FR2913015A1 - New secondary para-phenylenediamine compounds useful as an oxidation base for oxidation hair-coloring - Google Patents

Abstract

The present application relates to new para-phenylenediamines secondary functionalized on the amine by an aliphatic chain, a process for their preparation, their use in capillary oxidation dyeing, a composition for dyeing keratin fibers, and in particular keratin fibers human, such as the hair, containing, in a medium suitable for dyeing, at least one such secondary para-phenylenediamine and at least one oxidation coupler, a process for dyeing keratin fibers, the use of this composition in hair dyeing , as well as a "kit" of dyeing.

Description

B06 / 4607 EN FB / CV OA 07072 Société Anonyme known as L'OREAL PARAPHENYLENES

  ALIPHATIC SECONDARY DIAMINES IN CAPILLARY COLOR Invention of: SABELLE Stéphane METAIS Eric

2

  PARAPHENYLENES ALIPHATIC SECONDARY DIAMINES IN CAPILLARY COLORING

  The present application relates to a new family of secondary para-phenylenediamines functionalized on the amine by an aliphatic chain, their preparation and their use in capillary oxidation dyeing. It is known to dye keratinous fibers and in particular human hair with dyeing compositions containing oxidation dye precursors, generally known as oxidation bases, such as ortho or para-phenylenediamines, ortho or para-aminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, combined with oxidizing products, can give rise by a process of oxidative condensation to colored and coloring compounds. It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers, the latter being chosen in particular from meta-diaminobenzenes, meta-aminophenols and meta-diphenols. and certain heterocyclic compounds such as indole and pyridine compounds. The variety of molecules involved in oxidation bases and couplers, allows to obtain a rich palette of colors. The so-called "permanent" coloration obtained with these oxidation dyes must also meet a certain number of requirements. Thus, it must be harmless from the toxicological point of view, it must make it possible to obtain shades in the desired intensity and to have good resistance to external agents such as light,

3

  bad weather, washing, permanent undulations, perspiration and friction. The dyes must also make it possible to cover the white hair, and finally be the least selective possible, that is to say, to obtain the lowest possible color differences throughout the same keratin fiber, which is in general differently sensitized (ie damaged) between its tip and its root. Surprisingly and advantageously, the Applicant has just discovered that certain secondary para-phenylenediamine derivatives functionalized on the amine by an aliphatic chain are not only suitable for use as a base for oxidation dyeing, but also that they allow to lead to powerful colorations, in a wide range of colors, with low color differences throughout the same keratin fiber and having excellent properties of resistance to various attacks that can suffer the fibers (light, wash. ..). The present application also relates to a process for the preparation of these secondary paraphenylenediamines functionalized on the amine by an aliphatic chain, as well as on their use in capillary oxidation dyeing. Another subject of the invention relates to compositions for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, comprising at least one secondary para-phenylenediamine functionalized on the amine by an aliphatic chain making it possible to obtain stains with the previously mentioned advantages. The subject of the invention is also a dyeing process employing this composition, the use of the composition according to the present invention for dyeing keratinous fibers, in particular

4

  human keratin fibers such as the hair and a multi-compartment device or "kit" of dyeing. The composition of the present invention makes it possible in particular to obtain a keratinous fiber coloration which is very powerful, not very selective and tenacious, in particular in light. Other features, aspects, objects and advantages of the present invention will become more apparent upon reading the description and the examples which follow. The novel para-phenylenediamines secondary according to the present invention are para-phenylenediamines of general formula (I): H, N, Ak R1 wherein: Ak represents an unsubstituted linear or branched C4-C10 alkyl chain; R1 represents an unsubstituted alkyl radical; an unsubstituted alkoxy radical; or their addition salts or solvates with the exception of the following compounds: HN (CH 2) 5Me OMe HHN '1 NH 2 Preferably, the Ak group in formula (I) represents a 2-methylbutyl, 2-ethylbutyl, 1, 3 dimethylbutyl or isobutyl. Preferably, the group R 1 in the formula (I) represents a methyl group or a methoxy group. More preferably, the compounds of general formula (I) are chosen from: HN NH, HNHN, NH2 2-methyl-N1- (2-N1- (2-ethylbutyl) -2-diamine N4- (2- ethyl 1,4-methylbenzene-1,4-diamine NH 2 diamine Isobutyl-2-methyl-NH 2 -benzene-1,4-diamine benzene-1,4-NH 2 -NH-diamine N-1- (1,3-dimethyl-butyl) -2-methyl-benzene-1,4-diamine HN MeO N-1-Isobutyl-2-MeO N-1-Isobutyl-3-methoxy-benzene-1,4-methoxy-benzene-1,4-NH 2 -diamine HN HN NH 2 -NH 2 diamine N-1-Isobutyl-3-methyl benzene-1,4-diamine and their addition salts and solvates.

  In general, the addition salts that can be used for the oxidation bases and the oxidation couplers are in particular chosen from addition salts such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates. The compounds of the invention can also be envisaged in the form of solvates such as solvates with water or aliphatic alcohols. The compounds of formula (I) according to the present application can be prepared generally according to a method which comprises the following steps: the nucleophilic substitution of the halogen of parahalonitrobenzene by a primary amine of formula AkNH 2 in the presence of a base , Ak being defined as before; - reduction of the nitro function of the compound obtained in the preceding step in the amine function to obtain the compound of formula (I). HN NH 2 N-1- (1,3-Dimethyl-butyl) -2-methoxybenzene-1,4-diamine NH 2 N-1- (1,3-Dimethylbutyl) -3-methoxybenzene-1,4-diamine MeO MeO NO2 NO2 (II) The first synthesis step is described in the scientific journals Synthesis 1990 (12), 1147-1148 and Synth. Common. 1990, 20 (22), 3537-3545. The second step is a conventional reduction step, for example by carrying out a hydrogenation reaction by heterogeneous catalysis in the presence of Pd / C, Pd (II) / C, Raney Ni or by carrying out a reduction reaction with a metal. for example, zinc, iron, tin ... (Advanced Organic Chemistry, 4th edition, 1992, J. MARCH, Wiley Interscience, Reduction in Organic Chemistry, M. Hudlicky, Ellis Honwood Chemical Science Series). The present application also relates to the nitro compounds of formula (II) and to the processes for the preparation of the secondary para-phenylenediamine compounds of formula (I), in which a reduction step is carried out of the nitrated compound of formula (II) corresponding to: H, N, Ak base 1 Reduction R 1 + AkNH 2 R 1 R 1 H, N, Ak NH 2 (I) R 1 NO 2 (II) wherein: Ak represents an unsubstituted C 4 -C 10 linear or branched alkyl chain;

8

  R1 represents an unsubstituted alkyl radical; an unsubstituted alkoxy radical; or its addition salts or solvates; except for the following compounds:

  The present application also relates to the use of at least one compound of formula (III): ## STR1 ## The present application also relates to the use of at least one compound of formula (III) following: H, N, Ak NH 2 (III) wherein: Ak represents an unsubstituted C 4 -C 10 linear or branched alkyl chain; R represents a hydrogen atom, a C1-C6 alkyl radical, a C1-C6 alkoxy, a (C1-C6) alkoxy (C1-C6) alkyl, a C1-C6 hydroxyalkoxy, a (mono- or poly) hydroxy C 1 -C 6 alkyl; n represents an integer ranging from 0 to 2; or its addition salts or solvates,

  9 as an oxidation base for capillary oxidation dyeing.

  The present application also relates to a cosmetic composition for dyeing keratinous fibers, preferably human keratinous fibers such as the hair, comprising, in a medium suitable for dyeing, at least one compound of general formula (III), such as it has just been described and at least one oxidation coupler.

