FR2845387A1 - NEW HETEROAROMATIC TRINOCAL BLACK DIRECT COLORANTS - Google Patents

Abstract

The subject of the invention is novel hetero-aromatic tri-ring direct dyes, dye compositions containing these dyes and the process for dyeing keratin fibers using them. In particular, the subject of the invention is hetero-aromatic tri-ring direct dyes comprising a pyridine nucleus. These new dyes make it possible to obtain black shades which exhibit good tenacity and which exhibit good stability in dyeing compositions.

Description

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NOVEL DIRECT BLACK COLORANTS AT TRI-CORE
HETEROAROMATIC
The subject of the invention is new heteroaromatic tri-nucleus direct dyes, the dye compositions containing these dyes and the process for dyeing the keratin fibers using them. In particular, the subject of the invention is heteroaromatic tri-ring direct dyes comprising a pyridine ring.

 It is known to dye keratinous fibers, and in particular human hair, with dyeing compositions containing direct dyes. The standard dyes which are used are in particular nitro-benzene, anthraquinone, nitropyridine, azo, cationic azo, xanthene, acridine-azine, nitro-benzene nitro-benzene dyes or natural dyes.

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

 The resulting dyes are particularly chromatic colorations which are however temporary or semi-permanent because the nature of the interactions which bind the direct dyes to the keratinous fiber, and their desorption of the surface and / or core of the fiber are responsible for their low dyeing power and their poor resistance to washes or perspiration. These direct dyes are also generally sensitive to light because of the low resistance of the chromophore to photochemical attacks and lead in time to a fading of the hair coloring.

 The patent application EP 1166754 describes a dyeing composition which comprises cationic azino phenazinium direct dyes. Due to the presence of the azo function, these compounds when 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

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 light-stable, and resistant to bad weather, washes and perspiration, and in addition stable in a conventional coloring medium.

 In particular, the object of the present invention is to provide black direct dyes for dyeing hair in shades ranging from gray to black, without the need to thin the hair beforehand, as well as black direct dyes that while fading do not change color, for example by turning after the action of a wash, light or sweat to shades of blue, purple, red, green, etc. Finally, these black direct dyes must allow to preserve after several applications the shade obtained during the first application.

dans laquelle # R3 représente : - un atome d'hydrogène,

- une chaîne hydrocarbonée en C1-C10 linéaire ou ramifiée, pouvant former un ou plusieurs cycles carbonés comportant de 4 à 8 chaînons, et pouvant être saturées ou insaturées, dont un ou plusieurs atomes de carbone de la chaîne carbonée peuvent être remplacés par un atome d'oxygène, d'azote ou de soufre ou par un groupement SO2, et dont les atomes de carbone ~peuvent être, indépendamment les uns des autres, substitués par un ou plusieurs atomes d'halogènes ou radicaux hydroxy, amino, carboxy, sulfonique ou thiol ; R3 ne comportant pas de liaison peroxyde, ni de radicaux diazo ou nitroso,

- NR',R'2, R'1 et R'2 étant tels que définis pour R, et R2 # R1 et R2 représentent indépendamment l'un de l'autre : These objects are achieved with the present invention which relates to a dye composition comprising, in a suitable medium, a compound of formula (I) below:

in which # R3 represents: - a hydrogen atom,

a linear or branched C1-C10 hydrocarbon-based chain capable of forming one or more carbon-containing rings containing from 4 to 8 members, and which may be saturated or unsaturated, one or more carbon atoms of which may be replaced by an atom oxygen, nitrogen or sulfur or a group SO2, and whose carbon atoms ~ may be, independently of each other, substituted by one or more halogen atoms or hydroxyl, amino, carboxy, sulfonic radicals or thiol; R3 having no peroxide bond, or diazo or nitroso radicals,

- NR ', R'2, R'1 and R'2 being as defined for R, and R2 # R1 and R2 represent independently of one another:

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- une chaîne hydrocarbonée en C,-C,o linéaire ou ramifiée, pouvant former un ou plusieurs cycles carbonés comportant de 4 à 8 chaînons, et pouvant être saturées ou insaturées, dont un ou plusieurs atomes de carbone de la chaîne carbonée peuvent être remplacés par un atome d'oxygène, d'azote ou de soufre ou par un groupement SO2, et dont les atomes de carbone peuvent être, indépendamment les uns des autres, substitués par un ou plusieurs atomes d'halogènes ou radicaux hydroxy, amino, carboxy, sulfonique ou thiol; R, et R2 ne comportant pas de liaison peroxyde, ni de radicaux diazo ou nitroso, et R1 et R2 n'étant pas directement reliés à l'atome d'azote par un atome d'oxygène, de soufre, d'azote ou 8 2' - un radical onium Z, ou # R1 et R2 forment ensemble avec l'atome d'azote auquel ils sont rattachés un cycle de formule (II) :

dans laquelle : # R' représente : - un atome d'hydrogène - un atome d'halogène tel que fluor, chlore, brome ; - un radical alkyle en C,-C4 éventuellement substitué par un ou plusieurs radicaux choisis parmi les radicaux hydroxy, carboxy, alcoxycarbonyle en

C,-C4, alkyl(C1-C4)amido (alkyl(C,-C4)CONH-), alkyl(Cl-C4)carbamoyle (alkyl(C,-C4) NHCO-), alkyl(Cl-C4)SUIfonyle (alkyl(Cl-C4) S02-), alcoxy en Cl-C4, alkyl(CrC4)sulfonamido ( alkyl(C,-C4)S02NH-), alkyl(Cr C4)sulfamoyle (alkyl(Cl-C4) NH S02-), onium Z - NR'3R'4 ; - un radical carboxy ; - un radical alcoxycarbonyle en C1-C4 ; - a hydrogen atom

a linear or branched C, -C 0 hydrocarbon-based chain capable of forming one or more carbon rings containing from 4 to 8 ring members, and which may be saturated or unsaturated, one or more carbon atoms of the carbon chain may be replaced; by an oxygen, nitrogen or sulfur atom or by a group SO2, and the carbon atoms of which may be, independently of one another, substituted with one or more halogen atoms or with hydroxyl, amino or carboxy radicals sulfonic or thiol; R 2 and R 2 do not have a peroxide bond, or diazo or nitroso radicals, and R 1 and R 2 are not directly attached to the nitrogen atom by an oxygen, sulfur, nitrogen or carbon atom. 2 '- an onium radical Z, or # R1 and R2 together with the nitrogen atom to which they are attached form a ring of formula (II):

wherein: # R 'represents: - a hydrogen atom - a halogen atom such as fluorine, chlorine, bromine; a C 1 -C 4 alkyl radical optionally substituted by one or more radicals chosen from hydroxyl, carboxy and alkoxycarbonyl radicals,

C 1 -C 4 alkyl (C 1 -C 4) amido (C 1 -C 4 alkyl) CONH-), alkyl (C 1 -C 4) carbamoyl (C 1 -C 4 alkyl) NHCO-), alkyl (C 1 -C 4) SUIfonyl (C1-C4alkyl) SO2-), C1-C4alkoxy, alkyl (CrC4) sulfonamido (C1-C4alkyl) SO2NH-), alkyl (Cr4C) sulfamoyl (C1-C4alkyl) NHSO2- ), onium Z - NR'3R'4; a carboxy radical; a C1-C4 alkoxycarbonyl radical;

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- un radical alkyl(C,-C4)amido (alkyl(CrC4)CONH-); - un radical alkyl(C1-C4)sulfonyle (alkyIS02-) - un radical alkylsulfonamido (alkyl(C1-C4) SO2NH -), - un radical hydroxy ; - un radical alcoxy en C1-C4 ; - un radical hydroxyalcoxy en C2-C4 ; - un radical alkyl(C1-C4)carbamoyle (alkyl(C1-C4) NHCO-);

- alkyl(C1-C4)sulfamoyle (alkyl(C,-C4)-NH-SOZ-); - un radical thioéther en C1-C4 ; - un radical sulfonique (S03H) pouvant être sous forme de sel - un radical onium Z, R'3 et R'4, identiques ou différents, représentent, un atome d'hydrogène ; un radical alkyle en C1-C4 éventuellement substitué par un ou plusieurs radicaux

choisis parmi les radicaux hydroxy, alcoxy en C,-C4, amino, mono ou di alkylamino, alkyl(Cl-C4)CO-, alkyl(Cl-C4) NHCO-, alkyl(C,-CI)SO2 -, - n est un nombre entier compris entre 1 et 8, - m est un nombre entier compris entre 0 et 2, - Y représente un atome d'oxygène, un radical CR', un radical NR'5 ou un radical NR'6R'7 avec
R'5 qui représente un atome d'hydrogène ; une chaîne hydrocarbonée en C1-C10 linéaire ou ramifiée, pouvant être saturées ou insaturées, dont un ou plusieurs atomes de carbone de la chaîne carbonée peuvent être remplacés par un atome d'oxygène, d'azote ou de soufre ou par un groupement SO2, et dont les atomes de carbone peuvent être, indépendamment les uns des autres, substitués par un ou plusieurs atomes d'halogènes ou radicaux hydroxy, amino, carboxy, sulfonique ou thiol ; R'5 ne comportant pas de liaison peroxyde, ni de radicaux diazo ou nitroso, et R'5 n'étant pas directement reliés à l'atome d'azote par un atome d'oxygène, de soufre ou d'azote,
R'6 et R'7 qui représentent indépendamment une chaîne hydrocarbonée en C1-C10 linéaire ou ramifiée, pouvant être saturées ou insaturées, dont un ou plusieurs atomes de carbone de la chaîne carbonée

a (C 1 -C 4) alkyl radical amido (C 1 -C 4 alkyl) CONH-); a (C1-C4) alkylsulphonyl radical (alkylsoxy) - an alkylsulphonamido radical (C1-C4 alkyl) SO2NH-), a hydroxyl radical; a C1-C4 alkoxy radical; a C2-C4 hydroxyalkoxy radical; a (C1-C4) alkylcarbamoyl (C1-C4alkyl) NHCO-) radical;

(C1-C4) alkylsulfamoyl (C1-C4 alkyl) -NH-SO2-); a C1-C4 thioether radical; a sulphonic radical (SO 3 H) which may be in salt form; an onium radical Z, R '3 and R' 4, which may be identical or different, represent a hydrogen atom; a C1-C4 alkyl radical optionally substituted with one or more radicals

selected from hydroxyl, C 1 -C 4 alkoxy, amino, mono or di alkylamino, C 1 -C 4 alkyl, CO-, C 1 -C 4 alkyl NHCO-, C 1 -C 4 alkyl, SO 2 -, - n is an integer between 1 and 8, - m is an integer between 0 and 2, - Y represents an oxygen atom, a radical CR ', a radical NR'5 or a radical NR'6R'7 with
R'5 which represents a hydrogen atom; a linear or branched C1-C10 hydrocarbon-based chain which may be saturated or unsaturated, of which one or more carbon atoms of the carbon chain may be replaced by an oxygen, nitrogen or sulfur atom or by an SO 2 group, and wherein the carbon atoms can be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, carboxy, sulfonic or thiol radicals; R'5 having no peroxide bond, or diazo or nitroso radicals, and R'5 not being directly connected to the nitrogen atom by an oxygen atom, sulfur or nitrogen,
R'6 and R'7 which independently represent a linear or branched C1-C10 hydrocarbon chain, which may be saturated or unsaturated, including one or more carbon atoms of the carbon chain

