FR2917970A1 - Use of substituted heterocyclic cyanine compounds as a coloring agent of the keratin fibers, preferably human hair, and/or as an agent for optical brightening the fibers - Google Patents

Abstract

Use of one or more substituted heterocyclic cyanine compounds (I) as a coloring agent of the keratin fibers, preferably human hair, and/or as an agent for optical brightening the fibers, is claimed. Use of one or more substituted heterocyclic cyanine compounds of formula (I) as a coloring agent of the keratin fibers, preferably human hair, and/or as an agent for optical brightening the fibers, is claimed. A : unsaturated aromatic heterocycle with 5-12 chain link, which has at least a cationic charge on the nitrogen atom and contains at least another heteroatom of N, O, S and/or Se, where: the aromatic heterocycle is optionally substituted and optionally condensed with one or more aromatic cycle, and the aromatic cycle is able to condense with an optionally saturated cycle with 5-10 chain; n : 0-2; m : 0 or 1; X : alkylene (CH 2), O or carbonyl; either R 1>, R 2>H, a benzyl radical or optionally substituted aryl, which is condensed with one or more aromatic cycle, 1-24C, preferably 1-6C-alkyl radical (which is substituted and interrupted by one or more heteroatoms, preferably N, S or O), where the alkyl radical together forms a optionally saturated heterocycle having 5-15 chains, which is optionally substituted and optionally condenses with one or more aromatic cycle; or R 1>R 2>6 membered heterocycle, where the heterocycle comprises another heteroatom such as nitrogen, and the heteroatom is substituted by a substituted heterocyanine compound of formula (II) or (III); either R 3>, R 5>H, halo, 1-6C-carboxyalkoxy, alkoxy(1-6C)-carbonyl, substituted 1-6C-alkoxy, which is interrupted by one or more heteroatoms, substituted cyclic 1-6C-alkyl radical, which is interrupted by one or more heteroatoms; or R 3>R 5>C : aromatic cycle or 6-10C-heterocycle containing 5-10 chains and 1-5 heteroatoms, which is optionally condensed and optionally substituted by one or more 1-4C-alkyl or dialkyl(1-4C)-amino; R 4>H, 1-6C-alkyl, which is optionally substituted and interrupted by one or more heteroatom or carbonyl; R 6>cyclic 1-24C, preferably 1-6C-alkyl radical, which is optionally substituted or interrupted by one or more heteroatom, carbonyl and/or one or more heterocycles, a benzyl radical or optionally substituted aryl; Y1 ->an organic anion or mineral; ring A1, ring A2 : ring A; X1, X2 : X; o, q : n; p, r : m; R3a, R3b, R5a, R5b : R 3>; R4a, R4b : R 4>; and R6a, R6b : R 6>. Independent claims are included for: (1) a cosmetic composition for coloring comprising one or more direct dyes containing (I) in an appropriate medium; (2) the treatment of keratinous fibers, preferably human keratinous fibers, comprising applying the composition on the wet or dry fibers for sufficient time to obtain the color, rinsing the fibers using a shampoo and drying the fibers; and (3) device with several compartments or kit for coloring comprising a first compartment containing the composition and a second compartment containing another composition comprising an oxidizing agent. [Image] [Image].

Description

10 B07-0874FR GD / GL OA07226 Société Anonyme known as L'OREAL 15 USE

  OF AT LEAST ONE CATIONIC CYANINE DERIVATIVE FOR HAIR COLORING, COMPOSITION CONTAINING SAME, PROCESS FOR TREATING KERATIN FIBERS USING THE SAME, DEVICE AND USE 1 Invention of: Alain LAGRANGE USE OF AT LEAST ONE CATIONIC DERIVATIVE OF CYANINE FOR CAPILLARY COLORING, COMPOSITION CONTAINING THE SAME, PROCESS FOR TREATING KERATINOUS FIBERS USING THE SAME, DEVICE AND USE

  The invention relates to the use of at least one particular direct dye derived from cationic cyanine for hair dyeing.

  The invention also relates to a cosmetic composition comprising, in a medium suitable for staining, at least one particular direct dye derived from cationic cyanine. The subject of the invention is also a process for treating keratinous fibers involving this composition, as well as a device comprising it. Finally, it relates to the use of the composition according to the invention as a coloring agent for said fibers. The present invention relates to the field of dyeing keratinous fibers and more particularly to hair dyeing. There are essentially two types of staining.

  The first type of staining is so-called semipermanent staining or direct staining, which uses dyes capable of providing more or less marked modification to the natural coloration of the hair. The dyes involved are colored and coloring substances which have a certain affinity with the keratinous fiber. It should be noted that this type of color fades after several washes, which can be a disadvantage. In the case where it is desired to obtain a coloration lighter than the original color of the fibers, it is necessary to use with the direct dyes, at least one oxidizing agent, under conditions of alkaline pH. However, these processing conditions are not without consequences on the properties of the treated fibers. Indeed, in the long run,

  3 the fibers are more or less degraded and tend to become rough, dull, brittle and difficult to comb. The second type of staining is permanent staining or oxidation staining. This is carried out with oxidation dye precursors which are colorless or weakly colored compounds, comprising at least one oxidation base possibly associated with one or more couplers. Once mixed with oxidizing products, at the time of use, the precursors can give rise by a process of oxidative condensation to colored compounds and dyes. Given the necessary presence of an oxidizing agent in this type of coloration, the disadvantages mentioned above are also found in this case. It has recently been found that compositions comprising at least one fluorescent compound have an interesting alternative to conventional processes employing an oxidizing agent. Thus, for dark hair, more particularly whose pitch is less than or equal to 6 (dark blond), preferably less than or equal to 4 (chestnut), it has been found that there are areas for which the curve reflectance versus wavelength (between 500 and 700 nm) of the hair treated with the composition comprising the fluorescent compound was greater than the curve corresponding to untreated hair. As a result, the hair appears lightened, without the need to use an oxidizing agent.

  It is recalled that the notion of "tone" is based on the classification of natural nuances, a tone separating each nuance from that which immediately follows or precedes it. This definition and the classification of natural shades are well known to hair professionals and published in the book Sciences des treatments

  4 capillaries of Charles ZVIAK 1988, Ed.Masson, pp.215 and 278. The pitches ranged from 1 (black) to 10 (light light blond), a unit corresponding to a tone; the higher the number, the clearer the nuance.

  Furthermore, it is important to have compositions which make it possible to obtain staining which is sufficiently stubborn with regard to washes and the action of light, which is rarely the case with the colorations obtained with the direct dyes, which are fluorescent. or not fluorescent.

  While such compositions constitute an advance in this field, the fact remains that the storage stability of these compositions can be improved. There is therefore a real need to find compounds which do not have the drawbacks mentioned above.

  Surprisingly and advantageously, the Applicant has just discovered a new family of particular direct dyes derived from cationic cyanine for the preparation of dye compositions for keratinous fibers, in particular human keratin fibers such as hair which makes it possible to obtain colorations. with properties of stability and selectivity (color variation between different parts of a hair or a hair) and satisfactory tenacity. In particular, it has been observed that these particular direct dyes were more stable in an alkaline oxidizing medium. In addition, it has been observed that the fluorescence yield of these direct dyes derived from cyanine was notably increased relative to fluorescent direct dyes conventionally proposed in the capillary field. The present invention therefore particularly relates to the use of one or more compounds corresponding to the following formula (I): in which: n denotes 0, 1 or 2; m is 0 or 1; A represents an unsaturated aromatic heterocycle comprising 5 to 12 members, comprising at least one cationic charge on a nitrogen atom and optionally comprising at least one other heteroatom selected from nitrogen, oxygen, sulfur and / or selenium; said aromatic heterocycle being optionally substituted and may be condensed or not with one or more aromatic rings; said condensed aromatic ring (s) being themselves capable of being condensed with a saturated or unsaturated ring having 5 to 10 members; X denotes an alkylene group CH 2, an oxygen atom or a carbonyl group; R1 and R2 represent, independently of one another, a hydrogen atom; a benzyl or aryl radical optionally substituted and / or condensed with one or more aromatic rings; a linear or branched C1-C24, preferably C1-C6, alkyl radical which can be interrupted by one or more heteroatoms such as N, S or O and / or which can be substituted; when R 1 and R 2 represent a C 1 -C 24, preferably C 1 -C 6, alkyl radical which may be interrupted by one or more heteroatoms and / or may be substituted, said alkyl radicals may together form a saturated or unsaturated heterocycle comprising 15-membered ring, said heterocycle may be substituted and may be condensed or not with one or more aromatic rings; (I) Y-6 in the case where R1 and R2 together form a 6-membered heterocycle, then: (i) said heterocycle optionally comprises another heteroatom such as nitrogen, said heteroatom possibly being substituted by a group of formula ( II): (II) in which A ', X', R'3, R'4, R'5, R'6, n 'and m' have the same meanings as A, X, R3, R4, R5; R6, n and m in formula (I); or (ii) said heterocycle may be substituted by a group of the following formula (III): "wherein A", X ", R" 3, R 4 and R "5, R 6, n" and m "have the same A, X, R3, R4, R5, R6, n and m in the formula (I), R3 and R5 represent, independently of one another, a hydrogen atom; a (C 1 -C 6) carboxyalkoxy group, a (C 1 -C 6) alkoxycarbonyl group, a linear or branched C 1 -C 6 alkoxy group which may be interrupted by one or more heteroatoms and / or may be substituted; in C1-C6,

  7 linear, branched or cyclic, substituted or not, may be interrupted by one or more heteroatoms; R3 and R5 can form, with the carbon atoms to which they are attached, an aromatic or non-aromatic C 6 -C 10 or heterocyclic ring comprising in total from 5 to 10 ring members and from 1 to 5 heteroatoms; these rings being condensed or not, substituted or unsubstituted by one or more groups chosen from C 1 -C 4 alkyl and dialkyl (C 1 -C 4) amino groups; R4 represents a hydrogen atom or a linear or branched, substituted or unsubstituted C1-C6 alkyl radical which may be interrupted by one or more heteroatoms or a carbonyl group; R6 represents a C1-C24, preferably C1-C6, linear, branched or cyclic, substituted or unsubstituted alkyl radical which may be interrupted by one or more heteroatoms or a carbonyl group and / or by one or more heterocycles; a substituted or unsubstituted benzyl or aryl radical; Y- represents an organic or mineral anion. as a coloring agent for keratinous fibers, in particular human fibers, and / or as an agent for the optical lightening of these fibers. By optical brightening is meant a visible and visual lightening obtained without the use of oxidizing agent. These dyes make it possible to obtain powerful, chromatic, not very selective and tenacious colorings.

