MX2007002090A - Cationic azo dyes having julolidine unit, dyeing composition containing the same, and method for dyeing. - Google Patents

Abstract

The present application relates the use of keratin fibers for dyeing keratin fibers, in particular human keratin such as the hair, having cationic azo compound with julolidine units as direct dyes. The present application also relates to a dyeing composition for the dyeing of keratin fiber, in particular human keratin such as the hair, which comprises at least a cationic azo direct dye with julolidine units in a suitable dye medium. The present application also relates to a method for dyeing keratin fiber, in particular, human keratin such as the hair, employing the dyeing composition according to the invention. The present application also relates to certain particular cationic azo compound with julolidine units.

Description

AQUATIC AZORIC COLORANTS OF JULOLIDINE PORTIONS, DYES COMPOSITION CONTAINING THEM, COLORATION PROCEDURE FIELD OF THE INVENTION The present application has as an object the use for the coloration of keratin fibers, in particular of human keratin fibers, such as hair, of cationic azo compounds of julolidin portions as direct dyes, a dye composition containing these particular azo compounds, a method of coloring such fibers employing them, a compartment device and new cationic azo compounds of julolidin portions. BACKGROUND OF THE INVENTION It is known to dye keratin fibers and in particular human hair with dyeing compositions containing oxidation dye precursors, generally called oxidation bases, such as ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds. These oxidation bases are colorless or sparsely colored compounds which, associated with oxidizing products, can give rise to colored compounds by a process of oxidative condensation. It is also known that they can vary the Ref .: 179737 nuances obtained with these oxidation bases associating them with couplers or color modifiers, the latter being chosen mainly between aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds, such as indole compounds. The variety of molecules put into play at the level of oxidation bases and couplers allow obtaining a rich palette of colors. The coloration called "permanent" obtained thanks to these oxidation dyes, must therefore satisfy a certain number of requirements. Thus, it must be without inconvenience on the toxicological plan, it must allow to obtain new nuances in the desired intensity and present a good behavior in front of external agents, such as light, weathering, washing, permanent undulations, perspiration and rubbing. The dyes must also make it possible to cover the white hairs, and finally to be as non-selective as possible, that is, to obtain the smallest variations in coloration possible all along the same keratin fiber, which is in general differently sensitized (i.e. battered) between its tip and its root. It is also known to dye the keratin fibers by direct or semi-permanent coloring. The classic procedure used in direct dyeing is to apply direct dyes to the keratin fibers, which are colored molecules and dyes that have an affinity for the fibers for the fibers, allowing them to rest to allow the colored molecules to penetrate, by diffusion, into the interior of the hair, then rinse the fibers. Contrary to oxidation dyeing compositions, direct or semi-permanent dyeing compositions are employed without the mandatory presence of an oxidizing agent. These dyes can be made repeatedly without degrading the keratin fiber. It is known, for example, to use direct nitrobenzene, anthraquinone, nitropyridine, azo, xanthine, acridine, azine or triarylmethane dyes. Resulting frequently chromatic colorations which are however temporary or semi-permanent because of the nature of the bonds between the direct dyes and the keratin fiber. These interactions find that the desorption of the dyes from the surface and / or core of the fiber is easily done. The colorations generally present a bad behavior to washing or perspiration. There is a real desire to have colorants effective that allow me prayers in terms of dyeing homogeneity, depending on the quality of colored hair, of resistance to shampoos and after shampooing (tenacity), of limitation of washing that induces risks of staining, of color change in the times when they are associated with chromatic dyes of different respective tenacities. In addition, the use of known cationic direct dyes allows the obtaining of strong chromatic shades, but limited to a color field (yellow, orange, red). There is a desire for dyes located outside the known color field. Surprisingly and advantageously, the Applicant discovered that a class of cationic direct azo dyes with portions called "julolidine" allow these improvements. Cationic dyes with portions called "julolidine" are described in US Pat. No. 4,341,853 as photosensitizers in electrophotography. These azo compounds lead to dyes resistant to external agents (sun, weather) as well as shampoos and perspiration. These compositions have a good toxicological profile. In addition, these dyes allow to obtain intense reflections, mainly in the blue and violet colors. Alone or in combination with other traditional dyes, direct or oxidation, they allow to extend the ranges of colors. BRIEF DESCRIPTION OF THE INVENTION A first object of the present invention is directed to the use of cationic azo compounds of julolidine portion as direct dyes for keratin fibers, in particular human keratin fibers, such as hair. A second object of the present invention is a dyeing composition for dyeing keratin fibers, in particular human keratin fibers, such as hair comprising in a dyeing medium suitable for dyeing at least one cationic azo compound of julolidine portion according to the invention. The invention is also directed to a process for dyeing keratin fibers, in particular human keratin fibers, such as hair, using the dye composition according to the invention. Another object of the present invention is the use of the composition for dyeing keratin fibers, in particular human keratin fibers, such as hair. The invention further relates to a compartment or "kit" device comprising the dye composition according to the present invention.

Finally, a final subject of the invention relates to particular azoic cationic azo compounds. DETAILED DESCRIPTION OF THE INVENTION Other characteristics, aspects, objects and advantages of the invention will appear more clearly in the reading of the following description and examples. It is pointed out that in the following, and unless otherwise indicated, the limits of a field of values are included in this field. The cationic azo compounds of the julolidine portion according to the present invention correspond to the following compound of the formula (I): wherein A represents a cationic aromatic heterocycle selected from the compounds of the following general formulas: Ri represents independently of each other: • a straight or branched, saturated or unsaturated Ci-C hydrocarbon chain, which can form one or more carbon cycles comprising from 3 to 7 chains, optionally condensed with the optionally substituted aromatic ring, optionally interrupted by one or more groups chosen from heteroatoms such as oxygen, nitrogen or sulfur, and the carbonyl group; Ri does not understand the nitro, nitroso, peroxide and diazo bond; Ri is directly linked to the nitrogen atom, quaternized or not, of the heteroaromatic cycle A by the intermediary of a carbon atom. R2 represents independently of each other: a C1-C16 hydrocarbon chain; linear or branched, saturated or unsaturated, which can form one or more aromatic carbon cycles or not, comprising from 3 to 6 chains, optionally substituted, optionally interrupted by one or more heteroatoms or by one or more groups bearing at least one hetero atom , preferably chosen from oxygen, nitrogen; A hydroxyl group, a C1-C4 alkyloxy group, a C2-C4 (poly) hydroxyalkyloxy group; • an alkyloxycarbonyl group (R 0 -CO-) in which R n represents a C 1 -C 4 alkyl radical; · An alkylcarbonyloxy radical (R12CO-O-) in which R12 represents an alkyl radical is C1-C4; • an amino group, an amino group substituted by one or two C1-C4 alkyl radicals, identical or different, optionally carrying at least one hydroxyl group, the two alkyl radicals can optionally form with the nitrogen atom to which they are joined, a 5- or 6-chain heterocycle optionally carrying another heteroatom identical or different from nitrogen, for example oxygen, sulfur; · An alkylcarbonylamino group (R13CO-NR13-) and / or (R13CO-NH) in which the R13 radicals independently of each other represent a C1-C4 alkyl radical; A carbamoyl group ((Ri4) 2N-CO) in which the R14 radicals independently of one another, identical or not, represent a hydrogen atom, a C1-C4 alkyl radical; • a ureido group ((Ri5) 2N-CO-NRi6-) in which the radicals R15 and Ri6, independently of each other, represent a hydrogen atom, a C1-C4 alkyl radical; • a sulfonamide group ((Ri) 2N-S02-) in which the Ri radicals, independently of one another, represent a hydrogen atom, a C1-C4 alkyl radical,; • an alkylsulfonylamino group (Ri8S02-NRig-) in which the radicals Rie, R19, independently of one another, represent a hydrogen atom, a C1-C4 alkyl radical; · A guahidinio group ((R20) 2N-C (= NH2 +) -NR2i-) in which the radicals R2o and R21, independently of each other, represent a hydrogen atom, an alkyl radical of Ci-C4; • a nitro group; · A cyano group; • a halogen atom, preferably chlorine, fluorine; two radicals R2, carried by the adjacent carbon atoms can form, together with the carbon atom to which each is attached, a condensed, aromatic or non-aromatic