition thus obtained (composition / fiber ratio = 10/1). After 30 min, the hair is rinsed with water and then dried. This gives a black coloring of the hair.

Staining medium Hydroxyethyl cellulose 0.768% Parabens 0.064% Decyl glucoside 10% Benzyl alcohol 8% Propylene glycol 12% Buffer pH 7 10% Water qs 100%

Claims

1. Dye composition comprising, in an appropriate medium, a compound of the following formula (I) or one of its addition salts:

in which • R represents: - a hydrogen atom,

- a linear or branched C ₁ -C ₁₀ hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, of which one or more carbon atoms of the carbon chain can be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms; R ₃ having no peroxide bond, nor diazo or nitroso radicals,

- NR'ιR ' ₂ , R'i and R' ₂ being as defined for Ri and R ₂ • Ri and R ₂ represent independently of each other:

- a hydrogen atom

- a linear or branched C Cι ₀ hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 links, and which can be saturated or unsaturated, of which one or more carbon atoms of the carbon chain can be replaced by an atom oxygen, nitrogen or sulfur or with an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms; Ri and R ₂ having no peroxide bond, nor diazo or nitroso radicals, and R1 and R2 not being directly linked to the nitrogen atom by an oxygen, sulfur, nitrogen or SO atom ₂ ,

- an onium Z radical, or Ri and R ₂ together with the nitrogen atom to which they are attached form a cycle of formula (II):

formula (II) in which: R 'represents:

- a hydrogen atom;

- a halogen atom;

- a C 1 -C 4 alkyl radical optionally substituted by one or more radicals chosen from hydroxy, carboxy, alkoxycarbonyl radicals

CC ₄ , alkyl (C _r C) amido (alkyl (CC ₄ ) CONH-), alkyI (CC) carbamoyl (alkyl (C _r C ₄ ) NHCO-), alkyl (C _r C ₄ ) sulfonyl (alkyl (CC ₄ ) SO ₂ -), CC ₄ alkoxy, alkyl (CC ₄ ) sulfonamido (alkyl (CrC ₄ ) SO ₂ NH-), alkyl (CC ₄ ) sulfamoyl (alkyl (CC ₄ ) NH SO ₂ -), onium Z, - NR ' ₃ R'₄;

- a carboxy radical;

- a C C alkoxycarbonyl radical;

- an alkyl (CrC ₄ ) amido radical (alkyl (CC) CONH-);

- an alkyl (CC ₄ ) sulfonyl radical (alkylSO ₂ -) - an alkylsulfonamido radical (alkyl (CrC ₄ ) SO ₂ NH -),

- a hydroxy radical;

- a C C alkoxy radical;

- a C ₂ -C hydroxyalkoxy radical;

- a (C1-C4) carbamoyl (C1-C4) NHCO- alkyl radical; - alkyl (CC ₄ ) sulfamoyl (alkyl (CC ₄ ) -NH-SO ₂ -);

- a thioether radical in CC ₄ ;

- a sulfonic radical (SO ₃ H) which may be in the form of a salt,

- an onium Z radical,

R ' ₃ and R' ₄ , identical or different, represent a hydrogen atom; a C _r C ₄ alkyl radical optionally substituted by one or more radicals chosen from hydroxy, CC ₄ alkoxy, amino, mono or di alkylamino, (C _r C ₄ ) CO-, alkyl (CC ₄ ) NHCO- radicals , alkyl (C _r C ₄ ) SO ₂ -, - n is an integer between 1 and 8,

- m is an integer between 0 and 3, preferably from 0 to 2,

R ' ₅ which represents a hydrogen atom; a linear or branched C, -C o hydrocarbon chain which may be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen, nitrogen or sulfur atom or by a group SO ₂ , and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms; R ' ₅ not comprising a peroxide bond, nor of diazo or nitroso radicals, and R' ₅ not being directly connected to the nitrogen atom by an oxygen, sulfur or nitrogen atom, R ' ₆ and R ' ₇ which independently represent a linear or branched C ₁ -C ₁₀ hydrocarbon chain, which may be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen atom, nitrogen or sulfur or with an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms; R ' ₆ and R' ₇ not comprising a peroxide bond, nor of diazo or nitroso radicals, and R ' ₆ and R' ₇ not being directly linked to the nitrogen atom by an oxygen atom, of sulfur or nitrogen, W ₁ represents an aromatic heterocycle radical chosen from the following radicals

• Zi and Z ₃ , independently of one another, represent a hydroxy radical or

• Z ₂ , Z, Z ₆ independently of one another represent a nitrogen atom, a radical CR ₁₂ or NRn with the proviso that at least one of them represents a radical CR ₁₂ and that it cannot there are more than 3 contiguous nitrogen atoms,

• Z ₈ represents a nitrogen atom, a radical CR ₁₅ ;

• R ₆ , R ₇ , R ₈ , Rg, R ₁ 0, R ₁₁ , Ri ₂ , R ₁₅ independently of one another represent a hydrogen atom;

- a linear or branched C ₁ -C ₀ hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, of which one or more carbon atoms of the carbon chain can be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms; the radicals Re to R ₂ and R ₁₅ not comprising a peroxide bond, nor of diazo or nitroso radicals and the radical Ru not being connected directly to the nitrogen atom by an oxygen, sulfur or d atom 'nitrogen,

- p can take the values 4 to 8, - q can take the values 1 to 3, and

- r can take the values 0 to 2,

- * indicates the point of attachment of, W1 in formula (I).