  Preferably, the composition comprises the compound of formula (III) chosen from the following compounds and their salts or solvates: HN. HN NH 2 NH 2 NH N-isobutylbenzene-1,4-N- (1,3-N- (3-methylbutyl) benzene diamine dimethylbutyl) benzene 1,4-diamine 1 4 diamine HN NH 2 NH 2 HN, NH 2 HN 2-methyl-N 1 - (2-methylpentyl) benzene N 4 - (2-ethylbutyl) -2-methylbutyl) benzene 1,4 1,4-diamine methylbenzene-1,4-diamine N- (1-diamine HN HN) HN NH 2 NH 2 V N-octylbenzene-1,4-N hexylbenzene 1,4-diamine N- (sec-butyl) benzenediamine 1,4-diamine HZN-NH 4 HNHN / NH 2 Np entylb enzene-1,4-diamine N - (1,5-NH 2 -dimethylhexyl) benzene-N (2 1,4-diaminoethylhexyl) benzene-1,4-diamine H 2 NNH 3 HNH 2 NH 4 NH 2 N -butylbenzene-1,4-N- ( 1 - N- (2-ethylbutyl) benzene-1,4-diamine methylheptyl) benzenediamine 1,4-diamine HNHNHNNH 2 N- (2- NHzNH 2 methylbutyl) benzene-N- (1 - methylhexyl) benzene-1,4-Nl- (2-ethylbutyl) -2-1,4-diamine diamine methylbenzene-1,4-diamine NH 2 HNHNHN NH 2 NH 2 N- (1,2-N- (1, 2,2-N- (1-ethylpropyl) benzene 1,4-dimethylpropyl) benzene trimethylpropyl) benzene diamine -1 4-diamine -1,4-diamine HN N-Heptylbenzene-1,4-diamine HN N- (7-Methyloctyl) -NH- (2,2-Dimethyl-diamine) NH 2 -benzene-1, 4-diamine propyl) -benzene-1,4-NH 2 n C 9 H 19 HNHN NH 2 NH 2 N-decylbenzene-1,4-diamine N- (3,3-dimethylbutyl) benzene-1,4-diamine a particular embodiment, Ak is a branched alkyl radical. According to another variant, R is chosen from a hydrogen atom or an unsubstituted alkyl or alkoxy radical, preferably unsubstituted alkyl. Preferably, the composition comprises the compound of formula (III) chosen from the following compounds: HN NH 2 N-isobutylbenzene-1,4-diamine HN NH 2 N- (1,3-dimethylbutyl) benzene-1,4-diamine and their salts or solvates.

12

  Preferably, the concentration of the compound of general formula (III) is between 0.0001 and 20%, preferably between 0.005 and 6% by weight relative to the total weight of the composition. The oxidation coupler (s) can be chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers and heterocyclic couplers, as well as their addition salts. By way of example, mention may be made of 2-methyl-5-aminophenol, 5-N- (13-hydroxyethyl) amino-2-methylphenol, 6-chloro-2-methyl-5-aminophenol, 3- amino phenol, 1,3-dihydroxy benzene (or resorcinol), 1,3-dihydroxy-2-methyl benzene, 4-chloro-1,3-dihydroxy benzene, 2,4-diamino-1- (13-hydroxyethyloxy) benzene, 2-amino-4- (4-hydroxyethylamino) -1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3- ureido 1-dimethylamino benzene, sesamol, 1-β-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-hydroxy benzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N- (3-hydroxyethyl) amino-3, 4-methylene dioxybenzene, 2,6-bis- (β-hydroxyethylamino) toluene and their addition salts. Generally the concentration of the oxidation coupler (s) can be between 0.0001 and 20%, preferably between 0.005 and 6% by weight relative to the total weight of the composition.

  The medium suitable for dyeing is advantageously constituted by water or by a mixture of water and at least one organic solvent such as, for example, C1-C4 lower alcohols, branched or unbranched, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and

13

  diethylene glycol monomethyl ether, glycerol as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof. The solvents are preferably present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately. Advantageously, the cosmetic composition comprises at least one cosmetic adjuvant selected from the group consisting of antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, surfactants, conditioning agents, film-forming agents, polymers, ceramides, preservatives, pearlescent or opacifying agents, vitamins or provitamins.

  The 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. The composition according to the invention may contain at least one additional oxidation base different from the compound of formula (III).

  The conventional oxidation bases may especially be chosen from para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases and their addition salts. Among the para-phenylenediamines, para-phenylenediamine, para-toluenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine and 2,6-dimethyl para may be mentioned by way of example; phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N-dipropyl para phenylenediamine,

14

  4-amino N, N-diethyl-3-methylaniline, N, N-bis - ((3-hydroxyethyl) para-phenylenediamine, 4-N, N-bis - ((3-hydroxyethyl) amino 2-methyl aniline, 4-N, N-bis - ((3-hydroxyethyl) amino 2-chloroaniline, 2- (3-hydroxyethyl) para-phenylenediamine, 2-fluoro para-phenylenediamine, 2-isopropyl para-phenylenediamine, N - ((3-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, (3-hydroxyethyl) para-phenylenediamine, N - ((3-yl-dihydroxypropyl) para-phenylenediamine, N- (4'-aminophenyl) para-phenylenediamine, N-phenyl para-phenylenediamine, 2- (3-hydroxyethyloxy) para-phenylenediamine, acetylaminoethyloxy para-phenylenediamine, N- (P-methoxyethyl) para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl paraphenylene diamine, 2-hydroxyethylamino-5-amino toluene, 3-hydroxy-1- (4-aminophenyl) pyrrolidine, the 6- (4-Ami) no-phenylamino) -hexan-1-ol and their addition salts with an acid. Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-toluenediamine, 2-isopropyl paraphenylenediamine, 2-P-hydroxyethyl para-phenylenediamine, 2- (3-hydroxyethyloxy) para-phenylenediamine, dimethyl para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis - ((3-hydroxyethyl) para-phenylenediamine, 2-chloro-para-phenylenediamine, 2- (3-Acetylaminoethyloxy) para-phenylenediamine, 3-hydroxy-1- (4'-aminophenyl) pyrrolidine and their addition salts with an acid are particularly preferred, of which bis-phenylalkylenediamines may be exemplified; N, N'-bis - ((3-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, N, N'-bis - ((3-hydroxyethyl) N) , N'-bis- (4'-

15

  aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis - ((3-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-2- is exemplified by methyl phenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino amino-2-hydroxymethyl phenol, 4-amino-2-methoxymethyl phenol, 4-amino-2-aminomethyl phenol, 4-amino 2- (3-hydroxyethylaminomethyl) phenol, 4-amino-2-fluoro phenol, 4-amino amino-2,6-dichlorophenol, 4-amino-6 - [((5'-amino-2'-hydroxy-3'-methyl) phenyl) methyl] -2-methylphenol, bis (5'-amino) 2' hydroxy) phenylmethane and their addition salts with an acid. Among the ortho-aminophenols, mention may be made, for example, of 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, 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, 3,4-diamino pyridine, and their addition salts with an acid. Other pyridinic 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.