  The direct dye (s) according to the present invention make it possible to obtain lighter dyes than the original color of the keratin fibers, when it is applied to dark fibers, without the presence of an oxidizing agent being necessary. But of course, he is not

  It can not be ruled out that the dye (s) are used in the presence of such an agent. Similarly, the present invention relates to a cosmetic composition which comprises, in a medium suitable for staining, one or more direct dyes of formula (I) as defined above. Another subject of the present invention consists in a process for dyeing keratin fibers, in which the composition based on the particular direct dyes derived from cationic cyanine of formula (I) is applied to said fibers. Another object of the present application relates to a compartment device comprising the composition according to the invention. The present invention also relates to the use of the composition as a coloring agent or as an optical fiber brightener. But other features, aspects, objects and advantages of the present invention will become more apparent upon reading the description and examples which follow. Within the scope of the definitions of the groups R 1, R 2, R 3, R 4, R 5, R 6 and / or A, by the substituted term is meant substituted by a linear or branched C 1 -C 6 alkyl group, preferably a methyl group; a linear or branched C1-C6 alkoxy group, preferably a methoxy group; a hydroxyl group; a (C1-C6) alkyl thiol group, preferably a methylthiol group; a (C1-C6) alkoxycarbonyl group; an aryl radical optionally substituted with one of the abovementioned substituents. Preferably R3 and R5 represent, independently of one another, a hydrogen atom; a (C1-C6) alkoxycarbonyl group; a C1-C6 alkyl radical or can form with the carbon atoms

  9 to which they are attached an aromatic ring or not C6-C10 or a heterocycle comprising in total 5 to 10 members and 1 to 5 carbon atoms substituted or not. Preferably, R4 represents a hydrogen atom.

  Preferably, R6 represents a C1-C6 alkyl radical. According to one embodiment, A represents a non-condensed aromatic heterocycle selected from thiazolium, pyridinium, these rings being optionally substituted on the carbon atoms. Alternatively, A represents an aromatic heterocycle which is condensed with one or more aromatic rings. In this case, A may be chosen from benzoselenazolium, tetrahydronaphthothiazolium, quinolinium, indolium, benzothiazolium and benzoxazolium, these rings possibly being substituted on the carbon atoms. According to a first particular embodiment, A represents a pyridinium or quinolinium radical; X represents an alkylene group CH 2; n is 0 and m is 0 or 1; R1 and R2 represent a C1-C4 alkyl group, preferably an ethyl group or R1 and R2 form an optionally substituted saturated heterocycle; R3 and R5 represent a hydrogen atom or a C1-C4 alkyl group, preferably a methyl group; R4 represents a hydrogen atom; R6 represents a C1-C4 alkyl group, preferably a methyl group or an ethyl group. According to a second particular embodiment, A represents a benzothiazolium, benzoxazolium or benzoselenazolium radical optionally substituted on the carbon atoms by a C1-C6 alkoxy group; X represents an alkylene group CH 2; n is 0; m is 0 or 1; R1 and R2 represent, independently of one another, a C1-C4 alkyl group, preferably a methyl group, a phenyl group or an atom

  Hydrogen or R1 and R2 form an optionally substituted saturated heterocycle and optionally comprising another heteroatom such as oxygen or nitrogen; R3 and R5 represent, independently of one another, a hydrogen atom, a C1-C4 alkyl group, preferably a methyl group, or a (C1-C4) alkoxycarbonyl group; R4 represents a hydrogen atom; R6 represents a C1-C4 alkyl group, preferably an ethyl or methyl group. According to a third particular embodiment, A represents a thiazolium radical optionally substituted on the carbon atoms by at least one phenyl group or A represents a tetrahydronaphthothiazolium radical; X represents an alkylene group CH 2; n is 0 or 1; m is 0; R1 and R2 represent a C1-C4 alkyl group, preferably a methyl group, or R1 and R2 form an optionally substituted 5- or 6-membered saturated heterocycle; R3 and R5 represent a hydrogen atom, a C1-C4 alkyl group, preferably a methyl group; R6 represents a C1-C4 alkyl group, preferably an ethyl or methyl group.

  In the particular case where A represents a thiazolium radical, m denotes 0, n denotes 0 or 1, X denotes an alkylene group CH 2, R 3, R 4 and R 5 represent a hydrogen atom, R 6 represents a C 1 -C 4 alkyl group, preferably an ethyl group, and R1 and R2 together form a heterocycle with 6 members then said heterocycle a) optionally comprises another heteroatom such as nitrogen, said heteroatom may be substituted by a group of formula (II) below: (II ) in which A 'represents a thiazolium radical, m' denotes 0, n 'denotes 0 or 1, X' denotes an alkylene group CH2, R'3, R'4 and R'5 represent a hydrogen atom and R ' 6 represents a C1-C4 alkyl group, preferably an ethyl or methyl group; b) may be substituted by a group of the following formula R "3 (III) in which A" represents a thiazolium heterocycle, X "denotes an alkylene group CH 2, m" denotes 0; n "denotes 0 or 1; R" 3, R "4, R" 5 represent a hydrogen atom and R "6 represents a C1-C4 alkyl group, preferably an ethyl or methyl group. Particular embodiment, A represents a benzothiazolium or indolium radical optionally substituted with one or more C 1 -C 4 alkyl radicals, X represents an oxygen atom or a carbonyl group, n and m denote 0, R 1 and R 2 represent, independently, one on the other, a C 1 -C 4 alkyl group, preferably an ethyl or methyl group, an optionally substituted phenyl group or a hydrogen atom; R 3 and R 5 may form with the carbon atoms to which they are attached

  An aromatic ring optionally substituted by at least one group selected from a C1-C4 alkyl group represents a dialkyl (C1-C6) amino group. According to a fifth embodiment, A represents a benzoxazolium or benzothiazolium or tetrahydronaphthothiazolium radical; X represents an alkylene group CH 2; n is 1 or 2 and m is 0; R3, R4 and R5 represent a hydrogen atom; R6 represents a C1-C4 alkyl group, preferably a methyl or ethyl group; R1 and R2 represent, independently of one another, a hydrogen atom; a C1-C4 alkyl group, preferably a methyl or ethyl group, optionally substituted by at least one hydroxyl group, a phenyl, a hydrogen atom or R1 and R2 form a saturated heterocycle, preferably interrupted by one or more atoms oxygen.

  It should be noted that Y- may be an anion of mineral origin chosen in particular from halides, sulphates, hydrogen sulphates, nitrates, phosphates, hydrogen phosphates, dihydrogen phosphates, boronates, carbonates and hydrogenocarbonates.

  The Y- anion may also be of organic origin, and in this case, more particularly chosen from those originating from salts of mono- or polycarboxylic acids, sulphonic, sulfuric, saturated or unsaturated, aromatic or otherwise, optionally substituted with minus a hydroxyl, amino, or halogen atom.

  In particular, Y- is chosen from chloride, iodide, bromide, sulphate, methosulphate, ethosulphate, toluenesulphonate or perchlorate. It should be noted that the nature of the counterion Y- is not critical as regards the dyeing properties of the compounds of formula (I).

  Likewise, the invention encompasses the mesomeric forms of the compounds of formula (I). The direct dye according to the invention is generally a fluorescent molecule, that is to say which colors by itself, absorbs the light of the visible spectrum and possibly also the ultraviolet (wavelengths ranging from 360 to 760 nanometers) but which, unlike a conventional dye, transforms part of the energy absorbed into fluorescent light of longer wavelength than that absorbed, emitted in the visible part of the spectrum.