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radicaux diazo ou nitroso, et R',n'étant pas directement reliés à l'atome d'azote par un atome d'oxygène, de soufre ou d'azote, # W, représente un radical hétérocycle aromatique choisi parmi les radicaux suivants

Rs Rs Rs r N'>--Z1 NZ N/ N 1 N N R-T 11 (R1) i"'i.62 (RII) ' R9 Ra (RII I) (RIV) ?" Rs 6 R10 R6 * ""rr'' Ra R R6t(* j! J. R I / (,1 'q m' R9 N 1 NiRt R 7 ,.)lN/ R" 1 12 R 7 Ra N RII R7 Ra b N R'1 "N" Rn (R Re R" R8 N R, N, V) (RVI) (RVII) (RVIII) # Z1 et 23, représentent indépendamment les uns des autres un radical hydroxy ou NR11R12 # Z2, Z4, Z6 représentent indépendamment les uns des autres un atome d'azote, un radical CR12 ou NR11 sous réserve qu'au moins l'un d'entre eux représente un radical CR12 et qu'il ne puisse y avoir plus de 3 atomes d'azote contigus, # Z8 représente un atome d'azote, un radical CR15,

#R6, R7e RB, R9, Rloe Ru, R,2, représentent indépendamment les uns des autres - un atome d'hydrogène, - une chaîne hydrocarbonée en C1-C10 linéaire ou ramifiée, pouvant former un ou plusieurs cycles carbonés comportant de 4 à 8 chaînons, et pouvant être saturées ou insaturées, dont un ou plusieurs atomes de carbone de la chaîne carbonée peuvent être remplacés par un atome d'oxygène, d'azote ou de soufre ou par un groupement SO2, et dont les atomes de carbone peuvent être, indépendamment les uns des autres, substitués par un ou may be replaced by an oxygen, nitrogen or sulfur atom or by a group SO2, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxyl radicals, amino, carboxy, sulfonic or thiol; R'5 having no peroxide bond, or

radicals diazo or nitroso, and R ', not being directly connected to the nitrogen atom by an oxygen, sulfur or nitrogen atom, # W, represents an aromatic heterocycle radical chosen from the following radicals

Rs Rs Rs r N '> - Z1 NZ N / N 1 NN RT 11 (R1) i "' i.62 (RII) 'R9 Ra (RII I) (RIV)?" Rs 6 R 10 R 6 R 1 R 1 R 1 R 1 R 1 R 1 R 7 R 1 R 7 R 1 R 7 R 1 R 7 N R'1 "N" Rn (R6RR8NR, N, V) (RVI) (RVII) (RVIII) ## STR2 ## Z1 and R3 represent, independently of one another, a hydroxy radical or NR11R12 # Z2, Z4, Z6 represent, independently of one another, a nitrogen atom or a CR12 or NR11 radical provided that at least one of them represents a CR12 radical and that there can not be more than 3 nitrogen atoms contiguous, # Z8 represents a nitrogen atom, a CR15 radical,

# R6, R7e RB, R9, R10 R10, R, 2, independently of one another represent a hydrogen atom, a linear or branched C1-C10 hydrocarbon chain, which can form one or more carbon-containing rings containing 4 8-membered, and which may be saturated or unsaturated, one or more carbon atoms of the carbon chain may be replaced by an oxygen atom, nitrogen or sulfur or by a group SO2, and whose carbon atoms may be, independently of one another, substituted by one or

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 several halogen atoms or hydroxyl, amino, carboxy, sulfonic or thiol radicals; the radicals R6 to R12 having no peroxide bond, or diazo or nitroso radicals and the radical R11, not being connected directly 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 the formula (1).

When in the definition of Z2, Z4, Z6 which independently of one another represent a nitrogen atom, a radical CR12 or NR11, it is specified that there can not be more than 3 contiguous nitrogen atoms, it 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 keratinous fibers, in particular human keratinous fibers.

In the context of the present invention, the compounds of formula (I) 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 remainder of the description, only one of these tautomeric forms will be indicated.

 In formula (1), R 3 is preferably chosen from a hydrogen atom or a C 1 -C 4 alkyl radical optionally substituted with one or more radicals chosen from hydroxyl, C 1 -C 2 alkoxy and amino radicals (mono ) - or

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 (di) C1-C2alkylamino, 2-hydroxyethyl, 2-aminoethyl. By way of example, R 3 represents a hydrogen atom, a methyl, ethyl or 2-hydroxyethyl radical, even more preferable: a hydrogen atom or a methyl radical.

 The radicals R 1 and R 2 are preferably chosen from hydrogen, a C 1 -C 6 alkyl radical optionally substituted by a hydroxy, alkoxy, amine, (mono-) or (di) C 1 -C 4 alkylamino. By way of example R 1 and R 2 are selected from hydrogen, methyl, ethyl, hydroxyethyl, propyl, and the like.

méthyl homopipérazine, la N 3-hydroxyéthylhomopipérazine et leurs sels d'addition. De préférence, R, et R2 forment avec l'atome d'azote auquels ils sont rattachés un cycle ' pyrrolidinique éventuellement substitué. When R 1 and R 2 form, with the nitrogen atom to which they are attached, a 5- to 8-membered heterocycle, this heterocycle is preferably chosen from pyrrolidine, piperidine, homopiperidine, piperazine, homopiperazine and diazepane heterocycles. By way of example, the heterocycle is chosen from pyrrolidine, 3-hydroxypyrrolidine, 3-aminopyrrolidine, 3-N, N-dimethylaminopyrrolidine, 3-acetamidopyrrolidine, 3- (methylsulfonylamino) -pyrrolidine, proline, 3-hydroxyproline, piperidine, hydroxypiperidine, homopiperidine, diazepane, N-

methyl homopiperazine, N 3-hydroxyethylhomopiperazine and their addition salts. Preferably, R 1 and R 2 together with the nitrogen atom to which they are attached form 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 radical Z, that is to say a cationic radical of the quaternary ammonium type.

dans laquelle # D est une liaison covalente ou une chaîne alkylène en C1-C14, linéaire ou ramifiée pouvant contenir un ou plusieurs hétéroatomes choisis parmi l'oxygène, le soufre ou l'azote, SO2, une ou plusieurs fonctions cétone, la chaîne pouvant The onium radical Z may be represented by the following formula (III)

in which # D is a covalent bond or a linear or branched C1-C14 alkylene chain which may contain one or more heteroatoms chosen from oxygen, sulfur or nitrogen, SO2, one or more ketone functions, the chain being able to

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#R,6, R17 et R,8, pris séparément, représentent un radical alkyle en C1-C15 ; un radical monohydroxyalkyle en Ci-Ce ; un radical polyhydroxyalkyle en C2-C6 ; un radical alcoxy(Cl-C,)alkyle en Ci-Ce ; un radical aryle ; un radical benzyle ; un radical amidoalkyle en Ci-Ce ; un radical trialkyl(Cl-C,)silanealkyle en Ci-Ce ; un radical aminoalkyle en Ci-Ce ; un radical aminoalkyle en Ci-Ce dont l'amine est mono- ou di-substituée par un radical alkyle en C,-C4, alkyl(C,-Cs)carbonyle, amido ou alkyl(C1-C6)sulfonyle ; #R16, R17 et Ris ensemble, deux à deux, forment, avec l'atome d'azote auxquels ils sont rattachés, un cycle saturé carboné à 4,5, 6 ou 7 chaînons pouvant contenir un ou plusieurs hétéroatomes, le cycle cationique pouvant être substitué par un atome d'halogène, un radical hydroxyle, un radical alkyle en Ci-Ce, un radical monohydroxyalkyle en Ci-Ce, un radical polyhydroxyalkyle en C2-C6, un radical

alcoxy en Ci-Ce, un radical trialkyl(Cl-C,)silanealkyle en Ci-Ce, un radical amido, un radical carboxyle, un radical alkyl(C1-Cs)carbonyle, un radical thio, un radical thioalkyle en Ci-Ce, un radical alkyl(C1-Cs)thio, un radical amino, un radical amino mono- ou di-substitué par un radical alkyl(C1-Cs), alkyl(C1-Cs)carbonyle, amido ou alkyl(C1-Cs)sulfonyle; # R19 représente un radical alkyle en Ci-Ce ; un radical monohydroxyalkyle en C1-
C6 ; un radical polyhydroxyalkyle en C2-C6 ; un radical aryle ; un radical benzyle ; un radical aminoalkyle en Ci-Ce ; un radical aminoalkyle en Ci-Ce dont l'amine

est mono- ou di-subsitué par un radical alkyl(CrC6), alkyl(C1-Cs)carbonyle, amido ou alkyl(C,-Cs)sulfonyle ; un radical carboxyalkyle en Ci-Ce ; un radical carbamylalkyle en Ci-Ce ; un radical trifluoroalkyle en Ci-Ce ; un radical trialkyl(C1-Cs)silanealkyle en Ci-Ce ; un radical sulfonamidoalkyle en C,-C6 ; un radical alkyl(C1-Cs)carboxyalkyle en Ci-Ce ; un radical alkyl(C1-Cs)sulfinylalkyle en Ci-Ce ; un radical alkyl(C1-Cs)sulfonylalkyle en Ci-Ce ; un radical atky)(CiC6)carbonylalkyle en Ci-Ce ; un radical N-alkyl(Cl-C,)carbamylaikyle en Ci-Ce ; un radical N-alkyl(C,-C6)sulfonamidoalkyle en Ci-Ce ; # x est 0 ou 1, be substituted with one or more hydroxyl, C1-C6 alkoxy or amino, (mono) - or (di) C1-C4 alkylamino radicals

# R, 6, R17 and R, 8, taken separately, represent a C1-C15 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a C1-C6 alkoxy (C1-C4) alkyl radical; an aryl radical; a benzyl radical; a C1-C6 amidoalkyl radical; a C1-C6 trialkyl (C1-C4) silanalkyl radical; a C1-C6 aminoalkyl radical; a C 1 -C 6 aminoalkyl radical in which the amine is mono- or di-substituted with a C 1 -C 4 alkyl, C 1 -C 6 alkylcarbonyl, amido or (C 1 -C 6) alkylsulphonyl radical; # R16, R17 and Ris together, in pairs, form, with the nitrogen atom to which they are attached, a 4,5, 6 or 7-membered carbon saturated ring which may contain one or more heteroatoms, the cationic cycle being able to 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 2 -C 6 polyhydroxyalkyl radical, a radical