2. Dye composition according to claim 1 comprising, in a suitable medium, a compound of formula (I) below or one of its addition salts:

in which

• Rs represents: - a hydrogen atom,

- a linear or branched CC ₁₀ hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 links, and which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group, and whose carbon atoms may be, independently each other, substituted by one or more halogen atoms or hydroxy, amino, carboxy, sulfonic or thiol radicals; R ₃ having no peroxide bond, nor diazo or nitroso radicals,

- NR'ιR ' ₂ , R'i and R' ₂ being as defined for Ri and R ₂

• Ri and R ₂ represent independently of each other: - a hydrogen atom

- a linear or branched C ₁ -C ₁₀ hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, of which one or more carbon atoms of the carbon chain can be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino or carboxy radicals , sulfonic or thiol; R and R ₂ not comprising a peroxide bond, nor of diazo or nitroso radicals, and R1 and R2 not being directly linked to the nitrogen atom by an oxygen, sulfur, nitrogen or SO atom ₂ ,

- an onium Z radical, or

• Ri and R ₂ together with the nitrogen atom to which they are attached form a cycle of formula (II):

formula (II) in which: • R 'represents:

- a hydrogen atom;

- a halogen atom; - a C _r C alkyl radical optionally substituted by one or more radicals chosen from hydroxy, carboxy, CC ₄ alkoxycarbonyl, alkyl (CC ₄ ) amido (alkyI (CC ₄ ) CONH-), alkyl (CC ₄ ) carbamoyl (alkyl (CC ₄ ) NHCO-), alkyl (C _r C ₄ ) sulfonyl (alkyl (C _r C ₄ ) SO ₂ -), C _r C ₄ alkoxy, alkyl (CC ₄ ) sulfonamido (alkyl (CC ₄ ) SO ₂ NH-), alkyl (C _r C ₄ ) sulfamoyl (alkyl (C _r C ₄ ) NH SO ₂ -), onium Z,

- NR ' ₃ R'₄;

5 - a carboxy radical;

- a C 1 alkoxycarbonyl radical;

- an alkyl (CC ₄ ) amido radical (alkyl (CC ₄ ) CONH-);

- an alkyl radical (CC ₄ ) sulfonyl (alkylSO ₂ -)

- an alkylsulfonamido radical (alkyl (CC) SO ₂ NH -), 0 - a hydroxy radical;

- a C C alkoxy radical;

- a C ₂ -C ₄ hydroxyalkoxy radical;

- a (C1-C4) carbamoyl (C1-C4) NHCO- alkyl radical;

- alkyl (CrC ₄ ) sulfamoyl (alkyl (CC ₄ ) -NH-SO ₂ -); - a CC thioether radical;

- a sulfonic radical (SO ₃ H) which may be in the form of a salt,

- an onium Z radical,

R ' ₃ and R', identical or different, represent a hydrogen atom; a CC alkyl radical optionally substituted by one or more radicals 0 chosen from hydroxy, CC alkoxy, amino, mono or di alkylamino, alkyl (CC ₄ ) CO-, alkyl (CC ₄ ) NHCO-, alkyl (CC ₄ ) radicals ) SO ₂ -,

- n is an integer between 1 and 8,

- m is an integer between 0 and 3, preferably from 0 to 2,

- Y represents an oxygen atom, a radical CR ', a radical NR' ₅ or a radical 25 NR ' ₆ R' with

R ' ₅ which represents a hydrogen atom; a linear or branched CrC ₁₀ hydrocarbon chain, which may be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen, nitrogen or sulfur atom or by

An SO ₂ group, the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, carboxy, sulphonic or thiol radicals; R ' ₅ having no peroxide bond, nor diazo or nitroso radicals, and R' ₅ not being directly linked to the nitrogen atom

35. by an oxygen, sulfur or nitrogen atom, R ' ₆ and R' ₇ which independently represent a linear or branched C Cι ₀ hydrocarbon chain, which may be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen atom, of nitrogen or sulfur or with an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino or carboxy radicals; sulfonic or thiol; R ' ₆ and R' ₇ not comprising a peroxide bond, nor of diazo or nitroso radicals, and R ' ₆ and R' ₇ not being directly linked to the nitrogen atom by an oxygen atom, of sulfur or nitrogen, W represents an aromatic heterocycle radical chosen from the following radicals

• Zi and Z ₃ , independently of one another, represent a hydroxy radical or NRιιR _i2 ;