  In addition, the fluorescent dye according to the invention is a dye which generates a fluorescence on the support on which it is applied. In accordance with a particularly advantageous embodiment of the invention, the compound of formula (I) corresponds to one of the following compounds: ## STR1 ## and ## STR2 ## Salt of 2 - [(5,5-dimethyl-3-piperidino-2-cyclohexen-1-salt of 2 - [(5,5-dimethyl-3-piperidino-2-cyclohexen-1-ylidene) methyl] - 3-ethyl-benzoselenazolium-ylidene) methyl] -3-ethyl-4,5-diphenyl thiazolium SeMM MeMe Me IV HI / N + GN Me • Me c Y-Y- 2 - [(5,5-dimethyl) salt 3-Piperidino-2-cyclohexen-1 - 2 - [(5,5-dimethyl-3-piperidino-2-cyclohexen-1-ylidene) methyl] -3-ethyl-5-methoxy Benzoselenazolium ylidene) methyl] - 1-methyl-naphtho [1,2-d] thiazolium Me Me and 2-[(5,5-dimethyl-3-piperidino) -2- [(5,5-dimethyl-3-piperidino) -2- cyclohexen-1- 2 - [(5,5-dimethyl-3-piperidino-2-cyclohexen-1-ylidene) methyl] -3-ethyl-6,7,8,9-tetrahydro-naphtho [2,1- salt] salt; ylidene) methyl] -1-ethyl-quinolinium d] thiazolium S s + CH + CHùα Me and YY 2 - [(5,5-dimethyl) salt 3-ethyl-2 - [[3- (1-piperidinyl) -2-cyclohexen-1-ylidene) methyl] -3-ethyl-benzothiazolium-ylidene] methyl 3-ethyl-3-morpholino-cyclohexen-1-salt 3-Ethyl-2 - [[3- (phenylamino) -2-cyclohexen-1-2 - [[5,5-dimethyl-3- (1-pyrrolidinyl) -benzothiazolium Me] 2-Cyclohexen-ylidene] methyl] -benzothiazolium-1-ylidene] methyl] -3-methyl-benzothiazolium NMe 2 Me CH 1 + CH 2 Y 2 -COO 4 2 - [[3- (dimethylamino) -2- salt) 4,5-Dihydro-3-methyl-2 - [[5-methyl-3- (1-ylidene) methyl] -3-ethyl-benzothiazolium piperidinyl) -2-cyclohexen-1-ylidene] methyl] cyclohexen-1-chlorohexylate] -thiazolium Me Me Me N + Me ~ cx cx ~~ CH s Met 2 CIOâ CI04 2 - [[3- (dimethylamino) -5-methyl-2-diPerchlorate perchlorate of 2,2 '- [[4,4'- bipiperidine] -1,1'-diylbis (2-cyclohexen-1-ylidene) methyl] -4,5-dihydro-3-methyl-cyclohexen-3-yl-1-ylidenemethylidyne)] bis [4,5-dihydro- 3-thiazolium methyl-thiazolium, Me Me Me CH Me Me CH 2 -CH 2 -CH 2 -CH 2 O -CH 2 O - diol of 2,2 '- [1,4-piperazinediyl] 2 - [[5,5-dimethyl-3- (1-pyrrolidinyl) -2-cyclohexen-3-yl-1-ylidene) methylidyne]] bis [4,5-dihydro-bis [(5-methyl-2-iodide)] 3-cyclohexen-1-ylidene] methyl] -3-methyl-benzothiazolium, methyl-thiazolium, and CH 3 G + Me-I-ClO 3-ethyl-2 - [[3- (1-piperidinyl)] - 1-Methyl-4 - [[3- (1-piperidinyl) -2-ylidyl] methyl] -Benzothiazolium, cyclohexen-1-ylidene] methyl] quinolinium 2-cyclohexen-1-chlorohexyl Chloroacetate 4 - [[5,5-dimethyl-3- (1-piperidinyl) -2- perchlorate, 1-methyl-4 - [[3- (1-piperidinyl) -2-cyclohexen-1-ylidene] methyl perchlorate] 1-ethyl-2 - [[3- (1-piperidinyl) -2-cyclohexen-1-pyridine) -1-methyl-pyridinium cyclohexen-1-ylidene] methyl] -pyridinium salt and Me Me Me CH 1 CH 2 - [[5,5-dimethyl-3- (1-piperidinyl) -2-ylidene] methyl] -quinolinium, cyclohexen-1-ylidene] methyl] -1-methyl-pyridinium, Me N CH s + cm to N + ## STR2 ## Perchlorate of 1-methyl-2 - [[3- (1-piperidinyl) -2-perchlorate of 3-ethyl-2 - [[3- (1-pip)] Ridinyl) -2-cyclohexen-1-ylidene] methyl] -pyridinium cyclohexen-1-ylidene] methyl] -Naphtho [2,1-d] thiazolium and CH 2 -CH 2 Cl 2 CH 2 Cl 2 perchlorate 3-Ethyl-2 - [[3- (1-piperidinyl) -2cyclohexen-1-ylidene] methyl] -3-ethyl-benzothiazolium cyclohexen-1-5-dimethyl-3- (1-piperidinyl) -2-perchlorate -ylidene] methyl] -Benzoxazolium and Et + NMe2 CH ~I-CHCO4 4-ethyl-4 - [[3- (1-piperidinyl) -2-cyclohexen-iodide perchlorate of 2 - [[3- (dimethylamino)] 2-Cyclohexen-1-ylidene] methyl] -quinolinium-ylidene] methyl] -3-ethyl-benzothiazolium and 1-ethyl-2- [3-ethyl-2-yl] 3- [3- (phenylamino) -2-cyclohexen-1-salt of 2 - [[6- (ethoxycarbonyl) -3- (1-pyrrolidinyl) -2-ylidene] methyl] -Benzothiazolium, cyclohexen-1-ylidene] methyl] -3 Methyl benzothiazolium and CH 2 1 + N + Me CH 2 Me 2 Me 2 Y 2 EtO 2 CIO 4 2 - [[3- (dimethylamino) -5,5-dimethyl-2-cyclohexen perchlorate salt of 2 - [[6- ethoxycarbonyl) -3- (1-pyrrolidinyl) -1-ylidene] methyl] -3-ethyl Benzothiazolium-2-cyclohexen-1-ylidene] methyl] -3-ethyl-benzothiazolium Me Me N + CH 2 • Me 2 • V Me e e. Met CI04 2 - [(5,5-Dimethyl-3-piperidino-2-cyclohexen-1-cyclohexen-1-ylidene) 2 - [[3- (dimethylamino) -5,5-dimethyl-2-iodide] Methyl] -3-ethyl-benzothiazolium-ylidene) methyl] -1-methyl-Naphtho [1,2-d] thiazolium Et And Ph CH CH SN-IL-1 2 - [(5,5-Dimethyl-3-piperidino-2-cyclohexen-1-ylidene) methyl] - [(5,5-dimethyl-3-piperidino-2-cyclohexen-1-iodide)] iodide 3-ethyl-4,5-diphenyl-thiazoliumylidene) methyl] -1-ethyl-quinolinium, and 2 - [(5,5-Dimethyl-3-piperidino-2-cyclohexen-1-ylidene) methyl] -3-ethyl-5-methoxy-benzoselenazolium iodide, 5-dimethyl-3-piperidino-2-cyclohexen-1-iodide ylidene) methyl] -3-ethyl-benzoselenazolium and N + I ~ / I c ~ and ~ / ^ ~ II Me H ~ O / • z Me e • i iodide of 2 - [(5,5-dimethyl-3- 2 - [(5,5-dimethyl-3-morpholino-2-cyclohexen-1-ylidene) methyl] -3-ethyl-6,7,8,9-tetrahydro-naphthalate-2-cyclohexen-1-iodide Ho [2-ylidene) methyl] -3-ethyl-benzothiazolium d] thiazolium and 2-[[5,5-dimethyl-3- (1-piperidinyl) -2-cyclohexen] 1-ylidene] methyl] -3-ethyl-benzothiazolium NHPh 0 e CFù N + Me ClO 2 - [(2-Anilino-4H-naphtho [1,2-b] pyran-4-yl] ideyl) methyl] -3- Methylbenzothiazole i um xo PhiMu Mei ~ S 0 CH_e + CI04 cx ~ N CI04 2 - [[2- (o-Hydroxy-N-methylanilino) -4H- Perchlorate 3-Methyl-2 - [[ 2- (N-Methylanilino) -4H-naphtho [1,2-b] pyran-4-ylidene] methyl] 3-naphtho [1,2-b] pyran-4-ylidene] methyl] benzothiazolium methylbenzothiazolium Me 0 NHPh Me C104 2 - [[2-Anilino-7- (methyl-4H-1-benzopyran-4-ylidene) methyl] -3-methylbenzothiazole Me 2 N NE 2 Me H I + N-ClO 4 Perchlorate Perchlorate [[2- (bisethylamino) -7- (dimethylamino) -4H-1-benzopyran-4-yl] dien) methyl] -3-methylbenzothiazolium NHP2 0 Me N + CH Et2N to MeC104 v ~ HClO4 Perchlorate of 2 - [(4-Anilino-2H-1-benzopyran-2-perchlorate of 2 - [[3- (diethylamino)] 4-oxo-1 (4H) -ylidene) methyl] -3-methylbenzothiazolium naphthalenylidene] methyl] -3-methyl-benzothiazolium NHP2 Me CH 3 O-Me Me e e CH YY 3H-1,3,3 Salt -trimethyl-2 - [[4- (phenylamino) -2H-1-salt of 3-methyl-2 - [[7-methyl-2- [methyl] -2-benzopyran-2-ylidene] methyl] indolium (methylthio) phenyl] amino] -4H-1-benzopyran-4-yl] dene] methyl] benzothiazolium NHPh Me Me CHM MeS Me ICH .C1 N \ CIO4 1,3,3-trimethyl-2 - [[4-chloro] chloride - (phenylamino) -2H-1- 3-methyl-2 - [[7-methyl-2- [methyl [2-benzopyran-2-yl] idenyl] methyl] -3H-indolium (methylthio) phenyl] amino perchlorate] 4H-1-Benzopyran-4-ylidene] methyl] Benzothiazolium 2Y Y Me Me + N / CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 4a, 5,6-tetrahydro-7-salt of 1-ethyl-2 - [[4,4a, 5,6-tetrahydro-7- (1,4,7,10-naphthalenyl) -2 (3H) - ylidene) methylidyne]] bis [4,5-dihydro-3-tetraoxa-13-azacyclopentadec-13-yl] -2 (3H) -methyl thiazolium naphthalenylidene] methyl] naphtho [1,2-d] thiazolium O + CH ~ ~ N ~ OO 0 ~ ## STR1 ## Oxythioate salt of 3-ethyl-2 - [[4,4a, 5,6-tetrahydro-7- (1,4,7,10-tetraoxa) 3-ethyl perchlorate 2 - [[4,4a, 5,6-tetrahydro-7-13-azacyclopentadec-13-yl) -2 (3H) -naphthalenylidene] methyl] (1,4,7,10-tetraoxa-13-azacyclopentadec 13-yl) -2 (3H) -benzoxazolium naphthalenylidene] methyl] -benzothiazolium and CH 2 / NMe 2 ClO 2 - [[7- (dimethylamino) -4,4a, 5,6-tetrahydro-2 (3H) -naphthalenylidene] perchlorate Methyl] -3-ethyl-benzothiazolium ## STR4 ## 4-Perchlorate - 2 - [[7- (dimethylamino) -4,4a, 5,6-tetrahydro-3-methyl salt -2 - [[4,4a, 5,6-tetrahydro-72 (3H) -naphthalenylidene] methyl] -3-ethyl-benzoxazolium (phenylamino) -2 (3H) -naphthalenylidene] methyl] Benzothiazolium PhN ee CH-N + Elt CIO4 3-ethyl-2 - [[4,4a, 5,6,10,10a-hexahydro-7 (phenylamino) -2 (3H) -anthracenylidene] methyl] benzothiazolium perchlorate Me Me YC -HF CH CHCH Me N ~ CH CHUCH Mejme Meme I'el-I'odure of 2- [3- [5,5-dimethyl-3- (methylphenylamino) -2- iodide of 2- [3- [5,5-Dimethyl-3- (methylphenylamino) -2-cyclohexen-1-ylidene] -1-propenyl] -3-ethyl-benzothiazolium cyclohexen-1-ylidene] -1-propenyl] -1 , 3,3-trimethyl-3H-Indolium Me Me and CHùCH = CH ~NN CH CHH EtO C el * Y CIO4 2- [3- [3- (2,3-Dihydro-1H-indol-1-yl) perchlorate yl) -5.5- 2- [3- [6- (Ethoxycarbonyl) -3- (1-pyrrolidinyl) -2-dimethyl-2-cyclohexen-1-ylidene] -1-propenyl] -3-ethyl salt 1-Cyclohexen-1-ylidene] -1-propenyl] -1-ethyl-naphtho [1,2-benzoxazolium, d] thiazolium, Y-And I + N CHùCHùCH N CHùCHùCH 0b NN \ CùOEt Me e [1, CI04 Where Me e 2- [3- [3- [4- (ethoxycarbonyl) -1-dimethyl) -2- [3- [3- [4- (ethoxycarbonyl) -1-piperazinyl] -5,5-perchlorate salt; 2-Cyclohexen-1-ylidene] -1-propenyl] -3-ethyl-piperazinyl] -5,5-dimethyl-2-cyclohexen-1-ylidene] -1-benzoxazolium propenyl] -3-ethyl-benzothiazolium, and Et + H ## STR2 ## 2- [3- [5- [5,5-Dimethyl-3- (1-piperidinyl) -2-perchlorate] -4- [3- [3- (2, 4-chloro) perchlorate) 3-dihydro-indol-l-yl) -5,5-c 1-propenyl] -3-ethyl-benzoxazolium-dimethyl-2-cyclohexen-1-ylidene] -1-propenyl] -1-ethylquinolinium-1-ylidene] -1-propenyl] -3-ethyl-1-propenyl] -1-ethyl-quinolinium and Me ## STR5 ## I - Me CI04 2- [3- [2,3-Dihydro-1H-indol-1-yl] -5,5-iodide peroxide] 2- [3- [5,5-dimethyl] 3- (1-pyrrolidinyl) -2-dimethyl-2-cyclohexen-1-ylidene] -1-propenyl] -1-ethyl-cyclohexen-1-ylidene] -1-propenyl] -3-ethyl-Naphtho Naphtho [1,2-d] thiazolium d] thiazolium Me and CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 Me 2 pyrrolidinyl) -2- [2- [3- [5,5-dimethyl-3- (1-pyrrolidinyl) -2cyclohexen-1-ylidene] -1-propenyl] -1,3,3-trimethyl-3-cyclohexen-1-iodide 1-ethylidene] -1-propenyl] -3-ethyl-indolium benzothiazolium and Me and CH = CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 0 2- [3- [6- (Ethoxycarbonyl) -3- (1cyclohexen-1-ylidene) -1-propenyl] -3-ethyl-benzoxazolium pyrrolidinyl) -2-cyclohexen-1-pyrrolidinyl) -2- ylidene] -1-Propé nyl] -3-ethyl-benzothiazole and NN CH = CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 4 CH 2 CH 4 CH 2 CH 4 CH 3 CH 4 CH 2 CH 4 CH 2 CH 4 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 2- [3- [6- (Ethoxycarbonyl) -3- (1-cyclohexen-1-ylidene) 1-propenyl] -1-ethyl-pyrrolidinyl) -2-cyclohexen-1-ylidene] -1-propenyl perchlorate ] -3quinolinium ethyl-benzoxazolium These compounds are known molecules. Their synthesis has already been described. As an example of a synthesis of this type of compound, mention may be made of the two-step process from dehydrodimethoxynaphthol: R 1 N 1 R 2