16

  FR 2801308. By way of example, mention may be made of 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-aminopyrazolo [1,5-a] pyridin-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-aminopyrazolo [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] pyridine-3,7-diamine; 7-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; pyrazolo [1,5-a] pyridine-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 [1,5-a] pyridin-7-yl) - (2-hydroxyethyl) amino] ethanol; 3-amino-pyrazolo [1,5-a] pyridin-5-ol; 3-amino-pyrazolo [1,5-a] pyridine-4-ol; 3-amino-pyrazolo [1,5-a] pyridin-6-ol; 3-aminopyrazolo [1,5-a] pyridin-7-ol; as well as their addition salts with an acid. 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 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 their addition salts and tautomeric forms, when tautomeric equilibrium exists. 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 the 4.5 -diamino 1-methyl pyrazole, 4,5-diamino 1 - ((3-hydroxyethyl)

17

  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-phenyl pyrazole, 4-amino-1,3-dimethyl-5-hydrazino pyrazole, 1-benzyl-4,5-diamino-3-methyl-pyrazole, diamino 3-tert-butyl 1-methyl pyrazole, 4,5-diamino 1-tert-butyl 3-methyl pyrazole, 4,5-diamino 1 - ((3-hydroxyethyl) 3-methyl pyrazole, 4,5 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-methyl-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- (3-hydroxyethyl) amino 1-methyl pyrazole, and In general, the concentration of the additional oxidation base (s) is between 0.0001 and 20%, preferably between 0.005 and 6% by weight relative to the total weight of the composition. In general, the addition salts that can be used for the oxidation bases and the oxidation couplers are in particular chosen from addition salts such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

  The dye composition in accordance with the invention may also contain one or more direct dyes that may be chosen in particular from nitro dyes of the benzene series, which may be neutral, acidic or cationic, neutral azo direct dyes, acidic or cationic dyes, quinone direct dyes and in particular neutral, acidic or cationic anthraquinones, direct dyes

18

  azine, methine, azomethine, triarylmethane, indoamine direct dyes and natural direct dyes. Preferably, the composition according to the invention comprises at least one dye chosen from cationic direct dyes and natural direct dyes. Among the cationic direct dyes that may be used according to the invention, mention may be made of the cationic azo direct dyes described in the patent applications WO 95/15144, WO-95/01772 and EP-714954.

  Among these compounds, the following dyes may be mentioned in particular: 1,3-dimethyl-2 - [[4- (dimethylamino) phenyl] azo] -1H-imidazolium chloride, 1,3-dimethyl-2-chloride 1 - Methyl-4 - [(methylphenylhydrozono) methyl] pyridinium [(4-aminophenyl) azo] -1H-imidazolium, methylsulfate. Among the natural direct dyes that may be used according to the invention, lawsone, juglone, alizarin, purpurine, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin , curcumin, spinulosin, apigenidine. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from henna.

  The direct dye (s) preferably represent from 0.001 to 20% by weight approximately of the total weight of the ready-to-use composition and even more preferentially from 0.005 to 10% by weight approximately. A ready-to-use dye composition is obtained by adding one or more oxidizing agents conventionally used for the oxidation dyeing of keratin fibers, such as, for example, peroxide.

19

  hydrogen, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases, hydrogen peroxide being particularly preferred, to the dye composition as previously described. Of course, those skilled in the art will take care to choose the adjuvant (s), precursors of additional oxidation dyes, direct dyes in such a way that the advantageous properties intrinsically attached to the oxidation dyeing composition according to the invention are not, or not substantially, impaired by the addition or additions envisaged. The pH of the dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used for dyeing keratin fibers or else using conventional buffer systems. Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids other than dicarboxylic acids such as hydrochloric acid, ortho-phosphoric acid, sulfuric acid, carboxylic acids such as acid acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids. Among the alkalinizing agents that may be mentioned, by way of example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and formula: Ra Rb NWN. Rc Rd wherein W is a propylene residue optionally substituted by a hydroxyl group or a C1-C4 alkyl radical; Ra, Rb, Rc 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, or in any other form suitable for dyeing keratinous fibers, and especially human keratinous fibers, such as than human hair. Another object of the present application relates to a process in which the composition as defined above is applied to the fibers, and the color is revealed using an oxidizing agent. The color can be revealed at acidic, neutral or alkaline pH. The oxidizing agent can be added to the composition of the invention just at the time of use. It can be implemented from an oxidizing composition containing it, applied simultaneously or sequentially to the composition of the invention.

  According to a particular embodiment, the composition according to the present invention is mixed, preferably at the time of use, with a composition containing, in a medium suitable for dyeing, at least one oxidizing agent, this oxidizing agent being present in an amount sufficient to develop a coloration. The mixture obtained is then applied to the keratinous fibers. After a residence time of about 3 to 50 minutes, preferably about 5 to 30 minutes, the keratinous fibers are rinsed, washed with shampoo, rinsed again and then dried.

21

  The invention also relates to a multi-compartment device or "kit" of dyeing in which a first compartment contains a dye composition comprising at least one compound of formula (I) or (III) defined above and a second compartment contains an oxidizing composition. This device may be equipped with means for delivering the desired mixture to the hair, such as the devices described in patent FR-2 586 913 in the name of the applicant. From this device, it is possible to dye the keratinous fibers from a process which comprises mixing a dye composition according to the invention with an oxidizing agent as defined above, and the application of the mixture obtained. on the keratinous fibers for a time sufficient to develop the desired coloration.

  The examples which follow serve to illustrate the invention without, however, being limiting in nature. EXAMPLES OF SYNTHESIS Synthesis process in 2 steps: Synthesis of the nitro compounds R 1 + NO 2 (A) (B) HN'Ak NO 2 compound la-u Ak, NH base 2 solvent R125 Classical thermal channel:

  The para-fluoro-nitrobenzene derivative (A) (1 eq.) And the amine (B) are heated in the presence or absence of a base and / or a solvent.

  The reaction mixture is cooled and then poured into a water + ice mixture.

  -If a precipitate is formed, it is filtered, washed with water and dried. If no precipitate appears, the reaction mixture is extracted with ethyl acetate or dichloromethane and the organic phase is concentrated until a solid is obtained.

  la: 4-nitro-N-propylaniline Amine: propan-1-amine m = 4.2 g (2 eq.) Derivative A: para-fluoro-nitrobenzene (1 eq.) Solvent: NMP (20 ml) Base: triethylamine ( l, 5 eq.) Conditions: 90 C, 24 hours - Solid yellow m = 6.26 g, Yield = 98%

  Ib: N-isobutyl-4-nitroaniline Amine: isobutylamine m = 3.11 g (1.2 eq.) Derivative A: para-fluoro-nitrobenzene (1 eq.) Solvent: H2O (15 mL) Base: K2CO3 (1, 2 eq.) Conditions: 90 C, 24 hours Solid yellow m = 6.68 g, Yield = 97% 2230

23

  1c: N- (1,3-dimethylbutyl) -4-nitroaniline Amine: 4-methylpentan-2-amine m = 4.61g (1.5 eq.) Derivative A: para-fluoro-nitrobenzene (1 eq.) Solvent : NMP (20 ml) Base: triethylamine (1.5 eq.) Conditions: 90 C, 24 hours, extraction with AcOEt and concentration. • Yellow solid m = 5.86 g, Yield = 74% 1d: 2-methyl-N- (2-methylbutyl) -4-nitroaniline Amine: 2-methylbutan-1-amine m = 5.6 g (2 eq.) Derivative A: 4-fluoro-3-methyl-nitrobenzene (1 eq.) Solvent: none Base: triethylamine (1.5 eq.) Conditions: 90 C, 48 hours • Yellow solid m = 6.47g, Yield = 90.5 %

  1: N-hexyl-4-nitroaniline Amine: hexan-1-amine m = 7.08 g (2 eq.) Derivative A: para-fluoro-nitrobenzene (1 eq.) Solvent: THF (50 ml) Base: none Conditions: 80 C for 1 night • Yellow solid m = 6.43 g, Yield = 83% 1g: N- (sec-butyl) -4-nitroaniline Amine: sec butylamine m = 3.79 g (1.5 eq.) Derivative A: para-fluoro-nitrobenzene (1 eq.) Solvent: NMP 30 Base: triethylamine (1.2 eq.)