cycle; m represents an integer between 0 and 4; e is an integer between 0 and 2; p is an integer between 0 and 1; D represents a group CR2 or a nitrogen atom Q represents a group Ri, or an oxygen or sulfur atom; the bond has resulted from the formulas (lia), (Ilb) or (lie), linking group A to the azo group; in the case of the formulas (lia), (Ilb) or (lie) and when two radicals R2 carried by two adjacent carbon atoms form an aromatic cycle, the bond has been able to bind group A to the azo group through the cycle intermediary aromatic; the electroneutrality of the compounds is ensured by one or more anions, identical or not, cosmetically acceptable, among which chloride, methylsulfate, methosulfate, tosylate, acetate, X, Y and Z are defined as substitution possibilities respectively on the alkyl and aryl cycles of the tricyclic core; x is comprised between 0 and 2, and is comprised between 0 and 6, and Z is comprised between 0 and 6, x, y, and z are integers; or its addition salts or solvates, with the exception of 2- (9-julolidilazo) -3-methylbenzothiazolium perchlorate of 2- (9-julolidilazo) -3-ethylthiazolium perchlorate, known as sensitizers in electrophotography. In the following, and less than a different indication: When an alkyl radical or alkyl part of a radical is called (a) 4 substituted (a) ', then it comprises at least one substituent selected from the groups: • hydroxyl, • alkyloxy of C1-C4, C2-C4 (poly) hydroxyalkyloxy, amino, amino substituted by one or more identical or different C1-C4 alkyl groups optionally bearing at least one hydroxyl group, the alkyl radicals can form with the nitrogen to which they are attached, a 5 or 6 chain heterocycle, optionally comprising at least one heteroatom different or not from nitrogen. - When an aryl or heteroaryl radical or the aryl or heteroaryl part of a radical is called (a) 4 substituted (a) ', such as for example the substituent X on the aromatic nucleus of the tricycle, then comprises at least one substituent carried by a carbon atom, chosen from: a C 1 -C 16 alkyl radical, preferably Ci-Cs, optionally substituted by one or more radicals selected from the hydroxy, alkyloxy radicals of C1 -C2, C2-C4 (poly) -hydroxyalkyloxy, acylamino, amino substituted by one or two alkyl radicals, identical or different, of C1-C4, optionally bearing at least one hydroxyl group or, the two radicals which can form with the nitrogen atom to which they are attached, a heterocycle of 5 or 7 chains, preferably of 5 or 6 chains, optionally comprising a heteroatom identical or different from nitrogen; • a halogen atom such as chlorine, fluorine or bromine; • a hydroxyl group; · A C1-C2 alkyloxy radical; • a C2-C4 (poly) -hydroxyalkyloxy radical; • an amino radical; • an amino radical substituted by one or two alkyl radicals, identical or different, of C1-C4 optionally bearing at least one hydroxyl group; • an acylamino radical (-N31R-COR32) in which the radical R31 is a hydrogen atom, a C1-C4 alkyl radical optionally carries at least one hydroxyl group and the radical R32 is a C1-C2 alkyl radical; · A carbamoyl radical ((R33) 2N-CO-) in which the R33 radicals, identical or not, represent a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group; • an alkylsulfonylamino radical (R34 SO2-N35R-) in which the radical R34 represents a hydrogen atom, a C1-C4 alkyl radical optionally carries at least one hydroxyl group and the radical R35 represents a C1-C4 alkyl radical , a phenyl radical; • an aminosulfonyl radical ((R36) 2N-SO2-) in which the radicals R36, identical or not, represent a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group. - When the cyclic or heterocyclic part of a non-aromatic radical is called (a) 4 substituted (a) ', as for example the substituents Y and Z of aliphatic heterocycles of the tricycle, then it comprises at least one substituent carried by a carbon atom , chosen from the groups: • hydroxyl, • C1-C4 alkyloxy, (poly) hydroxy (C2-C4) alkyloxy, alkylcarbonylamino ((R41CO-NR42-) in which the radical R42 is a hydrogen atom, an alkyl radical of C1-C4 optionally carrying at least one hydroxyl group and the radical R4i is a C1-C2 alkyl radical, amino substituted by two identical or different C1-C4 alkyl groups optionally bearing at least one hydroxyl group, the alkyl radicals which can form, with the nitrogen atom to which they are attached, a 5- or 6-chain heterocycle optionally comprising at least one heteroatom which is different or non-nitrogen. - When one cycle does not carry the maximum number of substituents, then the one or more unsubstituted positions carry a hydrogen atom. Preferably Ri represents an alkyl or hydroxyalkyl group of Ci-Ce. According to a first variant, the formulas (Ha), (Ilb) and (lie) are such that they comprise two radicals R2 carried by adjacent carbon atoms, these so-called radicals which then form together with the carbon atom to which each is attached, an aromatic, optionally substituted, fused cycle. According to a second variant, e, m and p are worth 0. Preferably, x is 0 or 1 with X an alkyl, hydroxyl, hydroxyalkyl, alkyloxy, amino, alkylamino, dialkylamino, acylamino group; alkyl which means an optionally substituted Ci-C6 chain, acyl which means alkylcarbonyl. As an example of compounds of the formula (I) which can be used according to the invention, the following compounds can be mentioned: The dyes that respond to the formula can be obtained, for example, by four different synthesis routes, later called respectively route A, route B, route C and route D: In subsequent reaction schemes, the definition of B, the non-cationic precursor of A, responds to the following 3 formulas: In the following, HAL means a halogen group attached to Rx by one of its carbon atoms, preferably a chloro, bromo or iodo group, or an alkyl sulfate group, preferably methyl sulfate or ethyl sulfate or methyl sulfonate (mesylate) or aryl sulfonate ( tosylate) 1 / Synthesis path A The compound of the formula (I) is obtained in three successive stages according to the subsequent reaction scheme: (acid n The diazonium salt 2 of the heteroaromatic amine BN¾ 1 is prepared by the classical methods (H Zollinger, Color Chemistry, Wiley VCH Ed 2003 and The Chemistry of Synthetic dyes, Academic Press, London, vol II, 1952). The diazonium salt 2 is then reacted on a compound (an aromatic amine of a julolidine portion) to form the compound 4. This type of coupling is well known in the literature cited above. The third step consists in reacting the compound 4 with an alkylation reagent, such as an alkyl sulfate, an alkyl halide, an alkyl alkylsulfonate or an alkyl arylsulfonate, to form the compound 5_: a direct cationic azo dye of julolidina portion. The alkylation reaction is carried out, for example, in a halogenated solvent (dichloromethane) or ester (ethyl acetate), at a temperature below 150 ° C, preferably at reflux of the solvent. These conditions are mainly described in the literature. Referring to this type of reaction, one can cite for example Advanced Organic Synthesis 5th Ed M. Smith and J. March John Wiley & Sons Ed, 2001 and the international application WO 03/060015. 2 / Synthesis route B The compound of the formula (I) can be obtained by diazotization of the para-aminated derivative of an aromatic amine of julolidin portion 6, then the coupling of the salt of diazonium 1_ obtained with a heterocycle to lead to compound 8, then alkylation of the heterocyclic function to lead to compound 9_ (the cationic direct azoic dye of julolidine portion) according to the reaction scheme 9 All stages of synthesis are described in the literature and the references of route 1 are also applicable. More particularly, the second step consists in reacting the diazonium salt 7 previously obtained with a BH heterocycle (according to the preceding definition of B and H which represents a hydrogen atom attached to B on the position which will then be that of the azo group). 3 / Synthesis path C The compound of the formula (I) can also be obtain in two stages of synthesis: nucleophilic attack on a carbon atom of a cationic heterocycle [11] by a para-hydrazino compound of an aromatic amine of julolidin portion 10 then oxidation of compound 12_ obtained to lead to compound 1 ^ 3 (a cationic direct azoic dye of julolidine portion). These reactions are then exemplified by a cationic heterocycle of pyridinium type and more specifically with compound 11 according to the following reaction scheme: oxidation 13 The reaction to form the compound 12 can be carried out in a polar solvent, preferably an alcohol or DMF, at a temperature lower than 150 ° C, in the presence of a less nucleophilic base than the chosen hydrazine (J ". Med. Chem. 1996, 39 (2), 570-581) Oxidation can be carried out with the aid of usual oxidants: N- bromosuccinimide, ferric chloride, manganese oxide, chromium oxides, hydrogen peroxide, peracids, preferably in an acid medium and at a temperature below 100 ° C for less than twenty-four hours. 4 / Synthesis path D The compound of the formula (I) can also be obtained by oxidative coupling. This route is described in the literature. With reference to this type of reaction, one can cite, for example, Angew. Chem. 1958, 70, 215; Angew. Che. , Int. Ed., 1962, 1, 640 and H Zollinger, Color Chemistry 3fi Ed, VCH Wiley, 2003. The route is exemplified according to the following reaction scheme used to illustrate the pyridinium heterocycle, and more specifically compound 14 for lead to compound 11. (a cationic direct azoic dye of julolidine portion): The starting reagents are marketed or are obtained according to methods known to those skilled in the art, advantageously from commercially available compounds.