  The invention further relates to a cosmetic composition comprising the direct dye (s) of formulas (I) in a medium suitable for dyeing. The direct dye (s) of formula (I) may be present in a content by weight ranging from 0.001% to 20% by weight, preferably in a content by weight ranging from 0.001% to 15% by weight, and more preferably in a content by weight. ranging from 0.05 to 10% by weight, relative to the total weight of the composition. The appropriate medium for the coloration also called staining medium is a cosmetic medium generally consisting of water or a mixture of water and at least one organic solvent to solubilize compounds that are not sufficiently soluble in the water. water. By way of organic solvent, mention may be made, for example, of linear or branched C 1 -C 4 alkanols, such as ethanol and isopropanol; glycerol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, the like and their derivatives. mixtures. The solvent or solvents may be present in proportions ranging preferably from 1 to 40% by weight relative to the total weight of the dyeing composition, and even more preferably from 5 to 30% by weight approximately. The pH of the 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 the field.

  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 or tartaric acid. , citric acid, lactic acid, sulphonic acids. Among the alkalinizing agents that may be mentioned, by way of example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula (IV): wherein W is a propylene residue optionally substituted by a hydroxyl group or a C1-C6 alkyl radical; Rx, Ry, Rz and Rt, which may be identical or different, represent a hydrogen atom, a C1-C6 alkyl radical or a C1-C6 hydroxyalkyl radical.

  The cosmetic composition may further comprise one or more additional direct dyes of nonionic, cationic or anionic, and preferably cationic or nonionic nature, or combinations thereof. Generally, these direct dyes are chosen from nitro dyes of the benzene series, neutral, acidic or cationic, acid or cationic neutral azo direct dyes, quinone direct dyes and in particular neutral, acidic or cationic anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes, alone or as a mixture. They may for example in a variant be chosen from the following nitrated benzene dyes

  1-hydroxy-3-nitro-4-N- (γ-hydroxypropyl) amino benzene, N - ((3-hydroxyethyl) amino-3-nitro-4-amino benzene, 1-amino- 3-methyl-4-N - ((3-hydroxyethyl) amino-6-nitro benzene, 1-hydroxy-3-nitro-4-N - ((3-hydroxyethyl) amino benzene, diamino-2-nitrobenzene, 1-amino-2-nitro-4-methylamino benzene, N - ((3-hydroxyethyl) -2-nitro-para-phenylenediamine, 1-amino-2-nitro-4- (3-hydroxyethyl) amino-5-chloro-benzene, 2-nitro-4-amino-diphenylamine, 1α-amino-3-nitro-6-hydroxybenzene, 1- (3-aminoethyl) amino-2 -Nitro-4- (3-hydroxyethyloxy) benzene, 1- (R, y-dihydroxypropyl) oxy-3-nitro-4- (3-hydroxyethyl) amino benzene, 1-hydroxy-3-nitro-4 aminobenzene, 1-hydroxy-2-amino-4,6-dinitrobenzene, 1-methoxy-3-nitro-4- (3-hydroxyethyl) amino benzene, 2-nitro-4'-hydroxydiphenylamine, 1-amino-2-nitro-4-hydroxy-5-methylbenzene 1- (3-hydroxyethyloxy-3-methylamino-4-nitrobenzene) -1-methylamino-2-nitro-5- (3) there dihydroxypropyl) oxybenzene, 1 - ((3-hydroxyethyl) amino-2-methoxy-4-nitrobenzene, 1 - ((3-aminoethyl) amino-2-nitro-5-methoxybenzene, - 1,3-di ((3-hydroxyethyl) amino-4-nitro-6-chlorobenzene, 1-amino-2-nitro-6-methyl-benzene, 1 - ((3-hydroxyethyl) amino-2 4-hydroxy-4-nitrobenzene, N - ((3-hydroxyethyl) -2-nitro-4-trifluoromethylaniline,

  4 - ((3-hydroxyethyl) amino-3-nitro-benzenesulfonic acid, 4-ethylamino-3-nitro-benzoic acid, 4 - ((3-hydroxyethyl) amino-3-nitro chlorobenzene, 4 - ((3-hydroxyethyl) amino-3-nitro-methylbenzene, 4- (3,5-dihydroxypropyl) amino-3-nitro-trifluoromethylbenzene, 1 - ((3-ureidoethyl ) amino-4-nitrobenzene, 1,3-diamino-4-nitrobenzene, 1-hydroxy-2-amino-5-nitrobenzene, 1-amino-2- [tris (hydroxymethyl) methyl] amino 5-nitrobenzene, 1 - ((3-hydroxyethyl) amino-2-nitrobenzene, 4- (3-hydroxyethyl) amino-3-nitrobenzamide, 1- (3-hydroxyethyl) amino-4- N, N-bis- (3-hydroxyethyl) amino-2-nitrobenzene, 1- (γ-hydroxypropyl) amino-4-N, N-bis - ((3-hydroxyethyl) amino-2-nitrobenzene, ((3-hydroxyethyl) amino-4- (N-methyl, N- (3-hydroxyethyl) amino-2-nitrobenzene, 1 - ((3-hydroxyethyl) amino-4- (N-ethyl, N- (3-hydroxy ethyl) amino 2-nitrobenzene, 1- (3, y-dihydroxypropyl) amino 4- (N-ethyl, N- (3-hydroxyethyl) amino 2-nitrobenzene - 2-nitroparaphenylenediamines of the following formula NHRa NRbRc NO225

  In which: Rb represents a C1-C4 alkyl radical, a 13-hydroxyethyl or (3-hydroxypropyl or γ-hydroxypropyl radical, Ra and Rc, which may be identical or different, represent a 13-hydroxyethyl, - (3-hydroxypropyl) radical, γ-hydroxypropyl, or 13, γ-dihydroxypropyl, at least one of Rb, Rc or Ra being a γ-hydroxypropyl radical and Rb and Rc can not simultaneously designate a β-hydroxyethyl radical when Rb is a radical y hydroxypropyl, such as those described in French patent FR 2 692 572.