24

  Conditions: 90 C overnight, extraction with AcOEt and concentration. • Yellow oil m = 4.57 g, yield = 66% 1h: 4-nitro-N-octylaniline Amine: n-octylamine m = 5.12 g (2 eq.) Derivative A: para-fluoro-nitrobenzene (1 eq. .) Solvent: THF (50 ml) Base: triethylamine (2.2 eq.) Conditions: 80 C for 1 night. • Solid yellow m = 8.63g, Yield = 97%

  Li: 4-nitro-N-pentylaniline Amine: pentan-1-amine m = 16.43 ml (d = 0.752) (2 eq) Derivative A: para-fluoro-nitrobenzene (1 eq.) Solvent: THF (60 ml) Base: none Conditions: 80 C for 4.5 hours. • Yellow solid m = 10.52 g, Yield = 71.4% 20: N- (1,5-dimethylhexyl) -4-nitroaniline Amine: 6-methylheptan-2-amine (1.1 equiv.) Derivative A : para-fluoro-nitrobenzene (1 eq.) Solvent: NMP (14 ml) Base: Na2CO3 m = 2.65 g Conditions: 70 C, 15 hours • Yellow oil m = 4.3 g, Yield = 86% 30

25

  1k: N- (2-ethylhexyl) -4-nitroaniline Amine: 2-ethylhexan-1-amine (1, leq) Derivative A: para-fluoro-nitrobenzene (1 eq.) Solvent: NMP (14 ml) Base: Na2CO3 m = 2.65 g Conditions: 75 C, 15 hours Yellow oil m = 4.05 g, yield 81.6%

  11: N- (2-Ethylbutyl) -4-nitroaniline Amine: 2-ethylbutan-1-amine (1, 1 eq) Derivative A: para-fluoro-nitrobenzene (1 eq.) Solvent: NMP (14 ml) Base: Na2CO3 m = 2.65 g (1.25 eq.) Conditions: 70 C, 15 hours - Yellow oil m = 3.95 g, Yield = 89.6%

  1 m: N-butyl-4-nitroaniline Amine: N butylbenzylamine m = 4.24 g (1.2 eq) Derivative A: para-fluoro-nitrobenzene (1 eq.) Solvent: DMSO (4 ml) Base: triethylamine (1, 2 eq.) Conditions: 60 C for 1 night, extraction with dichloromethane and concentration Yellow oil m = 5.5 g, Yield = 91% ln: N- (1-methylheptyl) -4-nitroaniline Amine: octan-2-amine m = 2.56 g (1, eq.) Derivative A: para-fluoro-nitrobenzene (1 eq.) Solvent: NMP (14 ml) Base: Na2CO3 m = 2.65 g (1.25 eq.) Conditions: 70 C, 15 hours • Yellow oil m = 4.5 g, Yield = 90%

  L: N- (1-methylhexyl) -4-nitroaniline Amine: heptan-2-amine (1, leq) Derivative A: para-fluoro-nitrobenzene (1 eq.) Solvent: NMP (14 ml) Base: Na2CO3 m = 2.65 g Conditions: 75 C, 15 hours - Yellow oil m = 4.3 g, Yield = 91.2%

  lp: N- (2-ethylbutyl) -2-methyl-4-nitroaniline Amine: 2 ethyl-butylamine m = 2.6 g (2 eq.) Derivative A: 4-fluoro-3-methyl-nitrobenzene (1 eq.) Solvent : none Base: none Conditions: 80 C, 10 hours • Yellow solid m = 2.9 g, Yield = 95% lq: N- (2-methylbutyl) -4-nitroaniline Amine: 2-methylbutan-1-amine m = 2.16 g (2.48 eq.) Derivative A: para-fluoro-nitrobenzene (1 eq.) Solvent: none Base: none Conditions: 110 C, 10 minutes • Solid yellow m = 3 g, Yield = 94% 30

27

  1r: N- (1-ethylpropyl) -4-nitroaniline Amine: 1-ethylpropylamine m = 3.71 g (1.2 eq.) Derivative A: para-fluoro-nitrobenzene (1 eq.) Solvent: H2O (14 ml) Base: K2CO3 (1,2 eq.) Conditions: 90 C, 72 hours • Orange oil m = 4,77g, Yield = 65%

  N- (1-methylpentyl) -4-nitroaniline Amine: 1-methylpentylamine m = 4.61g (1.5 eq.) Derivative A: para-fluoro-nitrobenzene (1 eq.) Solvent: NMP (20m1) Base: triethylamine (1.5 eq) Conditions: 90 C, 24 hours, AcOEt extraction and concentration. • Yellow solid m = 6.34g, Yield = 80%

  Microwave channel: The para-fluoro-nitrobenzene derivative (A) (1 eq.) And the amine (B) are heated in the microwave at 140 ° C. or 220 ° C. The reaction mixture is cooled and then poured into a mixture of water and ice. The precipitate formed is then filtered, washed with water and then dried. N- (2-ethylbutyl) -3-methyl-4-nitroaniline Amine: 2-ethylbutan-1-amine m = 6.43 g (3 eq) Derivative A: 4-fluoro-2-methyl-nitrobenzene (1 eq) .) Conditions: 140 C, 15 minutes in the microwave • Yellow solid m = 4.58 g, Yield = 92% ls: N- (1,2-dimethylpropyl) -4-nitroaniline Amine: 3-methylbutan-2- amine m = 6.8g (3.3 eq.) Derivative A: para-fluoro-nitrobenzene (1 eq.) Conditions: 140 C, 1 hour in the microwave - Brown oil m = 4.71g, Yield = 97%

  4-nitro-N- (1,2,2-trimethylpropyl) aniline Amine: 3,3-dimethylbutan-2-amine m = 3.18 g (2.1 eq.) Derivative A: para-fluoro-nitrobenzene (1 eq.) Conditions: 220 C, 1.5 hours in the microwave Solid brown m = 2.1 g, Yield = 63%

  Synthesis of Amino Compounds 2: HN'Ak NO2 NH2 HN'Ak Nitro Compound 1 Amino Compound 2 Catalytic Hydrogenation Reduction:

  In a hydrogenator, the nitrated compound 1 and a catalyst are added to a solvent. The hydrogenator is put under a hydrogen pressure of about six bars and at a temperature of 50 C for a period of 3 hours. After returning to ambient temperature and filtering the catalyst under nitrogen, the filtrate is poured into aqueous hydrochloric acid. The filtrate is evaporated to dryness under reduced pressure. The product is then

29

  recrystallized from hydrochloric ethanol and dried at 40 ° C. under vacuum and over potassium hydroxide.

