FR2940310A1 - HYDRAZONE / DIAZOIC TYPE DICHROMOPHOREIC DICHROMOPHORIC COMPOUNDS, TINCTORIAL COMPOSITIONS COMPRISING SAME, METHOD FOR COLORING KERATIN FIBERS - Google Patents

Abstract

The subject of the present invention is dichromic dichromophoric compounds of the following formula, their mesomeric forms as well as their addition salts with an acid and their solvates: R, R, R, R, R, R represent a hydrogen or a C-alkyl Hydroxyl, C -C alkoxy, C -C hydroxyalkoxy, optionally substituted amino, C 1 -C 4 alkylcarbonylamino, carbamoyl, ureido, sulfonamide, C 1 -C 6 alkylsulphonylamino group, halogen; R 1 and R 3 represent a C 1 -C 6 alkyl and R 3 represent a hydrogen, a C 1 -C 6 alkyl and R or two radicals R or R or R or R, carried by adjacent carbon atoms, may be an aromatic ring condensed at 6 links; L represents a divalent C 1 -C 4 alkylene radical optionally interrupted by an imidazolium group; * m, n and p, vary from 0 to 4; from 0 to 5, the electroneutrality of the compounds of formula (1) being ensured by one or more cosmetically acceptable anions An, which are identical or different. It also relates to dye compositions comprising said compounds as a direct dye, and a keratinous fiber dyeing method using this composition and a multi-compartment device.

Description

The subject of the present invention is dicationic dichromophoric dyes comprising a hydrazone unit and a diazo unit, dyeing compositions comprising in a medium that is suitable for dyeing. Dichromorphologic Dichromorphic Dioxide Compounds Comprised of HyDaZONE / DIAZOIC TYPE, TINCTORIAL COMPOSITIONS COMPRISING SAME, METHOD FOR COLORING KERATINIC FIBERS keratinous fibers, such compounds as a direct dye, a method for dyeing keratin fibers using this composition, and a multi-compartment device.

It is known to dye keratinous fibers and in particular human keratinous fibers, such as the hair, with dyeing compositions containing direct dyes. These compounds are colored molecules and dyes having an affinity for the fibers. It is known, for example, to use direct dyes of the nitrobenzene type, anthraquinone dyes, nitropyridines, azo, xanthene, acridine, azine or triarylmethane type dyes, or even aromatic direct dyes comprising a hydrazone function. Usually, these dyes are applied to the fibers, optionally in the presence of an oxidizing agent, if it is desired to obtain a simultaneous effect of lightening the fibers. Once the pause time has elapsed, the fibers are rinsed, optionally washed and dried. Due to the nature of the dye / keratin fiber interactions, the colorations that result from the use of direct dyes are temporary or semi-permanent. Thus, after a few shampoos, there is a fading of the color, even a bend in the most unfavorable cases. Indeed, it is in most cases used mixtures of several dyes to obtain a particular shade, including natural shades. However, the dyes have variable affinities for the fibers, which can lead to a selective departure of certain dyes, thus causing a shift in the overall color.

This is one of the reasons why it has recently been proposed to link several dyes together. Such dyes make it possible to obtain a wide range of colors, ranging from very chromatic to more natural shades. It is still desired to increase the range of dyes making it possible to access natural shades, in particular dull shades, which have a good rise along the fiber and which are not very selective (uniformity of the distribution of color along the fiber).

These and other objects are achieved by the present invention which therefore relates to polycationic dichromophoric compounds of the following formula (I), its mesomeric forms, its addition salts with an acid and its solvates: Formula in which: The radicals R 1, R 2, independently of each other, represent a hydrogen atom, a linear or branched C 1 -C 6 alkyl radical, a C 1 -C 4 alkoxy radical or a halogen atom, preferably chlorine and fluorine; The radicals R 5, R 6, R 8 and R 11 represent, independently of each other: a linear or branched C 1 -C 6 alkyl radical, a hydroxyl radical, a C 1 -C 4 alkoxy radical or an amino radical, optionally substituted by one or two identical or different C 1 -C 4 alkyl groups; an alkylcarbonylamino radical (R 13 CO-NR 14) in which the radicals R 13 and R 14, which may be identical or different, represent a C 1 -C 4 alkyl radical; halogen, preferably chlorine and fluorine; The radicals R3 and R4, which may be identical or different, represent a linear or branched C1-C8 alkyl radical; The radicals R 1 and R 9, which may be identical or different, represent a hydrogen atom or a linear or branched C 1 -C 8 alkyl radical; The radical R 10 represents a hydrogen or a linear or branched C 1 -C 8 alkyl radical; the radicals R 1 and R 2, or two radicals R 5 or R 6 or R 8 or R 11, carried by adjacent carbon atoms, can form with each other and with the carbon atoms to which they are attached, a secondary condensed aromatic carbon ring with 6 members ; L represents a divalent C2-C20 alkylene radical, linear or branched, optionally interrupted by an imidazolium group; m, n and p, independently of each other, represent an integer from 0 to 4; q represents an integer ranging from 0 to 5; the electroneutrality of the compounds of formula (I) being ensured by one or more cosmetically acceptable anions An, which may be identical or different. The present invention also relates to dyeing compositions comprising, in a medium suitable for dyeing keratinous fibers, such compounds as direct dyes.

It further relates to a method for dyeing keratinous fibers comprising contacting a composition according to the invention with said fibers, dry or wet, for a time sufficient to obtain the desired effect.

It also relates to a multi-compartment device comprising, in a first compartment, the composition according to the invention, and in a second compartment, an oxidizing composition.

But other features and advantages of the present invention will emerge more clearly from the description and examples which will be presented. In what follows and unless another indication is given, the boundaries delimiting a range of values are included in this area.

As indicated before, the compounds according to the invention correspond to formula (I), their mesomeric forms as well as their addition salts with an acid and their solvates.

According to a first variant, the compounds of formula (I) are such that the radicals R 1 and R 2 represent a hydrogen atom.

According to an advantageous embodiment of the invention, the radicals R 5, R 6, R 8 and R 11 represent, independently of each other, a linear or branched C 1 -C 4 alkyl radical, a hydroxyl radical or an alkoxy radical. C1-C4, an amino radical, optionally substituted by one or two C1-C4 alkyl groups, identical or different to an alkylcarbonylamino radical (R13CO-NR14-) in which the radicals R13 and R14, which may be identical or different, represent an alkyl radical; C1-C4; or two radicals R5 and R8 respectively, carried by adjacent carbon atoms, together form with each other and with the carbon atoms to which they are attached, a fused 6-membered aromatic carbon ring.

Preferably, the radicals R 5, R 6, R 8 and R 11 represent, independently of each other: a linear or branched C 1 -C 4 alkyl radical, a hydroxyl radical, a methoxy radical, an amino radical or a methylcarbonylamino radical ( CH3CONH-) two R5 radicals carried by adjacent carbon atoms, form between them and with the carbon atoms to which they are connected, a 6-membered condensed aromatic carbon ring.