C1-C6 alkoxy, C1-C6 trialkyl (C1-C4) silanalkyl radical, amido radical, carboxyl radical, (C1-C8) alkylcarbonyl radical, thio radical, C1-C6 thioalkyl radical , a (C1-Cs) alkyl radical thio, an amino radical, an amino radical mono- or di-substituted with a (C1-Cs) alkyl radical, (C1-Cs) alkyl carbonyl, amido or (C1-Cs) alkyl radicals sulfonyl; # R19 represents a C1-C6 alkyl radical; a C1-C monohydroxyalkyl radical
C6; a C2-C6 polyhydroxyalkyl radical; an aryl radical; a benzyl radical; a C1-C6 aminoalkyl radical; a C1-C6 aminoalkyl radical including amine

is mono- or di-substituted with alkyl (CrC6), (C1-C5) alkylcarbonyl, amido or (C1-C8) alkylsulfonyl; a C1-C6 carboxyalkyl radical; a C1-C6 carbamylalkyl radical; a C1-C6 trifluoroalkyl radical; a C1-C6 trialkyl (C1-C8) silanalkyl radical; a C 1 -C 6 sulfonamidoalkyl radical; a C1-C6 alkyl (C1-Cs) carboxyalkyl radical; a C1-C6 alkyl (C1-Cs) sulfinylalkyl radical; a C1-C6 alkyl (C1-Cs) sulfonylalkyl radical; an (C1-C6) carbonyl (C1-C6) alkyl (C1-C6) alkyl radical; a C 1 -C 6 N-alkyl (Cl-C 4) carbamylalkyl radical; a C 1 -C 6 N-alkyl (C 1 -C 6) sulfonamidoalkyl radical; # x is 0 or 1,

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 when x = 0, then the linking arm D is attached to the nitrogen atom bearing the radicals R16 to R18, - when x = 1, then two of the radicals R16 to R18 form together with the nitrogen atom to which they are attached a 5- or 7-membered saturated ring and the linker D is connected to a carbon atom of the saturated ring; # T is a counter ion.

radical alcoxy(C,-C6)alkyle en Ci-C4, un radical amidoalkyle en Ci-Ce, un radical trialkyl(C,-C6)silanealkyle en Ci-Ce. According to a first variant of formula (III) when x is equal to 0, and R 16, R 17 and R 18 separately are preferably chosen from a C 1 -C 6 alkyl radical, a C 1 -C 4 monohydroxyalkyl radical or a C 2 polyhydroxyalkyl radical. -C4, a

(C1-C6) alkoxy (C1-C4) alkyl, C1-C6 amidoalkyl, (C1-C6) trialkyl) (C1-C6) silanalkyl radical.

C,-C6 ; un radical monohydroxyalkyle en Ci-Ce ; un radical polyhydroxyalkyle en C2-C6; un radical aminoalkyle en Ci-Ce, un radical aminoalkyle mono- ou di-substitué par un radical alkyl(Cl-C6), alkyl(C1-C6)carbonyle, amido ou alkyCVCsulfonyle ; un radical carbamylalkyle en Ci-Ce ; un radical trialkyl(C1-C6)silanealkyle en Ci-Ce ; un radical alkyl(C1-C6)carboxyalkyle en Ci-Ce ; un radical alkyl(C1-Ca)carbonylalkyle en Ci-Ce ; un radical N-alkyl(CrC6)carbamylalkyle en Ci-Ce. According to a second variant of formula (III), when x is equal to 0 and R16 together with R17 form an azetidine, pyrrolidine, piperidine, homopiperidine, piperazine, homopiperazine or morpholine ring, R 18 is then chosen from an alkyl radical.

C, -C6; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a C 1 -C 6 aminoalkyl radical, an aminoalkyl radical mono- or di-substituted with a (C 1 -C 6) alkyl, (C 1 -C 6) alkylcarbonyl, amido or alkylsulfonyl radical; a C1-C6 carbamylalkyl radical; a C1-C6 trialkyl (C1-C6) silanalkyl radical; a C1-C6 alkyl (C1-C6) carboxyalkyl radical; a C1-C6 alkyl (C1-Ca) carbonylalkyl radical; a C 1 -C 6 N-alkyl (CrC 6) carbamylalkyl radical.

Ci-Ce dont l'amine est mono ou disubstituée par un radical alkyl(Cl-C6), alkyl(Cr C6)carbonyle, amido ou alkyl-CgJsulfonyle ; un radical carbamylalkyle en Ci-Ce ; un radical trialkyl(C1-Ca)silanealkyle en Ci-Ce ; un radical alkyl(C1-Ca)carboxyalkyle en ClC6 ; un alkyl(C1-C6)carbonylalkyle en Ci-Ce ; un radical N-alkyl(CrC6)carbamylalkyle en Ci-Ce ; R16 avec R17 ensemble forment un cycle azétidine, pyrrolidine, pipéridine, homopipéridine, pipérazine, homopipérazine, morpholine, et R18 est alors choisi parmi un radical alkyle en Ci-Ce ; un radical monohydroxyalkyle en Ci-Ce ; un radical polyhydroxyalkyle en C2-C6; un radical aminoalkyle en Ci-Ce, un radical aminoalkyle en In formula (III), when x is 1, R19 is preferably selected from C1-C6 alkyl, C1-C6 monohydroxyalkyl; a C2-C6 polyhydroxyalkyl radical; a C 1 -C 6 aminoalkyl radical, an aminoalkyl radical

Ci-Ce whose amine is mono or disubstituted by a (C1-C6) alkyl, (C1-C6) alkylcarbonyl, amido or alkyl-C6 alkylsulfonyl radical; a C1-C6 carbamylalkyl radical; a C1-C6 trialkyl (C1-Ca) silanalkyl radical; a C1 -C6 alkyl (C1-Ca) carboxyalkyl radical; a C1-C6 alkyl (C1-C6) carbonylalkyl; a C 1 -C 6 N-alkyl (CrC 6) carbamylalkyl radical; R16 with R17 together form an azetidine, pyrrolidine, piperidine, homopiperidine, piperazine, homopiperazine, morpholine ring, and R18 is then selected from C1-C6 alkyl; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a C 1 -C 6 aminoalkyl radical, an aminoalkyl radical

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Ci-Ce dont l'amine est mono ou disubstituée par un radical alkyl(C,-C6), alkyl(Cr C6)carbonyle, amido ou alkyl(CrC6)sulfonyle ; un radical carbamylalkyle en Ci-Ce ; un radical trialkyl(C,-C6)silanealkyle en Ci-Ce ; un radical alkyl(C1-C6)carboxyalkyle en CiC6 ; un radical alkyl(C1-C6)carbonylalkyle en Ci-Ce ; un radical N-alkyl(C,- C6)carbamylalkyle en Ci-Ce.

Ci-Ce whose amine is mono or disubstituted by a (C 1 -C 6) alkyl, (C 1 -C 6) alkylcarbonyl, amido or (C 1 -C 6) alkylsulphonyl radical; a C1-C6 carbamylalkyl radical; a (C1-C6) trialkyl (C1-C6) silanalkyl radical; a C1-C6 alkyl (C1-C6) carboxyalkyl radical; a C1-C6 alkyl (C1-C6) carbonylalkyl radical; a C 1 -C 6 N-alkyl (C 1 -C 6) carbamylalkyl radical.

 According to a preferred embodiment, x is 0 and R16 R17 and R18 are alkyl radicals.

 In formula (III), D is preferably a covalent bond or a C 1 -C 6 alkylene chain which may be substituted.

dans laquelle # D est tel que défini précédemment, # les sommets E, G, J, L, identiques ou différents, représentent un atome de carbone, d'oxygène, de soufre ou d'azote pour former un cycle pyrazolique, imidazolique, triazolique, oxazolique, isooxazolique, thiazolique, isothiazolique, # a est un nombre entier compris entre 0 et 3 inclus ; # b est un nombre entier compris entre 0 et 1 inclus ; # a+b est un nombre entier compris entre 2 et 4 # R, identiques ou différents, représentent un atome d'hydrogène, d'halogène, un radical hydroxyle, un radical alkyle en Ci-Ce, un radical monohydroxyalkyle en

Cl-C6, un radical polyhydroxyalkyle en C2-CS' un radical alcoxy en Ci-Ce, un radical tria)ky)(Ci-C6)si)anea)ky)e en C,-C6, un radical amido, un radical carboxyle, un radical alkylcarbonyle en Ci-Ce, un radical thio, un radical thioalkyle en Ci-Ce, un radical alkyl(C1-Cs)thio, un radical amino, un radical amino mono ou di substituée par un radical alkyl(C1-Cs), alkyl(C,-C6)carbonyle, amido, alkyl(Cl-C6)sulfonyle ; un radical monohydroxyalkyle en Ci-Ce ou un The onium radical Z can also be represented by the formula (IV)

in which # D is as defined previously, # the vertices E, G, J, L, identical or different, represent a carbon, oxygen, sulfur or nitrogen atom to form a pyrazole, imidazole, triazole ring , oxazolic, isooxazole, thiazolic, isothiazolic, # a is an integer from 0 to 3 inclusive; # b is an integer between 0 and 1 inclusive; # a + b is an integer between 2 and 4 # R, identical or different, represent a hydrogen atom, a halogen atom, a hydroxyl radical, a C 1 -C 6 alkyl radical or a monohydroxyalkyl radical;

C1-C6, a C2-C18 polyhydroxyalkyl radical, a C1-C6 alkoxy radical, a C3-C6 tria) ky) (C1-C6) alkoxy radical, an amido radical, a radical; carboxyl, a C 1 -C 6 alkylcarbonyl radical, a thio radical, a C 1 -C 6 thioalkyl radical, a (C 1 -C 6) alkyl radical, an amino radical, an amino radical mono or di substituted by an alkyl radical (C 1 -C 6), Cs), (C 1 -C 6) alkylcarbonyl, amido, (C 1 -C 6) alkylsulphonyl; a C1-C6 monohydroxyalkyl radical or a

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C2-C6 polyhydroxyalkyl radical; it being understood that the R radicals are borne by a carbon atom, a benzyl radical or a phenyl radical optionally substituted with one or more radicals chosen from methyl, hydroxy, amino and methoxy radicals; it being understood that the R radicals are not a carbon atom, # R20 represents a C1-C6 alkyl radical, a C1-C monohydroxyalkyl radical;
C6, a C2-C6 polyhydroxyalkyl radical, a (C1-C6) trialkyl (C1-C6) silanalkyl radical, a (C1-C6) alkoxy (C1-C6) alkyl radical, a C1-C6 carbamylalkyl radical;
C6, a C1-C6 alkyl (C1-C6) carboxyalkyl radical, a benzyl radical; it being understood that the R20 radical is carried by a nitrogen atom, # R19 is as defined above, # x is equal to 0 or 1 - when x = 0, the linking arm D is attached to the atom of Nitrogen, when x = 1, the linking 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 counter-ion.

 Preferably, the vertices E, G, J and L form an imidazole, pyrazole, oxazole, thiazole and triazole ring.