The invention is also directed to the use of cationic azo compounds of the julolidin portion corresponding to the following compound of the formula (I): wherein A represents a cationic aromatic heterocycle selected from the compounds of the following general formulas: Ri represents independently of each other: a C1-C16 hydrocarbon chain, linear or branched, saturated or unsaturated, which can form one or more carbon cycles comprising from 3 to 7 chains, optionally condensed with the optionally substituted aromatic ring, optionally interrupted by one or more groups chosen from heteroatoms such as oxygen, nitrogen or sulfur, and the carbonyl group; Ri does not understand the nitro, nitroso, peroxide and diazo bond; Ri is directly linked to the nitrogen atom, quaternized or not, of the cycle heteroaromatic A by the intermediary of a carbon atom. R2 independently represents: • a hydrocarbon chain of C: -Ci6; linear or branched, saturated or unsaturated, which can form one or more aromatic carbon cycles or not, comprising from 3 to 6 chains, optionally substituted, optionally interrupted by one or more heteroatoms or by one or more groups bearing at least one hetero atom , preferably chosen from oxygen, nitrogen; A hydroxyl group, a C1-C4 alkyloxy group, a C2-C4 (poly) hydroxyalkyloxy group; • an alkyloxycarbonyl group (RuO-CO-) in which Ru represents a C 1 -C 4 alkyl radical; • an alkylcarbonyloxy radical (R12CO-O-) in which R12 represents an alkyl radical is C1-C4; • an amino group, an amino group substituted by one or two C1-C4 alkyl radicals, identical or different, optionally bearing at least one hydroxyl group, the two alkyl radicals can optionally form with the nitrogen atom to which they are joined, a 5- or 6-chain heterocycle optionally carrying another heteroatom identical or different from nitrogen, for example oxygen, sulfur; • an alkylcarbonylamino group (R13CO-NR13-) and / or (R13CO-H) in which the Ri3 radicals independently of one another represent a C1-C4 alkyl radical; • a carbamoyl group ((Ri4) 2N-CO) in which the R14 radicals independently of one another, identical or not, represent a hydrogen atom, a C1-C4 alkyl radical; • a ureido group ((R15) 2N-CO-NRi6-) in which the radicals R15 and Ri6, independently of each other, represent a hydrogen atom, a C1-C4 alkyl radical; · A sulfonamide group ((R17) 2N-S02-) in which the radicals R17, independently of one another, represent a hydrogen atom, a C1-C4 alkyl radical,; • an alkylsulfonylamino group (Ri8S02-NRig-) in which the radicals Rie, R19- independently from each other, represent a hydrogen atom, a C1-C4 alkyl radical; • a guanidinium group ((R20) 2N-C (= NH2 +) -NR2i ~) in which the radicals R20 and R2i, independently of one another, represent a hydrogen atom, an alkyl radical of Ci-C4; · A nitro group; • a cyano group; • a halogen atom, preferably chlorine, fluorine; two radicals R2, carried by the adjacent carbon atoms can form, together with the carbon atom to which each is attached, a condensed, aromatic or non-aromatic cycle; m represents an integer between 0 and 4; e is an integer between 0 and 2; p is an integer between 0 and 1; D represents a CR2 group or a nitrogen atom; Q represents a group NRi, or an oxygen or sulfur atom; the bond has resulted from the formulas (lia), (Ilb) or (lie), linking group A to the azo group; in the case of the formulas (lia), (Ilb) or (lie) and when two radicals R2 carried by two adjacent carbon atoms form an aromatic cycle, the bond has been able to bind group A to the azo group through the cycle intermediary aromatic; the electroneutrality of the compounds is ensured by one or more An ~ anions, identical or not, cosmetically acceptable, among which chloride, methyl sulfate, methosulfate, tosylate, acetate; X, Y and Z are defined as substitution possibilities respectively on the alkyl and aryl cycles of the tricyclic core; x is comprised between 0 and 2, and is comprised between 0 and 6, and Z is comprised between 0 and 6, x, y, and z are integers; or their addition salts or their solvates, In the following, and unless otherwise indicated: When an alkyl radical or alkyl part of a radical is called (a) 'substituted (a)', then it comprises at least one substituent chosen from the groups: hydroxyl, C 1 -C 4 alkyloxy, C 2 -C 4 (poly) hydroxyalkyloxy, amino, amino substituted by one or more identical or different C 1 -C 4 alkyl groups optionally bearing at least one group hydroxyl, the alkyl radicals can form with the nitrogen atom to which they are attached, a 5 or 6 chain heterocycle, optionally comprising at least one heteroatom different or not from the nitrogen. - When an aryl or heteroaryl radical or the aryl or heteroaryl part of a radical is called (a) 1 substituted (a) ', such as for example the substituent X on the aromatic nucleus of the tricycle, then it comprises at least one substituent carried by a carbon atom, selected from: a C1-C16 alkyl radical, preferably Ci-C8, optionally substituted by one or more radicals selected from hydroxy, C1-C2 alkyloxy, C2- (poly) -hydroxyalkyloxy radicals C4, acylamino, amino substituted by one or two alkyl radicals, identical or different, of C1-C4, optionally bearing at least one hydroxyl group or, the two radicals that can form with the nitrogen atom to which they are bound, a heterocycle of 5 or 7 chains, preferably of 5 or 6 chains, optionally comprising a heteroatom identical or different from nitrogen; · A halogen atom such as chlorine, fluorine or bromine; • a hydroxyl group; • an alkyloxy radical of Ci-C2; • a C2-C4 (poly) -hydroxyalkyloxy radical; • an araino radical; • an amino radical substituted by one or two alkyl radicals, identical or different, of C1-C4 optionally bearing at least one hydroxyl group; • an acylamino radical (-N3iR-COR32) in which the radical R31 is a hydrogen atom, a C1-C4 alkyl radical optionally carries at least one hydroxyl group and the radical R32 is a C1-C2 alkyl radical; • a carbamoyl radical ((R33) 2N-CO-) in which the radicals R33, identical or not, represent a hydrogen atom, a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group; • an alkylsulfonylamino radical (R34SO2-N35R-) in which the radical R3 represents a hydrogen atom, a C1-C4 alkyl radical optionally carries at least one hydroxyl group and the radical R3s represents a C1-C4 alkyl radical, a phenyl radical; • an aminosulfonyl radical ((R36) 2N-S02-) in which the radicals R36 / identical or not, represent a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group.

When the cyclic or heterocyclic part of a non-aromatic radical is called (a) 'its (a)', such as for example the Y and Z substituents of the tricyclic aliphatic heterocycles, then it comprises at least one substituent carried by a carbon atom, chosen from the groups: • hydroxyl, • C1-C4 alkyloxy, (poly i) C2-C4 hydroxyalkyloxy, • 1-carboni-lamino ((R41CO-NR42-) in which the radical R42 is a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group and the radical R41 is an Ci-C2 alkyl radical, amino substituted by two identical or different C1-C4 alkyl groups optionally bearing at least one a hydroxyl group, the alkyl radicals which can form with the nitrogen atom to which they are attached, a heterocycle of 5 or 6 chains, optionally comprising at least one heteroatom different or not from the nitrogen - When a cycle does not carry the number At the most of its ti tiyentes, then the or the positions not substituted carry a hydrogen atom. Preferably, Ri represents an alkyl group or hydroxyalkyl of Ci-C8. According to a first variant, the formulas (lia), (Ilb) and (lie) are such that they comprise two radicals R2 carried by adjacent carbon atoms, these named radicals which then form together with the carbon atom to which each is attached , an aromatic condensed cycle, optionally substituted. According to a second variant, e, m and p are worth 0. Preferably, x is 0 or 1 with X an alkyl, hydroxyl, hydroxyalkyl, alkyloxy, amino, alkylamino, dialkylamino, acylamino group; alkyl which means an optionally substituted C 1 -C 6 chain, acyl which means alkylcarbonyl. As an example of compounds of the formula (I) which can be used according to the invention, the following compounds can be mentioned: The invention is also directed to a dye composition for dyeing keratin fibers, in particular human keratin fibers, such as hair comprising in an appropriate dyeing medium, at least one azoic cationic compound as defined above for the use as a direct dye. The dye composition according to the present invention may comprise from 0.001 to 20%, preferably from 0.01 to 10% by weight of cationic direct azo dye of the formula (I) in relation to the total weight of the composition. The composition of the present invention can further understand at least one oxidation base. By way of example, the oxidation bases are chosen from phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts. Among the para-phenylenediamines, mention may be made, as an example, of para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediami-a, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine. ,?,? - dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine,?,? - dipropyl paraphenylenediamine, 4-amino?,? - diethyl 3-methyl aniline, N, N-bis- (b-hydroxyethyl) paraphenylenediamine, 4- N, N-bis- (β-hydroxyethyl) amino 2-methylaniline, 4-N, N-bis- (β-hydroxyethyl) amino 2-chloroaniline, 2 ^ -hydroxyethyl paraphenylenediamine, 2-fluoro paraphenylenediamine, 2-isopropyl paraphenylenediamine ,? - (ß-hydroxypropyl) paraphenylenediamine, 2-hydroxymethyl paraphenylenediamine,?,? - dimethyl 3-methyl paraphenylenediamine, N, N- (ethyl, β-hydroxyethyl) paraphenylenediamine,? - (ß,? - dihydroxypropyl) paraphenylenediamine, N - ('-aminophenyl) para-phenylenediamine, N-phenyl paraphenylenediamine, 2-β-hydroxyethyl-oxy paraphenylenediamine, 2 ^ -acetylaminoethyloxy paraf enylenediamine, N- (β-methoxyethyl) para-phenylenediamine, 4-aminophenyl pyrrolidine, 2-thienyl paraphenylenediamine, 2-β hydroxyethylamino-5-amino toluene, 3-hydroxy-l- (4'-aminophenyl) pyrrolidine and their addition salts with an acid. Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-tolylenediamine, 2-isopropyl paraphenylenediamine, 2-p-hydroxyethyl paraphenylenediamine, 2-p-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N- bis- (β-hydroxyethyl) para-phenylenediamine, 2-chloro-para-phenylenediamine, 2- acetylamino-ethyloxy-para-phenylenediamine, and their addition salts with an acid are particularly preferred. Among the bis-phenylalkylenediamines, mention may be made, as an example, of N, '-bis- (.beta.-hydroxyethyl). -bis- (4'-aminophenyl) 1,3-diamino propanol, N, N'-bis- (p-hydroxyethyl)?,? ' -bis- (4'-aminophenyl) ethylenediamine,?,? '- bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (p-hydroxyethyl)?,?' -bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methyl-aminophenyl) tetramethylenediamine, N, N'-bis- (ethyl)?,? ' -bis- (4 '-amino, 3' -methylphenyl) ethylenediamine, 1,8-bis- (2,5-diamino phenoxy) -3,6-dioxaoctane, and their addition salts. Among the para-aminophenols, mention may be made, as an example, of para-aminophenol, 4-amino-3-methyl phenol, 4-amino-3-fluoro-phenol, 4-amino-3-chlorophenol, 4-amino 3-hydroxymethyl phenol, 4-amino-2-methyl phenol, 4-amino-2-hydroxymethyl phenol, 4-amino-2-methoxymethyl phenol, 4-amino-2-aminomethyl-phenol, 4-amino-2- (-hydroxyethyl-aminomethyl) phenol, 4-amino-2-fluoro-phenol, and its addition salts with an acid. Among the ortho-aminophenols, mention may be made, as an example, of 2-amino phenol, 2-amino-5-methyl phenol, 2-amino-6-methyl phenol, 5-acetamido-2-amino phenol and their addition salts. Among the heterocyclic bases, mention may be made, as an example, of pyridic derivatives, pyrimidine derivatives and their pyrazole derivatives. Among the pyridine derivatives, mention may be made of the compounds described, for example, in GB 1 026 978 and GB 1 153 196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino 3-amino pyridine, 3, 4-diamino pyridine, and its addition salts. Other pyridine oxidation bases useful in the present invention are the 3-amino pyrazolo- [1, 5-a] -pyridines oxidation bases or their addition salts described for example in the patent application FR 2801308. As an example, there may be mentioned pyrazolo [1, 5-a] pyridin-3-ylamine; 2-acetylamino pyrazolo- [1, 5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo [1, 5-a] pyridin-3-ylamine; 3-amino-pyrazolo [1,5-a] pyridine-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-a] pyridin-3-ylamino; (3-amino-pyrazolo [1, 5- a] pyridin-7-yl) -methanol; 2- (3-Amino-pyrazolo [1, 5-a] pyridin-5-yl) -ethanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-7-yl) -ethanol; (3-Amino-pyrazolo [1,5-a] pyridin-2-yl) -methanol; 3, 6-diamino-pyrazolo [1,5-a] pyridine; 3, 4-diamino-pyrazolo [1,5-a] pyridine; pyrazolo [1,5-a] pyridin-3,7-diamine; 7-morpholin-4-yl-pyrazolo [1, 5-a] pyridin-3-ylamine; pyrazolo [1, 5-a] pyridin-3, 5-diamine; 5-morpholin-4-yl-pyrazolo [1, 5-a] pyridin-3-ylamine; 2- [(3-Amino-pyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) -amino] -ethanol; 2- [(3-Amino-pyrazolo [l, 5-a] pyridin-7-yl) - (2-hydroxyethyl) -amino] -ethanol; 3-Amino-pyrazolo [1,5-a] pyridin-5-ol; 3-Amino-pyrazolo [1,5-a] iridin-4-ol; 3-amino-pyrazolo [1, 5-a] pyridin-6-ol; 3-Amino-pyrazolo [1,5-a] pyridin-7-ol; as well as its addition salts. Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in DE 2359399; JP 88-169571; JP 05-63124; EP 0770375 or patent application WO 96/15765 as 2, 4, 5, 6-tetra-aminopirimidine, 4-hydroxy 2,5-, 6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4-dihydroxy 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and its addition salts and their tautomeric forms, when there is a tautomeric equilibrium. Among the pyrazole derivatives, mention may be made of the compounds described in DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 as 4.5 -diamono 1-methyl pyrazole, 4,5-diamino 1- (β-hydroxyethyl) irazole, 3,4-diamino pyrazole, 4,5-diamino 1- (4'-chlorobenzyl) pyrazole, 4,5-diamino 1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenyl-pyrazole, 4,5-diamino-1-methyl-3-phenyl-pyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 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- (-hydroxy-ethyl) -3-methyl-pyrazole, , 5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl 1-methyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethylpyrazole, 3, 4, 5-triamino pyrazole, 1-methyl 3,4-, 5-triamino pyrazole, 3,5-diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino 4- (-hydroxyethyl) amino 1-methyl pyrazole , and its addition salts. 4-5-Diamino 1- (β-methoxyethyl) pyrazole can also be used. The oxidation base or bases present in the composition of the invention are present, in general, in an amount ranging from 0.001 to 20% by weight approximately of the total weight of the dye composition, preferably ranging from 0.005 to 6%. If the composition contains at least one oxidation base, the composition according to the invention preferably contains one or more couplers conventionally used for dyeing keratin fibers. Among these couplers, mention may be made in particular of meta-phenylenediamines, meta-aminophenols, meta-di-phenols, naphthalene couplers, heterocyclic couplers and their addition salts. As an example, mention may be made of 1,3-dihydroxy benzene, 1,3-dihydroxy-2-methyl benzene, 4-chloro-1,3-dihydroxy benzene, 2,4-diamino 1- (β-hydroxyethyl-oxy) benzene, 2-amino 4- (β-hydroxyethylamino) 1-methoxybenzene, 1,3-diamino benzene, 1,3-bis- (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol , 1-P-hydroxyethylamino-3,4-methylenedioxybenzene, 1-a-naphthol, 2-methyl-1-naphthol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy-N-methyl indole, 2-amino-3- hydroxy pyridine, 6-hydroxy benzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1 -? - (β-hydroxyethyl) amino-3, -methylene dioxybenzene, 2,6-bis-2-hydroxyethylamino) toluene and its addition salts. In the composition of the present invention, the coupler (s) are generally present in an amount ranging from 0.001 to 20% by weight approximately of the total weight of the dye composition, preferably ranging from 0.005 to 6%. In a general manner, the addition salts of the oxidation bases and couplers usable in the context of the invention are chosen mainly from the salts of addition with an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and the addition salts with a base such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines. The dye composition according to the invention can additionally contain one or more additional direct dyes other than the cationic direct azo dyes of the formula (I) according to the invention, in particular they can be selected from the neutral, acidic or cationic benzene nitrate dyes. , the direct neutral azo dyes, acidic or cationic dyes, the direct quinonoic and in particular anthraquinone neutral dyes, acidic or cationic dyes, the direct azine dyes, the direct triarylmethanic dyes, the direct indoamine dyes and the natural direct dyes. As non-limiting examples, nitcene benzene dyes, azo, azomethin, methinic, tetraazapentamethin, anthraquinone, naphthoquinone, benzoquinone, phenothiazine indigoid, xanthine, phenanthridine, phthalocyanine, those derived from triarylmethane and natural dyes, alone or in mixtures. Among the direct benzene dyes which can be used according to the invention, they can be mentioned limiting the following compounds: 1,4-diamino-2-nitrobenzene, l-amino-2-nitro-4-hydroxyethylaminobenzene, l-amino-2-nitro-4-bis (b-hydroxyethyl) -aminobenzene - 1, 4-Bis (ß-hydroxyethylamino) -2-nitrobenzene-l- -hydroxyethylamino-2-nitro-4-bis- (ß-hydroxyethylamino) -benzene-lp-hydroxyethylamino-2-nitro-4-aminobenzene-lp -hydroxyethylamino-2-nitro-4- (ethyl) (β-hydroxyethyl) -aminobenzene-1-amino-3-methyl-4-p-hydroxyethylamino-6-nitrobenzene-1-amino-2-nitro-4-hydroxyethylamino -5-chlorobenzene-1,2-diamino-4-nitrobenzene-l-amino-2-b-hydroxyethylamino-5-nitrobenzene-1,2-Bis- (b-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-nitrobenzene-1 -Hydroxy-2-amino-4,6-dinitrobenzene-l ^ -hydroxyethyl-oxy-2 ^ -hydroxyethylamino-5-nitrobenzene - l-Methoxy-2-β-hydroxyethylamino-5-nitro-enne-β-β-hydroxyethyl-oxy-3-methylamino-4-nitrobenzene - β-β, Y-dihydroxypropyloxy-3-methylamino-4-nitrobenzene - lp-hydroxyethylamino- 4-, Y-dihydroxypropyloxy-2-nitrobenzene-1-β, Y-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene-1, -hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene-1-hydroxyethylamino-3-methyl-2 -nitrobenzene-l ^ -aminoethylamino-5-methoxy-2-nitrobenzene-1-hydroxy-2-chloro-6-ethylamino-4-nitrobenzene-1-hydroxy-2-chloro-6-araino-4-nitrobenzene-1 Hydroxy-6-bis- (β-hydroxyethyl) -amino-3-nitrobenzene-β-β-hydroxy-ylamino-2-nitrobenzene-1-Hydroxy-4 ^ -hydroxyethylamino-3-nitrobenzene. Among the direct azo dyes used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO-95/01772 and EP-714954 whose contents form an integral part of the invention. Among these comds, the following dyes can be mentioned in particular: - 1,3-dimethyl-2- [[4- (dimethylamino) phenyl] azo] -lH-imidazolium chloride, - L-methyl-4- [(methylphenylhydrazono) methyl] -pyridinium methylsulfate. The following colorants, described in COLOUR INDEX INTERNATIONAL 3rd edition, can also be mentioned among direct azo dyes: - Disperse Red 17 - Acid Yellow 9 - Acid Black 1 - Basic Red 22 - Basic Red 76 - Basic Yellow 57 - Basic Coffee 16 - Acid Yellow 36 - Acid Orange 7 - Acid Red 33 - Acid Red 35 - Basic Coffee 17 - Acid Yellow 23 - Acid Orange 24 - Disperse Black 9. Mention may also be made of 1- (4'-aminodiphenylazole) -2-methyl -4bis- (β-hydroxyethyl) aminobenzene and 4-hydroxy-3- (2-methoxyphenylazo) -1-naphthalenesulfonic acid.