  The composition used in the context of this variant may also comprise, in addition to or in substitution for these nitrated benzene dyes, one or more direct dyes chosen from azo dyes, anthraquinone, naphthoquinone or benzoquinone dyes, indigo dyes, or dyes derived from triarylmethane. These direct dyes may in particular be basic dyes among which may be mentioned more particularly the dyes known in the Color Index, 3rd edition, under the names "Basic Brown 16", "Basic Brown 17", "Basic Yellow 57", "Basic Red 76 "," Basic Violet 10 "," Basic Blue 26 "and" Basic Blue 99 ", or acid direct dyes, among which are more particularly the dyes known in the Color Index, 3rd edition, under the names" Acid 7 "Orange, 24" Orange Acid, "36 Acid Yellow", 33 "Acid Red," Acid Red 184 "," Acid Black 2 "," Acid Violet 43 ", and" Acid Blue 62 ", or dyes cationic direct agents such as those described in patent applications WO 95/01772, WO 95/15144 and EP 714954 and the content of which forms an integral part of the present invention, and in particular the Basic Red 51, Basic Orange 31 and Basic Yellow 87 dyes. .

  Among the natural direct dyes that may be mentioned are henna, chamomile, indigo, among others. When they are present, the additional direct dye or dyes preferably represent 0.01 to 20% by weight, and even more preferably 0.05 to 10% by weight relative to the total weight of the composition. When it is intended for the oxidation dyeing, the cosmetic composition in accordance with the invention further comprises at least one oxidation base chosen from the oxidation bases conventionally used for the oxidation dyeing and of which one mention may especially be made of para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases and their addition salts with an acid or with an alkaline agent. Among the paraphenylenediamines, para-phenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl paraphenylenediamine, 2,5-dimethyl paraphenylene diamine, N, N-dimethyl para-phenylenediamine, N, N-diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl-3-methylaniline, N, N-bis - ((3-hydroxyethyl) para-phenylenediamine, 4-N, N-bis - ((3-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis - ((3 hydroxyethyl paraphenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N - ((3-hydroxy-propyl) para-phenylenediamine, 2-hydroxy-methyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, (3-hydroxyethyl) para-phenylene diamine , N- (3, γ-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine,

  N-phenyl paraphenylenediamine, 2-P-hydroxyethyloxy para-phenylenediamine, 2-P-acetylaminoethyloxy para-phenylene diamine, N- (P-methoxyethyl) paraphenylenediamine and 4'-aminophenyl 1- (3hydroxy) pyrrolidine, and their salts thereof; addition with an acid or with an alkaline agent. Of the para-phenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-P-hydroxyethyl paraphenylenediamine, 2-P-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, , 6-methyl-para-phenylene diamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis - ((3-hydroxyethyl) para-phenylenediamine, 2-chloro-para-phenylene diamine, 2- (3-acetylaminoethyloxy) para-phenylene diamine, and their salts; addition with an acid or with an alkaline agent.

  Among the bis-phenylalkylenediamines, N, N'-bis- (13-hydroxyethyl) N, N'-bis- (4'-aminophenyl) -1,3-diaminopropanol may be mentioned by way of example, N, N'-bis - ((3-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'- bis- (β-hydroxyethyl) N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylene diamine, N, N'-bis (ethyl) N, N'-bis- (4'-amino, 3'-methylphenyl) ethylene-diamine, 1,8-bis- (2,5-diamino phenoxy) -3,5-dioxaoctane, and their addition salts with a acid or with an alkaline agent.

  Among the para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino

  2- (3-hydroxyethylaminomethyl) phenol, 4-amino-2-fluoro phenol, and their addition salts with an acid or with an alkaline agent. Among the ortho-aminophenols, 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-amino phenol may be mentioned by way of example, and their addition salts with an acid or with an alkaline agent. Among the heterocyclic bases, there may be mentioned more particularly by way of example, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives and their addition salts with an acid or with an alkaline agent. Of particular note are 1-13-hydroxyethyl-4,5-diaminopyrazole and its salts. When used, the oxidation base (s) preferably represent from 0.005 to 15% by weight, and even more preferably from 0.01 to 10% by weight, relative to the total weight of the composition. When it is intended for the oxidation dyeing, the composition according to the invention may also comprise at least one coupler so as to modify or enrich in glints the shades obtained by using the direct dyes and the dye base (s). 'oxidation.

  The couplers which may be used may be chosen from the couplers conventionally used in oxidation dyeing and among which mention may especially be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic couplers and their addition salts with an acid or with an agent. alkaline.

  These couplers are more particularly chosen from 2-methyl-5-amino phenol, 5-N - ((3-hydroxyethyl) amino 2-methyl phenol, 3-amino phenol, 1,3-dihydroxy benzene, 1, 3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1- (R-hydroxyethyloxy) benzene, 2-amino-4 - ((3-hydroxyethylamino) 1-

  Methoxy benzene, 1,3-diamino benzene, 1,3-bis- (2,4-diaminophenoxy) propane, sesamol, α-naphthol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazole-5-one, 1-phenyl-3-methylpyrazole-5-one, 2,6-dimethyl pyrazolo [1,5-b] -1,2,4-triazole, 2,6-dimethyl [3,2-c] -1,2,4-triazole, 6-methyl pyrazolo [ 1,5-a] -benzimidazole, and their addition salts with an acid or with an alkaline agent. When present, the coupler or couplers preferably represent from 0.001 to 15% by weight, and even more preferably from 0.05 to 10% by weight relative to the total weight of the composition. In general, the addition salts with an acid that can be used in the context of the compositions of the invention (oxidation bases and couplers) are chosen especially from hydrochlorides, hydrobromides, sulphates, citrates and succinates. , tartrates, tosylates, benzenesulfonates, lactates and acetates. The addition salts with an alkaline agent that can be used in the context of the compositions of the invention (oxidation bases and couplers) are chosen in particular from the addition salts with the alkaline or alkaline-earth metals, with ammonia, with organic amines including alkanolamines and compounds of formula (IV). The composition according to the invention makes it possible to obtain lighter dyes than the original color of the keratin fibers, when it is applied to dark fibers, without the presence of an oxidizing agent being necessary. But of course, it is not excluded that the composition according to the invention comprises such an agent. The cosmetic composition according to the invention may also comprise a cosmetic adjuvant.

  The cosmetic adjuvant (s) which are conventionally used in cosmetic compositions, especially for dyeing human keratinous fibers, may be chosen from anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof; mineral thickeners; antioxidants; penetrants; sequestering agents; perfumes ; buffers; dispersants; conditioning agents such as, for example, cations, cationic or amphoteric polymers, chitosans, volatile or non-volatile silicones, modified or unmodified; film-forming agents; ceramides; preservatives; stabilizing agents; opacifying agents. Of course, one skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the composition according to the invention are not, or not substantially, impaired by the addition or additions considered. The adjuvants above are generally present in an amount for each of them between 0 and 20% by weight relative to the total weight of the composition. In a preferred variant of the invention, the compositions according to the invention contain one or more thickening polymers. For the purposes of the present invention, the term "thickening polymer" means any polymer whose presence in the composition makes it possible to increase the viscosity by at least 100 cp at a temperature of 25 ° C. and at a shear rate of 1 s, this viscosity can be determined by a Rheometer or a cone / plane viscometer. In another preferred variant of the invention, the compositions according to the invention comprise one or more surfactants. This or these

  The surfactants may be nonionic, anionic, cationic or amphoteric. The composition according to the invention may be in various forms, such as in the form of liquids, shampoos, creams, gels, or in any other suitable form. A particularly preferred form according to the present invention is a dyeing shampoo and / or lightening comprising in a cosmetically acceptable aqueous medium, at least one direct dye as defined above, and at least one surfactant preferably nonionic surfactant. The more particularly preferred nonionic surfactants are chosen from alkylpolyglucosides. It is not excluded, even if this does not correspond to a preferred embodiment of the invention, that the composition contains at least one oxidizing agent chosen, for example, from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and enzymes such as peroxidases and two- or four-electron oxidoreductases. The use of hydrogen peroxide or enzymes is particularly preferred.

  Another subject of the invention consists of a process for treating keratinous fibers, in particular human keratinous fibers. According to a first variant, a composition as defined is applied to said fibers, dry or wet, for a sufficient time, after which it is rinsed, optionally washed with shampoo, rinsed again and the fibers are dried or allowed to dry. resulting. According to a second variant of the process, a composition as defined is applied to said fibers, dry or wet, without final rinsing.

  The first variant can be used for any type of compositions, whether or not these comprise an oxidizing agent and / or a direct dye and / or an oxidation base possibly associated with a coupler.

  The second variant is particularly suitable for compositions containing no oxidation dye (oxidation base and optionally coupler) or oxidizing agent. In the case of the first variant of the method, the application time is usually sufficient to develop the desired coloration and / or lightening (s). As an indication, the duration of application of the composition is about 1 to 60 minutes and more particularly about 5 to 45 minutes. Moreover, the temperature at which the process according to the invention is carried out is generally between room temperature (15 to 25 ° C.) and 210 ° C. and more particularly between 15 and 45 ° C. In the case where the composition comprises a oxidizing agent, the method according to the invention comprises a preliminary step of separately storing, on the one hand, a composition comprising, in a medium suitable for staining, one or more direct dyes corresponding to formula (I), optionally one or more additional direct dyes and / or optionally one or more oxidation bases optionally associated with one or more couplers, and secondly, a composition comprising, in a cosmetically acceptable medium, one or more oxidizing agents, then mix them at the time of use. Once this is done, the process according to the invention is carried out in accordance with what has been mentioned before.