According to a particular embodiment, the coefficient p is zero or 2 with the two radicals R8, carried by two adjacent carbon atoms, forming between them and with the carbon atoms to which they are connected, an aromatic carbon ring condensed at 6 membered ring.

As regards the R 3 and R 4 radicals, the latter, which are identical or different, represent a linear or branched C 1 -C 4 alkyl radical, and even more preferably a methyl radical.

The radicals R 1 and R 9 are more particularly, independently of one another, a hydrogen atom, a linear or branched C 1 -C 4 alkyl radical, and more advantageously a hydrogen atom or a methyl radical.

According to a particularly advantageous embodiment, R 1 represents a methyl radical and R 9 represents a hydrogen atom. As for the radical R10, it more particularly represents a hydrogen atom or a linear or branched C1-C4 alkyl radical, and more advantageously a hydrogen atom or a methyl radical.

According to a particular embodiment, the coefficient q is 0 or 1. Preferably, the coefficient n is 0 or 1, and preferably n is 0.

According to another embodiment, the coefficient p is zero or 2 with the two radicals R8, carried by two adjacent carbon atoms, forming between them and with the carbon atoms to which they are connected, an aromatic carbon ring condensed at 6 membered ring. Preferably L represents a divalent C2-C20 alkylene radical, linear or branched, optionally interrupted by an imidazolium group.

In the formulas of the compounds of formulas (I), An represents an anion or a mixture of anions, organic or inorganic, making it possible to balance the charge (s) of the compounds of formula (I), for example chosen from a halide such as chloride bromide, fluoride, iodide; a hydroxide; sulphate; a hydrogen sulfate; an alkyl sulphate for which the linear or branched alkyl part is C1-C6, such as the methyl sulphate or ethyl sulphate ion; carbonates and hydrogen carbonates; salts of carboxylic acids such as formate, acetate, citrate, tartrate, oxalate; alkylsulphonates for which the linear or branched alkyl part is C1-C8, such as the methylsulphonate ion; arylsulphonates for which the aryl part, preferably phenyl, is optionally substituted by one or more C1-C4 alkyl radicals such as, for example, 4-toluylsulphonate; alkylsulfonyls such as mesylate; a perchlorate.

The acid addition salts of the compounds of formulas (I) may be by way of example the addition salts with an organic or inorganic acid such as hydrochloric acid, hydrobromic acid or sulfuric acid. or (alkyl- or phenyl) sulfonic acids such as p-toluenesulfonic acid or methylsulfonic acid.

The solvates of the compounds of formulas (I) represent the hydrates of such compounds and / or the combination of a compound of formula (1) with a linear or branched C1-C4 alcohol such as methanol or ethanol. , isopropanol, n-propanol. According to a particular embodiment, the compounds of formula (I) are represented by the following formulas, as well as their resonant forms and / or their addition salts with an acid and / or their solvates: H2 NX iN 1 NX OMe OMe N HAc MeO N'N1%) N '' N NY N OMe N, NYJ N X X X- representing a cosmetically acceptable anion or a mixture of anions, as defined previously.

Preferably, L represents a divalent C 2 -C 20 alkylene radical, linear or branched.

It is specified that the addition salts with an acid of the compounds of formulas (I) may be by way of example the addition salts with an organic or inorganic acid such as hydrochloric acid, hydrobromic acid, sulfuric acid or (alkyl- or phenyl) sulfonic acids such as p-toluenesulphonic acid or methylsulphonic acid.

The solvates of the compounds of formula (I), more particularly represent the hydrates of such compounds and / or the combination of a compound of formula (I), with a linear or branched C1-C4 alcohol such as methanol, ethanol, isopropanol, n-propanol.

The compounds according to the invention may be prepared by way of example using the following reaction scheme: Step 1: Synthesis of the compound F11 Obtaining this compound is known in the literature and in particular in Efficient Unimolecular Deprotonation of Aniline Radical Cations Dombrowski, G; Dinnocenzo, J.P .; Zielinski, P.A .; Farid, S.; J. Org. Chem., 2005, 70 (10), 3791-3800. The solvent used in these reactions is a polar solvent such as acetonitrile; the alkylation reaction is generally carried out using a strong base such as 2,6-lutidine. Thus, an equimolar amount of substituted aniline can be contacted with potassium carbonate with stirring. The reaction medium is then heated to 78 ° C. The same molar amount as each of the preceding compounds is then added to the mixture as a hydroxyl-brominated derivative. The reaction medium is then left stirring for 24 hours at 78 ° C. compound 1 compound? compound 3 compound 4 compound 5 compound 6 compound 3 compound 7

24 hours, T.A. (R6) n. (Rs) P + J NH, 0 ° C then T.A., 1 h. OL i., O'sx0 03 R1 N 'NN 1), R2 r' '', R, 1q 2 NH compound, NaNOz CI- (R5) m HN ~ R7 K, CO3 BriLr OH reflux 78`C 24h (R6 The mixture is cooled, filtered and the filtrate is concentrated, the residue thus obtained is purified, in particular by flash chromatography. on silica gel (for example eluent heptane / ethyl acetate: 8/2).

Step 2: Synthesis of compound [31 The synthesis of compound 3 is also described in the literature, for example in the article by Meth-Cohn, O .; Smith, D .; Tetrahedron Letters, 2001, 42 (41), 7237-7240. The compound [1] obtained above is stirred at room temperature in the presence of a solvent, such as, for example, dichloromethane. An equimolar amount of tosyl chloride previously solubilized in a solvent, preferably the same as that in which the compound [1] is dissolved, is then rapidly added to the above mixture. A base, preferably an organic amine, is also slowly added to the reaction mixture. After 24 hours of reaction, at room temperature, the reaction medium is concentrated and the residue obtained is purified by adding a solvent such as acetone, followed by filtration. Compound [3] is purified using standard methods, such as flash silica gel chromatography (for example eluent heptane / ethyl acetate 8/2). Step 3: Synthesis of compound F61 An example of synthesis of this type of compound can be found, for example, in patent application WO 2004/072183.

Thus, compound [5] preferably diluted in a solvent, such as ethanol, for example, in the presence of acetic acid, is slowly contacted with the same molar amount of compound [4]. Subsequently, the reaction medium is heated at 65 ° C. for 13 hours. After cooling, the reaction medium is purified by means of a water / ice mixture with stirring. The solid product that has appeared is then filtered, purified and dried.