Among the direct quinone dyes, the following colorants can be mentioned: - Disperse Red 15 - Violet Solvent 13 - Violet Acid 43 - Violet Scattered 1 - Violet Scattered 4 - Scattered Blue 1 - Violet Scattered 8 - Scattered Blue 3 - Scattered Red 11 - Blue Acid 62 - Dispersed Blue 7 - Basic Blue 22 - Disperse Violet 15 - Basic Blue 99 as well as the following compounds: 1-N-Methylmorpholinopropylamino-4-hydroxyanthraquinone-1-Aminopropylamino-4-methylaminoanthraquinone-1-Aminopropylaminoanthraquinone-5-hydroxyethyl -l, 4-diaminoanthraquinone-2-Aminoethylaminoanthraquinone-1,4-Bis- (β, β-dihydroxypropylamino) -anthraquinone. Among the azinic dyes, mention may be made of the following compounds: - Basic Blue 17 - Basic Red 2. Among the triarylmethanic dyes which can be used according to the invention, the following compounds can be mentioned: - Basic Green 1 - Basic Blue 9 - Basic Violet 3 - Basic Violet 14 - Basic Blue 7 - Violet Acid 49 - Basic Blue 26 - Acid Blue 7 Among the indoamic dyes which can be used according to the invention, the following compounds can be mentioned: - 2-p-hydroxyethylamino-5- [bis- (β-4 '-hydroxy ethyl) amino] anilino-1,4-benzoquinone-2-hydroxyethylamino-5- (2'-methoxy-4'-amino) anilino-1, -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-l, 4-benzoquinone iraine. Among the tetraazapentamethin type dyes which can be used according to the invention, mention may be made of the following compounds which appear in the following table, An is defined as follows: Among the natural direct dyes which can be used according to the invention, mention may be made of lawsone, juglone, alizarin, glitter, carminic acid, querneic acid, purpurogaline, protocatecaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin. You can also use extracts or decoctions containing these natural dyes and mainly poultices or extracts based on henna. The direct dye (s) other than those of the formula (I) preferably represent 0. 001 to 20% by weight approximately of the total weight of the composition, and more preferably 0. 005 to 10% by weight approximately. The composition according to the invention can also comprise at least one oxidizing agent conventionally used for the oxidation dyeing of keratin fibers, such as for example hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidases enzymes among which may be mentioned peroxidases, 2-electron oxido-reductases such as uricases and 4-electron oxygenates such as laccases. Hydrogen peroxide is particularly preferred. The appropriate medium for the dye also called dye support is a cosmetic medium generally constituted by water or by a mixture of water and at least one organic solvent to solubilize the compounds which will not be sufficiently soluble in the water. As an organic solvent, there may be mentioned, for example, the lower alkanes of C1-C4, such as ethanol and isopropanol; polyols and ethers of polyols such as 2-butoxyethanol, propylene glycol, glycerol, propylene glycol momomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof. The solvents are preferably present in proportions preferably between 1 and 40% by weight, based on the total weight of the dye composition, and more preferably between 5 and 30% by weight. The dyeing composition according to the invention can also include various adjuvants conventionally used in dyeing compositions for hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or their mixtures, anionic, cationic, nonionic, amphoteric polymers. , zwitterionic or their mixtures, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric associative thickeners, antioxidants, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, agents preservatives and opacifying agents. The adjuvants mentioned above, in general, are present in an amount comprised for each of them between 0. 01 and 20% by weight in relation to the weight of the composition. Of course, the person skilled in the art will take care to choose this or these possible complementary compounds so that the advantageous properties intrinsically linked to the dye composition according to the invention are not, or are not substantially altered by the contemplated additive (s). The pH of the dye composition according to the invention is generally between 3 and 12, preferably between 5 and 11, and even more particularly from 6 to 10. 5 . It can be adjusted to the desired value by means of acidifying or alkalizing agents commonly used in dyeing keratin fibers or even with the aid of conventional buffer systems. Among the acidifying agents, mention may be made, as an example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, acid lactic, sulfonic acids. Among the alkalizing agents can be mentioned, as an example, ammonia, alkali carbonates, alkanolamines, such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and the compounds of formula (II) below: (?) wherein W is a propylene residue optionally substituted by a hydroxyl group or an alkyl radical of Ci-C; Ra, ¾ Re and identical or different, represent a hydrogen atom, an alkyl radical of Ci-C < Or Ci-C4 hydroxyalkyl. The dyeing composition according to the invention can be presented in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and mainly human hair. The process of the present invention is a process in which the composition according to the present invention is applied to the fibers as defined above, then the fibers are rinsed. According to a particular embodiment, the composition of the invention is applied on the fibers keratin in the presence of an oxidizing agent, then refers in this case to a clarifying coloring procedure. The oxidizing agent can be added to the composition of the invention just at the time of use or it can be used from an oxidizing composition containing it., applied simultaneously or sequentially to the composition of the invention. Preferably, in this particular embodiment, the composition of the invention contains at least one oxidation base. The compositions with or without oxidant are applied to the keratin materials and after a standing time of about 3 minutes to about 1 hour, preferably about 15 minutes to about 45 minutes, the keratin fibers are rinsed, shampooed, rinsed again afterwards. dried. The oxidizing composition may also contain various adjuvants conventionally used in hair dyeing compositions and as defined above. The pH of the oxidizing composition containing the oxidizing agent is such that after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers preferably ranges from about 3 to about 12, still more preferably between 5 and 11 and even more particularly between 6 and 10. 5 can be adjusted to the desired value by means of acidifying or alkalizing agents commonly used in coloring keratin fibers and as defined a. The ready-to-use composition which is finally applied to the keratin fibers can be presented in various forms, such as in the form of liquids, creams, gels or in any other form suitable for coloring keratin fibers, and especially The invention also relates to the use of the dye composition according to the invention for the dyeing of keratin fibers The invention also relates to a multi-compartment device or coloring kit, in which a first compartment contains the dye composition according to the invention and a second compartment contains an oxidizing agent This device can be equipped with a means that allows to release on the hair the desired mixture, such as the devices described in patent FR-2 586 913 by way of the applicant The following examples serve to illustrate the invention without, however, presenting a limitative character.