  Another object of the invention is a multi-compartment device, comprising at least one compartment containing a composition comprising one or more direct dyes corresponding to formula (I) according to the invention, and one or more other compartments of which at least one contains a composition comprising at least one oxidizing agent. This device may be equipped with means for delivering the desired mixture to the hair, such as the devices described in patent FR 2586913. Note that in the case where the composition contains one or more additional direct dyes and / or or more oxidation bases optionally associated with one or more couplers, according to a first variant, this or these compounds are in the first compartment of the device previously described. According to a second variant, the additional direct dye (s) and / or the oxidation base (s) / coupler (s) are stored in a third compartment. It is specified that it would not be excluded to have a third variant combining the two previous ones, in which the additional direct dye (s) and / or the oxidation base (s) and possibly the coupler (s) would be partly in the first compartment, with the direct dye (s) according to the invention and partly in a third compartment. The following examples are intended to illustrate the invention without limiting its scope.

  Examples of dyeing compositions Example 1: The dye (A) has the following structure (A) The dye (A) is used in the following composition: Components Quantities (in active materials) Dyestuff of formula (A) 0.5 % Alkyl (C8 / C10 50/50) polyglucoside 5% sold by the company SEPPIC under the name Oramix CG110 PEG-8 6% Benzyl alcohol 4% Hydroxyethylcellulose sold by the 2% Aqualon company under the name Natrosol250MR Buffer pH9 50% Water qsp 100 This coloring composition is applied to hair with 90% natural white and 90% white permed. The temperature and the pause time are 15 C and 30 minutes, respectively. 510 36 After rinsing, shampooing and helmet drying for 30 minutes, the hair has a powerful red copper color. The color obtained is stubborn to shampoos. The composition is storage stable.

Example 2

  The dye (B) has the following structure: (B)

  The dye (B) is used in the following dye composition Components Quantities (in active materials) Dyestuff of formula (B) 0.5% Alkyl (C8 / C10 50/50) polyglucoside 5% sold by the company SEPPIC under the denomination Oramix CG110 PEG-8 6% Benzyl alcohol 4% Hydroxyethylcellulose sold by the 2% Aqualon company under the name Natrosol250MR Buffer pH9 50% Water qs 100 This coloring composition is applied to hair with 90% natural whites and 90% whites permed. The temperature and the pause time are respectively 25 C and 30 minutes. After rinsing, shampooing and drying with a helmet for 30 minutes, the hair is red-purple.

  The color obtained is stubborn to shampoos. The composition is storage stable.

  Analogous formulations were made by replacing the pH9 buffer with pH4 and pH7 buffers. The red copper for the structure dye (A) and the purple red for the structural dye (B) are found.

Claims (34)