• Z ₂ , Z ₄ , Z ₆ independently of one another represent a nitrogen atom, a radical CR ₁ 2 or NRn with the proviso that at least one of them represents a radical CR ₂ and that it cannot be more than 3 contiguous nitrogen atoms,

• Z ₈ represents a nitrogen atom, a radical CR ₁₅ ; • R ₆ , R, R ₈ , Rg. Rio. Ru. R12. R15 represent independently of each other

- a hydrogen atom;

- a linear or branched C Cιo hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 links, and which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which can be replaced by an atom d oxygen, nitrogen or sulfur or by an SO ₂ group, and whose carbon atoms can be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, carboxy, sulfonic or thiol radicals; the radicals R ₆ to R12 and R _i5 not comprising a peroxide bond, nor of diazo or nitroso radicals and the radical Ru not being connected directly to the nitrogen atom by an oxygen, sulfur or d atom 'nitrogen,

- p can take the values 4 to 8, q can take the values 1 to 3, and

- r can take the values 0 to 2,

- * indicates the point of attachment of W1 in formula (I).

3. Dye composition according to claim 1 comprising, in a suitable medium, a compound of formula (I) below or one of its addition salts:

in which

• R ₃ represents:

- a hydrogen atom,

- a linear or branched C ₁ -C ₁ ₀ hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy or amino radicals, ( di) Cι-C ₂ alkylamino, C _r C ₂ alkoxy, carboxy, sulfonic or thiol; R ₃ having no peroxide bond, nor diazo or nitroso radicals,

- NR ', R'2, R'i and R' ₂ being as defined for Ri and R ₂

• Ri and R ₂ represent independently of each other:

- a hydrogen atom - a linear or branched C1-C10 hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, including one or more carbon atoms of the carbon chain can be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group, and whose carbon atoms can be, independently of each other, substituted by one or more halogen atoms or hydroxy, amino, (di) C 1 -C ₂ alkylamino, C ₄ -C alkoxy, carboxy, sulfonic or thiol radicals; Ri and R ₂ having no peroxide bond, nor diazo or nitroso radicals, and R1 and R2 not being directly linked to the nitrogen atom by an oxygen, sulfur, nitrogen or SO atom ₂ , - an onium Z radical, or

Ri and R ₂ together with the nitrogen atom to which they are attached form a cycle of formula (II):

formula (II) in which: R 'represents:

- a hydrogen atom;

- a halogen atom;

CC ₄ , alkyl (Ç C ₄ ) amido (alkyl (CC ₄ ) CONH-), alkyl (CC ₄ ) carbamoyl (alkyl (CC ₄ ) NHCO-), alkyl (CC) sulfonyl (alkyl (CrC ₄ ) SO ₂ - ), CC alkoxy, alkyl (CC ₄ ) sulfonamido (alkyl (CC ₄ ) SO ₂ NH-), alkyl (d- C ₄ ) sulfamoyl (alkyl (CC) NH SO ₂ -), onium Z, - NR ' ₃ R '₄;

- a carboxy radical;

- a C C alkoxycarbonyl radical;

- an alkyl (CC ₄ ) amido radical (alkyl (CC ₄ ) CONH-);

- an alkyl (CC) sulfonyl radical (alkylSO ₂ -) - an alkylsulfonamido radical (alkyl (CC ₄ ) SO ₂ NH -),

- a hydroxy radical;

- a CrC ₄ alkoxy radical; - a C ₂ -C ₄ hydroxyalkoxy radical;

- a (C1-C4) carbamoyl (C1-C4) NHCO- alkyl radical;

- alkyl (C _r C ₄ ) sulfamoyl (alkyl (CC ₄ ) -NH-SO ₂ -); ^• - a thioether radical in CrC ₄ ; - a sulfonic radical (SO ₃ H) which may be in the form of a salt,

- an onium Z radical,

R ' ₃ and R' ₄ , identical or different, represent a hydrogen atom; a CC ₄ alkyl radical optionally substituted by one or more radicals chosen from hydroxy, Cι-C alkoxy, amino, mono or di alkylamino, alkyl (CC ₄ ) CO-, alkyl (CC ₄ ) NHCO-, alkyl ( C _r C ₄ ) SO ₂ -,

- n is an integer between 1 and 8,

- m is an integer between 0 and 3, preferably from 0 to 2,

- Y represents an oxygen atom, a radical CR ', a radical NR' ₅ or a radical NR ' ₆ R' ₇ with R ' ₅ which represents a hydrogen atom; a linear or branched C ₁ -C ₁ 0 hydrocarbon chain, which may be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen, nitrogen or sulfur atom or by a SO ₂ group, and whose carbon atoms can be, independently of each other, substituted by one or more halogen atoms or hydroxy, amino, carboxy, sulfonic or thiol radicals; R ' ₅ not comprising a peroxide bond, nor of diazo or nitroso radicals, and R'5 not being directly connected to the nitrogen atom by an oxygen, sulfur or nitrogen atom, R' ₆ and R ' ₇ which independently represent a linear or branched C ₁ -C ₁₀ hydrocarbon chain, which may be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen or nitrogen atom or sulfur or with an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, carboxy, sulphonic or thiol radicals; R ' ₆ and R' ₇ not comprising a peroxide bond, nor of diazo or nitroso radicals, and R ' ₆ and R' ₇ not being directly linked to the nitrogen atom by an oxygen atom, of sulfur or nitrogen, represents an aromatic heterocycle radical chosen from the following radicals