Step 4: Synthesis of compound [71 Compound [6] is solubilized, if necessary by heating, in an aromatic solvent, for example toluene. Once the solution has been obtained, a molar amount 2.5 times lower than that of the compound [6] is added to the compound [3], preferably previously suspended in the same solvent as above. The reaction mixture is stirred at 90 ° C for 24 hours. At the end of this period, the cooled reaction mixture is filtered and the precipitate is purified and dried. Step 5: Synthesis of compound F91 In particular, reference can be made to the publication by Deligeorgiev, T.G. Zaneva, D. A; Simeonova, N. A .; Simov, D .; Dyes and Pigments, 1996, Vol. 31, No. 3, 219-224.

The compound [8] is commercially available but it can also be synthesized according to the protocol described by Deligeorgiev.

The compound [8] is solubilized in the presence of water, methanol and hydrochloric acid. Next, as many moles of sodium nitrite as of compound [8] are added to the reaction mixture previously cooled to 0 ° C and maintained at 0 to 5 ° C. The reaction medium is then left for about 35 minutes with stirring. The diazonium salt thus obtained is then added slowly to a solution cooled to 0 ° C comprising the compound [7] previously solubilized in a mixture of methanol and acetic acid.

After addition, the pH of the reaction medium is reduced to 6 with the aid of a basic solution, more particularly potassium carbonate. The water is then evaporated by successive addition of methanol and concentration in vacuo. The resulting residue is then washed, in particular with isopropanol, to precipitate the inorganic salts, which are removed by filtration. The filtrate is concentrated and then purified by conventional means (for example semi-preparative HPLC). Step No. 1: Synthesis of Compound II The compounds according to the invention can also be prepared according to the following synthetic scheme: Compound 5 compound Ethanol, AcOH cat. + I NHz 0 ° C then 65 ° C, 4 h. (R1t) q Compound 11 Compound a (R1t) q NHz Cl HCl, McOH / H0 95/5 0-5 ° C Compound 12 A solution was prepared from compound [6] in an ethanol / glacial acetic mixture. The mixture is added with an equimolar amount of compound [10] with stirring at 0 ° C. After addition of the aldehyde, the mixture is heated at 70 ° C for 4 hours. The reaction medium is then on a water-ice mixture (1/3) to obtain the compound [II] in solid form, which is then purified in the usual manner.

Step 2: Synthesis of the Compound F121 The compound [11] is described in the literature (see, by way of example, the patent EP2004050101).

A solution of compound [II] and toluene is prepared and the compound [3] is then added in a molar amount that is half that of compound [II], previously suspended in toluene. The reaction medium is then stirred for 24 hours at 90 ° C. preferably. At the end of this time, the mixture is cooled to room temperature and the precipitate is filtered, purified in a conventional manner and dried to give the compound [12].

Step 3: Synthesis of Compound [131] Reference may be made to the description given in the context of the preceding reaction scheme corresponding to the fifth step, compound [12] replacing compound [7]. Another subject of the present invention consists of a composition comprising, in a medium suitable for dyeing keratin fibers, at least one compound of formula (I), or its addition salts with an acid, as direct dye .

The concentration of compound of formula (I) may vary between 0.001 and 20% by weight relative to the total weight of the dye composition, more particularly between 0.01 and 10% by weight, and preferably between 0.05 and 5% by weight. % in weight.

The composition according to the invention may further comprise an oxidation base. This oxidation base may be chosen from the oxidation bases conventionally used in oxidation dyeing, for example para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases. Among the para-phenylenediamines, para-phenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine and 2,6-diethyl may be mentioned by way of example; paraphenylenediamine, 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N-dipropyl-para-phenylenediamine, 4-amino-N, N-diethyl-3-methylaniline, N N-bis - ([3-hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (3-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- (3-hydroxyethyl) amino 2-chloroaniline, 2- [3-hydroxyethyl paraphenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (13-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl 3-methyl paraphenylenediamine, N, N- (ethyl, 13-hydroxyethyl) paraphenylenediamine N- (13'-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-13-hydroxyethyloxy para-phenylenediamine, 2-13-acetylaminoethyloxy para-phenylenediamine, (13-methoxyethyl) paraphenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl paraphenylene diamine, 2-13-hydroxyethylamino-5-amino toluene and their acid addition salts.

Of the paraphenylenediamines mentioned above, para-phenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-hydroxy-3-hydroxyethyl paraphenylenediamine, 2-hydroxy-3-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (13-hydroxyethyl) paraphenylenediamine, 2-chloro-para-phenylenediamine, 2-13-acetylaminoethyloxy-para-phenylenediamine, and their acid addition salts are particularly preferred . Among the bis-phenylalkylenediamines, mention may be made, by way of example, of N, N'-bis- (13-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, N N, N'-bis- (13-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- ( 13-hydroxyethyl) N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) N, N ' -bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diamino phenoxy) -3,6-dioxaoctane, and their addition salts with an acid. 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- (13-hydroxyethylaminomethyl) phenol, 4- amino 2-fluoro phenol, and their addition salts with an acid. Among the ortho-aminophenols, there may be mentioned by way of example, 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-amino phenol, and their addition salts with an acid. Among the heterocyclic bases that may be mentioned by way of example are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives. Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino-3-amino pyridine, 2,3-diamino-6-methoxy pyridine, 2- (R-methoxyethyl) amino-3-amino-6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid. Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in DE 2 359 399; JP 88-169,571; JP 05 163 124; EP 0 770 375 or patent application WO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in the patent application FR-A-2,750,048 and among which mention may be made of pyrazolo - [1,5-a] -pyrimidine-3,7-diamine; 2,5-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; pyrazolo [1,5-a] pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-amino pyrazolo [1,5-a] pyrimidin-7-ol; 3-amino pyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-amino pyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol, 2- (7-amino pyrazolo [1,5-a] pyrimidin-3-ylamino) - ethanol, 2 - [(3-amino-pyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol, 2 - [(7-amino-pyrazolo [ 1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol, 5,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5-N, 7-N-7-tetramethyl pyrazolo [1,5-a] pyrimidine-3, 7-diamine, 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo [1,5-a] pyrimidine and their acid addition salts and their tautomeric forms, when tautomeric equilibrium exists.

Among the pyrazole derivatives, mention may be made of the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 as 4,5-diamino-1-methyl pyrazole, 4,5-diamino-1-yl-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino 1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenyl pyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl -hydrazino pyrazole, 1-benzyl 4,5-diamino-3-methyl pyrazole, 4,5-diamino-3-tert-butyl-1-methyl pyrazole, 4,5-diamino-1-tert-butyl-3-methyl-pyrazole, 4,5-diamino-1-yl-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methyl pyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole, 4,5-diamino-3- m 1-isopropyl pyrazole, 4-amino 5- (2'-aminoethyl) amino 1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino-4-β-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts with an acid.