Examples of preparations of compounds according to the invention 1) Example 1 by route A To 200 g of solution at 40% w / v of nitrosylsulfuric acid in sulfuric acid, 100 ml of anhydrous acetic acid and 500 ml of anhydrous propionic acid were added, then the mixture was brought to a temperature below 5 ° C, introduced progressively 50 g of 4-aminopyridine. The mixture thus obtained was diluted by the addition of 200 ml of propionic acid and 40 ml of acetic acid, then a solution of 50 g of julolidin in 200 ml of methanol was added dropwise, keeping the temperature below 10 ° C. The reaction mixture was neutralized after 16 hours of reaction at a temperature below 5 ° C by introduction of 500 ml of water, 300 g of ice then 500 ml of 30% sodium hydroxide. The product (A) was extracted with ethyl acetate, purified by chromatography on silica gel. To 5 g of pure product (A), diluted in 50 ml of dichloromethane, 5 ml of dimethyl sulfate were added, then the reaction mixture was kept under stirring for 2 hours. The medium was concentrated by distillation under vacuum of solvents, then the obtained residue was purified by solubilization in the methyl ethyl ketone followed by precipitation with heptane. 7.12 g of a blue powder were thus obtained. The analyzes indicated it as expected [i]. 2) Example 2 by route A Tonic Exchange resin [H] To 13.21 g of aminoimidazole suspension in 100 ml of water, 30 ml of 35% hydrochloric acid were added, the mixture was cooled to -5 ° C then a solution of 7 g of sodium nitrite was added dropwise. in 10 ml of water, maintaining a temperature below 0 ° C. 5 g of sulfanilic acid were then added, and the mixture was poured onto an acid solution of julolidin previously obtained by mixing 8.75 g of julolidine, 175 ml of water and 225 ml of water. my acetic acid and 40 g of sodium acetate and kept at 0 ° C. After 2 h at 5 ° C, the reaction mixture was diluted, brought to pH 8 by the soda. The product (B), precipitated, was filtered and washed with water. 5 g of (B) were solubilized in 50 ml of dichloromethane; successively, 5 ml of dimethyl sulfate and 1 ml were added. 53 g of sodium acetate. After 2 hours of stirring, the mixture was concentrated under reduced pressure, it was recovered in 100 ml of methyl ethyl ketone then 100 ml of heptane was added. The precipitate obtained was washed by heptane, 4 were obtained. 5 g of black violet powder. An ion exchange on resin was then carried out to obtain the expected product [ii] in the form of hydrochloride (2.56 g). The analyzes indicated it as expected [ii]. 3) Example 3 through route A [i ü] 3-aminopyridine, 17 ml of ac 35% hydrochloric acid and 65 g of ice were mixed in a 500 ml three neck flask. A solution of 5.08 g of sodium nitrite in 20 ml of water was added dropwise, keeping the temperature of the mixture at 0 ° C. Once the addition was achieved, the mixture was kept stirred for 20 minutes at 0 ° C then a solution of 400 mg of urea in 10 ml of water was added. A solution of julolidin 11.6 g in a mixture of ethanol (25 ml), 35% hydrochloric acid (16 ml), ice (22 g) was added dropwise while maintaining a temperature below 10 ° C. After 3 hours at 5 ° C, the reaction mixture was neutralized by addition of ammonia, until obtaining a pH of 9.5. The paste obtained was extracted with ethyl acetate with the addition of water. The organic phase was dried and concentrated under vacuum; the product thus obtained was purified by chromatography (silica gel, heptane / ethyl acetate eluent) and a pure fraction of a dark red powder (4.3 g) was obtained, as expected (product (C)). The product obtained during the previous step (127 mg) was solubilized in toluene (5 ml), 86 μ? of dimethyl sulfate were added and the reaction mixture was kept stirred for 72 hours. The toluene was removed under vacuum, the product obtained was treated with water for 4 hours at room temperature then dried under vacuum, a dark violet solid (170 mg) was obtained. The analyzes indicated it as expected [iii]. 4) Example 4 by route A [iv] 10 g of 2-amino-1-methyl benzimidazole were solubilized in a mixture of 60 ml of orthophosphoric acid and 20 ml of hot acetic acid. 26 g of nitrosyl sulfuric acid (40% in sulfuric acid) were diluted in 25 ml of 98% phosphoric acid at 10 ° C in a 250 ml three neck flask fitted with a thermometer and an argon inlet. The first solution was poured drop by drop on the second, maintaining the temperature between 2 and 5 ° C in 30 minutes. The mixture was stirred for 15 minutes, 3.3 g of sulfamic acid were added and the mixture was stirred for 15 minutes. 13 g of previously melted julolidine were solubilized in 25 ml of DMF to 9 g of acetic acid. The diazonium salt obtained during the preceding operation was poured dropwise onto this solution maintaining a temperature below 10 ° C. The mixture of reaction was diluted with 50 ml of water then kept at 0 ° C for 18 hours. 500 g of ice were then added 100 ml of 30% sodium hydroxide; again 500 g of ice and 150 ml of 30% sodium hydroxide. The mixture thus obtained was then diluted with 2 l of water and then brought to pH 7 by the addition of sodium hydrogen carbonate (190 g). The precipitate obtained was filtered (9.6 g) and dried. 1 g was purified by chromatography (silica, eluent dichloromethane / methanol). 100 mg of a red powder was obtained. The analyzes indicated it as expected (D). 100 mg of D were solubilized in 20 ml of dichloromethane, and 500 μl was added dropwise to this mixture. of dimethyl sulfate at room temperature. The solution was stirred for 5 minutes, then poured into 250 ml of ethyl ether. The precipitate was filtered and washed with 4 x 50 ml of ethyl ether. After drying, 50 mg of a black paste was recovered. The analyzes indicated it as expected [iv]. 5) Example 5 by route A [v] 11. 8 g of julolidine were dissolved at 40 ° C in 100 ml of water added with 5.7 ml of 35% hydrochloric acid. 10 g of pyridin-2-amin-1-oxide (prepared according to the methods described in Synth, Commun, 1977, 509-514) were dissolved in 100 ml of added water of 17.4 ml of 35% hydrochloric acid. A solution of 4.7 g of sodium nitrite dissolved in 10 ml of water were added, maintaining the mixing temperature at 0 ° C. The mixture was stirred 30 minutes at 0 ° C. It was then poured over the acid solution of julolidine, maintaining the temperature below 10 ° C. The mixture was brought to room temperature in two hours. The addition of 70 g of sodium acetate allowed to bring the pH of the mixture to 4.2. After extraction with dichloromethane, rinsed with water, dried over sodium sulfate, filtered, concentrated in vacuo, triturated in ether, the obtained powder was filtered and dried under vacuum, 10 g of dark violet powder were obtained. The analyzes indicated that they were in accordance with the expected product (E), with minor impurities. 5 g of (E) were dissolved in 20 ml of Rimethylpyrrolidinone (NMP) and the solution was heated to 60 ° C. 4.05 g of dimethyl sulfate were added to the mixture. After 2 hours 30 minutes, the solution was cooled to room temperature. 50 ml of 20% ammonia solution were added. After 15 hours at room temperature, the mixture was extracted with dichloromethane (2 x 100 mL), washed with water, dried and concentrated under vacuum. The dark blue oil obtained was washed twice with isopropyl ether, then triturated in a third fraction. After filtration, it was rinsed with ether and dried under vacuum, 2 g of chestnut powder was obtained. The analyzes indicated that they were in accordance with the expected product [v].

Examples of dyes (non-rinsing conditions) The dyeing compositions were prepared in following proportions: Solution 1 Solution 2: pH 9.5 SHOCK ABSORBER Solution 3: SHOCK ABSORBER pH 7 The coloring compositions were obtained dissolving the dye indicated below (5x10 mol / 1) in solution 1 then adding an equivalent volume of buffer 2 or 3 (pH 7 or 9.5). Each composition was applied on 90% white hair, (1 g of wick per 6 g of solution). After 30 minutes of rest, the wicks were rinsed, washed with a standard shampoo, rinsed again then dried.

The following dye results were obtained Examples of dyes (clarifying conditions): The dyeing compositions were prepared in the following proportions: Coloring 0.25 g Hydroxyethylcellulose Natrosol 250MR 0.72 g Alkyl C8 / C10 (50: 50) hydroxyethylcellulose 5 g At the time of use, this formulation was mixed weight by weight with hydrogen peroxide 40 volumes, then applied on BN (Natural White) and BP (Permanent White) wicks - 1 g of wick per 6 g of solution. After 30 min of rest, the wicks were rinsed, washed with a standard shampoo, rinsed again then dried.