• Zi and Z ₃ , independently of one another, represent a hydroxy radical or

• Z ₂ , Z, Z ₆ independently of one another represent a nitrogen atom, a radical CR ₂ or NRn with the proviso that at least one of them represents a radical CR ₁₂ and that it cannot there are more than 3 contiguous nitrogen atoms,

• Z ₈ represents a nitrogen atom, a radical CR ₁₅ ;

• Rβ, R, R ₈ , Rg, R10, R11, ι _2l i ₅ represent independently of each other - a hydrogen atom;

- a linear or branched C ₁ -C ₁₀ hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, of which one or more carbon atoms of the carbon chain can be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino or carboxy radicals , sulfonic or thiol

; the radicals R ₆ to R12 and R ₁₅ not comprising a peroxide bond, nor of

. diazo or nitroso radicals and the Ru radical not being directly connected to the nitrogen atom by an oxygen, sulfur or nitrogen atom,

- p can take the values 4 to 8,

- q can take the values 1 to 3, and

- r can take the values 0 to 2,

- * indicates the point of attachment of W1 in formula (I).

4. Composition according to claim 1 in which R ₃ is chosen from a hydrogen atom or a CC alkyl radical optionally substituted by a or more radicals chosen from hydroxyl, alkoxy, -C _2, amino, (di) alkylamino CC _2.

5. Composition according to claim 1 or 4 in which Ri and R ₂ are chosen separately from a hydrogen atom, an alkyl radical in CrC ₆ optionally substituted by a hydroxy, alkoxy, amino, (di) alkylamino in CC ₄ .

6. Composition according to claim 1 or 4 in which Ri and R ₂ , together with the nitrogen atom to which they are attached, form a 5 to 8-membered heterocycle chosen from the heterocycles pyrrolidine, piperidine, homopiperidine, piperazine, homopiperazine, diazepane possibly substituted.

7. Composition according to Claim 6, in which Ri and R ₂ form a heterocycle chosen from pyrrolidine, 3-hydroxypyrrolidine, 3-aminopyrrolidine, 3-acetamidopyrrolidine, 3- (methylsulfonylamino) -pyrrolidine, praline, 3 - hydroxyproline, piperidine, hydroxypiperidine, homopiperidine, diazepane, N-methyl homopiperazine, N β-hydroxyethylhomopiperazine and their addition salts

8. Composition according to any one of claims 6 or 7 in which Ri and R ₂ form with the nitrogen atom to which they are attached an optionally substituted pyrrolidine ring.

9. Composition according to any one of claims 1 to 8 in which the onium radical Z corresponding to formula (III)

in which

• D is a covalent bond or a linear or branched CrCu alkylene chain which may contain one or more heteroatoms chosen from oxygen, sulfur or nitrogen, SO ₂ , one or more ketone functions, the chain may be substituted by one or more hydroxyl, alkoxy in CrC ₆ or amino, (di) alkylamino in CC ₄ ;

• Laugh. R17 and Rι ₈ , taken separately, represent a C ₁ -C ₁₅ alkyl radical; a monohydroxyalkyl radical in CrC ₆ ; a C ₂ -C ₆ polyhydroxyalkyl radical; alkoxy (CrC ₆₎ alkyl -C _6; an aryl radical; a benzyl radical; a CC ₆ amidoalkyl radical; a CC ₆ trialkyl (CrC ₆ ) silanealkyl radical; a CrC ₆ aminoalkyl radical; an aminoalkyl radical -C ₆ whose amine is mono- or di-substituted by an alkyl radical in C _r C alkyl (Ci-C ₆₎ alkylcarbonyl, amido or alkyl (Ci-C ₆₎ alkylsulphonyl radical; a C 1 -C ₆ carbamylalkyl radical; an alkyl (C, -C ₆₎ carboxy-C, -C ₆ alkyl; an alkyl (C, -C ₆₎ alkoxycarbonyl, C, - C _6; an N-alkyl (CC ₆ ) carbamylalkyl radical in C Ce.