  2a: N-propylbenzene-1,4-diamine dihydrochloride Nitro compound la: 4-nitro-N-propylaniline, 2 g Solvent: absolute ethanol, 250 ml Catalyst: 5% Pd / C (50% in water ), 437 mg Cream solid, m = 1.52 g, Yield = 62% 2d: 2-methyl-N- (2-methylbutyl) benzene-1,4-diamine dihydrochloride Nitrate compound 1d: 2-methyl-N- (2-methylbutyl) -4-nitroaniline, 2g Solvent: absolute ethanol, 100 ml Catalyst: 5% Pd / C (50% in water), 360 mg -Solid cream, m = 1.09 g, Yield = 67%

  2e: N4- (2-ethylbutyl) -2-methylbenzene-1,4-diamine dihydrochloride Nitro compound 1: N- (2-ethylbutyl) -3-methyl-4-nitroaniline, 2.5 g Solvent: absolute ethanol , 300m1 Catalyst: 5% Pd / C (50% in water), 420 mg White solid, m = 2.75g, Yield = 95% 2f: N-hexylbenzene-1,4-diamine dihydrochloride Nitrated compound 1f: N-hexyl-4-nitroaniline, 6.43 g Solvent: absolute ethanol, 500 ml Catalyst: 5% Pd / C (50% in water), 2 g White solid, m = 5.47 g Yield = 83% 30

30

  2g: N- (sec-butyl) benzene-1,4-diamine dihydrochloride Nitrate compound 1g: N- (sec-butyl) -4-nitroaniline, 4.6 g Solvent: absolute ethanol 250 ml Catalyst: Pd / C at 5% (50% in water), 1.2 g - White solid, m = 4.6g, Yield = 82%

  2h: N-octylbenzene-1,4-diamine dihydrochloride Nitro compound 1h: 4-nitro-N-octylaniline, 2.3 g Solvent: absolute ethanol, 500 ml Catalyst: 5% Pd / C (50% in theory) water), 230 mg • Solid white, m = 7.68g, Yield = 77%

  2i: N-pentylbenzene-1,4-diamine dihydrochloride Nitro compound: 4-nitro-N-pentylaniline, 10 g Solvent: absolute ethanol, 500 ml Catalyst: 5% Pd / C (50% in water ), 1.6g • White solid, m = 6.9 g, Yield = 67%

  2j: N- (1,5-dimethylhexyl) benzene-1,4-diamine dihydrochloride Nitro compound 1: N- (1,5-dimethylhexyl) -4-nitroaniline, 3.12 g Solvent: absolute ethanol 100 ml Catalyst : 5% Pd / C (50% in water), 0.4 g • White solid, m = 3 g, Yield = 82.2% 2k: N- (2-ethylhexyl) benzene-1 dihydrochloride, 4-diamine Nitro compound 1k: N- (2-ethylhexyl) -4-nitroaniline, 3.72 g Solvent: absolute ethanol, 100 ml Catalyst: Pd / C at 5% (50% in water), 0.4g - White solid, m = 3.4g, Yield = 78.2%

31

  21: N- (2-ethylbutyl) benzene-1,4-diamine dihydrochloride Nitro compound 11: N- (2-ethylbutyl) -4-nitroaniline, 2.23 g Solvent: absolute ethanol, 100 ml Catalyst: Pd / C at 5% (50% in water), 0.4g • Solid m = 2 g, Yield = 75.5%

  2n: N- (1-methylheptyl) benzene-1,4-diamine dihydrochloride Nitro compound 1n: N- (1-methylheptyl) -4-nitroaniline, 3 g Solvent: absolute ethanol, 100 ml Catalyst: Pd / C to 5% (50% in water), 0.4g • Beige solid, m = 3.16g, Yield = 90%

  2o: N- (1-methylhexyl) benzene-1,4-diamine dihydrochloride Nitro compound: N- (1-methylhexyl) -4-nitroaniline, 3.89 g Solvent: absolute ethanol, 100 ml Catalyst: Pd / C at 5% (50% in water), 0.4g • Beige solid, m = 4g, Yield = 87.8% 2u: N- (1-methylpentyl) benzene-1,4-diamine dihydrochloride Nitro compound: N- (1-methylpentyl) -4-nitroaniline, 900 mg Solvent: absolute ethanol, 200 ml Catalyst: 5% Pd / C (50% in water), 200 mg • White solid, m = 366 mg, Yield = 30% Reduction with (cyclohexene + Pd / C) + microwave:

  In a crimped flask suitable for the microwave, the nitrated compound 1, the catalyst (5% Pd / C (50% in water)), cyclohexene and absolute ethanol are placed.

32

  The reduction is carried out in the microwave at a temperature of 140 ° C. for 10 minutes. After filtration of the catalyst, pour over aqueous hydrochloric acid. Diethyl ether is added until a precipitate forms which is filtered and dried at 40 ° C. under vacuum and over potassium hydroxide.

  2b: N-Isobutylbenzene-1,4-diamine dihydrochloride Nitro compound lb: N-isobutyl-4-nitroaniline, 2 g Catalyst: 5% Pd / C (50% in water), 406 mg Cyclohexene: 9 , 8 ml Ethanol absolute: 12 ml White solid, m = 639 mg, Yield = 23%

  2c: N- (1,3-dimethylbutyl) benzene-1,4-diamine dihydrochloride Nitrated compound: N- (1,3-dimethylbutyl) -4-nitroaniline, 2 g Cyclohexene: 7 ml Catalyst: Pd / C at 5% (50% in water), 354 mg Ethanol absolute: 10.5 ml - Solid gray, m = 2.03 g, Yield = 86%

  2q: N- (2-methylbutyl) benzene-1,4-diamine dihydrochloride Nitro compound 1q: N- (2-methylbutyl) -4-nitroaniline, 2.2 g Ethanol absolute: 11 ml Cyclohexene: 7 ml Catalyst: Pd / C at 5% (50% in water), 380mg Solid gray, m = 1.96g, Yield = 74%

33

  2 r: N- (1-ethylpropyl) benzene-1,4-diamine dihydrochloride Nitro compound 1r: N- (1-ethylpropyl) -4-nitroaniline, 2 g Cyclohexene: 9.8 ml Ethanol absolute: 12 ml Catalyst: 5% Pd / C (50% in water), 400mg • White solid, m = 1.75g, Yield = 100%

  2s: N- (1,2-dimethylpropyl) benzene-1,4-diamine dihydrochloride Nitric compound: N- (1,2-dimethylpropyl) -4-nitroaniline, 2 g Ethanol absolute: 11 ml Cyclohexene: 7, 5 ml Catalyst: 5% Pd / C (50% in water), 378 mg • White solid, m = 1.76 g, Yield = 88% 2t: N- (1,2,2-trimethylpropyl) dihydrochloride ) 1,4-diamino-1,4-diamine Nitrate compound: 4-nitro-N- (1,2,2-trimethylpropyl) aniline, 500 mg Ethanol absolute: 2 ml Cyclohexene: 1.8 ml Catalyst: 5% Pd / C (50% in water), 90 mg • Solid gray m = 400 mg, Yield = 51% Reduction to (ammonium formate + Pd / C)

  250 g of N-butyl-4-nitroaniline (5 g), 50 ml of absolute ethanol, 0.5 g of 5% palladium on carbon (50% in water) are introduced into a 250 ml flask and finally 4.44 g of ammonium formate. The 25th

34

  The reaction medium is stirred at room temperature for five minutes. Then filtered through celite, poured the filtrate into water and extracted with dichloromethane. Hydrochloric ethanol and diethyl ether are added; a precipitate is formed which is filtered, rinsed with ether and dried at 40 ° C. under vacuum and over potassium hydroxide (beige solid, m = 2.81 g, yield = 73%).

  Zinc Reduction In a 500 ml three-necked flask, 60 g of zinc and 200 ml of absolute ethanol are refluxed, then 10 ml of hydrochloric acid are added dropwise, followed by spatula 2.9 g of N- ( 2-ethylbutyl) -2-methyl-4-nitroaniline 1p. The reaction medium is heated for 30 minutes and then filtered through Celite in a solution of hydrochloric isopropanol. A powder precipitates. This is filtered and then dried in a desiccator (white solid m = 3.93 g, yield = 100%).