  1. Use of one or more compounds of the following formula (I) (I) wherein: n is 0, 1 or 2; m is 0 or 1; A represents an unsaturated aromatic heterocycle comprising 5 to 12 members, comprising at least one cationic charge on a nitrogen atom and optionally comprising at least one other heteroatom selected from nitrogen, oxygen, sulfur and / or selenium; said aromatic heterocycle being optionally substituted and may be condensed or not with one or more aromatic rings; said condensed aromatic ring or rings which can themselves be condensed with a saturated or unsaturated ring having 5 to 10 members; X denotes an alkylene group CH 2, an oxygen atom or a carbonyl group; R1 and R2 represent, independently of one another, a hydrogen atom; a benzyl or aryl radical optionally substituted and / or condensed with one or more aromatic rings; a linear or branched C1-C24, preferably C1-C6, alkyl radical which can be interrupted by one or more heteroatoms such as N, S or O and / or which can be substituted; when R1 and R2 represent a C1-C24, preferably C1-C6, alkyl radical which may be interrupted by one or more heteroatoms and / or may be substituted, said alkyl radicals may together form a saturated or unsaturated heterocycle, comprising 5 to 15 members, said heterocycle may be substituted and may be condensed or not with one or more aromatic rings; in the case where R1 and R2 together form a heterocycle with 6 members then: (i) said heterocycle optionally comprises another heteroatom such as nitrogen, said heteroatom may be substituted by a group of formula (II) below: in which A ', X', R'3, R'4, R'5, R'6, n 'and m' have the same meanings as A, X, R3, R4, R5, R6, n and m in the formula ( I); or (ii) said heterocycle may be substituted by a group of the following formula (III): (III) in which A, X ", R 3, R 4 and R 5, R 6, n and m" have the same meanings as A, X, R3, R4, R5, R6, n and m in the formula (I) R3 and R5 represent, independently of one another, a hydrogen atom; a halogen atom; a C1-C6 carboxyalkoxy group; a (C1-C6) alkoxycarbonyl group; a linear or branched C1-C6 alkoxy group which may be interrupted by one or more heteroatoms and / or may be substituted; a linear, branched or cyclic, substituted or unsubstituted C1-C6 alkyl radical which may be interrupted by one or more heteroatoms; R3 and R5 can form, with the carbon atoms to which they are attached, an aromatic or non-aromatic C 6 -C 10 or heterocyclic ring comprising in total from 5 to 10 ring members and from 1 to 5 heteroatoms; these rings being condensed or not, substituted or unsubstituted by one or more groups chosen from C 1 -C 4 alkyl and dialkyl (C 1 -C 4) amino groups; R4 represents a hydrogen atom or a linear or branched, substituted or unsubstituted C1-C6 alkyl radical which may be interrupted by one or more heteroatoms or a carbonyl group; R6 represents a C1-C24, preferably C1-C6, linear, branched or cyclic, substituted or unsubstituted alkyl radical which may be interrupted by one or more heteroatoms or a carbonyl group and / or by one or more heterocycles; a substituted or unsubstituted benzyl or aryl radical; Y- represents an organic or mineral anion; as a coloring agent for keratinous fibers, in particular human fibers, and / or as an agent for the optical lightening of these fibers.   2. Use according to claim 1, characterized in that R3 and R5 represent, independently of one another, a hydrogen atom; a (C1-C6) alkoxycarbonyl group; a C 1 -C 6 alkyl radical or may form, with the carbon atoms to which they are attached, a C 6 -C 10 aromatic or non-aromatic ring or a heterocycle comprising in total 5 to 10 ring members and from 1 to 5 substituted or unsubstituted carbon atoms; R4 represents a hydrogen atom and R6 represents a C1-C6 alkyl radical. 41   3. Use according to claim 1 or 2, characterized in that A is chosen from imidazolium, thiazolium, tetrahydronaphthothiazolium, pyridinium, indolium, quinolinium, benzothiazolium and benzoxazolium, these cycles being able to be substituted as well. on the carbon atoms.   4. Use according to any one of claims 1 to 3, characterized in that A represents a pyridinium or quinolinium radical; X represents an alkylene group CH 2; n is 0 and m is 0 or 1; R1 and R2 represent a C1-C4 alkyl group, preferably an ethyl group or R1 and R2 form an optionally substituted saturated heterocycle; R3 and R5 represent a hydrogen atom or a C1-C4 alkyl group, preferably a methyl group; R4 represents a hydrogen atom; R6 represents a C1-C4 alkyl group, preferably a methyl group or an ethyl group.   5. Use according to any one of claims 1 to 3, characterized in that A represents a benzothiazolium, benzoxazolium or benzoselenazolium optionally substituted on the carbon atoms by a C1-C6 alkoxy group; X represents an alkylene group CH 2; n is 0; m is 0 or 1; R1 and R2 represent, independently of one another, a C1-C4 alkyl group, preferably a methyl group, a phenyl group or a hydrogen atom or R1 and R2 form an optionally substituted saturated heterocycle and optionally comprising another heteroatom such as oxygen or nitrogen; R3 and R5 represent, independently of one another, a hydrogen atom, a C1-C4 alkyl group, preferably a methyl group, or a (C1-C4) alkoxycarbonyl group; R4 represents a hydrogen atom; R6 represents a C1-C4 alkyl group, preferably an ethyl group or an ethyl group. 42   6. Use according to any one of claims 1 to 3, characterized in that A represents a thiazolium radical optionally substituted with at least one phenyl group or a tetranapthothiazolium radical; X represents an alkylene group CH 2; n is 0 or 1; m is 0; R1 and R2 represent a C1-C4 alkyl group, preferably a methyl group, or R1 and R2 form an optionally substituted 5- or 6-membered saturated heterocycle; R3 and R5 represent a hydrogen atom, a C1-C4 alkyl group, preferably a methyl group; R6 represents a C1-C4 alkyl group, preferably an ethyl group or a methyl group or an ethyl group.   7. Use according to claim 1 or 6, characterized in that, in the case where A represents a thiazolium radical, m denotes 0, n denotes 0 or 1, X denotes an alkylene group CH2, R3, R4 and R5 represent an atom. of hydrogen, R6 represents a C1-C4 alkyl group, preferably an ethyl group, and R1 and R2 together form a 6-membered heterocycle, then said heterocycle a) optionally comprises another heteroatom such as nitrogen, said heteroatom which may be substituted by a group of formula (II) below: (II) in which A 'represents a thiazolium radical, m' denotes 0, n 'denotes 0 or 1, X' denotes an alkylene group CH2, R'3, R R'5 and R'5 represent a hydrogen atom and R'6 represents a C1-C4 alkyl group, preferably an ethyl or methyl group; b) may be substituted by a group of the following formula (III) in which A "represents a thiazolium heterocycle, X" denotes an alkylene group CH 2; m "is 0; n" is 0 or 1; R "3, R" 4, R "5 represent a hydrogen atom and R" 6 represents a C 1 -C 4 alkyl group, preferably an ethyl or methyl group.   8. Use according to any one of claims 1 to 3, characterized in that A represents a benzothiazolium or indolium radical optionally substituted by one or more C1-C4 alkyl radicals, X represents an oxygen atom or a carbonyl group; n and m are 0; R1 and R2 represent, independently of one another, a C1-C4 alkyl group, preferably an ethyl or methyl group, an optionally substituted phenyl group or a hydrogen atom; R3 and R5 can form with the carbon atoms to which they are attached an aromatic ring optionally substituted by at least one group selected from a C1-C4 alkyl group represents a dialkyl (C1-C6) amino group.   9. Use according to any one of claims 1 to 3, characterized in that A represents a benzoxazolium or benzothiazolium or tetrahydronaphthothiazolium radical; X represents an alkylene group CH 2; n is 1 or 2 and m is 0; R3, R4 and R5 represent a hydrogen atom; R6 represents a C1-C4 alkyl group, preferably a methyl or ethyl group; R1 and R2 represent, independently of one another, a hydrogen atom; A C 1 -C 4 alkyl group, preferably a methyl or ethyl group, optionally substituted by at least one hydroxyl group, a phenyl, a hydrogen atom or R 1 and R 2 form a saturated heterocycle, preferably interrupted by one or more oxygen atoms.   10.Use according to any one of the preceding claims, characterized in that the anion of mineral origin is chosen from halides, sulphates, hydrogen sulphates, nitrates, phosphates, hydrogen phosphates, dihydrogen phosphates, boronates, carbonates, hydrogen carbonates; and in that the anion of organic origin is chosen from those originating from salts of mono- or polycarboxylic acids, sulphonic acids, sulfuric acids, whether saturated or unsaturated, aromatic or otherwise, optionally substituted with at least one hydroxyl radical, amino, or halogen atoms.   11.Use according to any one of the preceding claims, characterized in that the anion is selected from chloride bromide, perchlorate, iodide, sulfate, methosulphate, ethosulphate and toluenesulphate.   12. Use according to any one of the preceding claims, characterized in that the compound of formula (I) is chosen from the group consisting of: - salt of 2 - [(5,5-dimethyl-3-piperidino-2) cyclohexyl-lylidene) methyl] -3-ethylbenzoselenazolium, 2 - [(5,5-dimethyl-3-piperidino-2-cyclohexen-1-ylidene) methyl] -3-ethyl-4,5,5-salt diphenyl thiazolium; 2 - [(5,5-dimethyl-3-piperidino-2-cyclohexen-1-ylidene) methyl] -3-ethyl-5-methoxy benzoselenazolium salt; 2 - [(5,5-dimethyl-3-piperidino-2-cyclohexenylidene) methyl] -1-methyl-naphtho [1,2-d] thiazolium salt; 2 - [(5,5-dimethyl-3-piperidino-2-cyclohexen-1-ylidene) methyl] -3-ethyl-6,7,8,9-tetrahydro-naphtho [2,1-d salt thiazolium; - salt of 2 - [(5,5-dimethyl-3-piperidino-2-cyclohexenylidene) methyl] -1-ethyl-quinolinium; 2 - [(5,5-dimethyl-3-morpholino-2-cyclohexen-1-ylidene) methyl] -3-ethyl-benzothiazolium salt; 3-ethyl-2 - [[3- (1-piperidinyl) -2-cyclohexenylidene] methyl] benzothiazolium salt - the salt of 3-ethyl-2 - [[3- (phenylamino) -2- cyclohexen-1-ylidene] methyl] benzothiazolium - 2 - [[5,5-dimethyl-3- (1-pyrrolidinyl) -2-cyclohexenylidene] methyl] -3-methyl-benzothiazolium salt; 2 - [[3- (dimethylamino) -2-cyclohexen-1-ylidene] methyl] -3-ethyl-benzothiazolium salt; 4,5-dihydro-3-methyl-2 - [[5-methyl-3- (1-piperidinyl) -2-cyclohexen-1-ylidene] methyl] thiazolium perchlorate; 2 - [[3- (dimethylamino) -5-methyl-2-cyclohexen-1-ylidene] methyl] -4,5-dihydro-3-methyl-thiazolium perchlorate; 2,2 '- [[4,4'-bipiperidine] -1,1'-diylbis (2-cyclohexen-3-yl-1-ylidenemethylidyne)] bis [4,5-dihydro-3-methylthiazolium diPerchlorate ; 2,2 '- [1,4-piperazinediylbis [(5-methyl-2-cyclohexen-3-yl-1-ylidene) methylidyne]] bis [4,5-dihydro-3-methyl-thiazolium diPerchlorate; 2 - [[5,5-dimethyl-3- (1-pyrrolidinyl) -2-cyclohexenylidene] methyl] -3-methyl-benzothiazolium iodide; 3-ethyl-2 - [[3- (1-piperidinyl) -2-cyclohexenylidene] methyl] benzothiazolium iodide 46 - 1-methyl-4 - [[3- (1-piperidinyl) perchlorate) -2-cyclohexenylidene] methyl] quinolinium; 4 - [[5,5-dimethyl-3- (1-piperidinyl) -2-cyclohexenylidene] methyl] -1-methyl-pyridinium perchlorate; 1-methyl-4 - [[3- (1-piperidinyl) -2-cyclohexenylidene] methyl] pyridinium perchlorate; salts of 1-ethyl-2 - [[3- (1-piperidinyl) -2-cyclohexenylidene] methyl] quinolinium; 2 - [[5,5-dimethyl-3- (1-piperidinyl) -2-cyclohexen-1-ylidine] methyl] -1-methyl-pyridinium perchlorate; 1-methyl-2 - [[3- (1-piperidinyl) -2-cyclohexenylidene] methyl] pyridinium