• i6. R ₁ 7 and R ₁₈ together, two by two, form, with the nitrogen atom to which they are attached, a saturated carbonaceous cycle with 4, 5, 6 or 7 links which can contain one or more heteroatoms, the cationic cycle can be substituted by a halogen atom, a hydroxyl radical, a C ₁ -C ₆ alkyl radical, a C 1 -C ₆ monohydroxyalkyl radical, a C ₆ -C ₆ polyhydroxyalkyl radical

C ₂ -C ₆ , an alkoxy radical in CrC ₆ , a trialkyl (CrC ₆ ) silanealkyl radical in CrC ₆ , an amido radical, a carboxyl radical, an alkyl (CrC ₆ ) carbonyl radical, a thio radical, a thioalkyl radical in CrC ₆ , an alkyl radical (CrC ₆ ) thio, an amino radical, an amino radical mono- or di-substituted by an alkyl (CrC ₆ ), alkyl (CrC ₆ ) carbonyl, amido or alkyl (CC ₆ ) sulfonyl radical;

• Rig represents a CC ₆ alkyl radical; a CC ₆ monohydroxyalkyl radical; a C ₂ -C ₆ polyhydroxyalkyl radical; an aryl radical; a benzyl radical; a CC ₆ aminoalkyl radical; a CrC ₆ aminoalkyl radical in which the amine is mono- or di-substituted by an alkyl (CrC ₆ ), alkyl (CrC ₆ ) carbonyl, amido or alkyl (CrC ₆ ) sulfonyl radical; a carboxyalkyl radical -C _6; a CC ₆ carbamylalkyl radical; a CrC ₆ trifluoroalkyl radical; a trialkyl (CrC ₆ ) silanealkyl radical in CrC ₆ ; a sulphonamidoalkyl radical -C _6; an alkyl radical (CC ₆₎ -C ₆ carboxyalkyl; an O | -C ₆ alkyl (CrC ₆ ) sulfinylalkyl radical; an alkyl (CrC ₆₎ -C ₆ sulfonylalkyl; an alkyl radical (CC ₆₎ carbonylalkyl -C _6; an N-alkyl (Ci-C ₆₎ carbamyl -C _6; an N-alkyl (CrC ₆ ) sulfonamidoalkyl radical in CrC ₆ ;

• x is 0 or 1,

- when x = 0, then the link arm D is attached to the nitrogen atom carrying the radicals Rie to Rι ₈ , - when x = 1, then two of the radicals Rie to Rι ₈ form jointly with the atom d nitrogen to which they are attached a saturated cycle with 5, 6 or 7 members and the link arm D is connected to a carbon atom of the saturated cycle;

• T is a counter ion.

10. The composition of claim 9 wherein x is equal to 0, and Rι ₆ , Rι ₇ and Rι ₈ separately are chosen from an alkyl radical in CC ₆ , a monohydroxyalkyl radical in C _r C ₄ , a polyhydroxyalkyl radical in C ₂ -C, an alkoxy radical (CC ₆ ) alkyl CC _4, a radical amidoalkyl C _r C _6l ^a radical tri (Ci-C ₆₎ alkylsilane -C _6, or x is 0 and Rι ₆ with Rι together form an azetidine, pyrrolidine, piperidine, homopiperidine, piperazine, homopiperazine, morpholine, Rι ₈ being chosen in this case from an alkyl radical in CrC ₆ ; a monohydroxyalkyl radical in CrC ₆ ; a C ₂ -C ₆ polyhydroxyalkyl radical; an aminoCyl radical in CrC ₆ , an aminoalkyl radical in which the amine is mono- or di-substituted by an alkyl (CrC ₄ ), alkyl (CrC ₆ ) carbonyl, amido or alkyl (CrC ₆ ) sulfonyl radical; a C1-C6 carbamylalkyl radical; a trialkyl (CrC ₆ ) silanealkyl radical in CrC ₆ ; an alkyl radical (-C ₆₎ carboxyalkyl -C _6; an alkyl (CrC ₆₎ carbonylalkyl -C _6; an N-alkyl (CC ₆ ) carbamylalkyl radical in CrC ₆ .

11. Composition according to Claim 9, in which x is equal to 1, R ₁₉ is chosen from a CC ₆ alkyl radical; a monohydroxyalkyl radical in CrC ₆ ; a C ₂ -C ₆ polyhydroxyalkyl radical; a C ₆ aminoalkyl radical, a CC ₆ aminoalkyl radical in which the amine is mono or disubstituted by an alkyl radical (C 1 -C ₆ ), alkyl (CrC ₆ ) carbonyl, amido or alkyl (CrC ₆ ) sulfonyl; a CC ₆ carbamylalkyl radical; a trialkyl (CrC ₆ ) silanealkyl radical in CrC ₆ ; a C _r C ₆ carboxyalkyl (C ₁ -C ₆ ) alkyl radical; alkyl (CrC ₆₎ carbonylalkyl -C _6; an N-alkyl radical (C

-C ₆₎ carbamyl -C _6; Rie svec Rι ₇ together form a ring azetidine, pyrrolidine, piperidine, homopiperidine, piperazine, homopiperazine, morpholine, Rι ₈ being chosen in this case from an alkyl radical in CrC ₆ ; a monohydroxyalkyl radical in CrC ₆ ; a C ₂ -C ₆ polyhydroxyalkyl radical; a C ₆ aminoalkyl radical, a CC ₆ aminoalkyl radical the amine of which is mono or disubstituted by an alkyl (CC), alkyl (CrC ₆ ) carbonyl, amido or alkyl (CC ₆ ) sulfonyl radical; a carbamylalkyl radical in CrC ₆ ; a trialkyl radical (-C ₆₎ alkylsilane Cι-C _6; an alkyl radical (CC ₆₎ -C ₆ carboxyalkyl; an alkyl radical (CC ₆₎ carbonylalkyl CC _6; an N-alkyl (CC ₆ ) carbamylalkyl radical in CrC ₆ .