The following dye results were obtained: The wicks thus colored were subjected to a wash resistance test which consists of performing 12 shampoos (with a standard shampoo) and evaluating the color after these 12 washes with shampoo. After the 12 washes with shampoo, the wicks were always colored. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (27)

1. CLAIMS Having described the invention as above, the contents of the following claims are claimed as property: 1. Use of at least one azoic cationic compound of the julolidine portion of the formula (I): wherein A represents a cationic aromatic heterocycle selected from the compounds of the following general formulas: wherein Ri independently represents between: • a C1-C16 hydrocarbon chain, linear or branched, saturated or unsaturated, which can form one or more carbon cycles comprising from 3 to 7 chains, optionally condensed with the optionally substituted aromatic ring, optionally interrupted by one or more groups chosen from heteroatoms such as oxygen, nitrogen or sulfur, and the carbonyl group; Ri does not understand the nitro, nitroso, peroxide and diazo bond; Ri is directly linked to the nitrogen atom, quaternized or not, of the heteroaromatic cycle A by the intermediary of a carbon atom. R2 represents independently of each other: a C1-C16 hydrocarbon chain; linear or branched, saturated or unsaturated, which can form one or more aromatic carbon cycles or not, comprising from 3 to 6 chains, optionally substituted, optionally interrupted by one or more heteroatoms or by one or more groups bearing at least one hetero atom , preferably chosen from oxygen, nitrogen; A hydroxyl group, a C1-C4 alkyloxy group, a C2-C4 (poly) hydroxyalkyloxy group; · An alkyloxycarbonyl group (RnO-CO-) in which Ru represents a C 1 -C 4 alkyl radical; • an alkylcarbonyloxy radical (R12CO-O-) in which Ri2 represents an alkyl radical is C1-C4; • an amino group, an amino group substituted by one or two C 1 -C 4 alkyl radicals, identical or different, optionally carriers of at least one hydroxyl group, the two alkyl radicals can optionally form with the nitrogen atom to which they are attached, a 5- or 6-chain heterocycle optionally carrying another heteroatom identical or different from nitrogen, for example oxygen , the sulfur; • an alkylcarbonylamino group (R13CO-NR13-) and / or (R13CO-H) in which the R13 radicals independently of each other represent a C1-C4 alkyl radical; · A carbamoyl group ((Ri4) 2N-CO) in which the R14 radicals independently of one another, identical or not, represent a hydrogen atom, an alkyl radical of Ci-C4; • a ureido group ((R3.5) 2N-CO-NR16-) in which the radicals R15 and Ri6, independently of each other, represent a hydrogen atom, a C1-C4 alkyl radical; • a sulfonamide group ((R17) 2N-SO2 -) in which the radicals R17, independently of one another, represent a hydrogen atom, a C1-C4 alkyl radical,; • an alkylsulfonylamino group (Ri8S02-NRi9-) in which the radicals Rie, R19 / independently from each other, represent a hydrogen atom, an alkyl radical of C1-C4; • a guanidinium group ((R20) 2N-C (= NH2 +) -NR21 -) in which the radicals R20 and R21 »independently from each other, represent a hydrogen atom, an alkyl radical of Ci-C4; • a nitro group; • a group ciand; • a halogen atom, preferably chlorine, fluorine; two radicals R2, carried by the adjacent carbon atoms can form, together with the carbon atom to which each is attached, a condensed, aromatic or non-aromatic cycle; m represents an integer between 0 and 4; e is an integer between 0 and 2; p is an integer between 0 and 1; D represents a CR2 group or a nitrogen atom; Q represents a group NRi, or an oxygen or sulfur atom; the bond has resulted from the formulas (lia), (Ilb) or (lie), linking group A to the azo group; in the case of the formulas (lia), (Ilb) or (lie) and when two radicals R2 carried by two adjacent carbon atoms form an aromatic cycle, the bond has been able to bind group A to the azo group through the cycle intermediary aromatic; the electroneutrality of the compounds is ensured by one or more anions ", identical or not, cosmetically acceptable, X, Y and Z are defined as substitution possibilities respectively on the alkyl and aryl cycles of the tricyclic core, x is between 0 and 2, and is between 0 and 6, and Z is between 0 and 6, x, y, and z are numbers whole; or their addition salts or their solvates, when an alkyl radical or the alkyl part of a radical is called (a) (substituted (a) '), then it comprises at least one substituent selected from the groups: • hydroxyl, • C1 alkyloxy -C4, C2-C4 (poly) hydroxyalkyloxy, amino, amino substituted by one or more identical or different C1-C4 alkyl groups optionally bearing at least one hydroxyl group, the alkyl radicals can form with the nitrogen atom to which they are attached, a heterocycle of 5 or 6 chains, optionally comprising at least one heteroatom different or not from the nitrogen, when an aryl or heteroaryl radical or the aryl or heteroaryl part of a radical is called (a) 'substituted (a) ', as for example the substituent X on the aromatic nucleus of the tricycle, then comprises at least one substituent carried by a carbon atom, selected from: a C1-C16 alkyl radical, preferably Ci-Ce, opc optionally substituted by one or more radicals chosen from hydroxy, C1-C2 alkyloxy, C2-C4 (poly) -hydroxyalkyloxy, acylamino, amino radicals substituted by one or two identical or different alkyl radicals of C1-C4, optionally carriers of at least one hydroxyl group or, the two radicals that can form with the nitrogen atom to which they are attached, a heterocycle of 5 or 7 chains, preferably of 5 or 6 chains, optionally comprising a heteroatom identical or different from nitrogen; • a halogen atom such as chlorine, fluorine or bromine; • a hydroxyl group; • a C1-C2 alkyloxy radical; • a C2-C4 (poly) -hydroxyalkyloxy radical; • an amino radical; • an amino radical substituted by one or two alkyl radicals, identical or different, of C1-C4 optionally bearing at least one hydroxyl group; • an acylamino radical (-N31R-COR32) in which the radical R3i is a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group and the radical R32 is an alkyl radical of Ci-C2; • a carbamoyl radical ((R33) 2N-CO-) in which the radicals R33, identical or not, represent a hydrogen atom, a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group; • an alkylsulfonylamino radical (R34SO2-N35R-) in which the radical R34 represents a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group and the radical R35 represents a C1-C4 alkyl radical, a phenyl radical; • an aminosulfonyl radical ((R36) 2N-S02-) in which the R36 radicals, identical or not, represent a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group; when the cyclic or heterocyclic part of a non-aromatic radical is called (a) 'substituted (a)', such as for example the substituents Y and Z of aliphatic heterocycles of the tricycle, then it comprises at least one substituent carried by a carbon atom, chosen from the groups: hydroxyl, C1-C4 alkyloxy, C2-C4 (poly) hydroxyalkyloxy, alkylcarbonylamino ((R4iCO-NR42-) in which the radical R42 is a hydrogen atom, an alkyl radical of Ci -C4 optionally carrying at least one hydroxyl group and the radical R4i is a C1-C2 alkyl radical, amino substituted by two identical or different C1-C4 alkyl groups optionally bearing at least one hydroxyl group, the alkyl radicals which can be forming with the nitrogen atom to which they are attached, a heterocycle of 5 or 6 chains, optionally comprising at least one heteroatom different or not from nitrogen, when a cycle does not carry the maximum number of substitutes ntes, then the or the unsubstituted positions carry a hydrogen atom; as a direct dye for keratin fibers, in particular human keratin fibers, such as hair 2. Use according to claim 1, wherein Ri represents an alkyl or hydroxyalkyl group of Ci-C8. 3. Use according to claim 1 or 2, wherein the formulas (lia), (Ilb) and (lie) are such that they comprise two radicals R2 carried by adjacent carbon atoms, these radicals then forming together with the atom of carbon to which each is attached, an aromatic condensed cycle, optionally substituted. 4. Use according to any of claims 1 to 3, wherein e, m and p are 0. 5. Use according to any of claims 1 to 4, wherein x is 0 or x is 1 with X representing a group alkyl, hydroxyl, hydroxyalkyl, alkyloxy, amino, alkylamino, dialkylamino, acylamino. 6. Use according to any of claims 1 to 5, wherein the compound of the formula (I) has one of the following structures: 7. Dyeing composition for dyeing keratin fibers, in particular human keratin fibers such as hair, characterized in that it comprises, in an appropriate dyeing medium, at least one azoic cationic compound as defined in any of claims 1 to 6. 8. Composition in accordance with the claim 7, characterized in that it comprises from 0.001 to 20%, preferably from 0.01 to 10% of direct dye (s) of the formula (I) in relation to the total weight of the composition. 9. Composition according to claim 7 or 8, characterized in that it comprises an oxidation base chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts. Composition according to any of claims 7 to 9, characterized in that it comprises an amount comprised between 0.001 to 20% by weight and preferably between 0.005 and 6% by weight of oxidation bases relative to the total weight of the composition. Dye composition according to any of claims 7 to 10, characterized in that it further comprises a coupler chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers, heterocyclic couplers and their addition salts. 12. Composition according to claim 11, characterized in that the coupler is chosen from the .1, 3-dihydroxy benzene, 1,3-dihydroxy-2-methyl benzene, 4-chloro-1,3-dihydroxy benzene, 2,4- diamino 1- (β-hydroxyethyloxy) benzene, 2-amino 4- (β-hydroxyethylamino) 1-methoxybenzene, 1,3-diamino benzene, 1,3 -bis- (2,4-diaminophenoxy) propane, 3-ureido aniline , 3-ureido 1-dimethylamino benzene, sesamol, lp-hydroxyethylamino-3,4-methylenedioxybenzene, 1-naphthol, 2-methyl-l-naphthol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy-N-methyl indole, 2-amino-3-hydroxy pyridine, 6-hydroxy benzomorpholine, 3,5-diamino-2, 6- dimethoxypyridine, 1-N- (β-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- (β-hydroxyethylamino) toluene and their addition salts. 13. Composition according to claim 11 or 12, characterized in that the coupler (s) are present in an amount comprised between 0.001 and 20%, preferably between 0.005 and 6% by weight relative to the total weight of the composition. 