 According to a particular embodiment of formula (III), x is equal to 0 and D is a covalent bond or a C 1 -C 4 alkylene chain which may be substituted.

dans laquelle : # D, R, R19 sont tels que définis précédemment, # les sommets E, G, J, L et M identiques ou différents, représentent un atome de carbone ou d'azote et forment un cycle choisi parmi les cycles pyridiniques, pyrimidiniques, pyraziniques, triaziniques et pyridaziniques, The onium radical Z can be represented by the formula (V)

in which: # D, R, R19 are as defined above, # the vertices E, G, J, L and M identical or different, represent a carbon or nitrogen atom and form a ring selected from pyridine rings, pyrimidine, pyrazine, triazine and pyridazine

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 # d is an integer between 3 and 5 inclusive; # x is equal to 0 or 1 - when x = 0, the linking arm D is attached to the nitrogen atom, - when x = 1, the linking 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 ring form a ring chosen from pyridine, pyrimidine, pyridazine and pyrazine rings.

un radical polyhydroxyalkyle en C2-C6, un radical alcoxy en Ci-Ce, un radical trialkyl(Cr C6)silanealkyle en Ci-Ce, un radical amido, un radical alkylcarbonyle en Ci-Ce, un

radical amino, un radical amino mono- ou di-substitué par un radical alkyl(C1-C6), alkyl(C,-C6)carbonyle, amido ou alkyl(Cl-C,)sulfonyle ; un radical monohydroxyalkyle en Ci-Ce ou un radical polyhydroxyalkyle en C2-C6; étant entendu que les radicaux R sont portés par un atome de carbone. According to a variant of the formula (V), x is equal to 0 and R is chosen from a hydroxyl radical, a C 1 -C 6 alkyl radical and a C 1 -C 6 monohydroxyalkyl radical;

a C2-C6 polyhydroxyalkyl radical, a C1-C6 alkoxy radical, a C1-C6 trialkyl (Cr C6) silanalkyl radical, an amido radical, a C1-C6 alkylcarbonyl radical, a

amino radical, an amino radical mono- or di-substituted with a (C1-C6) alkyl, (C1-C6) alkylcarbonyl, amido or (C1-C4) alkylsulphonyl radical; a C1-C6 monohydroxyalkyl radical or a C2-C6 polyhydroxyalkyl radical; it being understood that the R radicals are borne by a carbon atom.

Ci-Ce dont l'amine est mono- ou di- substituée par un radical alkyl(C,-C6), alkyl(C,C6)carbonyle, un radical amido ou un radical alkyl(Ci-C6)sulfonyle ; un radical carbamylalkyle en Ci-Ce ; un radical trialkyl(C1-C6)silanealkyle en Ci-Ce ; un radical alkyl(C1-C6)carbonylalkyle en Ci-Ce ; un radical N-alkyl(C1-C6)carbamylalkyle en Ci-Ce ; R est choisi parmi un radical hydroxyle, un radical alkyle en Ci-Ce, un radical monohydroxyalkyle en Ci-Ce, un radical polyhydroxyalkyle en C2-C6, un radical alcoxy

en Ci-Ce, un radical trialkyl(Cl-C6)silanealkyle en Ci-Ce, un radical amido, un radical alkylcarbonyle en Ci-Ce, un radical amino, un radical amino mono- ou di- substitué par un radical alkyl(Cl-C6), alkyl(C1-C6)carbonyle, amido ou alkyl(C1-C6)sulfonyle. According to another variant of the formula (V), x is equal to 1, R19 is chosen from a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a C 1 -C 6 aminoalkyl radical, an aminoalkyl radical

Wherein the amine is mono- or di-substituted with (C1-C6) alkyl, (C1-C6) alkylcarbonyl, amido or (C1-C6) alkylsulphonyl; a C1-C6 carbamylalkyl radical; a C1-C6 trialkyl (C1-C6) silanalkyl radical; a C1-C6 alkyl (C1-C6) carbonylalkyl radical; a C 1 -C 6 N-alkyl (C 1 -C 6) carbamylalkyl radical; R is selected from a hydroxyl radical, a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, an alkoxy radical;

Ci-Ce, a (C1-C6) trialkyl (C1-C6) silanalkyl radical, an amido radical, a C1-C6 alkylcarbonyl radical, an amino radical, an amino radical mono- or disubstituted by an alkyl radical (Cl -C6), (C1-C6) alkylcarbonyl, amido or (C1-C6) alkylsulphonyl.

 In a preferred embodiment, R 19 is a C 1 -C 4 alkyl radical which may be substituted and R 1 is a hydrogen radical, a C 1 -C 4 alkyl radical may be substituted.

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When the compound of formula (I) is a cationic compound substituted by a radical Z, preferably at least one of the radicals R 1 and R 2 represents an onium radical Z. According to a particular embodiment, R 1 and R 2 form the ring of formula (II) in which R 'is an onium radical Z, preferably with Y equal to NR'6R'7-
In the formula (1), W 1 represents in particular the radicals 5aminopyrazole, 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.

 According to a particular embodiment, W 1 is chosen from the 5-aminopyrazole, 5-hydroxypyrazole radicals of formula (R 1).

 In this case, W1 is preferably chosen from the 5aminopyrazole and 5-hydroxypyrazole radicals in which R6 and R11, which are identical or different, are chosen from a hydrogen atom; a linear or branched C1-C10 hydrocarbon-based chain capable of forming one or more carbon-containing rings containing from 4 to 8 members, and which may be saturated or unsaturated, one or more carbon atoms of which may be replaced by a carbon atom; oxygen, nitrogen or sulfur or by a group SO2, and whose carbon atoms can be, independently of one another, substituted by one or more halogen atoms or hydroxyl, amino, carboxy, sulfonic or thiol radicals ; the radicals R6 to R, 2 having no peroxide bond, or diazo or nitroso radicals and the radical R11, not being directly connected to the nitrogen atom by an oxygen, sulfur or phosphorus atom; nitrogen.

 According to a particularly preferred embodiment of (R1), R6 and R11 are independently chosen from a hydrogen atom or a linear or branched C1-C4 hydrocarbon-based chain, which can form one or more carbon rings containing 6 members, and which can be saturated or unsaturated, the carbon atoms may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino radicals.

 According to another particular embodiment, W 1 represents

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R6, R7, R8, R9 et Z8 étant tels que définis précédemment.

R6, R7, R8, R9 and Z8 being as defined above.

 In this particular case, W1 may be a pyrazolo [1,5-b] pyridine radical in which R6, R7, R8, R9 and R15, identical or different, are chosen from # a hydrogen atom, # a hydrocarbon chain linear or branched C1-C10, which can form one or more carbon rings containing 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 atom, nitrogen or sulfur or by a group SO2, and whose carbon atoms can be, independently of one another, substituted by one or more halogen atoms or hydroxyl, amino, carboxy, sulfonic or thiol radicals; the radicals having no peroxide bond, or diazo or nitroso radicals and not being directly connected to the nitrogen atom by an oxygen, sulfur or nitrogen atom, # hydroxy or amino radicals, the amine may be substituted by a linear or branched C 1 -C 4 hydrocarbon-based chain which may form one or more carbon rings having 6 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.

 When W 1 is a pyrazolo [1,5-b] pyridine radical, the radicals R 6, R 7, R 8, R 9 and R 15 are preferably chosen from a hydrogen atom, a linear or branched C 1 -C 4 hydrocarbon-based chain and 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.

 W1 may also be a pyrazolo [1,5-a] pyrimidine radical in which R7 and R9 are chosen from a hydrogen atom, a linear or branched C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2C6 polyhydroxyalkyl radical; a C 1 -C 6 aminoalkyl radical, a C 1 -C 6 aminoalkyl radical of which the amine is

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mono- ou di- substituée par un radical alkyl(C1-Cs), alkyl(Cl-C6)carbonyle, un.radicaux hydroxy ou amino, l'amino pouvant être substitué par une chaîne hydrocarbonée en C1- C10 linéaire ou ramifiée, pouvant former un ou cycles carbonés comportant de 6 chaînons, et pouvant être saturées ou insaturées, les atomes de carbone peuvent être, indépendamment les uns des autres, substitués par un ou plusieurs atomes d'halogènes ou radicaux hydroxy, amino ; et R8 sont choisis parmi un atome d'hydrogène, un radical alkyle en Ci-Ce linéaire ou ramifiée ; unradical monohydroxyalkyle en C1-C6 ; un radical polyhydroxyalkyle en C2-C6 ; un radical aminoalkyle en Ci-Ce, un radical aminoalkyle en Ci-Ce dont l'amine est mono- ou di-

substituée par un radical alkyl(C1-Cs), alkyl(Cl-C6)carbonyle. Dans ce cas, R7 et R9 sont de préférence choisis parmi un atome d'hydrogène ; un radical alkyle en C1-C4 linéaire ou ramifiée; un radical monohydroxyalkyle en C1-C4 ; un radical polyhydroxyalkyle en C2-C4 ; un radical aminoalkyle en C1-C4, un radical aminoalkyle en C1-C4 dont l'amine est mono- ou di- substituée par un radical alkyl(C1-C2), radicaux hydroxy or amino, l'amino pouvant être substitué par une chaîne hydrocarbonée en C1C4 linéaire ou ramifiée, les atomes de carbone peuvent être, indépendamment les uns des autres, substitués par un ou plusieurs radicaux hydroxy, amino, et R6 et R8 sont de préférence choisis parmi un atome d'hydrogène, un radical alkyle en C,-C4 linéaire ou ramifiée ; unradical monohydroxyalkyle en C,-C4 ; un radical polyhydroxyalkyle en

C2-C4 ; un radical aminoalkyle en Cl-C4, un radical aminoalkyle en Ci-C4 dont l'amine est mono- ou di- substituée par un radical alkyl(Cl-C2).

mono- or di-substituted with an alkyl radical (C1-Cs), alkyl (C1-C6) carbonyl, a.radicals hydroxy or amino, the amino may be substituted by a linear or branched C1-C10 hydrocarbon chain, which may be forming one or more carbon rings having 6 members, and being saturable or unsaturated, the carbon atoms may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino radicals; and R8 are chosen from a hydrogen atom, a linear or branched C1-C6 alkyl radical; C1-C6 monohydroxyalkyl unradical; a C2-C6 polyhydroxyalkyl radical; a C 1 -C 6 aminoalkyl radical; a C 1 -C 6 aminoalkyl radical, the amine of which is mono- or di-

substituted with a (C1-C5) alkyl or (C1-C6) alkylcarbonyl radical. In this case, R7 and R9 are preferably chosen from a hydrogen atom; a linear or branched C1-C4 alkyl radical; a C1-C4 monohydroxyalkyl radical; a C2-C4 polyhydroxyalkyl radical; a C 1 -C 4 aminoalkyl radical, a C 1 -C 4 aminoalkyl radical, the amine of which is mono- or disubstituted by a (C 1 -C 2) alkyl radical, hydroxy or amino radicals, the amino being able to be substituted by a chain linear or branched C1-C4 hydrocarbon radical, the carbon atoms may be, independently of one another, substituted by one or more hydroxyl or amino radicals, and R6 and R8 are preferably chosen from a hydrogen atom, a C-alkyl radical; , -C4 linear or branched; unradical C 1 -C 4 monohydroxyalkyl; a polyhydroxyalkyl radical

C2-C4; a C1-C4 aminoalkyl radical, a C1-C4 aminoalkyl radical, the amine of which is mono- or disubstituted by an alkyl radical (C1-C2).

 According to a particularly preferred embodiment, W 1 is a pyrazolopyridine or pyrazolopyrimidine derivative in which R 6, R 7, R 8 and R 9 are preferably chosen from hydrogen, a C 1 -C 4 alkyl radical, an amino radical or a mono- or di-radical. C1-C4 alkylamino, C1-C4 hydroxyalkyl radical; a C1-C4 alkoxy radical, a C1-C4 alkylamido radical.