12. Composition according to any one of claims 9 or 10 in which x is equal to 0 and R ₁₆ R ₁₇ and Rι ₈ are alkyl radicals.

13. Composition according to any one of claims 9 to 12 in which D is a covalent bond in which a CC ₆ alkylene chain can be substituted.

14. Composition according to any one of claims 1 to 8 in which the onium radical Z corresponding to formula (IV)

(IV), in which • D is as defined in claim 9 or 13,

The vertices E, G, J, L, identical or different, represent a carbon, oxygen, sulfur atom of nitrogen to form a pyrazolic, imidazolic, triazolic, oxazolic, isooxazolic, thiazolic, isothiazolic cycle,

• a + b is an integer between 2 and 4;

• R, identical or different, represent a hydrogen atom, a halogen atom, a hydroxyl radical, a CC ₆ alkyl radical, a Cr C ₆ monohydroxyalkyl radical, a C ₂ -C ₆ polyhydroxyalkyl radical, an alkoxy radical in CrC ₆ , a trialkyl (CrC ₆ ) silanealkyl radical in CrC ₆ , an amido radical, a carboxyl radical, an alkylcarbonyl radical in CrC ₆ , a thio radical, a thioalkyl radical in CrC ₆ , an alkyl (CrC ₆ ) thio radical, an amino radical, an amino radical mono or di substituted by an alkyl (CrC ₆ ), alkyl (Cι-C ₆ ) carbonyl, amido, alkyl (CrC ₆ ) sulfonyl radical; monohydroxyalkyl radical -C ₆ polyhydroxyalkyl radical or a C ₂ -C _6; a benzyl radical; a phenyl radical optionally substituted by one or more radicals chosen from methyl, hydroxy, amino and methoxy radicals; it being understood that the radicals R are carried by a carbon atom;

• R ₂₀ represents an alkyl radical in CrC ₆ , a monohydroxyalkyl radical in d- C ₆ , a polyhydroxyalkyl radical in C ₂ -C ₆ , a trialkyl (CrC ₆ ) silanealkyl radical in CC ₆ , an alkoxy (CrC ₆ ) alkyl radical in CrC ₆ , a carbamylalkyl radical CC ₆ , an alkyl radical (CrC ₆ ) carboxyalkyl in CrC ₆ , a benzyl radical; it being understood that the radical R ₂₀ is carried by a nitrogen atom,

• Rι ₉ is as defined in claim 9 or 11, • x is 0 or 1

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

- when x = 1, the link arm D is attached to one of the vertices E, G, J or L when E, G, J or L represents a carbon atom, • T is a counterion.

15. Composition according to claim 14 in which the vertices E, G, J and L form an imidazolic, pyrazolic, oxazolic, thiazolic and triazolic cycle.

16. Composition according to claim 14 or 15 in which x is equal to 0, D is a single bond or a CC ₄ alkylene chain which can be substituted.

17. Composition according to any one of claims 1 to 8 in which the onium radical Z corresponding to formula (V)

(V) in which:

• D, R, R g are as defined in claim 14, “the vertices E, G, J, L and M which are identical or different, represent a carbon or nitrogen atom and form a cycle chosen from the cycles pyridine, pyrimidine, pyrazine, triazine and pyridine,

• d is an integer between 3 and 5 inclusive;

• x is equal to 0 or 1 - when x = 0, the link arm D is attached to the nitrogen atom,

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

• T represents a counter ion.

18. A composition according to claim 17 in which the vertices E, G, J, L and M with the nitrogen of the cycle form a cycle chosen from pyridine, pyrimidine, pyridine and pyrazine cycles.

19. Composition according to any one of claims 14 to 18 in which x is equal to 0 and R is chosen from a hydroxyl radical, a d-Ce alkyl radical, a monohydroxyalkyl radical in CrC ₆ , a polyhydroxyalkyl radical in C ₂ -C ₆ , an alkoxy radical in CrC ₆ , a trialkyl (CrC ₆ ) silanealkyl radical in CrC ₆ , an amido radical, an alkylcarbonyl radical in CrC ₆ , an amino radical, an amino radical mono- or di-substituted by an alkyl radical (CrC ₆ ), alkyl (CrC ₆ ) carbonyl, amido or alkyl (CC ₆ ) sulfonyl; a dC ₆ monohydroxyalkyl radical or a C ₂ -C ₆ polyhydroxyalkyl radical; it being understood that the radicals R are carried by a carbon atom.