Preferably, a 4,5-diaminopyrazole and even more preferably 4,5-diamino-1-β-hydroxyethylpyrazole and / or one of its salts will be used. As pyrazole derivatives, mention may also be made of diamino N, N-dihydropyrazolopyrazolones and especially those described in application FR-A-2 886 136 such as the following compounds and their addition salts: 2,3-diamino-6 7-Dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] ] pyrazol-1-one, 2-amino-3-isopropylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3- (pyrrolidin-1) -yl) -6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 4,5-diamino-1,2-dimethyl-1,2-dihydro-pyrazol-3 -one, 4,5-diamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one, 4,5-diamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro pyrazol-3-one, 2-amino-3- (2-hydroxyethyl) amino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3 6-Dimethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2,3-diamino-5,6,7,8-tetrahydro-1H, 6H-pyridazino [1,2-a] pyrazol-1-one, 4-amino-1,2-diethyl-5- (pyrrolidin-1-yl) -1,2-dihydro-pyrazol-3-one, 4-amino-5 - (3-di methylamino-pyrrolidin-1-yl) -1,2-diethyl-1,2-dihydro-pyrazol-3-one, 2,3-diamino-6-hydroxy-6,7-dihydro-1H, 5H-pyrazolo [ 1,2-a] pyrazol-1-one. It will be preferred to use 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one and / or a salt thereof. As heterocyclic bases, 4,5-diamino-1- (R-hydroxyethyl) pyrazole and / or 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2 will be used preferentially. -a] pyrazol-1-one and / or a salt thereof.

The composition according to the invention may also contain one or more couplers conventionally used for dyeing keratinous fibers. Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers and heterocyclic couplers. By way of example, mention may be made of 2-methyl-5-aminophenol, 5-N- (B-hydroxyethyl) amino-2-methylphenol, 6-chloro-2-methyl-5-aminophenol and 3-amino phenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1- (B-hydroxyethyloxy) benzene, 2- amino 4- (B-hydroxyethylamino) 1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene , sesamol, 1-13-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy N-methyl indole, 2-amino-3-hydroxy pyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N- (B-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- (13-hydroxyethylamino) toluene and their addition salts with an acid.

In the composition of the present invention, the coupler or couplers are generally present in an amount of between 0.001 and 10% by weight of the total weight of the dye composition and more preferably from 0.005 to 6% by weight. The oxidation base (s) are present in an amount preferably of between 0.001% to 10% by weight relative to the total weight of the dye composition, and more preferably from 0.005% to 6% by weight.

In general, the addition salts with an acid that can be used in the context of the dyeing compositions of the invention for the oxidation bases and the couplers are chosen in particular from hydrochlorides, hydrobromides, sulphates and citrates. succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

The composition according to the invention may optionally comprise at least one additional direct dye other than the compounds of formula (I). The latter are chosen in particular from ionic or nonionic species, preferably cationic or nonionic. Examples of suitable direct dyes that may be mentioned include azo direct dyes; methinic; carbonyls; azinic; nitro (hetero) aryl; tri- (hetero) aryl methanes; porphyrins; phthalocyanines and natural direct dyes, alone or in mixtures.

More particularly, the azo dyes comprise a function -N = N- whose two nitrogen atoms are not simultaneously engaged in a ring. However, it is not excluded that one of the two nitrogen atoms of the sequence -N = N- is engaged in a cycle.

The dyes of the family of methines are more particularly compounds comprising at least one sequence chosen from> C = C <and -N = C <whose two atoms are not simultaneously engaged in a ring. It is however specified that one of the nitrogen or carbon atoms of the chains can be engaged in a cycle. More particularly, the dyes of this family are derived from methine, azomethine, mono- and di-arylmethane compounds, indoamines (or diphenylamines), indophenols, indoanilines, carbocyanines, azacabocyanines and their isomers, diazacarbocyanines and their isomers, tetraazacarbocyanines, hemicyanines. As regards the dyes of the carbonyl family, mention may be made, for example, of the dyes chosen from acridone, benzoquinone, anthraquinone, naphthoquinone, benzanthrone, anthranthrone, pyranthrone, pyrazolanthrone, pyrimidinoanthrone, flavanthrone, idanthrone, flavone, (iso) violanthrone, isoindolinone, benzimidazolone, isoquinolinone, anthrapyridone, pyrazoloquinazolone, perinone, quinacridone, quinophthalone, indigo, thioindigo, naphthalimide, anthrapyrimidine, diketopyrrolopyrrole, coumarin.

As regards the dyes of the family of cyclic azines, there may be mentioned in particular azine, xanthene, thioxanthene, fluorindine, acridine, (di) oxazine, (di) thiazine, pyronine. The nitro (hetero) aromatic dyes are more particularly nitrobenzene or nitro pyridinic direct dyes. With regard to porphyrin or phthalocyanine dyes, it is possible to use cationic or non-cationic compounds, optionally comprising one or more metals or metal ions, for example alkali and alkaline earth metals, zinc and silicon.

By way of example of particularly suitable direct dyes, mention may be made of the nitro dyes of the benzene series; azo direct dyes; azomethines; methinic; azacarbocyanines such as tetraazacarbocyanines (tetraazapentamethines); quinone direct dyes and in particular anthraquinone, naphthoquinone or benzoquinone dyes; direct azine dyes; xanthenics; triarylmethanics; indoamines; indigoids; phthalocyanines, porphyrins and natural direct dyes, alone or in mixtures.

Among the benzene direct dyes that may be used according to the invention, the following compounds may be mentioned in a nonlimiting manner: 1,4-diamino-2-nitrobenzene, 1-amino-2-nitro-4-B-hydroxyethylaminobenzene-1-amino 2-nitro-4-bis (13-hydroxyethyl) -aminobenzene-1,4-bis (3-hydroxyethylamino) -2-nitrobenzene-1-B-hydroxyethylamino-2-nitro-4-bis (13-hydroxyethylamino) - benzene - 1-B-hydroxyethylamino-2-nitro-4-aminobenzene-1-13-hydroxyethylamino-2-nitro-4- (ethyl) (β-hydroxyethyl) -aminobenzene-1-amino-3-methyl-4-13 hydroxyethylamino-6-nitrobenzene-1-amino-2-nitro-4-13-hydroxyethylamino-5-chlorobenzene-1,2-diamino-4-nitrobenzene-1-amino-2-13-hydroxyethylamino-5-nitrobenzene-1 2-bis- (13-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-1-13-hy Hydroxyethyloxy-2-13-hydroxyethylamino-5-nitrobenzene-1-methoxy-2-13-hydroxyethylamino-5-nitrobenzene-1-13-hydroxyethyloxy-3-methylamino-4-nitrobenzene-1-yl-dihydroxypropyloxy-3- methylamino-4-nitrobenzene-1-β-hydroxyethylamino-4-13, γ-dihydroxypropyloxy-2-nitrobenzene-1-β-γ-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene-1-β-hydroxyethylamino-4-trifluoromethyl; 2-Nitrobenzene-1 -13-hydroxyethylamino-3-methyl-2-nitrobenzene-1-amino-13-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 (13-hydroxyethyl) -amino-3-nitrobenzene-1-13-hydroxyethylamino-2-nitrobenzene-1-hydroxy-4- 13-hydroxyethylamino-3-nitrobenzene.