 The compound of formula (I) can be represented by the following formula

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dans laquelle R1, R2, R6 sont tels que définis précédemment.

wherein R1, R2, R6 are as previously defined.

x? NH2 H2NNH Me N yY" w..r0 NJ--NANO H2N\ l'/ NANl H2N, / ,nu2 N'N NH2 N Hz ci / N#N \ \J N \ NHZ HzN N NH / NH / N NnNH NXXNH ~N tI)" r N N N N N N L~/ H,C \N / N-N rN- N N.NH, N N w \ NHZ \ N-< -: 2 (7N-- NyyNH2 À..A N N H / By way of example, the compounds of formula (I) may be mentioned

x? ## STR1 ## ## STR1 ##

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Ni NN N-N N-y NaNH2 NaNH2 N N N N N 1 N N N /NIÍ--i' N N N-N NH Nu NH fNNN./ fNN-y, NII NIN NXXNH W" ' rOH 9.N OH
La composition de l'invention contient de préférence une quantité de composé (I) comprise entre 0,01 et 10 % en poids, de préférence de 0,1 à 5 %.

NaNH 2 NN NaNH 2 NaNH 2 NNNNN 1 NNN / NN NNN NH N NH nNNN./NH-N, NII NIN NXXNH W "OH 9N OH
The composition of the invention preferably contains an amount of compound (I) of from 0.01 to 10% by weight, preferably from 0.1 to 5%.

 The dyeing composition according to the invention may further contain direct dyes different from the compounds of formula (1). These direct dyes that are useful according to the invention are, for example, chosen from neutral, acidic or cationic nitro-benzene direct dyes, acid or cationic neutral azo direct dyes, direct quinone dyes, and in particular neutral, acidic or cationic anthraquinone dyes, direct dyes. azines, triarylmethane direct dyes, direct indoamine dyes and natural direct dyes.

 Among the benzene direct dyes, mention may be made in a nonlimiting manner of the following compounds: -1,4-diamino-2-nitrobenzene

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-1-amino-2 nitro-4-bis(p-hydroxyéthyl)-aminobenzène -1,4-Bis((3-hydroxyéthylamino)-2-nitrobenzène -1-(3-hydroxyéthylamino-2-nitro-4-bis-((3-hydroxyéthylamino)-benzène -1-p-hydroxyéthylamino-2-nitro-4-aminobenzène -1-(3-hydroxyéthylamino-2-nitro-4-(éthyl)(i-hydroxyéthyl)-aminobenzène -1-amino-3-méthyl-4-(3-hydroxyéthylamino-6-nitrobenzène -1 -amino-2-nitro-4-p-hydroxyéthylamino-5-chlorobenzène -1,2-Diamino-4-nitrobenzène -1-am ino-2 -r3-hydroxyéthylamino-5-nitrobenzène -1,2-Bis-(>hydroxyéthylamino)-4-nitrobenzène -1-amino-2-tris-(hydroxyméthyl)-méthylamino-5-nitrobenzène -1-Hydroxy-2-amino-5-nitrobenzène -1-Hydroxy-2-amino-4-nitrobenzène -1-Hydroxy-3-nitro-4-aminobenzène -1-Hydroxy-2-amino-4,6-dinitrobenzène

-1 -p-hydroxyéthyloxy-2-p-hydroxyéthylamino-5-nitrobenzène -1-Méthoxy-2-(3-hydroxyéthylamino-5-nitrobenzène -1-(3-hydroxyéthyloxy-3-méthylamino-4-nitrobenzène -1-p,y-dihydroxypropyloxy-3-méthylamino-4-nitrobenzène -1-p-hydroxyéthylamino-4-p,y-dihydroxypropyloxy-2-nitrobenzène -1 -P,y-dihydroxypropylamino-4-trifluorométhyl-2-nitrobenzène -1-p-hydroxyéthylamino-4-trifluorométhyl-2-nitrobenzène -1-p-hydroxyéthylamino-3-méthyl-2-nitrobenzène -1-p-aminoéthylamino-5-méthoxy-2-nitrobenzène -1-Hydroxy-2-chloro-6-éthylamino-4-nitrobenzène -1-Hydroxy-2-chloro-6-amino-4-nitrobenzène

-1-Hydroxy-6-bis-(p-hydroxyéthyl)-amino-3-nitrobenzène -1-p-hydroxyéthylamino-2-nitrobenzène -1 -Hydroxy-4-p-hydroxyéthylamino-3-nitrobenzène. 1-amino-2-nitro-4- (3-hydroxyethylaminobenzene

1-amino-2-nitro-4-bis (p-hydroxyethyl) -aminobenzene -1,4-bis ((3-hydroxyethylamino) -2-nitrobenzene -1- (3-hydroxyethylamino-2-nitro-4-bis) ((3-hydroxyethylamino) -benzene -1-p-hydroxyethylamino-2-nitro-4-aminobenzene -1- (3-hydroxyethylamino-2-nitro-4- (ethyl) (i-hydroxyethyl) -aminobenzene -1-amino 3-methyl-4- (3-hydroxyethylamino-6-nitrobenzene -1-amino-2-nitro-4-p-hydroxyethylamino-5-chlorobenzene -1,2-Diamino-4-nitrobenzene -1-amin-2 3-hydroxyethylamino-5-nitrobenzene -1,2-bis ((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-p-hydroxyethyloxy-2-p-hydroxyethylamino-5-nitrobenzene -1-methoxy-2- (3-hydroxyethylamino-5-nitrobenzene -1- (3-hydroxyethyloxy-3-methylamino-4-nitrobenzene -1-p N, N-dihydroxypropyloxy-3-methylamino-4-nitrobenzene -1-p-hydroxyethylamino-4-p, y-dihydroxypropyloxy-2-nitrobenzene -1-p, y-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene -1-p 4-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene -1-p-hydroxyethylamino-3-methyl-2-nitrobenzene -1-p-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- (p-hydroxyethyl) -amino-3-nitrobenzene -1-p-hydroxyethylamino-2-nitrobenzene -1-hydroxy-4-p-hydroxyethylamino-3-nitrobenzene.

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 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.

-chlorure de 1,3-diméthyl-2-[[4-(diméthylamino)phényl]azo]-1H-Imidazolium, -chlorure de 1 ,3-diméthyl-2-[(4-aminophényl)azo]-1 H-Imidazolium, - méthylsulfate de 1-méthyl-4-[(méthylphénylhydrazono)méthyl]-pyridinium. Among these compounds, mention may be made in particular of the following colorants:

1,3-dimethyl-2 - [[4- (dimethylamino) phenyl] azo] -1H-imidazolium chloride, 1,3-dimethyl-2 - [(4-aminophenyl) azo] -1H-chloride Imidazolium, 1-methyl-4 - [(methylphenylhydrazono) methyl] -pyridinium methylsulfate.

The following dyes, described in the COLOR INDEX INTERNATIONAL 3rd edition, may also be mentioned among the azo direct dyes: -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.

We may also mention 1- (4'-aminodiphenylazo) -2-methyl-4bis- (β-hydroxyethyl) aminobenzene and 4-hydroxy-3- (2-methoxyphenylazo) -1-naphthalenesulfonic acid.

 Among the quinone direct dyes, mention may be made of the following dyes: -Disperse Red 15 -Solvent Violet 13

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-5-p-hydroxyéthyi-1,4-diaminoanthraquinone -2-Aminoéthylaminoanthraquinone -1,4-Bis-(p,y-dihydroxypropylamino)-anthraquinone. -Acid Violet 43 -Disperse Violet 1 -Disperse Violet 4 -Disperse Blue 1 -Disperse Violet 8 -Disperse Blue 3 -Disperse Red 11 -Acid Blue 62 -Disperse Blue 7- -Basic Blue 22 -Disperse Violet 15 -Basic Blue 99 that the following compounds: -1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone -1-Aminopropylamino-4-methylaminoanthraquinone -1-Aminopropylaminoanthraquinone

5-p-hydroxyethyl-1,4-diaminoanthraquinone -2-aminoethylaminoanthraquinone -1,4-bis (p, y-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

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-2-i-hydroxyéthlyamino-5-[bis-((3-4'-hydroxyéthyl)amino]anilino-1,4-benzoquinone -2-[3-hydroxyéthylamino-5-(2'-méthoxy-4'-amino)anilino-1,4-benzoquinone -3-N(2'-Chloro-4'-hydroxy)phényl-acétylamino-6-méthoxy-1,4-benzoquinone imine -3-N(3'-Chloro-4'-méthylamino)phényl-uréido-6-méthyl-1,4-benzoquinone imine -3-[4'-N-(Ethyl,carbamylméthyl)-amino]-phényl-uréido-6-méthyl-1,4-benzoquinone imine
Parmi les colorants directs naturels utilisables selon l'invention, on peut citer la lawsone, la juglone, l'alizarine, la purpurine, l'acide carminique, l'acide kermésique, la purpurogalline, le protocatéchaldéhyde, l'indigo, l'isatine, la curcumine, la spinulosine, l'apigénidine. On peut également utiliser les extraits ou décoctions contenant ces colorants naturels et notamment les cataplasmes ou extraits à base de henné. Indoamino dyes include the following compounds:

-2-i-hydroxyethlyamino-5- [bis - ((3-4'-hydroxyethyl) amino] anilino-1,4-benzoquinone -2- [3-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 that may be used according to the invention, lawsone, juglone, alizarin, purpurine, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin , curcumin, spinulosin, apigenidine. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from 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 preferentially from 0.005 to 10% by weight approximately.

 The composition of the present invention may further contain oxidation bases and couplers conventionally used for oxidation dyeing.

 By way of example, there may be mentioned para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.

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

 When present, the bases and the couplers are each generally present in an amount of between 0.001 and 10% by weight of the total weight of the dyeing composition, preferably between 0.005 and 6%.

 The medium suitable for dyeing, also known as dyeing medium, generally consists of water or a mixture of water and at least one organic solvent for solubilizing compounds that are not sufficiently soluble in water. As organic solvent, there may be mentioned for example lower alkanols C1-C4, such as ethanol and isopropanol; polyols and polyol ethers as the

<Desc / Clms Page number 22>

 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and 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 a suitable 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 compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or their mixtures, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.

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

 Of course, one skilled in the art will take care to choose this or these optional additional compounds such that the advantageous properties intrinsically attached to the oxidation dyeing composition according to the invention are not, or not substantially impaired by the addition or additions envisaged.

 The pH of the dyeing composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately.

 It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used for dyeing keratin fibers or else using conventional buffer systems.

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 Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids.

dans laquelle W est un reste propylène éventuellement substitué par un

groupement hydroxyle ou un radical alkyle en CrC4 ; R6, R7, R8 et Rg, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en C,-C4 ou hydroxyalkyle en C1-C4. Among the alkalinizing agents, mention may be made, for example, of ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and compounds of formula (III) below:

wherein W is a propylene residue optionally substituted with a

hydroxyl group or a C 1 -C 4 alkyl radical; R6, R7, R8 and Rg, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl or C1-C4 hydroxyalkyl radical.

 The dye composition according to the invention may be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratinous fibers, and especially 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 keratinous fibers. After a pause, the keratinous fibers are rinsed revealing colored fibers. The pause time is generally between about 3 to 50 minutes, preferably about 5 to 30 minutes.

 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, 2-oxido reductases

<Desc / Clms Page number 24>

 electrons such as uricases and 4-electron oxygenases 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 hair and as defined above.