20. Composition according to any one of claims 14 to 18 in which x is equal to 1, Rι ₉ is chosen from a dC ₆ alkyl radical; a CC ₆ monohydroxyalkyl radical; a C ₂ -C ₆ polyhydroxyalkyl radical; an aminoalkyl radical -C ₆ aminoalkyl radical -C ₆ whose amine is mono- or di- substituted with an alkyl (CrC ₆₎ alkyl (dC ₆₎ alkylcarbonyl, amido radical or an alkyl radical (CrC ₆ ) sulfonyl; a carbamylalkyl radical in CrC ₆ ; a trialkyl (CC ₆ ) silanealkyl radical in CrC ₆ ; a CC ₆ alkyl (dC ₆ ) carbonylalkyl radical; N- alkyl radical (-C ₆₎ carbamyl -C _6; R is chosen from a hydroxyl radical, an alkyl radical -C ₆ monohydroxyalkyl radical -C ₆ polyhydroxyalkyl radical a C ₂ -C ₆ alkoxy radical -C ₆ trialkyl radical (d- C ₆₎ alkylsilane CrC ₆ , an amido radical, a CrC ₆ alkylcarbonyl radical, an amino radical, an amino radical mono- or di-substituted by an alkyl (CrC ₆ ), alkyl (dC ₆ ) carbonyl, amido or alkyl (CrC ₆ ) radical sulfonyl.

21. Composition according to any one of claims 14 to 20 in which R and Rι ₉ are dC alkyl radicals which may be substituted.

22. Composition according to any one of claims 1 to 21 in which W1 is chosen from the radicals 5-aminopyrazole, 5-hydroxypyrazole, pyrazolo- [1, 5-b] -pyridine, pyrazolo- [1,5-a] -pyrimidine, pyrazolo [3,2-c] triazole, pyrazolo [1,5-b] triazole, aminopyrimidines, triaminopyrimidine, hydroxyaminopyrimidines, 2-aminopyridine, indoline and indole.

23. The composition as claimed in claim 22 in which W1 is chosen from the 5-aminopyrazole, 5-hydroxypyrazole radicals of formula (R1).

24. The composition as claimed in claim 23 in which W1 is chosen from the 5-aminopyrazole and 5-hydroxypyrazole radicals in which R6 and R11, identical or different, are chosen from a hydrogen atom; a linear or branched C -C ₀ hydrocarbon chain, which can form one or more carbon rings having from 4 to 8 members, and which can be saturated or unsaturated, of which one or more carbon atoms of the carbon chain can be replaced by an atom of oxygen, nitrogen or sulfur or with an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or several halogen atoms or hydroxy, amino, carboxy, sulfonic or thiol radicals; the radicals R ₆ to R ₂ not comprising a peroxide bond, nor of the diazo or nitroso radicals and the radical Ru, not being connected directly to the nitrogen atom by an oxygen, sulfur or nitrogen.

25. The composition as claimed in claim 24 in which R6 and R11 are independently chosen from a hydrogen atom or a linear or branched Cι-C hydrocarbon chain, which can form one or more carbon rings comprising from 5 to 6 members, and which can be saturated or unsaturated, the carbon atoms can be, independently of each other, substituted by one or more halogen atoms or hydroxy or amino radicals.

26. Composition according to claim 1 or 22 in which W1 represents

R6, R7, R8, R9 and Z8 being such that

is lying.

27. The composition as claimed in claim 26 in which W1 is a pyrazolo- [1,5-b] -pyridine radical in which Re, R ₇ , R ₈₎ R ₉ and Rι ₅ , which are identical or different, are chosen from

• a hydrogen atom,

• a linear or branched C ₁ -C ₁₀ hydrocarbon chain, which can form one or more carbon rings having 4 to 8 members, and which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino or carboxy radicals , sulfonic or thiol; radicals not comprising a peroxide bond, nor of diazo or nitroso radicals,

• hydroxy or amino radicals, - the amine which can be substituted by a linear or branched dC ₄ hydrocarbon chain, which can form one or more carbon rings comprising from 5 to 6 members, and which can be saturated or unsaturated, the carbon atoms can be, independently of each others, substituted by one or more halogen atoms or hydroxy, amino radicals.

28. The composition as claimed in claim 27, in which W1 is a pyrazolo- [1,5-b] -pyridine radical in which R ₆ , R ₇ , R ₈ , R ₉ and R ₁₅ , identical or different, are chosen from

• a hydrogen atom,

• a linear or branched C -C ₁₀ hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by a oxygen, nitrogen or sulfur atom or by an SO ₂ group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino or carboxy radicals , sulfonic or thiol; the radicals comprising no peroxide bond, nor diazo or nitroso radicals,

Hydroxy or amino radicals, the amine possibly being substituted by a linear or branched C _r C hydrocarbon chain, possibly forming one or more carbon rings comprising 6 members, and possibly being saturated or unsaturated, the carbon atoms can be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino radicals.