TINCTORIAL EVALUATIONS:

  Examples 1 to 13: Dyeing composition from N4- (2-ethylbutyl) -2-methylbenzene-1,4-diamine dihydrochloride (2e)

  Examples 1-7: Acid Dyeing The following dye compositions are prepared. EXAMPLE 1 N4- (2-10-3) 10-3 10-3 10-3 10-3 3 10-3 ethylbutyl) 2 methylbenzene mole mole mole mole mole mole 1,4-diamine (2e) Benzene-1,3-diol 10 3 mole 5-Amino-2-methyl-phenol 10 3 mole 1H-Indol-6ol 3 mole 2-aminopyridin-3-ol 3 moles 3,6-Dimethyl-1H-pyrazolo [5.1-10-3 c] [1,2,4] triazole mole 2- (2,4) -Diamino-phenoxy) - 10-3 ethanol, hydrochloride mole 3-Amino-2-chloro-6-methyl-3-phenol, hydrochloride mole Dye carrier (1) (*) (*) (*) (*) (*) (*) (*) (*) Demineralized water qs 100g 100g 100g 100g 100g 100g 100g (*): dyeing medium (1) pH 7 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylene triamine pentasodium salt -pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 Na 2 HPO 4 0.28 g KH 2 PO 4 0.46 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 7 is obtained.

36

  Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. The shades obtained are shown in the table below: Example 1 2 3 4 5 6 7 Observed shade brown gray purple gray red red red blue blue orange intense intense intensive intense intense - Examples 8 to 13: dyeing in basic medium Dyeing compositions 10-3 mol 10-3 mol 10-3 mol 10-3 mol 10-3 mol N4 (2 ethylbutyl) 2 methylbenzene-1,4-diamine 10-3 mol 10-3 mol 10-3 mol (2e) 5-Amino-2-methyl-10-mole phenol 1H-Indol-6-ol 10-3 mole 2-Amino-pyridin-3- 10 -3 mole ol 3,6-Dimethyl-1 H10-3 mole pyrazolo [5,1-c] [1,2,4] triazole 2- (2,4-Diamino-3-mole phenoxy) -ethanol hydrochloride 3-Amino-2-chloro-6-10-3 mole methyl-phenol hydrochloride Dye carrier (*) (*) (*) (*) (*) (*) (2) Demineralized water 100g 100g 100g 100g 100g 100g qs (*): Dye carrier (2) pH 9.5 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulphite 0.23 g MA diethylenetriamine pentaacetic acid pentasodium salt in solution 0, 48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 g NH4Cl 4.32 g Ammonia at 20% NH3 2.94 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 is obtained. Each mixture obtained is applied to locks of gray hair at 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

  The shades obtained are shown in the table below: Example 8 9 10 11 12 13 Shade gray purple-brown red brown red red green-blue blue observed intense intense blue intense 15

  Examples 14 to 27: Dyeing composition from N- (secbutyl) benzene-1,4-diamine dihydrochloride (2g) Examples 14 to 20: Acid dyeing The following dyeing compositions are prepared: Example 14 N- (sec-10-3 10-3 10-3 10-3 10-3 10 -3-butyl) benzene-1,4-diamine dihydrochloride (2 g) mole mole mole mole mole mole mole Benzene-1,3-diol 10 3 mole 5-Amino-2-methyl-phenol 10 mole 1H-Indol-6-ol 10-3 mole 2-Amino-pyridin-3-ol 10 3 mole 3 6-Dimethyl-1H-pyrazolo [5,1- 10-3c] [1,2,4] triazole mole 2- (2,4-Diamino-phenoxy) -10-3 ethanol, hydrochloride mole 3-Amino -2-chloro-6-methyl-3-phenol, hydrochloride mole Dye carrier (2) (*) (*) (*) (*) (*) (*) (*) Demineralized water qs 100g 100g 100g 100g 100g 100g 100g (*): dyeing medium (2) pH 7 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylene triamine pentasodium salt -pentaacetic 40% aqueous solution 0.48 g MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 0.28 g 0.46 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 7 is obtained. Na2HPO4 KH2PO4

  Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. The shades obtained are shown in the table below: Example 14 15 16 17 18 19 20 Shade brown purple brown gray gray blue violet - observed intense intense or e purple-purple-intense blue g red intense red intense intense intense - Examples 21 to 27: dyeing in basic medium The following dye compositions are prepared: Example 21 22 23 24 25 26 27 N-10-3 dihydrochloride 10-3 10-3 10-3 10-3 10-3 10-3 (butyl sec benzene 1.4 mole mole mole mole mole mole mole diamine (2g) Benzene-1,3-diol 10 mole 5-Amino-2-methyl-phenol 10 mole 1H-Indol-6ol 3 mole 2-Amino pyridin-3-ol 3 mole 3,6-Dimethyl-1H-pyrazolo [5,1-e] [1,2 mole, 4] triazole 2- (2,4-Diamino-phenoxy) -10- 3 ethanol, hydrochloride mole 3-Amino-2-chloro-6-methylphenol, hydrochloride Dye carrier (2) (*) (*) (*) (*) (*) (*) (*) (*) Demineralized water qs 100g 100g 100g 100g 100g 100g 100g 15 (*): dyeing medium (2) pH 9.5 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulphite 0.23 g MA diethylene glycol pentasodium salt triamine-pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3, 0 g NH4Cl 4.32 g Ammonia at 20% NH3 2.94 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 is obtained. Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

  The shades obtained are shown in the table below: Example 21 22 23 24 25 26 27 Shade observed brown violet red brown violet-blue violet-intense intense intense red intense red intense blue intense chromatic intense Examples 28 to 41: Dye composition to from N- (1,5-dimethylhexyl) benzene-1,4-diamine dihydrochloride (2j) Examples 28 to 34: Acid Dyeing The following dye compositions are prepared: Example 28 29 30 31 32 N- (1,5-10-3 10-3 10-3 10-3 10-3 10-3 10-3 dimethylhexyl) benzene dihydrochloride 1,4 mole mole mole mole mole mole mole diamine (2 d) Benzene-1,3-diol 10 3 mole 5-Amino-2-methyl-phenol 10 moles 1 H-Indol-6ol 3 moles 2-Aminopyridin-3-ol 3 moles 3,6-Dimethyl-1 H pyrazolo [5.1-10-3 c] [1,2,4] triazole mole 2- (2,4-Diamino-phenoxy) -10-3 ethanol, hydrochloride mole 3-Amino-2-chloro-6- methyl-3-phenol, hydrochloride mole Dye carrier (1) (*) (*) (*) (*) (*) (*) (*) Water demi q.s. 100g 100g 100g 100g 100g 100g 100g (*): dyeing medium (1) pH 7 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylene triamine pentasodium salt -pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 Na 2 HPO 4 0.28 g KH 2 PO 4 0.46 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 7.5 is obtained.

  Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. The shades obtained are shown in the table below: Example 28 29 30 31 32 33 34 Shade observed gray violet red gray gray blue intense blue intense violet-intense intense intense intense intense red - Examples 35 to 41: dyeing in basic medium The compositions The following dyestuffs are prepared: EXAMPLE 35 N-10-3 10-3 10-3 10-3 10-3 10-3 dihydrochloride (1.5 mole mole mole mole mole mole mole dimethylhexyl) benzene-1,4-diamine (2) Benzene-1,3-diol 3 mole 5-Amino-2-methyl-phenol 3 mole 1H-Indol-6-ol 10-3 mole 2-Amino-pyridin 3-ol 10 moles 3,6-Dimethyl-1H-10-3 pyrazolo [5.1mol e] [1,2,4] triazole 2- (2,4-Diamino-phenoxy) -10-3 ethanol, hydrochloride mole 3-Amino-2-chloro-6-methylphenol, hydrochloride Dye carrier (2) (*) (*) (*) (*) (*) (*) (*) Water demineralized qs 100g 100g 100g 100g 100g 100g 100g 10 (*): dyeing medium (2) pH 9.5 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulphite 0.23 g MA diethylene glycol pentasodium salt triamine-pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3, 0 g NH4Cl 4.32 g Ammonia at 20% NH3 2.94 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 is obtained. Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