Among the azo, azomethine, methine or tetraazapentamethine direct dyes that may be used according to the invention, mention may be made of the cationic dyes described in patent applications WO 95/15144, WO 95/01772 and EP 714954; FR 2189006, FR 2285851, FR-2140205, EP 1378544, EP 1674073.

Thus, the following dyes of the following formulas (a) or (b) can in particular be mentioned: R 1 AD = DN 1 (1) x -R 2 R 3 in which: D represents a nitrogen atom or the group -CH, R 1 and R2, which may be identical or different, represent a hydrogen atom; a C 1 -C 4 alkyl radical which may be substituted by a -CN, -OH or -NH 2 radical or form, with a carbon atom of the benzene ring, an optionally oxygenated or nitrogen-containing heterocycle, which may be substituted by one or more alkyl radicals in 1 -C4; a 4'-aminophenyl radical, R3 and R'3, which may be identical or different, represent a hydrogen or halogen atom chosen from chlorine, bromine, iodine and fluorine, a cyano radical, alkyl 1- C4, C1-C4 alkoxy or acetyloxy, X - represents an anion preferably selected from chloride, methyl sulfate and acetate, A represents a group chosen from the following structures A1 to A18, preferably A1, A4, A7 , A13 and A18: R4 RN 4 A4 R4 A7 A5 R4 A8 R4 A3 Al2 / RR 4/4 IN + NI N + III SS A11 A10 - N + R4 A13 A14 A15 R, R, / R, / R4 \ / 4 R 4 IINIIN Wherein R 4 represents a C 1 -C 4 alkyl radical which may be substituted by a hydroxyl radical and R 5 represents a C 1 -C 4 alkoxy radical; R14 E D1uD2u (N) m R13 (III) in which:

R13 represents a hydrogen atom, a C1-C4 alkoxy radical, a halogen atom such as bromine, chlorine, iodine or fluorine,

R14 represents a hydrogen atom, a C1-C4 alkyl radical or forms, with a carbon atom of the benzene ring, an optionally oxygenated heterocycle and / or substituted by one or more C1-C4 alkyl groups,

R15 represents a hydrogen or halogen atom such as bromine, chlorine, iodine or fluorine,

D1 and D2, which are identical or different, represent a nitrogen atom or the group -CH, m = 0 or 1

X - represents an anion preferably chosen from chloride, methyl sulfate and acetate,

E represents a group chosen by the following structures E1 to E8, preferably E1, E2 and E7: ## STR2 ##

In which R 'represents a C 1 -C 4 alkyl radical, and when m = 0 and D 1 represents a nitrogen atom, then E may also designate a group with the following structure E 9, R' N + 20 N "LNR 'R' E7 E8 In which R 'represents a C 1 -C 4 alkyl radical In the structures defined above, the C 1 -C 4 alkyl or alkoxy group preferably denotes methyl, ethyl, butyl, methoxy or ethoxy. the compounds of formulas (a) and (b), the following compounds are preferred: ## STR1 ## ## STR1 ##

## STR1 ## ## STR1 ## ## STR1 ## ## STR2 ## The direct dyes that may be used may also be methine dyes, such as the Basic Red 14. , and also the azo direct dyes 15 chosen in particular from the following dyes, described in the COLOR INDEX INTERNATIONAL 3rd edition: - Disperse Red 17 - Basic Red 22 - Basic Red 76 20 - Basic Yellow 57 - Basic Brown 16 - Basic Brown 17 - Disperse Black 9. Mention may also be made of 1- (4'-aminodiphenylazo) -2-methyl-4bis- (13-hydroxyethyl) aminobenzene. Among the quinone direct dyes, the following dyes may be mentioned: - Disperse Red 15 - Solvent Violet 13 - Disperse Violet 1 30 - Disperse Violet 4 19 R 'E9 X-N CH3 10 = N - N ù ~ H 1 CH3 OCH3 X- - Disperse Blue 1 - Disperse Blue 8 - Disperse Blue 3 - Disperse Blue 11 - Disperse Blue 7 - Blue 22 - Disperse Violet 15 - Basic Blue 99 and the following compounds: - 1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone - 1 -Aminopropylamino-4-methylaminoanthraquinone-1-aminopropylaminoanthraquinone-5-13-hydroxyethyl-1,4-diaminoanthraquinone-2-aminoethylaminoanthraquinone-1,4-bis-03-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 that can be used according to the invention, mention may be made of the following compounds: - Basic Green 1 - Basic Violet 3 - Basic Violet 14 Among the indoamine dyes that can be used according to the invention, mention may be made of the following compounds: 2- [3-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 tetraazapentamethine type dyes that can be used according to the invention, mention may be made of the following compounds appearing in the table below: ## STR1 ## ## STR2 ## , N + N + NNN HXNN * NYN NN OH OH X, NNNN / x 1 NN% NNXN NN NNIXI NNN ON NHN -H OH OH OH X- represents an anion preferably selected from chloride, iodide, methyl sulfate, ethyl sulfate, acetate and perchlorate.

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, orceins. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from henna.

If present, the content of additional direct dye (s) in the composition generally varies from 0.001 to 20% by weight relative to the weight of the composition, and preferably from 0.01 to 10% by weight. weight relative to the weight of the composition.

The appropriate medium for dyeing, also called dyeing medium, is generally constituted by water or a mixture of water and at least one organic solvent to solubilize compounds that are not sufficiently soluble in water . More particularly, the organic solvents are chosen from monoalcohols or diols, linear or branched, preferably saturated, comprising 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2-methyl 2,4-pentanediol), neopentyl glycol and 3-methyl-1,5-pentanediol; aromatic alcohols such as benzyl alcohol, phenylethyl alcohol; glycols or glycol ethers such as, for example, ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or its ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol; and the alkyl ethers of diethylene glycol, especially C1-C4, for example diethylene glycol monoethyl ether or monobutyl ether, alone or as a mixture. The usual solvents described above, if present, usually represent from 1 to 40% by weight, more preferably from 5 to 30% by weight, based on the total weight of the composition.

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, cationic polymers, nonionic, amphoteric, zwitterionic or mixtures thereof, 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 nonvolatile 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 complementary compounds in such a way that the advantageous properties intrinsically attached to the oxidation dyeing composition according to the invention are not, or not substantially, altered 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. Acidifying agents include, for example, inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid and the like. , citric acid, lactic acid, sulphonic acids. 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 the following formula: wherein R is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 4 alkyl radical; Ra, Rb, R, and Rd, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a 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, pastes or in any other form suitable for dyeing keratinous fibers, and especially human hair.