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

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

The compounds of the invention of formula (I) can be prepared as follows:

<Tb>
<tb> CAN.NaOH
<tb> 2 <SEP> equivalents <SEP> of <SEP> + <SEP> 1 <SEP> equivalent <SEP> of <SEP> coupler <SEP>#<SEP> dye <SEP> direct <SEP> gray <SEP > of <SEP> type
<Tb>

base d'oxydation h2o, ciicn tri-noyau
On entend par base d'oxydation, les bases d'oxydation hétérocycliques classiquement utilisées en coloration pouvant après réaction avec le coupleur formé un radical W1. Le coupleur utilisé est un coupleur 2,3 diaminopyridinique substitué en position 6 par un groupe partant tel qu'un alcoxy, un atome d'halogène, un aryloxy,- OS02R, un radical -OCOR, un radical trifluoroalcoxy en C1-C3, avec R représentant un radical alkyle.

oxidation base h2o, ciicn tri-nucleus
The term "oxidation base" is understood to mean the heterocyclic oxidation bases conventionally used for coloring which, after reaction with the coupler formed, can form a radical W1. The coupler used is a 2,3-diaminopyridine coupler substituted at the 6-position with a leaving group such as an alkoxy, a halogen atom, an aryloxy, -SO 2 R, a -OCOR radical or a C 1 -C 3 trifluoroalkoxy radical with R representing an alkyl radical.

 As a heterocyclic oxidation base, mention may be made of pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

<Desc / Clms Page number 25>

 According to a particular embodiment, the base and the coupling are mixed with a solvent, for example acetonitrile. A base is added to this mixture, for example sodium hydroxide and CAN. After a (period) 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 butanol phase is subsequently dried, filtered and concentrated, and then purified.

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

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EXAMPLES Example 1 Preparation of a compound of formula

3-Amino-7-diethylaminopyrazolopyrimidine (A: 0.440g), 2-pyrrolidino-3-amino-6-methoxypyridine (B: 0.386g), ethanol / water ((60/40), 40g), H 2 O 2 (20 vol, 50g) and buffer pH 7 (10g buffer: H 2 PO 4, 13.6g, HK 2 PO 4 26.1g and Water qs 100ml) are mixed and stirred at room temperature for 1 hour. The reaction mixture is then precipitated and the resulting dye (C) is purified by column chromatography.

MS/MS m/z=485 [M+H-HCN]+ ;m/z=350 [M+H-CaH1oN4]+ et m/z=323 [M+HHCN-C$HoN4j+ et m/z=176 [C08848-H]+ Exemple 2 : préparation d'un composé de formule :

NMR (CD30D 1H, 400 MHz), 3.18 ppm (s, 12H); 3.97 ppm (s, 4H); 6.21 ppm (s, 1H); 6.27 ppm (s, 1H); 6.62 ppm (d, 1H), 6.71 ppm (d, 1H); 7.95 ppm (s, 1H); 8.39 ppm (d, 1H); 8.41 ppm (d, 1H); 8. 83 ppm (s, 1H) ESI + / MS M = 511 (2 exchangeable protons)

MS / MS m / z = 485 [M + H-HCN] +; m / z = 350 [M + H-CaH1oN4] + and m / z = 323 [M + HHCN-C $ HoN4] + and m / z = 176 [C08848-H] + Example 2: Preparation of a compound of formula:

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 In 80 ml of absolute ethanol, 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: 0.6 mmol; .). 8 ml of hydrogen peroxide at 6% 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 (1H, DMSO-d 6,400 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); (S,
1H); 10. 21 (s expanded, 1 H exchangeable).

Dans 80ml d'éthanol absolu, on dissous 0,222g du 3-aminopyrazolopyridine (A : 1,31 mmoles ; 2 eq. ) et 0,138g du 2,3-diamino-6-methoxypyridine ( B : 0,65 mmoles ; 1 eq.). Mass (ES +): m / z: 458 (MH +). EXAMPLE 3 Preparation of a compound of formula

In 80 ml of absolute ethanol, 0.222 g of 3-aminopyrazolopyridine (A: 1.31 mmol, 2 eq.) And 0.138 g of 2,3-diamino-6-methoxypyridine are dissolved (B: 0.65 mmol, 1 eq. .).

8 ml of hydrogen peroxide at 6% are then added, and stirring is continued at room temperature. After one week, the mixture is filtered, and the solid dye (C) NMR (1H, DMSO-d 6,400 MHz) is recovered: 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 extended, 2H exchangeable); 10. 66 (widened, 1 H exchangeable).

Mass (ES +): m / z: 370 (MH +). EXAMPLE 4 Preparation of a compound of formula

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In 10 ml of acetonitrile, 0.097 g of A (0.45 mmol, 2 eq.) And 0.050 g of B (0.22 mmol, 1 eq.) Are introduced. 338 mg of 35% sodium hydroxide diluted in 10 ml of water are then added, followed immediately by 499 mg of CAN. The solution takes a few minutes blue-gray tint. After stirring for 4 hours, 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 butanol phase is subsequently dried over sodium sulfate, filtered and concentrated. The product is taken up in ethanol (2 ml) and then precipitated again in diisopropyl ether. A black powder is obtained (C: m = 0.881 g).

Dans 10 ml d'acétonitrile, on introduit 0,169 g de A (0,45 mmole ; 2 eq. ) et 0,050 g de B (0,22 mmole ; 1 eq. ). On rajoute alors 338 mg de soude 35 % diluée dans 10 ml d'eau,

puis immédiatement 499 mg de CAN (Cérium (IV) Ammonium Nitrate : (NH4)2Ce(NO3)6). Mass (ES +): m / z: 428 (MH +) Example 5: Preparation of a compound of formula:

In 10 ml of acetonitrile, 0.169 g of A (0.45 mmol, 2 eq) and 0.050 g of B (0.22 mmol, 1 eq) are added. 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: (NH4) 2Ce (NO3) 6).

 The solution takes a few minutes in a gray tint. After stirring for 4 hours, 100 ml of water are added. The aqueous phase is extracted with ethyl acetate.

<Desc / Clms Page number 29>

The organic phase is eliminated. The aqueous phase is again extracted with butanol. The butanol phase is subsequently dried over sodium sulfate, filtered and 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

10 ml of acetonitrile are charged with 0.238 g of A (0.45 mmol, 2 eq) and 0.050 g of B (0.22 mmol, 1 eq). 338 mg of 35% sodium hydroxide diluted in 10 ml of water are then added, followed immediately by 499 mg of CAN. The solution takes a few minutes in a gray tint. After stirring for 4 hours, 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 butanol phase is subsequently dried over sodium sulfate, filtered and 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

<Desc / Clms Page number 30>

In 10 ml of acetonitrile, 0.097 g of A (0.45 mmol, 2 eq) and 0.050 g of B (0.22 mmol, 1 eq) are introduced. 338 mg of 35% sodium hydroxide diluted in 10 ml of water are then added, followed immediately by 499 mg of CAN. The solution takes a few minutes blue-gray tint. After stirring for 4 hours, 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 butanol phase is subsequently dried over sodium sulfate, filtered and 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:

In 10 ml of acetonitrile, 0.097 g of A (0.45 mmol, 2 eq.) And 0.058 g of B (0.22 mmol, 1 eq.) Are introduced. 338 mg of 35% sodium hydroxide diluted in 10 ml of water are then added, followed immediately by 499 mg of CAN. The solution takes a few minutes blue-gray tint. After stirring for 4 hours, 100 ml of water are added. The sentence

<Desc / Clms Page number 31>

aqueous is extracted with ethyl acetate. The organic phase is eliminated. The aqueous phase is again extracted with butanol. The butanol phase is subsequently dried over sodium sulfate, filtered and 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 +)
Following the synthesis method described above, the following compounds can be obtained according to the indicated synthetic scheme:

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Evaluation en coloration de fibres kératiniques, Chacun des colorants des exemples précédents est mélangé dans le milieu suivant pour former une composition de teinture (colorant 0,5% en poids). Des fibres kératiniques sont alors ajoutées à la composition ainsi obtenue (rapport composition/fibres = 10/1). Après 30 min, les cheveux sont rincés à l'eau puis séchés.

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

This gives a black color 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 (42)

1. Dyeing composition comprising, in a suitable medium, a compound of formula (I) below:

 in which # R3 represents: - a hydrogen atom, - a linear or branched C1-C10 hydrocarbon-based chain which can form one or more carbon-containing rings containing from 4 to 8 members, and which can be saturated or unsaturated, of which one or more carbon atoms of the carbon chain 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 atoms halogens or hydroxy, amino, carboxy, sulfonic or thiol radicals; R3 having no peroxide bond, or diazo or nitroso radicals, - NR ', R'2, R'1 and R'2 being as defined for R1 and R2 # R1 and R2 independently represent one of the other: - a hydrogen atom - a linear or branched C1-C10 hydrocarbon-based chain capable of forming one or more carbon rings containing from 4 to 8 members, and which may be saturated or unsaturated, including one or more carbon atoms of the carbon chain 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 with one or more halogen atoms or radicals hydroxy, amino, carboxy, sulfonic or thiol; R 2 and R 2 having no peroxide bond, or <Desc / Clms Page number 34>  - (C 1 -C 4) alkylsulfamoyl (C 1 -C 4 alkyl) -NH-SO 2 -; a C1-C4 thioether radical;

 a (C1-C4) alkyl radical amido (C1-C4 alkyl) CONH-); a (C 1 -C 4) alkylsulphonyl radical (alkylsoxy) - an alkylsulphonamido (C 1 -C 4 alkylsulfonyl) radical; - a hydroxy radical; a C1-C4 alkoxy radical; a C2-C4 hydroxyalkoxy radical; a (C1-C4) alkylcarbamoyl (C1-C4alkyl) NHCO-) radical;

 C, -C4, (C1-C4) alkylamido (C1-C4alkyl) CONH-), (C1-C4) alkylcarbamoyl (C1-C4alkyl) NHCO-), (C1-C4) alkylsulfonyl ( alkyl (C 1 -C 4) SO 2 -), C 1 -C 4 alkoxy, alkyl (C 1 -C 4) sulfonamido (C 1 -C 4 alkyl) SO 2 NH-), α-kyl (C 1 -C 4) sulfamoyl (C 1 -C 4 alkyl) NH 2 SO 4 ), onium Z, - NR'3R'4; a carboxy radical; a C1-C4 alkoxycarbonyl radical;

 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 hydroxyl, carboxy and alkoxycarbonyl radicals,

 diazo or nitroso radicals, and R1 and R2 not being directly connected to the nitrogen atom by an oxygen atom, sulfur, nitrogen or 802, - an onium radical Z, or # R, and R2 together with the nitrogen atom to which they are attached form a cycle of formula (II): <Desc / Clms Page number 35> C10 linear or branched, which may be saturated or unsaturated, one or more carbon atoms of the carbon chain may be replaced by an oxygen atom, nitrogen or sulfur or by a group SO2, and whose carbon atoms can be, independently of one another, substituted by one or more halogen atoms or hydroxyl, amino, carboxy, sulfonic or thiol radicals; R'5 having no peroxide bond, or diazo or nitroso radicals, and R'5 not being directly connected to the nitrogen atom by an oxygen, sulfur or nitrogen atom, # W1 represents an aromatic heterocycle radical chosen from the following radicals R'6 and R'7 which independently represent a hydrocarbon chain in C1- Linear or branched C1-C10, which may be saturated or unsaturated, one or more carbon atoms of the carbon chain may be replaced by an oxygen atom, nitrogen or sulfur or by a group SO2, and whose atoms of carbon may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, carboxy, sulfonic or thiol radicals; R'5 having no peroxide bond, or diazo or nitroso radicals, and R'5 not being directly connected to the nitrogen atom by an oxygen atom, sulfur or nitrogen, R'5 which represents a hydrogen atom; a hydrocarbon chain in  selected from hydroxy, C 1 -C 4 alkoxy, amino, mono or di alkylamino, C 1 -C 4 alkylC 1-6 alkyl, C 1 -C 4 alkyl NHCO-, C 1 -C 4 alkyl, SO 2 -, - n is a integer between 1 and 8, - m is an integer between 0 and 2, - Y represents an oxygen atom, a radical CR ', a radical NR'5 or a radical NR'6R'7 with

 a sulphonic radical (SO 3 H) which may be in salt form, an onium radical Z, R '3 and R' 4, which may be identical or different, represent a hydrogen atom; a C1-C4 alkyl radical optionally substituted with one or more radicals <Desc / Clms Page number 36>  # R6, R7, R8, R9, R10, R11 'R12 represent, independently of each other - a hydrogen atom - a linear or branched C1-C10 hydrocarbon-based chain which can form one or more carbon rings containing from 4 to 8-membered, and which may be saturated or unsaturated, one or more carbon atoms of the carbon chain may be replaced by an oxygen atom, nitrogen or sulfur or by a group SO2, and whose carbon atoms may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, carboxy, sulfonic or thiol radicals; the radicals R6 to R12 having no peroxide bond, or diazo or nitroso radicals and the radical R11, not being connected directly 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 the formula (1).