perchlorate; 3-ethyl-2 - [[3- (1-piperidinyl) -2-cyclohexenylidene] methyl] -Naphtho [2,1-d] thiazolium perchlorate; 2 - [[5,5-dimethyl-3- (1-piperidinyl) -2-cyclohexenylidene] methyl] -3-ethyl-benzothiazolium perchlorate; 3-ethyl-2 - [[3- (1-piperidinyl) -2-cyclohexenylidene] methyl] -Benzoxazolium perchlorate; 1-ethyl-4 - [[3- (1-piperidinyl) -2-cyclohexen-1-ylidene] methyl] quinolinium perchlorate; 2 - [[3- (dimethylamino) -2-cyclohexen-1-ylidene] methyl] -3-ethyl-benzothiazolium iodide; 3-ethyl-2 - [[3- (phenylamino) -2-cyclohexen-1-ylidene] methyl] benzothiazolium iodide; - 2 - [[6- (ethoxycarbonyl) -3- (1-pyrrolidinyl) -2-cyclohexenylidene] methyl] -3-ethyl benzothiazolium salt; 2 - [[3- (dimethylamino) -5,5-dimethyl-2-cyclohexen-1-ylidene] methyl] -3-ethyl benzothiazolium salt; 2 - [[6- (ethoxycarbonyl) -3- (1-pyrrolidinyl) -2-cyclohexen-1-ylidene] methyl] -3-ethylbenzothiazolium perchlorate; 2 - [[3- (dimethylamino) -5,5-dimethyl-2-cyclohexen-1-ylidene] methyl] -3-ethyl-benzothiazolium perchlorate; 2 - [(5,5-dimethyl-3-piperidino-2-cyclohexen-1-ylidene) methyl] -1-methyl-naphtho [1,2-d] thiazolium iodide; 2 - [(5,5-dimethyl-3-piperidino-2-cyclohexen-1-ylidene) methyl] -3-ethyl-4,5-diphenylthiazolium iodide; 2 - [(5,5-dimethyl-3-piperidino-2-cyclohexen-1-ylidene) methyl] -1-ethyl-quinolinium iodide; 2 - [(5,5-dimethyl-3-piperidino-2-cyclohexen-1-ylidene) methyl] -3-ethyl-5-methoxy-benzoselenazolium iodide; 2 - [(5,5-dimethyl-3-piperidino-2-cyclohexen-1-ylidene) methyl] -3-ethyl-benzoselenazolium iodide; 2 - [(5,5-dimethyl-3-piperidino-2-cyclohexen-1-ylidene) methyl] -3-ethyl-6,7,8,9-tetrahydro-naphtho [2,1-iodide] iodide thiazolium; 2 - [(5,5-dimethyl-3-morpholino-2-cyclohexen-1-ylidene) methyl] -3-ethyl-benzothiazolium iodide - 2 - [[5,5-dimethyl] iodide 3- (1-piperidinyl) -2-cyclohexenylidene] methyl] -3-ethyl-benzothiazolium; 2 - [(2-Anilino-4H-naphtho [1,2-b] pyran-4-ylidene) methyl] -3-methylbenzothiazolium perchlorate - 2 - [[2- (o-Hydroxy-N) perchlorate methylanilino) -4H-naphtho [1,2-b] pyran-4-ylidene] methyl] -3-methylbenzothiazolium; 3-Methyl-2 - [[2- (N-methylanilino) -4H-naphtho [1,2-b] pyran-4-ylidene] methyl] benzothiazolium perchlorate; 2 - [[2-Anilino-7- (methyl-4H-1-benzopyran-4-ylidene) methyl] -3-methylbenzothiazolium perchlorate - 2 - [[2- (diethylamino) -7- perchlorate ( dimethylamino) -4H-1-benzopyran-4-ylide) methyl] -3-methylbenzothiazolium; 48 - 2 - [(4-Anilino-2H-1-benzopyran-2-ylidene) methyl] -3-methylbenzothiazolium perchlorate; 2 - [[3- (diethylamino) -4-oxo-1 (4H) -naphthalenylidene] methyl] -3-methyl-benzothiazolium perchlorate; 3H-1,3,3-trimethyl-2 - [[4- (phenylamino) -2H-1-benzopyran-2-ylidene] methyl] indolium salt; - 3-methyl-2 - [[7-methyl-2- [methyl [2- (methylthio) phenyl] amino] -4H-1-benzopyran-4-ylidene] methyl] benzothiazolium salts; 1,3,3-trimethyl-2 - [[4- (phenylamino) -2H-1-benzopyran-2-ylidene] methyl] -3H-indolium chloride; 3-methyl-2 - [[7-methyl-2- [methyl [2- (methylthio) phenyl] amino] -4H-1-benzopyran-4-ylidene] methyl] benzothiazolium perchlorate; salts of 2,2 '- [1,4-piperazinediylbis [(4,4a, 5,6-tetrahydro-7-naphthalenyl-2 (3H) -ylidene) methylidyne]] bis [4,5-dihydro-3] methyl thiazolium; salts of 1-ethyl-2 - [[4,4a, 5,6-tetrahydro-7- (1,4,7,10-tetraoxa-13-azacyclopentadec-13-yl) -2 (3H) -naphthalenylidene) ] methyl] Naphtho [1,2-d] thiazolium; salts of 3-ethyl-2 - [[4,4a, 5,6-tetrahydro-7- (1,4,7,10-tetraoxa-13-azacyclopentadec)   13-yl) -2 (3H) -naphthalenylidene] methyl] benzoxazolium; 3-ethyl-2 - [[4,4a, 5,6-tetrahydro-7- (1,4,7,10-tetraoxa-13-azacyclopentadec-13-yl) -2 (3H) naphthalenylidene perchlorate] methyl] benzothiazolium; 2 - [[7- (dimethylamino) -4,4a, 5,6-tetrahydro-2 (3H) -naphthalenylidene] methyl] -3-ethyl-benzothiazolium perchlorate; 2 - [[7- (dimethylamino) -4,4a, 5,6-tetrahydro-2 (3H) -naphthalenylidene] methyl] -3-ethyl-benzoxazolium perchlorate; 3-methyl-2 - [[4,4a, 5,6-tetrahydro-7- (phenylamino) -2 (3H) -naphthalenylidene] methyl] benzothiazolium salts; 3-ethyl-2 - [[4,4a, 5,6,10,10a-hexahydro-7 (phenylamino) -2 (3H) -anthracenylidene] methyl] -benzothiazolium perchlorate; 2- [3- [5,5-dimethyl-3- (methylphenylamino) -2-cyclohexen-1-ylidene] -1-propenyl] -3-ethyl-benzothiazolium iodide; 2- [3- [5,5-dimethyl-3- (methylphenylamino) -2-cyclohexen-1-ylidene] -1-propenyl] -1,3,3-trimethyl-3H-indolium iodide; 2- [3- [3- (2,3-dihydro-1H-indol-1-yl) -5,5-dimethyl-2-cyclohexen-1-ylidine] -1-propenyl] -3-perchlorate; ethyl-benzoxazolium - salts of 2- [3- [6- (ethoxycarbonyl) -3- (1-pyrrolidinyl) -2-cyclohexen-1-ylidene] -1-propenyl] -1-ethyl-naphtho [1,2 thiazolium; 2- [3- [3- [4- (ethoxycarbonyl) -1-piperazinyl] -5,5-dimethyl-2-cyclohexen-1-ylidene] -1-propenyl] -3-ethyl-benzoxazolium salts; 2- [3- [3- [4- (ethoxycarbonyl) -1-piperazinyl] -5,5-dimethyl-2-cyclohexen-1-ylidene] -1-propenyl] -3-ethyl-benzothiazolium perchlorate; 2- [3- [5,5-dimethyl-3- (1-piperidinyl) -2-cyclohexen-1-ylidine] -1-propenyl] -3-ethyl-benzoxazolium perchlorate; 4- [3- [3- (2,3-dihydro-1H-indol-1-yl) -5,5-dimethyl-2-cyclohexen-1-ylidine] -1-propenyl] -1-perchlorate; ethyl quinolinium; 2- [3- [3- (2,3-dihydro-1H-indol-1-yl) -5,5-dimethyl-2-cyclohexenyl-1-yl] propenyl] perchlorate; ethyl-Naphtho [1,2-d] thiazolium; 2- [3- [5,5-dimethyl-3- (1-pyrrolidinyl) -2-cyclohexen-1-ylidene] -1-propenyl] -3-ethyl-naphtho [1,2-d] iodide; thiazolium; 2- [3- [5,5-dimethyl-3- (1-pyrrolidinyl) -2-cyclohexenylidene] -1-propenyl] -1,3,3-trimethyl-3H-indolium iodide; 2- [3- [5,5-dimethyl-3- (1-pyrrolidinyl) -2-cyclohexen-1-ylidene] -1-propenyl] -3-ethyl-benzothiazolium iodide; 2- [3- [5,5-dimethyl-3- (1-pyrrolidinyl) -2-cyclohexenylidene] -1-propenyl] -3-ethyl-benzoxazolium iodide; 2- [3- [6- (ethoxycarbonyl) -3- (1-pyrrolidinyl) -2-cyclohexen-1-ylidene] -1-propenyl] -3-ethyl-benzothiazolium perchlorate; 4- [3- [5,5-dimethyl-3- (1-pyrrolidinyl) -2-cyclohexen-1-ylidene] 1-propenyl] -1-ethyl-quinolinium perchlorate; 2- [3- [6- (ethoxycarbonyl) -3- (1-pyrrolidinyl) -2-cyclohexen-1-ylidene] -1-propenyl] -3-ethyl-benzoxazolium perchlorate; 13. Cosmetic composition comprising, in a medium suitable for staining, one or more direct dyes defined in one of the preceding claims.   14.Composition according to claim 12, characterized in that the content of direct dye (s) is between 0.001 to 20% by weight, preferably in a content by weight ranging from 0.001 to 15% by weight, and more preferably in a content by weight ranging from 0.05 to 10% by weight, relative to the total weight of the composition.   15. Cosmetic composition according to claim 13 or 14, characterized in that the medium suitable for coloring consists of water or a mixture of water and at least one organic solvent.   16. Cosmetic composition according to any one of claims 13 to 15, characterized in that it comprises one or more additional direct dyes of nonionic, cationic or anionic nature.   17. Composition according to Claim 16, characterized in that the additional direct dye is chosen from nitro dyes of the benzene series, neutral, acidic or cationic, acid or cationic neutral azo direct dyes, quinone direct dyes and in particular anthraquinone dyes. neutral, acidic or cationic, the 51 direct azine dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.   18. Cosmetic composition according to claim 16 or 17, characterized in that the additional direct dye (s) are present in an amount of between 0.01% to 20% by weight and preferably between 0.05% to 10% by weight relative to to the total weight of the composition.   19. Cosmetic composition according to any one of claims 13 to 17, characterized in that it comprises at least one oxidation dye precursor selected from oxidation bases and couplers.   20. Cosmetic composition according to claim 19, characterized in that the oxidation base (s) are chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.   21. Cosmetic composition according to claim 19 or 20, characterized in that the oxidation base (s) are present in an amount of between 0.005 to 15% by weight and preferably between 0.01 to 10% by weight relative to the total weight of the composition.   22. Cosmetic composition according to claim 19, characterized in that the coupler is chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts.   23. Cosmetic composition according to claim 22, characterized in that the coupler is chosen from 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene and 4-diamino 1- (13-hydroxyethyloxy) benzene, 2-amino-4- (13-hydroxyethylamino) -1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane , 3-ureido aniline, 3-ureido 52 1-dimethylamino benzene, sesamol, 1-B-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6- hydroxy indole, 4-hydroxyindole, 4-hydroxy N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine 3,5-diamino-2,6-dimethoxypyridine, 1-N - (13-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- (β-hydroxyethylamino) toluene and their addition salts.   24. Cosmetic composition according to claim 22 or 23, characterized in that the coupler or couplers are present in an amount of between 0.001 to 15% by weight, preferably between 0.05 to 10% by weight relative to the total weight of the composition. composition   25. Cosmetic composition according to claim 13, further comprising at least one cosmetic adjuvant.   26. Cosmetic composition according to claim 25, characterized in that the cosmetic adjuvant is selected from surfactants, polymers, ceramides and pseudo-ceramides, vitamins and pro-vitamins, sunscreens, solid compounds such as pigments, pearlescent or opacifying agents, sequestering agents, plasticizing agents, solubilizing agents, acidifying agents, basifying agents, neutralizing agents, mineral and organic thickeners, antioxidants, hydroxy acids solvents, penetrating agents, buffers, dispersing agents, conditioning agents and preservatives.   27. Cosmetic composition according to any one of claims 13 to 26, characterized in that it comprises one or more thickening polymers. 53   28. Cosmetic composition according to any one of claims 13 to 27, characterized in that it comprises one or more surfactants.   29. Cosmetic composition according to one of claims 13 to 28, characterized in that it comprises at least one oxidizing agent.   30. Cosmetic composition according to claim 29, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and enzymes. such as peroxidases and oxido-reductases with two or four electrons.   31. A process for treating keratinous fibers, more particularly human keratinous fibers, characterized in that a composition as defined according to any one of claims 13 to 30 for a period of time is applied to said fibers, dry or wet. sufficient to obtain the coloring, and after rinsing and optionally shampooing, the resulting fibers are dried or allowed to dry.   32. Process for treating keratinous fibers, more particularly human keratinous fibers, characterized in that a composition as defined according to any one of Claims 13 to 30, without final rinsing, is applied to said fibers, dry or wet. .   33.Dispositif multi-compartment or Kit dyeing, characterized in that it comprises a first compartment containing a composition as defined in any one of claims 13 to 28 and a second compartment containing a composition comprising an oxidizing agent.   34.Utilization of the coloring composition as defined in any one of claims 13 to 30 for the dyeing of 4 keratinous fibers, in particular human keratin fibers such as the hair.