The composition according to the invention may further comprise at least one oxidizing agent.

In this case, we speak of ready-to-use compositions. By ready-to-use composition is meant in the sense of the present invention, the composition intended to be applied immediately to the keratinous fibers, that is to say that it can be stored as it is before use or result from extemporaneous mixing of two or more compositions.

According to this variant, the composition of the invention comprises at least one oxidizing agent in order notably to obtain a lightening of the fibers. The oxidizing agents conventionally used for dyeing keratinous fibers are, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes, among which one mention may be made of peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. According to one particular embodiment, the composition contains a peroxide-type oxidizing agent and / or a persalt-type oxidizing agent, for example a mixture of hydrogen peroxide and persulfates, hydrogen peroxide alone or persulfate alone.

The content of oxidizing agent is generally between 1 and 40% by weight, relative to the weight of the ready-to-use composition, preferably between 1 and 20% by weight relative to the weight of the ready-to-use composition. . Generally, the oxidizing composition used is an aqueous composition and may be in the form of a solution or an emulsion.

Usually, the oxidant-free composition is mixed with about 0.5 to 10 equivalents by weight of the oxidizing composition. Note that the pH of the ready-to-use composition is more particularly between 4 and 12, preferably between 7 and 11.5. The pH of the composition may be adjusted by means of an alkalinizing or acidifying agent, chosen in particular from those mentioned above, in the context of the description according to the invention.

The subject of the invention is also a dyeing method which comprises the application of a dyeing composition according to the invention to keratinous fibers, dry or wet.

The application to the fibers of the dye composition comprising the compound (s) of formula (I) or its addition salts with an acid, optionally at least one oxidation base optionally associated with at least one coupler, optionally at least one additional direct dye can be carried out in the presence of an oxidizing agent. This oxidizing agent may be added to the composition comprising the compound (s) of formula (I) and any additional oxidation bases, couplers and / or direct dyes, either at the time of use or directly on the keratinous fiber. . 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 keratin fibers preferably varies between 4 and 12 approximately, and even more preferably between 7 and 11. 5. 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.

According to a particular embodiment, the composition according to the invention is free of oxidation base and coupler. The composition applied may optionally comprise at least one oxidizing agent.

The composition is therefore applied to the keratin fibers, dry or wet, and then left for a sufficient exposure time to obtain the desired color. Whichever variant is chosen (with or without an oxidizing agent), the exposure time is generally between a few seconds and one hour, preferably between 3 and 30 minutes.

The temperature at which the composition is allowed to act is generally between 15 and 220 ° C, more particularly between 15 and 80 ° C, preferably between 15 and 40 ° C.

At the end of the exposure time, the composition is removed by rinsing with water, optionally followed by washing with a shampoo, then optionally drying. Another object of the invention is a multi-compartment device or dye "kit" in which a first compartment contains the dye composition of the invention and a second compartment contains the oxidizing composition. This device may be equipped with a means for delivering the desired mixture onto the hair, such as the devices described in patent FR-2 586 913. The following examples serve to illustrate the invention without however having a character limiting.

EXAMPLES OF SYNTHESIS

Scheme I: Synthesis of compound F91 compound 36, compound 7 + Br + K, CO 3 OH 6 reflux 78`C 24h compound 1 OH TsCI, Et3N 6 CHzCl2

24 h, T.A. N compound 3 EtOH, AcOH cat. I NHz 0`C then T.A., 1 hr. Toluene, 90 ° C, 24h '' N Compound 4 Compound 4 Compound 6 HCl, McOH / H20 95/5 0-5 `C Compound 8 6 o ,. ## STR2 ## Step # 1: Synthesis of 6-Fmethyl (phenyl) aminolhexan-1-ol In a 100 ml three-necked flask equipped with a condenser, a thermometer and a dropping funnel, 15.20 mL of N-methylaniline (140 mmol) was stirred in the presence of 19.35 g of potassium carbonate (140 mmol). The reaction medium is then heated to 78 ° C. 18.95 mL of 6-bromohexan-1-ol (140 mmol) previously placed in a K2CO3 OH 6 reflux 78 ° C 24h compound 1 compound 2 90% 10% + Br N s ~ OH N 6 6 OH +

dropping funnel are then added dropwise to the preceding reaction medium; the addition is carried out in 30 minutes. The reaction medium is then stirred for 24 hours at 78 ° C. After cooling, the heterogeneous reaction medium is filtered beforehand and the filtrate is concentrated. The residue thus obtained is purified by flash chromatography on silica gel (eluent Heptane / ethyl acetate: 8/2). The compound [1] is obtained in the form of a colorless translucent oil (16.29 g). The NMR spectra and the mass spectra are in accordance with the expected product [1].

Step 2: Synthesis of 6-Fmethvl (phenyl) aminolhexyl 4-methylbenzenesulfonate F31 In a 100 ml three-necked flask equipped with a condenser, a thermometer and a dropping funnel, 2 g of the compound [1] ( 10 mmol) are stirred at room temperature in the presence of 20 ml of dichloromethane. A solution consisting of 1.91 g of tosyl chloride (10 mmol) dissolved beforehand in 10 ml of dichloromethane is rapidly added to the preceding reaction medium using a syringe. 1.4 ml of triethylamine are then added dropwise to the preceding reaction medium. After 24 hours of reaction, the reaction medium is concentrated and the residue thus obtained is taken up in acetone; the insoluble salts are removed by filtration. The resulting juice is concentrated again, and the resulting residue is purified by flash silica gel chromatography (eluent heptane / ethyl acetate: 8/2). The compound [3] is then obtained in the form of a colorless translucent oil (2.01 g). The NMR spectra and the mass spectra are in accordance with the expected product [3].

Step 3: Synthesis of 4 - {(E) -finethyl (phenyl) hydroxyronylmethyl} pyridine F61 TsCI, Et3N CH2Cl2 24 h, TA compound 1 compound 3 N OH 6 N 30 In a knitted fabric topped with a refrigerant, a thermometer, 58.76 g of N-methylphenylhydrazine [5] (0.4809 mol) are diluted in 50 ml of ethanol and 1.5 ml of acetic acid. The reaction medium is then stirred. Using a dropping funnel, 51.5 g of 4-pyridinecarboxaldehyde [4] (0.4808 mol) are added slowly. The addition is carried out in 30 minutes. Subsequently, the reaction medium is heated at 65 ° C. for 13 hours. After cooling, the reaction medium (dark oil) is poured into an ice-water mixture (1/3). The mixture is vigorously stirred.