  The shades obtained are shown in the table below: Example 35 36 37 38 39 40 41 Shade Observed Brown Gray Brown Gray Purple-Blue Let-Purple Red Purple- Deep Red Purple Intense Intense Red Intense Intense Deep Blue Intense Examples 42 to 55: Dyeing composition from N- (2-ethylhexyl) benzene-1,4-diamine dihydrochloride (2k) Examples 42 to 48: Acid dyeing The following dye compositions are prepared: Example 42 43 44 45 N- (2 10-3 10-3 10-3 10-3 10-3 10-3 10-3 ethylhexyl) benzene 1-4 diamine mole mole mole mole mole mole mole (2k) Benzene-1 3-diol 10 moles 5-Amino-2-methyl-phenol 10 moles 1 H-Indol-6-ol 3 moles 2-Aminopyridin-3-ol 3 moles 3,6-Dimethyl-1 H- pyrazolo [5,1-10-3 c] [1,2,4] triazole mole 2- (2,4-Diamino-phenoxy) -10-3 ethanol, hydrochloride mole 3-Amino-2-chloro-6-methyl - 10-3 phenol, hydrochloride mole Dyeing medium (1) (*) (*) (*) (*) (*) (*) (*) Demineral water isée q.s.p. 100g 100g 100g 100g 100g 100g 100g (*): dyeing medium (1) pH 7 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylene triamine pentasodium salt -pentaacetic 40% aqueous solution 0.48 g MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 0.28 g 0.46 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 7 is obtained. Na2HPO4 KH2PO4 Each mixture obtained is applied to locks of gray hair at 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. The shades obtained are shown in the table below: Example 42 43 44 45 46 47 48 gray gray gray violet violet-violet- gray blue violet intense Intense intense blue intense red intense intense intense intense intense red - Examples 49 to 55: dyeing in basic medium The following dye compositions are prepared: Example 49 50 51 52 53 54 55 N- (2- 10-3 10-3 10-3 10-3 10-3 10-3 10-ethylhexyl) benzene dihydrochloride 1 4 mole mole mole mole mole mole diamine (2k) Benzene-1,3-diol 10 mole 5-Amino-2-methyl-phenol 10 mole 1H-Indol-6-ol 10 mole 2-Amino-pyridine 3-Molar 3,6-dimethyl-1H-3-pyrazolo [5,1-mole e] [1,2,4] triazole 2- (2,4-Diamino-phenoxy) -10-3 ethanol, hydrochloride mole 3-Amino-2-chloro-6-methylphenol, hydrochloride Dye carrier (2) (*) (*) (*) (*) (*) (*) (*) Water demineralized qs 100g 100g 100g 100g 100g 100g 100g10 (*): dyeing medium (2) pH 9.5 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylenetriamine pentasodium salt -pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 4.24 g Ammonia at 20% NH.sub.2 2.94 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 is obtained. Each mixture obtained is applied to locks of gray hair at 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

  The shades obtained are given in the table below: Example 49 50 51 52 53 54 55 Shade brown gray brown gray purple-blue violet- observed intense ivioletntense red red red i intense blue intense intense intense intense Examples 56 to 69: Dye composition to Starting from the dihydrochloride of N- (2-ethylbutyl) benzene-1,4-diamine (21). Examples 56 to 62: Dyeing in an acidic medium The following dyeing compositions are prepared: Example 56 57 58 59 60 61 62 dihydrochloride N- (2-10-3 10-3 10-3 10-3 10-3 10-3 10-3 ethylbutyl) benzene 1-4 diamine mole mole mole mole mole mole mole (21) Benzene-1,3- diol 3 moles 5-Amino-2-methyl-phenol 3 moles 1H-Indol-6-ol 3 moles 2-Aminopyridin-3-ol 3 moles 3,6-Dimethyl-1H-pyrazolo [5, 1-10-3 c] [1,2,4] triazole mole 2- (2,4-Diamino-phenoxy) -10-3 ethanol, hydrochloride mole 3-Amino-2-chloro-6-methyl-10-3 phenol, hydrochloride mole Dye carrier (1) (*) (*) (*) (*) (*) (*) (*) Demineralised water q.s. 100g 100g 100g 100g 100g 100g 100g (*): dyeing medium (1) pH 7 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylene triamine pentasodium salt -pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 Na 2 HPO 4 0.28 g KH 2 PO 4 0.46 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). We obtain a final pH of 7.5

48

  Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

  The shades obtained are shown in the table below: Example 56 57 58 59 60 61 62 Shade observed gray purple gray gray gray blue intense violet intense intense violet intense intense intense blue red intense intense red intense - Examples 63 to 69: dyeing in basic medium The following dye compositions are prepared: Example 63 64 65 66 67 68 69 N- (2- 10-3 10-3 10-3 10-3 10-3 10-3 10-3 ethylbutyl) benzene dihydrochloride 1.4 mole mole mole mole mole mole mole diamine (21) benzene-1,3-diol 10 mole 5-Amino-2-methyl-phenol 10 mole 1H-Indol-6ol 3 mole 2-Amino-pyridin 3-ol 3 mole 3,6-Dimethyl-1H-3-pyrazolo [5,1-mole e] [1,2,4] triazole 2- (2,4-Diamino-phenoxy) -10-3 ethanol , hydrochloride mole 3-Amino-2-chloro-6-methylphenol, hydrochloride Dye carrier (2) (*) (*) (*) (*) (*) (*) (*) Demineralized water qs 100g 100g 100g 100g 100g 100g 100g10 (*): dyeing medium (2) pH 9.5 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylenetriamine pentasodium salt -pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 4.24 g Ammonia at 20% NH.sub.2 2.94 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 is obtained. Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

  The shades obtained are shown in the table below: Example 63 64 65 66 67 68 69 Shade observed brown violet brown gray violet-blue violet-intense intense red red intense red intense blue intense intense intense Examples 70 to 82: Dye composition from N-butylbenzene-1,4-diamine dihydrochloride (2c) Examples 70 to 76: Acidic acid tincture The following dye compositions are prepared: Example 70 71 72 73 74 75 76 Dihydrochloride of the N-103 10-3 10-3 10-3 10-3 10-3 10-3 butylbenzene-1,4-diamine (2c) mole mole mole mole mole mole mole Benzene-1,3-diol 10 3 mole 5-Amino-2 3-methyl-phenol 3 mol 1H-Indol-6-ol 10-3 mol 2-Amino-pyridin-3-ol 3 moles 3,6-Dimethyl-1H-pyrazolo [5,1- 10-3] [1,2,4] triazole mole 2- (2,4-Diamino-phenoxy) - 10-3 ethanol, hydrochloride mole 3-Amino-2-chloro-6-methyl-3-phenol, hydrochloride mole Dyeing medium (1) (*) (*) (*) (*) (*) (*) (*) Demineralized water qs 100g 100g 100g 100g 100g 100g 100g (*): dye support (1) pH 7

  96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulphite 0.23 g MA diethylene triamine pentaacetic acid pentasodium salt 40% aqueous solution 0.48 g MA C8-Cio alkyl polyglucoside in 60% aqueous solution 3.6 g MA Benzyl alcohol 2.0 g Polyethylene glycol with 8 ethylene oxide units 3.0 g 0.28 g 0.46 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 7 is obtained. Na2HPO4 KH2PO4