NR11R12 # Z2, Z4, Z6 represent, independently of each other, a nitrogen atom, a CR12 or NR11 radical provided that at least one of them represents a radical CR12 and that there can be no more of 3 contiguous nitrogen atoms, # Z8 represents a nitrogen atom, a radical CR15  R6t {* R6t (.Rs NN / 'Z NN / Z2 N / N 1 I to Z NN 11 46 (R ") R ..., ::: N 11 (R1) Z4 6 (RI I) 9 (RI II) (RIV) Ryo '' '' - 'R6t {* Y 1 NR'2 Xj3> mR9 N, / R11 R11 1 (R Ra \ R11 R8 \ R11 and V) (RVI), (RVI1) (RVIII) # Z1 and Z3 independently represent a hydroxy radical or

<Desc / Clms Page number 37>  2. Composition according to claim 1 wherein R3 is chosen from a hydrogen atom or a C1-C4 alkyl radical optionally substituted with one or more radicals chosen from hydroxyl, C1-C2 alkoxy, amino, (di) radicals. C1-C2 alkylamino.  3. A composition according to claim 1 or 2 wherein R 1 and R 2 are independently selected from hydrogen, a C 1 -C 6 alkyl radical optionally substituted by hydroxy, alkoxy, amine, (di) C 1 -C 4 alkylamino.  4. Composition according to claim 1 or 2 wherein R1 and R2 form, with the nitrogen atom to which they are attached, a 5- to 8-membered heterocycle chosen from pyrrolidine, piperidine, homopiperidine, piperazine, homopiperazine and diazepane heterocycles.  5. A composition according to claim 4 wherein R 1 and R 2 form a heterocycle selected from pyrrolidine, 3-hydroxypyrrolidine, 3-aminopyrrolidine, 3-acetamidopyrrolidine, 3- (methylsulfonylamino) -pyrrolidine, proline, 3-hydroxyproline. piperidine, hydroxypiperidine, homopiperidine, diazepane, N-

 methyl homopiperazine, N p-hydroxyethylhomopiperazine and their addition salts 6. Composition according to any one of claims 1 to 5 wherein R, and R2 together with the nitrogen atom to which they are attached an optionally substituted pyrrolidine ring.  7. Composition according to any one of claims 1 to 6 wherein the onium radical Z corresponding to formula (III)

 in which # D is a covalent bond or a linear or branched C1-C14 alkylene chain which may contain one or more heteroatoms chosen from oxygen, sulfur or nitrogen, SO2, one or more ketone functions, the chain being able to be substituted with one or more hydroxyl, C 1 -C 6 alkoxy or amino, C 1 -C 4 (di) alkylamino radicals <Desc / Clms Page number 38>  is mono- or di-substituted with (C1-C6) alkyl, (C1-C6) alkylcarbonyl, amido or (C1-C6) alkylsulphonyl; a C1-C6 carboxyalkyl radical; a C1-C6 carbamylalkyl radical; a C1-C6 trifluoroalkyl radical; a C 1 -C 6 trialkyl (CrC 6) silanalkyl radical; a C 1 -C 6 sulfonamidoalkyl radical; a C1-C6 alkyl (C1-C6) carboxyalkyl radical; a C1-C6 alkyl (C1-C6) sulfinylalkyl radical; a C1-C6 (C1-C6) alkylsulfonylalkyl radical; a C1-C6 alkyl (C1C6) carbonylalkyl radical; a C 1 -C 6 N-alkyl (C 1 -C 6) carbamylalkyl radical; a C 1 -C 6 N-alkyl (C 1 -C 6) sulfonamidoalkyl radical; # x is 0 or 1, - when x = 0, then the linking arm D is attached to the nitrogen atom bearing the radicals R16 to R18,

C6; a C2-C6 polyhydroxyalkyl radical; an aryl radical; a benzyl radical; a C1-C6 aminoalkyl radical; a C1-C6 aminoalkyl radical including amine  C 1 -C 6 alkoxy, C 1 -C 6 trialkyl (C 1 -C 6) silanalkyl radical, amido radical, carboxyl radical, (C 1 -C 6) alkylcarbonyl radical, thio radical, C 1 -C 6 thioalkyl radical, radical alkyl (C 1 -C 6) thio, an amino radical, an amino radical mono- or di-substituted with a (C 1 -C 6) alkyl, (C 1 -C 6) alkylcarbonyl, amido or (C 1 -C 6) alkylsulphonyl radical ; # R19 represents a C1-C6 alkyl radical; a C1-C monohydroxyalkyl radical

 C 1 -C 6 amidoalkyl radical; a radical tria) ky! (Ci-C6) siianea! ky) e in Ci-Ce; a C1-C6 aminoalkyl radical; a C 1 -C 6 aminoalkyl radical, the amine of which is mono- or di-substituted with a C 1 -C 4 alkyl, C 1 -C 6 alkylcarbonyl, amido or (C 1 -C 6) alkylsulphonyl radical; # R16, R17 and R18 together, in pairs, form, with the nitrogen atom to which they are attached, a 4,5, 6 or 7-membered saturated carbon ring which may contain one or more heteroatoms, the cationic ring being able to 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 2 -C 6 polyhydroxyalkyl radical, a radical

 # R, 6, R 17 and R 18 'taken separately represent a C 1 -C 5 alkyl radical or a C 1 -C 6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a C1-C6 alkoxy (C1-C6) alkyl radical; an aryl radical; a benzyl radical; a

<Desc / Clms Page number 39>  when x = 1, then two of the radicals R16 to R18 form, together with the nitrogen atom to which they are attached, a saturated 5-, 6- or 7-membered ring and the linking arm D is connected to a carbon atom of saturated cycle; # T is a counter ion.  8. Composition according to claim 7 wherein x is 0, and R16, R17 and R18 separately are selected from a C1-C6 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a

 C1-C4 alkoxy (C1-C6) alkyl radical, C1-C6 amidoalkyl radical, C1-C6 trialkyl (CrC6) silanalkyl radical, or x is 0 and R16 with R17 together form an azetidine, pyrrolidine ring , piperidine, homopiperidine, piperazine, homopiperazine, morpholine, R18 being chosen in this case from a C 1 -C 6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a Ci-Ce aminoalkyl radical, a radical

 aminoalkyl mono- or di-substituted with (C1-C5) alkyl, (C1-C5) alkylcarbonyl, amido or (C1-C5) alkylsulphonyl; a C1-C6 carbamylalkyl radical; a C1-C6 trialkyl (C1-C8) silanalkyl radical; a C1-C6 alkyl (C1-Cs) carboxyalkyl radical; a C1-C6 alkyl (C1-Cs) carbonylalkyl radical; a C 1 -C 6 N-alkyl (C 1 -C 8) carbamylalkyl radical 9. Composition according to claim 7 wherein x is equal to 1, R19 is selected from a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a Ci-Ce aminoalkyl radical, a radical

 C 1 -C 6 aminoalkyl wherein the amine is mono or disubstituted by (C 1 -C 5) alkyl, (C 1 -C 5) alkylcarbonyl, amido or (C 1 -C 6) alkylsulphonyl; a C1 -Cs carbamylalkyl radical; a C1-C6 trialkyl (C1-C8) silanalkyl radical; a C1-C6 alkyl (C1-Cs) carboxyalkyl radical; C 1 -C 6 alkylC 1-4Carybonylalkyl; a C 1 -C 6 N-alkyl (Cr Cs) carbamylalkyl radical; R16 with R17 together form an azetidine, pyrrolidine, piperidine, homopiperidine, piperazine, homopiperazine, morpholine ring, R18 being chosen in this case from a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a C 1 -C 6 aminoalkyl radical, a C 1 -C 6 aminoalkyl radical, the amine of which is mono or

 disubstituted by (C1-C5) alkyl, (C1-C5) alkylcarbonyl, amido or alkyl (C, - <Desc / Clms Page number 40>  C6) sulfonyl; a C1-C6 carbamylalkyl radical; a radical tria) ky! (Ci-Ce) if) aneatky) e Ci-Ce; a C1-C6 alkyl (C1-C4) carboxyalkyl radical; a C1-C6 alkyl (C1C5) carbonylalkyl radical; a C 1 -C 6 N-alkyl (C 1 -C 6) carbamylalkyl radical.

 10. Composition according to any one of claims 1 to 9 wherein x is 0 and R16 R17 and R18 are alkyl radicals.  11. A composition according to any one of claims 7 to 10 wherein D is a covalent bond or a C 1 -C 6 alkylene chain which may be substituted.  12. Composition according to any one of claims 1 to 6 wherein the onium radical Z corresponding to formula (IV)

 in which # D is as defined in claim 7 or 11, # the vertices Ë, G, J, L, identical or different, represent a carbon, oxygen, sulfur or nitrogen atom to form a ring pyrazole, imidazole, triazole, oxazole, isooxazole, thiazole, isothiazole, # a is an integer from 0 to 3 inclusive; # b is an integer between 0 and 1 inclusive; # a + b is an integer between 2 and 4 # R, identical or different, represent a hydrogen atom, a halogen atom, a hydroxyl radical, a C 1 -C 6 alkyl radical or a C 1 -C 6 monohydroxyalkyl radical; , a C2-C6 polyhydroxyalkyl radical, a C1-C6 alkoxy radical, a

 C1-C6 trialkyl (CrC6) silanalkyl radical, an amido radical, a carboxyl radical, a C1-C6 alkylcarbonyl radical, a thio radical, a C1-C6 thioalkyl radical, a (C1-C6) alkyl radical, a amino radical, an amino radical mono or di substituted by a (C 1 -C 6) alkyl, (C 1 -C 6) alkylcarbonyl, amido, (C 1 -C 6) alkylsulphonyl radical; a C1-C6 monohydroxyalkyl radical or a <Desc / Clms Page number 41>  , R2o identical or different, represents a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a (C1-C6) trialkyl radical, a C1-C6 silanalkyl radical, an alkoxy radical; (C 1 -C 6) C 1 -C 6 alkyl, a C 1 -C 6 carbamylalkyl radical, a C 1 -C 6 alkyl (C 1 -C 6) carboxyalkyl radical, a benzyl radical; it being understood that the radical R20 is borne by a nitrogen atom, # R19 is as defined in claim 7 or 9, # x is equal to 0 or 1 - when x = 0, the linking arm D is attached to the nitrogen atom, - when x = 1, the linking 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 counter-ion.