A yellow powder is obtained which is filtered and then washed several times with water. After drying under active vacuum in the presence of P2O5, a yellow powder corresponding to compound [6] is obtained (83.6 g). The NMR spectra and the mass spectra are in accordance with the expected product [6] Etane 4: Synthesis of 146-Imethyl (phenyl) aminolhexyl} -4 (E) - [methyl (phenyl) hydroxrazonolmethyl] pyridinium 4-methvibenzenesulfonate salt [T1] In a 100 ml knit equipped with a thermometer, a condenser, 1.23 g of the compound [6] (5.2 mmol) are stirred in the presence of 25 ml of toluene, the reaction medium is heated. at 90 ° C so as to completely solubilize the compound [66]. Then, 0.850 g (2 mmol) of the compound [3] previously suspended in 15 ml of toluene are rapidly added to the preceding reaction medium. The light orange reaction medium is then placed for 24 hours under stirring at 90 ° C. The latter heterogeneous (formation of a large precipitate) of red color is cooled to room temperature. The precipitate is filtered, washed with toluene and then with ethyl acetate and finally dried under vacuum. The compound L7] is obtained in the form of an orange powder (0.826 g). The NMR spectra and the mass spectra are in accordance with the expected product [77]. Step 5: Synthesis of the double chloride salt and 4-methylbenzenesulfonate 1- {6-ff4- (E) - {4 - ((E) - {4-f (E) - (1,3-dimethyl)} 1H-Imidazol-3-ium-2-yl) diazenylphenyl (diazenyl) phenyl (methylene) aminolhexyl} -4 - {(E) -ethethyl] (phenyl) hydroxrazonol methyl} pyridinium F91 in a 100 mL tricol a refrigerant and a thermometer, 99 mg of the compound [8] (0.5 mmol) are solubilized in the presence of 270 L of 5-6N hydrochloric acid (commercial solution in isopropanol), 1 ml of methanol and 0.5 mL of water. The reaction medium is left under magnetic stirring at room temperature until complete solubilization, then cooled to 0 ° C. A solution previously cooled to 0 ° C consisting of 35 mg of sodium nitrite (0.5 mmol) solubilized in 1.23 mL of water is added slowly dropwise to the reaction medium taking care to maintain the temperature between 0 ° C and 5 ° C. The reaction medium is then left stirring for 35 minutes. A tip of sulfamic acid spatula is added. The diazonium salt thus obtained is then slowly added dropwise to a solution cooled to 0 ° C. and consisting of 150 mg of compound [7] (0.5 mmol) previously solubilized in 0.5 ml of methanol and 0.34 ml of acetic acid. After addition, the medium takes a dull green color and the pH of the reaction medium then at 2 is gradually reduced to 6 with a potassium carbonate solution. The water is then evaporated by successive addition of methanol to the mixture and concentration in vacuo. The residue thus obtained is then washed with isopropanol in order to precipitate the inorganic salts. These are removed by filtration and the filtrate is then evaporated at 20 ° C. The product obtained is placed for 48 hours under high vacuum in the presence of P2O5. After purification by semi-preparative HPLC, the compound [9] is obtained in the form of a dark green-black powder (80 mg). The NMR spectra and the mass spectra are in accordance with the expected product [9]. Scheme II: Synthesis of Compound F131 Compound 10 Compound 11 Compound 3 Compound 12 EtOH, AcOH cat. NHz 0`C then 65`C, 4 hrs. Toluene, 90.degree. C., 24h + compound 12, compound 13HCl, McOH / H.sub.2 O 95/5 0-5 ° C compound 8NHz, NaNO.sub.2CI Step 1: Synthesis of 4 - {(E) -finethvl (phenyl) In a three-neck topped with a condenser, one equivalent of N-methylphenylhydrazine [6] (4.1 g, 0.033 mol) was diluted in 25 ml of ethanol and 0.5 ml of glacial acetic acid. The reaction medium is then stirred at 0 ° C. 1 equivalent of 4-formylquinoline [10] (5.28 g, 0.033 mol) is added. After addition of the aldehyde, the reaction medium is heated at 70 ° C. for 4 hours. Subsequently, the reaction medium (dark oil) is poured into a water-ice mixture (1/3). The mixture is then placed under stirring. A yellow-orange powder is obtained which is filtered and then washed several times with water. After drying, 7.9 g of the compound [II] are obtained. The NMR spectra and the mass spectra are in accordance with the expected product [11].

Step 2: Synthesis of 1- {6-finethyl (phenyl) aminol hexyl} -4- {(E) -finethyl] (phenyl) hydrazonolmethyl] quinolinium 4-methylbenzenesulfonate salt In a 100 mL three-necked flask a thermometer, a condenser, 2.57 g of the compound [11 (9.8 mmol) are stirred in the presence of 35 ml of toluene, the reaction medium is heated to 90 ° C. so as to completely solubilize the compound [ 11]. Then, 2.125 g (5 mmol) of the compound [3] previously suspended in 25 ml of toluene are rapidly added to the preceding reaction medium. The dark orange reaction medium is then placed for 24 hours with stirring at 90 ° C. At the end of this time, the heterogeneous reaction mixture (formation of a large precipitate) of red color is cooled to room temperature. The precipitate is filtered, washed with toluene and then with ethyl acetate and finally dried under vacuum. The compound [12] is obtained in the form of an orange powder (1.27 g). The NMR spectra and the mass spectra are consistent with the expected product [2].

Step 3: Synthesis of the double chloride salt and 4-methylbenzenesulfonate 1- {6-ff4- (E) - {4 - ((E) - {4-f (E) - (1,3-dimethyl) -1- 1H-Imidazol-3-ium-2-yl) diazenylphenyl (diazenyl) phenyl (methylene) aminol hexyl} -4- {(E) -thinyl] phenyl) hydroxrazonolmethyl} quinolinium in a 100 mL tricol a refrigerant and a thermometer, 198 mg of the compound [8] (1 mmol) are solubilized in the presence of 540 L of 5-6N hydrochloric acid (commercial solution in isopropanol), 2 ml of methanol and 1 mol. mL of water. The reaction medium is left under magnetic stirring at room temperature until complete solubilization, then cooled to 0 ° C; a solution previously cooled to 0 ° C consisting of 70 mg of sodium nitrite (1 mmol) solubilized in 2.46 mL of water is added slowly dropwise to the reaction medium taking care to maintain the temperature between 0 ° C and 5 ° C. The reaction medium is then left stirring for 35 minutes. A tip of sulfamic acid spatula is added. The diazonium salt thus obtained is then slowly added dropwise to a solution cooled to 0 ° C. and consisting of 622 mg of compound [12] (1 mmol), previously solubilized in 1 ml of methanol and 0.68 ml of acetic acid. After addition, the medium takes a dull brown color and the pH of the reaction medium then at 2 is gradually reduced to 6 with a potassium carbonate solution. The water is then evaporated by successive additions of methanol to the mixture and concentration in vacuo. The residue thus obtained is then washed with isopropanol in order to precipitate the inorganic salts. These are removed by filtration and the filtrate is then evaporated at 20 ° C. The product obtained is placed for 48 hours under high vacuum in the presence of P2O5. After purification by semi-preparative HPLC, the compound [13] is obtained in the form of a dark purplish brown powder (151 mg). The NMR spectra and the mass spectra are in accordance with the expected product [13].