29. Composition according to claim 27 in which W1 is a pyrazolo- [1,5-b] -pyridine radical in which Re, R ₇ , R ₈ , R ₉ and R ₁₅ , identical or different, are chosen from

• a hydrogen atom, • a linear or branched C Cι ₀ hydrocarbon chain, which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, and whose carbon atoms can be, independently each other, substituted by one or more halogen atoms or hydroxy, amino, mono or disubstituted amino, C1-C4 alkoxy, C1-C4 thioether, carboxy, sulfonic or thiol;

• hydroxy or amino radicals, the amine possibly being substituted by a linear or branched dC hydrocarbon chain, which can form one or more carbon rings comprising from 5 to 6 members, and which can be saturated or unsaturated, the carbon atoms can be , independently of each others, substituted by one or more halogen atoms or hydroxy, amino radicals.

30. The composition as claimed in claim 27 in which the radicals R6, R7, R8, R9 and R15 are chosen from a hydrogen atom, a linear or branched dd hydrocarbon chain and which may be saturated or unsaturated, the carbon atoms may be , independently of one another, substituted by one or more halogen atoms or hydroxy, amino radicals.

31. A composition according to claim 26 in which W1 is a pyrazolo- [1,5-a] -pyrimidine radical in which R7 and R9 are chosen from a hydrogen atom, a linear or branched dC ₆ alkyl radical; a C _r C ₆ monohydroxyalkyl radical; a C ₂ -C ₆ polyhydroxyalkyl radical; an aminoalkyl radical -C ₆ aminoalkyl -C ₆ whose amine is mono- or disubstituted with an alkyl (CrC ₆₎ alkyl (Ci-C ₆₎ alkoxycarbonyl; a hydroxy or amino radical, the amino possibly being substituted with a hydrocarbon chain C1 _0-C linear or branched, which can form one or more carbon rings having 5 to 6 ring members, and which may be saturated or unsaturated, the carbon atoms may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino radicals; R6 and R8 are chosen from a hydrogen atom, a linear or branched dC ₆ alkyl radical; a monohydroxyalkyl radical at dC ₆ ; a C ₂ -C ₆ polyhydroxyalkyl radical; an aminoalkyl radical -C ₆ aminoalkyl radical -C ₆ whose amine is mono- or disubstituted with an alkyl (dC ₆₎ alkyl (dC ₆₎ alkoxycarbonyl.

32. A composition according to claim 31 in which R7 and R9 are chosen from a hydrogen atom; a linear or branched C _r C ₄ alkyl radical; a CC monohydroxyalkyl radical; a C ₂ -C ₄ polyhydroxyalkyl radical; a dC aminoalkyl radical, a CrC ₄ aminoalkyl radical in which the amine is mono- or disubstituted by an alkyl radical (CrC ₂ ); a hydroxy or amino radical, the amino being able to be substituted by a linear or branched CC hydrocarbon chain, the carbon atoms can be, independently of one another, substituted by one or more hydroxy, amino, and R6 and R8 radicals are chosen from a hydrogen atom, a linear or branched dd alkyl radical; a C _r C ₄ monohydroxyalkyl radical; a C ₂ -C polyhydroxyalkyl radical; a dd aminoalkyl radical, a CC ₄ aminoalkyl radical in which the amine is mono- or disubstituted by an alkyl radical (CC ₂ ); a C 1 -C ₂ alkoxy radical.

33. Composition according to claim 32 in which R6, R7, R8 and R9 are chosen from a hydrogen atom; a C1-C4 alkyl radical; an amino radical; a mono or di C1-C4 alkylamino radical; a C1-C4 hydroxyalkyl radical; a dC ₂ alkoxy radical.

34. Composition according to any one of claims 1 to 33 in which the compound of formula (I) is a cationic compound substituted with at least one onium radical Z.

35. Composition according to claim 34 in which at least one of the radicals Ri and R ₂ is an onium radical Z.

36. Composition according to claim 35, in which Ri and R ₂ form a cycle of formula (II) in which R 'is an onium radical Z.

37. The composition of claim 36 in which Y is NR ' _Θ RV-

38. Composition according to any one of the preceding claims, in which the compound of formula (I) represents

in which R1, R2, R6 are as defined above.

39. Composition according to any one of claims 1 to 38 in which the compound of formula (I) is chosen from

40. Composition according to any one of claims 1 to 39 in which the amount of dye of formula (I) is between 0.01 and 10% by weight

41. Composition according to any one of claims 1 to 40 further comprising an oxidation base chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, and their salts addition with an acid.

42. A composition according to claim 41 in which the oxidation base or bases are present in an amount between 0.001 and 10%.

43. Composition according to any one of claims 1 to 42 comprising at least one coupler chosen from metaphenylenediamines, meta-aminophenols, metadiphenols, naphthalene couplers and heterocyclic couplers and their addition salt with an acid.

44. Composition according to any one of claims 1 to 43 further comprising an oxidizing agent.

45. Direct dye of formula (I) as defined in any one of claims 1 to 44.

46. Process for coloring keratin fibers which comprises applying the composition according to any one of claims 1 to 44 for a time sufficient to obtain the desired coloring.