14. Composition according to any of claims 7 to 13, characterized in that it comprises one or more additional direct dyes other than compounds of the formula (I), chosen from the neutral dyes of the benzene series neutral, acidic or cationic dyes direct azo neutral, acidic or cationic, the direct dyes quinonic and in particular anthraquinone neutral, acidic or cationic dyes, the direct direct dyes, the direct triarylmethanic dyes, the direct tetraazapentametin dyes, the direct indoamine dyes and the natural direct dyes. 15. Composition according to claim 16, characterized in that the additional direct dye (s) are present in an amount comprised between 0.001 to 20% by weight and preferably between 0.005 and 10% by weight relative to the total weight of the composition. composition. Composition according to any of claims 7 to 15, characterized in that it comprises at least one oxidizing agent chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidases enzymes, and preferably hydrogen peroxide. 17. Composition according to any of claims 7 to 16, characterized in that it comprises at least one hydroxylated solvent, such as ethanol, propylene glycol, glycerol, monoesters of polyols. 18. Composition according to any of claims 7 to 17, characterized in that it comprises at least one adjuvant chosen from anionic surfactants., cationic, nonionic, amphoteric, zwitterionic, or their mixtures, the anionic, cationic, nonionic, amphoteric, zwitterionic or their mixtures, the mineral or organic thickening agents, and in particular the associative thickeners anionic, cationic, nonionic polymers and amphoteric, antioxidant agents, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as volatile or non-volatile silicones, modified or unmodified, film forming agents, ceramides, the conservative agents, the opacifying agents. Process for dyeing keratin fibers, characterized in that it comprises the following steps: - the dye composition according to one of claims 7 to 18 is applied to the keratin fibers, - it is allowed to stand for a period comprised between 3 minutes and 1 hour. hour and preferably between 15 minutes and 45 minutes, then - the fibers are rinsed. 20. Use of a composition according to one of claims 7 to 18 for dyeing keratin fibers. 21. Multi-compartment device or coloring kit, characterized in that it comprises a first compartment containing a composition as defined according to claims 7 to 18 and a second compartment containing a composition which. comprises an oxidizing agent. 22. Azoic cationic compound of the julolidine portion of the formula (I): (I) characterized in that A represents a cationic aromatic heterocycle chosen from the compounds of the following general formulas: wherein: Ri independently represents: a linear or branched, saturated or unsaturated Ci-C ^ hydrocarbon chain, which can form one or more carbon cycles comprising from 3 to 7 chains, optionally condensed with the aromatic ring, optionally substituted, optionally interrupted by one or more groups chosen from heteroatoms such as oxygen, nitrogen or sulfur, and the carbonyl group; Ri does not understand the nitro, nitroso, peroxide and diazo bond; Ri is directly linked to the nitrogen atom, quaternized or not, of the heteroaromatic cycle A by the intermediary of a carbon atom. R2 represents independently of each other: a C1-C16 hydrocarbon chain; linear or branched, saturated or unsaturated, which can form one or several aromatic carbon cycles or not, comprising from 3 to 6 chains, optionally substituted, optionally interrupted by one or more heteroatoms or by one or more groups bearing at least one heteroatom, preferably chosen from oxygen, nitrogen; A hydroxyl group, a C1-C4 alkyloxy group, a C2-C4 (poly) hydroxyalkyloxy group; • an alkyloxycarbonyl group (RuO-CO-) in which Ru represents a C 1 -C 4 alkyl radical; · An alkylcarbonyloxy radical (R12CO-O-) in which R12 represents an alkyl radical is C1-C4; • an amino group, an amino group substituted by one or two C1-C4 alkyl radicals, identical or different, optionally carrying at least one hydroxyl group, the two alkyl radicals can optionally form with the nitrogen atom to which they are joined, a 5- or 6-chain heterocycle optionally carrying another heteroatom identical or different from nitrogen, for example oxygen, sulfur; · An alkylcarbonylamino group (R13CO-NR13 -) and / or (R13CO-NH-) in which the R13 radicals independently of one another represent a C1-C4 alkyl radical; • a carbamoyl group ((Ri4) 2N-CO) in which the R14 radicals independently of one another, identical or not, represent a hydrogen atom, a C1-C4 alkyl radical; • a ureido group ((R15) 2 -CO- R16-) in which the radicals R15 and Ri6, independently of one another, represent a hydrogen atom, a C1-C4 alkyl radical; • a sulfonamide group ((Ri7) 2N-SO2 -) in which the radicals R17, independently of each other, represent a hydrogen atom, a C1-C4 alkyl radical,; • an alkylsulfonylamino group (Ri 8S02 -NRi 9 -) in which the radicals Rie, R 19, independently of one another, represent a hydrogen atom, a C 1 -C 4 alkyl radical; · A guanidinium group ((R20) 2N-C (= NH2 +) -NR2i -) in which the radicals R2o and R2i, independently of each other, represent a hydrogen atom, an alkyl radical of Ci-C; • a nitro group; · A cyano group; • a halogen atom, preferably chlorine, fluorine; two radicals R2, carried by the adjacent carbon atoms can form, together with the carbon atom to which each is attached, a condensed, aromatic or non-aromatic cycle; m represents an integer between 0 and 4; e is an integer between 0 and 2; p is an integer between 0 and 1; D represents a CR2 group or a nitrogen atom; Q represents a group NRi, or an oxygen or sulfur atom; the bond has resulted from the formulas (lia), (Ilb) or (lie), linking group A to the azo group; in the case of the formulas (lia), (Ilb) or (lie) and when two radicals R2 carried by two adjacent carbon atoms form an aromatic cycle, the bond has been able to bind group A to the azo group through the cycle intermediary aromatic; the electroneutrality of the compounds is ensured by one or several anions, identical or not, cosmetically acceptable, X, Y and Z are defined as substitution possibilities respectively on the alkyl and aryl cycles of the tricyclic core, x is between 0 and 2, and is comprised between 0 and 6, and Z is comprised between 0 and 6, x, y, and z are integers, or their addition salts or their solvates, when an alkyl radical or the alkyl part of a radical is called (a) 'substituted (a)', then it comprises at least one substituent chosen from the groups: hydroxyl, Ci-C4 alkyloxy, C2-C4 (poly) hydroxyalkyloxy, amino, amino substituted by one or more identical or different alkyl groups of Ci-C4 optionally bearing at least one hydroxyl group, the alkyl radicals can form with the nitrogen atom to which they are attached, a 5- or 6-chain heterocycle, optionally comprising at least one heteroatom which is different or non-nitrogen, when an aryl or heteroaryl radical or the aryl or heteroaryl part of a radical is called (a) 1 substituted (a) ', for example the substituent X on the aromatic nucleus of the tricycle, then comprises at least one substituent carried by a carbon atom, chosen from: a C1-C16 alkyl radical, preferably Ci-Ce, optionally substituted by one or several radicals chosen between the hydroxy radicals, C1-C2 alkyloxy, C2-C4 (poly) -hydroxyalkyloxy, acylamino, amino substituted by one or two identical or different alkyl radicals of C1-C4, optionally bearing at least one hydroxyl group or , the two radicals which can form with the nitrogen atom to which they are attached, a heterocycle of 5 or 7 chains, preferably of 5 or 6 chains, optionally comprising an heteroatom identical or different from the nitrogen; • a halogen atom such as chlorine, fluorine or bromine; • a hydroxyl group; · An alkyloxy radical of C1-C2; • a C2-C4 (poly) -hydroxyalkyloxy radical; • an amino radical; • an amino radical substituted by one or two alkyl radicals, identical or different, of C1-C4 optionally bearing at least one hydroxyl group; • an acylamino radical (-N31R-COR32) in which the radical R31 is a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group and the radical R32 is an alkyl radical of Ci-C2; · A carbamoyl radical ((R33) 2N-CO-) in which the radicals R33, identical or not, represent a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group; • an alkylsulfonylamino radical (R34S02-N35R-) in which the radical R34 represents a hydrogen atom, a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group and the radical R 35 represents a C 1 -C 4 alkyl radical, a phenyl radical; • an aminosulfonyl radical ((R36) 2N-SO2-) in which the radicals R36, identical or not, represent a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group; when the cyclic or heterocyclic part of a non-aromatic radical is called (a) 'substituted (a)', such as for example the substituents Y and Z of aliphatic heterocycles of the tricycle, then it comprises at least one substituent carried by a carbon atom, chosen from the following groups: • hydroxyl, • C1-C4 alkyloxy, (C2-C4) (poly) hydroxyalkyloxy, • alkylcarbonylamino ((R41CO-NR42-) in which the radical R42 is a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group and the radical R41 is a C1-C2 alkyl radical, amino substituted by two identical or different C1-C4 alkyl groups optionally carriers of at least one hydroxyl group, the alkyl radicals which can form with the nitrogen atom to which they are attached, a 5- or 6-chain heterocycle, optionally comprising at least one heteroatom different or not from the nitrogen; when one cycle does not carry the maximum number of substituents, then the one or more unsubstituted positions carry a hydrogen atom; with the exception of 2- (9-julolidilazo) -3-methylbenzothiazolium perchlorate of 2- (9-julolidilazo) -3-ethylthiazolium perchlorate. 23. Compound according to claim 22, characterized in that Ri represents an alkyl or hydroxyalkyl group of Ci-Ce. Compound according to claim 22 or 23, characterized in that the formulas (lia), (Ilb) and (lie) are such that they comprise two radicals R2 carried by adjacent carbon atoms, these radicals which then form together with the carbon atom to which each is attached, an aromatic, optionally substituted, fused cycle. 25. Compound according to any of claims 22 to 24, characterized in that e, m and p are 0. 26. Compound according to any of claims 22 to 25, characterized in that x is 0 or ox is 1 with X representing an alkyl group, hydroxyl, hydroxyalkyl, alkyloxy, amino, alkylamino, dialkylamino, acylamino. 27. Compound according to any of claims 22 to 26, characterized in that the compound of the formula (I) has one of the following structures: ?