TINCTORIAL RESULTS The dyeing compositions were prepared in the following proportions: Solution 1 Alkyl (C8 / C10 50/50) polyglucoside (2) in 120 g aqueous 60% pure absolute ethanol 200 g Polyethylene glycol (8 0E) 400 60 q Pure benzyl alcohol 40 q Demineralized water qs 1000q Solution 2: BUFFER pH 9.5 Ammonium chloride (NH4Cl) 54 g Ammonia in soil. at 20% qs pH = 9.5 (about 40 ml) Demineralized water qs 1000 ml Solution 3: BUFFER pH 7 KH2PO4 0.026mo1 / l Na2PO4 0.041 mol / I Demineralized water qs 500m1 At pH 7, the coloring compositions are obtained dissolving the dye indicated below (5x10-3mol / I) in solution 1 and then adding an equivalent volume of buffer solution 3. In lightening alkaline condition, the coloring compositions are obtained by dissolving the dye indicated below ( 5x10-3mo1 / l) in solution 1 and then adding an equivalent volume of buffer solution 2 and a volume of oxygenated water to 40 volumes. Each composition is applied to gray hair at 90% white, (1g of wick for 6g of solution). After 30 minutes break, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

The following dyeing results were obtained After coloring Condition alkaline pH7 lightening Compound 9 Brown with green reflection Brown with green reflection Compound 13 Dull brown Dull brown 32

Claims (18)

REVENDICATIONS1. Polycationic dichromophoric compounds of the following formula, their mesomeric forms as well as their addition salts with an acid and their solvates: (R) Q Formula in which: hydrogen atom, a linear or branched C1-C6 alkyl radical, a C1-C4 alkoxy radical, a halogen atom, preferably chlorine and fluorine; The radicals R 5, R 6, R 8, R, 1 represent, independently of each other: a linear or branched C 1 -C 6 alkyl radical, a hydroxyl radical, a C 1 -C 4 alkoxy radical, an amino radical, optionally substituted with one or two identical or different C1-C4 alkyl groups, an alkylcarbonylamino radical (R13CO-NR14-) in which the radicals Rt3 and R14, which may be identical or different, represent a C1-C4 alkyl radical, an atom halogen, preferably chlorine and fluorine; The radicals R3 and R4, which may be identical or different, represent a linear or branched C1-C8 alkyl radical; The radicals R 1 and R 2, which are identical or different, represent a hydrogen atom or a linear or branched C 1 -C 8 alkyl radical; The radical R10 represents a hydrogen, a linear or branched C1-C8 alkyl radical; the radicals R 1 and R 2, or two radicals R 5 or R 6 or R 8 or R 4, carried by adjacent carbon atoms, can form with each other and with the carbon atoms to which they are attached a secondary condensed aromatic carbon-carbon ring 6-membered; L represents a divalent C 2 -C 20 alkylene radical, linear or branched, optionally interrupted by an imidazolium group; * m, n and p, independently of each other, represent an integer ranging from 0 to 4; q represents an integer ranging from 0 to 5; the electroneutrality of the compounds of formula (I) being ensured by one or more cosmetically acceptable anions An, which are identical or different. 2. Compounds according to the preceding claim, characterized in that the radicals R1 and R2 represent a hydrogen atom. 3. Compounds according to the preceding claim, characterized in that the radicals R3 and R4i identical or different, represent a linear or branched C1-C4 alkyl radical, and preferably a methyl radical. 10 4. Compounds according to one of the preceding claims, characterized in that the radicals R5, R8, R8, R11i represent, independently of each other: a linear or branched C1-C4 alkyl radical, a hydroxyl radical, a C1-C4 alkoxy radical, an amino radical, optionally substituted with one or two C1-C4 alkyl groups, identical or different, an alkylcarbonylamino radical (R13CO-NR14-) in which the radicals R13 and R14, which may be identical or different, represent a C1-C4 alkyl radical; Or two R5 or R8 radicals, carried by adjacent carbon atoms, form between each other and with the carbon atoms to which they are attached, a fused 6-membered aromatic carbon ring. 5. Compounds according to one of the preceding claims, characterized in that the coefficient p is zero or 2 with the two R8i radicals carried by two adjacent carbon atoms, forming between them and with the carbon atoms to which they are attached, a 6-membered condensed aromatic carbon ring. 6. Compounds according to one of the preceding claims, characterized in that the radicals R7, R9 and Rio represent, independently of each other, a hydrogen atom, a linear or branched C1-C4 alkyl radical, and preferably a hydrogen atom or a methyl radical. 7. Compounds according to one of the preceding claims, characterized in that the radicals R7 and R9 represent a hydrogen atom. 8. Compounds according to one of the preceding claims, characterized in that the coefficient q is 0 or 1. 40 9. Compounds according to one of the preceding claims, characterized in that the coefficient n is 0 or 1. 10. Compounds according to any one of the preceding claims, characterized in that the cosmetically acceptable An anion is chosen from halides; hydroxides; sulphates; hydrogen sulphates; carbonates, hydrogen carbonates; perchlorates; carboxylic acid salts; alkyl sulphates for which the linear or branched alkyl part is C1-C6; alkylsulphonates for which the linear or branched alkyl part is C1-C6; arylsulphonates for which the aryl part, preferably phenyl, is optionally substituted by one or more C1-C4 alkyl radicals; alkylsulfonyls. 11. Compounds according to any one of the preceding claims, characterized in that they correspond to the following formulas, to their mesomeric forms, to their addition salts with an acid or to their solvates: Y1. NY1. ## STR2 ## representing one or more cosmetically acceptable anions. 12. Compounds according to any one of the preceding claims, characterized in that L represents a C2-C10 alkylene radical. 13. Dyeing composition comprising in a medium suitable for dyeing keratin fibers, as direct dye, at least one compound of formula (I) according to any one of the preceding claims, as well as its mesomeric forms, its salts, and addition with an acid and its solvates. 14. Composition according to the preceding claim, characterized in that the content of compound of formula (I) varies between 0.001 and 20% by weight, relative to the total weight of the dye composition. 15 15. Composition according to any one of claims 13 or 14, characterized in that it comprises at least one additional direct dye, at least one oxidation base optionally associated with at least one coupler, or mixtures thereof. 16. Composition according to any one of claims 13 to 15, characterized in that it comprises at least one oxidizing agent. 17. A process for dyeing keratinous fibers comprising contacting a composition according to any one of claims 13 to 16 with said fibers, dry or wet, for a time sufficient to obtain the desired effect. 18. A multi-compartment device in which a first compartment contains the composition according to any one of claims 13 to 16 and a second compartment containing an oxidizing composition. 10