 C2-C6 polyhydroxyalkyl radical; it being understood that the R radicals are borne by a carbon atom, a benzyl radical or a phenyl radical optionally substituted with one or more radicals chosen from methyl, hydroxy, amino and methoxy radicals; it being understood that the radicals R are not carried by a carbon atom,  13. The composition of claim 12 wherein the vertices E, G, J and L form an imidazole, pyrazole, oxazolic, thiazolic and triazole ring.  The composition of claim 12 or 13 wherein x is 0, D is a single bond, or a C 1 -C 4 alkylene chain which may be substituted.  15. Composition according to any one of claims 1 to 14 wherein the onium radical Z corresponding to formula (V)

 (R19) X \ 11, E N ± (R) a #D 1: +) ± (R) d L1-1 T (V) in which: # D, R, R19 are as defined in claim 12, <Desc / Clms Page number 42>  # the vertices E, G, J, L and M identical or different, represent a carbon or nitrogen atom and form a ring selected from the pyridine, pyrimidine, pyrazine, triazine and pyridazine rings, # d is an integer inclusive between 3 and 5 inclusive; # x is equal to 0 or 1 - when x = 0, the linking arm D is attached to the nitrogen atom, - when x = 1, the linking 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.  16. The composition of claim 15 wherein the vertices E, G, J, L and M with the ring nitrogen form a ring selected from pyridine, pyrimidine, pyridazine and pyrazine rings.  17. Compositions according to any one of claims 12 to 16 wherein x is 0 and R is selected from a hydroxyl radical, a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2 polyhydroxyalkyl radical. C6,

 a C1-C6 alkoxy radical, a C1-C6 trialkyl (C1-C5) silanalkyl radical, an amido radical, a C1-C6 alkylcarbonyl radical, an amino radical, an amino radical mono- or di-substituted with a radical; alkyl (CrC6), alkyl (CrC6) carbonyl, amido or (C6) alkylsulphonyl; a C1-C6 monohydroxyalkyl radical or a C2-C6 polyhydroxyalkyl radical; it being understood that the R radicals are borne by a carbon atom.  18. Composition according to any one of claims 12 to 16 wherein x is equal to 1, R19 is selected from a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a C 1 -C 6 aminoalkyl radical; a C 1 -C 6 aminoalkyl radical, the amine of which is mono- or di-

 substituted with a (C1-C6) alkyl, (C1-C6) alkyl carbonyl radical, an amido radical or a (C1-C6) alkylsulphonyl radical; a C1-C6 carbamylalkyl radical; a trialkyl (Cr C6) silanalkyl radical C 1 -C 6; a C1-C6 alkyl (C1-Cs) carbonylalkyl radical; a C 1 -C 6 Nalkyl (Cl-C 6) carbamylalkyl radical; R is selected from a hydroxyl radical, a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a C1-C6 alkoxy radical, a C1-C6 trialkyl-Csilanalkyl radical, an amido radical, a C1-C6 alkylcarbonyl radical, an amino radical, an amino radical <Desc / Clms Page number 43>  mono- or di-substituted with an alkyl radical (C1-Ca), alkyl (Ci-Ce) carbonyl, amido or alkyl (C1-Ca) sulphonyl.

 19. Composition according to any one of claims 12 to 18 wherein R and R19 are C 1 -C 4 alkyl radicals which may be substituted.  20. Composition according to any one of claims 1 to 19 wherein W1 is selected from the 5-aminopyrazole, 5-hydroxypyrazole, pyrazolo [1,5-b] pyridine, pyrazolo [1,5-a] radicals. pyrimidine, pyrazolo [3,2-c] triazole, pyrazolo [1,5-b] triazole, aminopyrimidines, triaminopyrimidine, hydroxyaminopyrimidines, 2-aminopyridine, indoline and indole.  21. The composition of claim 20 wherein W1 is selected from 5-aminopyrazole, 5-hydroxypyrazole radicals of formula (R1).  22. The composition according to claim 21, wherein W1 is chosen from the 5-aminopyrazole and 5-hydroxypyrazole radicals in which R6 and R11, which are identical or different, are chosen from a hydrogen atom; a linear or branched C1-C10 hydrocarbon-based chain capable of forming one or more carbon-containing rings containing from 4 to 8 members, and which may be saturated or unsaturated, one or more carbon atoms of which may be replaced by a carbon atom; oxygen, nitrogen or sulfur or by a group SO2, and whose carbon atoms can be, independently of one another, substituted by one or more halogen atoms or hydroxyl, amino, carboxy, sulfonic or thiol radicals ; the radicals Re to R12 having no peroxide bond, or diazo or nitroso radicals and the radical R11, not being directly connected to the nitrogen atom by an oxygen atom, sulfur or nitrogen.  23. Composition according to claim 22, in which R6 and R11 are independently chosen from a hydrogen atom or a linear or branched C1-C4 hydrocarbon-based chain which can form one or more carbon rings containing 6 members, and which 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.  24. The composition of claim 21 wherein W1 represents <Desc / Clms Page number 44>  R6, R7, R8, R9 and Z8 being as defined above.

 25. The composition according to claim 24, wherein W1 is a pyrazolo [1,5-b] pyridine radical in which R6, R7, R8, R9 and R15, identical or different, are chosen from ## EQU1 ## a linear or branched C1-C10 hydrocarbon-based chain capable of forming one or more carbon-containing rings containing from 4 to 8 members, and which may be saturated or unsaturated, one or more carbon atoms of which may be replaced by a carbon atom; oxygen, nitrogen or sulfur or by a group SO2, and whose carbon atoms can be, independently of one another, substituted by one or more halogen atoms or hydroxyl, amino, carboxy, sulfonic or thiol radicals ; the radicals having no peroxide bond, or diazo or nitroso radicals and not being directly connected to the nitrogen atom by an oxygen, sulfur or nitrogen atom, # hydroxy or amino radicals, the amine may be substituted by a linear or branched C1-C4 hydrocarbon chain, which may form one or more carbon rings having 6 members, and which may be saturated or unsaturated, the carbon atoms may be, independently of each other, substituted by one or more halogen atoms or hydroxy, amino radicals.  26. A composition according to claim 25 wherein the radicals R6, R7, R8, R9 and R15 are chosen from a hydrogen atom, a linear or branched C 1 -C 4 hydrocarbon-based chain which may be saturated or unsaturated, the carbon may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino radicals.  27. The composition according to claim 24, wherein W1 is a pyrazolo [1,5-a] pyrimidine radical in which R7 and R9 are chosen from a hydrogen atom or a linear or branched C1-C6 alkyl radical; a radical <Desc / Clms Page number 45>  substituted with a (C 1 -C 6) alkyl, (C 1 -C 6) alkylcarbonyl radical.

 substituted by an alkyl (CrC6), alkyl (C1-C6) carbonyl radical, a hydroxy or amino radical, the amino may be substituted by a linear or branched C1-C10 hydrocarbon chain, which may form one or more carbon rings containing 6-membered, and which may be saturated or unsaturated, the carbon atoms may be, independently of one another, substituted with one or more halogen atoms or hydroxy, amino radicals; and R8 are chosen from a hydrogen atom, a linear or branched C1-C6 alkyl radical; C1-C6 monohydroxyalkyl unradical; '; a C2-C6 polyhydroxyalkyl radical; a C 1 -C 6 aminoalkyl radical; a C 1 -C 6 aminoalkyl radical, the amine of which is mono- or di-

 C1-C6 monohydroxyalkyl; a C2-C6 polyhydroxyalkyl radical; a C 1 -C 6 aminoalkyl radical; a C 1 -C 6 aminoalkyl radical, the amine of which is mono- or di-  28. The composition of claim 27 wherein R7 and R9 are selected from a hydrogen atom; a linear or branched C1-C4 alkyl radical; C1-C4 monohydroxyalkyl unradical; a C2-C4 polyhydroxyalkyl radical; a radical

 C1-C4 aminoalkyl, a C1-C4 aminoalkyl radical, the amine of which is mono- or disubstituted by an alkyl (C1-C2) radical, hydroxy or amino radicals, the amino may be substituted by a C1-hydrocarbon chain; -C4 linear or branched, the carbon atoms can be, independently of each other, substituted with one or more hydroxyl radicals, amino, and R6 and R8 are chosen from a hydrogen atom, a C1-C4 alkyl radical; linear or branched; C1-C4 monohydroxyalkyl unradical; a C2-C4 polyhydroxyalkyl radical; a radical

 C1-C4 aminoalkyl, a C1-C4 aminoalkyl radical in which the amine is mono- or disubstituted by an (C1-C2) alkyl radical.  29. Composition according to claim 28, in which R6, R7, R8 and R9 are chosen from hydrogen, a C1-C4 alkyl radical, an amino radical, a mono- or di-C1-C4 alkylamino radical or a hydroxyalkyl radical. C1-C4; a C1-C4 alkoxy radical, a C1-C4 alkylamido radical.  30. Composition according to any one of claims 1 to 29 wherein the compound of formula (I) is a cationic compound substituted with at least one onium radical Z.  31. The composition of claim 30 wherein at least one of the radicals R 1 and R 2 is an onium radical Z. <Desc / Clms Page number 46>  32. The composition of claim 31 wherein R1 and R2 form the ring of formula (II) wherein R 'is an onium radical Z.  33. The composition of claim 32 wherein Y is NR'6R'7.  34. Composition according to any one of the preceding claims, in which the compound of formula (1) represents

 wherein R1, R2, R6 are as previously defined.  35. Composition according to any one of claims 1 to 34 wherein the compound of formula (I) is chosen from

 ## STR2 ## ## STR2 ## ## STR2 ## ## STR1 ## N, NH, N); H, N N ......... N N N N H3 C <Desc / Clms Page number 47>  N-NN N N N N NH 2 N NHZ NyyNH 2 / R L, NN / 1 - N 'N N N N N NN N N N N N N N NH 2 N, NH 2 N / N' NN, 1 NN NN 1 NN 1 NN CI ~ NI! ...... rN 'N ~ r- \ NN / NH N ~ N / NH IN i, - ;; h I N i, - ;; ## STR2 ## N N N N N OH OH N N N OH N N OH

36. Composition according to any one of claims 1 to 35 wherein the amount of dye (I) is between 0.01 and 10% by weight. 37. A composition according to any one of claims 1 to 36 further comprising an oxidation base selected from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, and their salts. addition with an acid. <Desc / Clms Page number 48>  38. Composition according to claim 37 wherein the oxidation base (s) are present in an amount of between 0.001 and 10%.  39. Composition according to any one of claims 1 to 38 comprising at least one coupler chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers and heterocyclic couplers and their addition salt with an acid.  40. Composition according to any one of claims 1 to 39 further comprising an oxidizing agent.  41. Direct dye of formula (I) as defined in any one of claims 1 to 40.  42. A process for dyeing keratinous fibers which comprises applying the composition according to any one of claims 1 to 41 for a time sufficient to obtain the desired coloration.