51

  Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

  The shades obtained are shown in the table below: Example 70 71 72 73 74 75 76 Shade observed brown purple gray gray brown blue intense purple intense violet-violet-intense red blue red intense red intense intense intense - Examples 77 to 82: dyeing in a basic medium The following dye compositions are prepared: Example 77 78 79 80 81 82 N-10-3 dihydrochloride 10-3 10-3 10-3 10- 3 10-3 butylbenzene 1 4 diamine mole mole mole mole mole mole (2c) 5-Amino-2-methyl-phenol 3 mole 1H-Indol-6-ol 3 mole 2-Amino-pyridin-3-ol 3 moles 3,6-Dimethyl-1H-3 pyrazolo [5.1-mole e] [1,2,4] triazole 2- (2,4-Diamino-phenoxy) -10-3 ethanol, hydrochloride mole 3-Amino-2-chloro-6-methyl-3-methyl mole phenol, hydrochloride Dye carrier (2) (*) (*) (*) (*) (*) (*) Demineralized water qs 100g 100g 100g 100g 100g 100g 15 (*): dyeing medium (2) pH 9.5 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylene triamine pentasodium salt -pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 4.24 g Ammonia at 20% NH.sub.2 2.94 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 is obtained. Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

  The shades obtained are given in the table below: Example 77 78 79 80 81 82 Grade observed gns violet brown brown red blue violet-intense red intense orange intense blue intense intense intense Examples 83 to 96: Dyeing composition from the dihydrochloride of the N- (1-methylheptyl) benzene-1,4-diamine (2n) - Examples 83 to 89: Tincture in an acidic medium The following dye compositions are prepared: EXAMPLE 83 84 85 86 87 88 89 N- (1) dihydrochloride 10-3 10-3 10-3 10-3 10-3 10-3 10-3 methylheptyl) benzene 1.4 mole mole mole mole mole mole diamine (2n) Benzene-1,3-diol 10 mole -Amino-2-methyl-phenol 10 moles 1H-Indol-6-ol 10 moles 2-Amino-pyridin-3-ol moles 3,6-Dimethyl-1H-pyrazolo [5,1- 3 e] [1,2,4] triazole mole 2- (2,4-Diamino-phenoxy) -10-3 ethanol, hydrochloride mole 3-Amino-2-chloro-6-methyl-3-phenol, hydrochloride mole Dyeing medium (1) (*) (*) (*) (*) (*) (*) (*) Demineralized water qs 100g 100g 100g 100g 100g 100g 100g (*): dyeing medium (1) pH 7 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylene triamine pentasodium salt -pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 Na 2 HPO 4 0.28 g KH 2 PO 4 0.46 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 7 is obtained.

54

  Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. The shades obtained are shown in the table below: Example 83 84 85 86 87 88 89 Shade observed gray violet gray gray gray blue intense violet intense red intense intense intense deep blue intense intense red - Examples 90 to 96: dyeing in basic medium The following dye compositions are prepared: Example 90 91 92 93 94 95 96 N- (1-10-3 10-3 10-3 10-3 10-3 10-3 10-3 methylheptyl) benzene mole mole mole mole mole mole mole 1,4-diamine (2n) Benzene-1,3-diol 10 mole 5-Amino-2-methyl-phenol 10 mole 1H-Indol-6-ol 3 mole 2-Amino-pyridine 3-Molar 3,6-dimethyl-1H-3-pyrazolo [5,1-mole e] [1,2,4] triazole 2- (2,4-Diamino-phenoxy) -10-3 ethanol, hydrochloride mole 3-Amino-2-chloro-6- 10-3 methylmol phenol, hydrochloride Dye carrier (2) (*) (*) (*) (*) (*) (*) (*) (*) Demineralized water qs 100g 100g 100g 100g 100g 100g 100g 15 (*): dyeing medium (2) pH 9.5 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulphite 0.23 g MA diethylene glycol pentasodium salt triamine-pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3, 0 g NH4Cl 4.32 g Ammonia at 20% NH3 2.94 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 is obtained. Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. 10 The shades obtained are shown in the table below: Example 90 91 92 93 94 95 96 Shade observed gray gray brown gray violet-blue violet- intense inviolet intense red red intense red intense blue intense intense intense Examples 97 to 110: Dyeing composition from the dihydrochloride of N- (1-methylhexyl) benzene-1,4-diamine (2o). Examples 97 to 103: Acidic acid dyeing The following dye compositions are prepared: Example 97 98 99 100 101 102 N- (1-10-3 10-3 10-3 10-3 10-3 10-3 10-3 methylhexyl) benzene dihydrochloride 1,4 mole mole mole mole mole mole diamine (2o) Benzene-1 3-Diol 3 mole 5-Amino-2-methyl-phenol 3 mole 1H-Indol-6-ol 10 moles 2-Amino-pyridin-3-ol 3 moles 3,6-Dimethyl-1 H- pyrazolo [5.1- 10-3 c] [1,2,4] triazole mole 2- (2,4-Diamino-phenoxy) -10-3 ethanol, hydrochloride mole 3-Amino-2-chloro-6-methyl - 10-3 phenol, hydrochloride mole Dyeing medium (1) (*) (*) (*) (*) (*) (*) (*) mineralized q.s. 100g 100g 100g 100g 100g 100g 100g (*): dyeing medium (1) pH 7 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylene triamine pentasodium salt -pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 Na 2 HPO 4 0.28 g KH 2 PO 4 0.46 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 7 is obtained.

  Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. The shades obtained are shown in the table below: Example 97 98 99 100 101 102 103 Shade observed gray violet brown gray gray blue intense violet intense red violet- intense intense intense blue intense intense red -Examples 104 to 110: dyeing in basic medium The following dye compositions are prepared: EXAMPLE 104 N- (1-10-3 10-3 10-3 10-3 10-3 10-3 10 -3-methylhexyl) benzene mole mole mole mole mole mole diamine (2o) Benzene-1,3-diol 10 3 mole 5-Amino-2-methyl-phenol 10 3 mole 1H-Indol-6ol 10 mole 2-Amino-pyridin-3-ol 3 mole 3,6-dimethyl-1H-pyrazolo [5,1-mole e] [1,2,4] triazole 2- (2,4-Diamino-phenoxy) -10-3 ethanol, hydrochloride mole 3-Amino-2-chloro-6- 3-methylmol phenol, hydrochloride Dye carrier (2) (*) (*) (*) (*) (*) (*) (*) Demineralized water qs 100g 100g 100g 100g 100g 100g 100g10 (*): dyeing medium (2) pH 9.5 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylenetriamine pentasodium salt -pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 4.24 g Ammonia at 20% NH.sub.2 2.94 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 is obtained.

  Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

  The shades obtained are shown in the table below: Example 104 105 106 107 108 109 110 Shade observed gray violet brown gray violet blue intense violet intense violet intense intense intense blue intense intense intense red Examples 111 to 123: Dye composition from Nl- (2-ethylbutyl) -2-methylbenzene-1,4-diamine dihydrochloride (2p) Examples 111 to 117: Tincture in an acid medium The following dye compositions are prepared: Example 111 112 113 114 115 Nl- (2-10-3 10-3 10-3 10-3 10-3 10-3 10-3 ethylbutyl) 2 methylbenzene dihydrochloride mole mole mole mole mole mole mole 1,4-diamine (2p) Benzene-1,3-diol 10 moles 5-amino-2-methyl-phenol 10 moles 1 H -indol-6-ol 3 moles 2-aminopyridin-3-ol moles 3, 6-dimethyl 1 H-pyrazolo [5,1- 10-3 c] [1,2,4] triazole mole 2- (2,4-Diamino-phenoxy) -10-3 ethanol, hydrochloride mole 3-Amino-2-chloro 6-methyl-3-phenol, hydrochloride mole Dye carrier (1) (*) (*) (*) (*) (*) (*) (*) Demineralized water q.s. 100g 100g 100g 100g 100g 100g 100g (*): dyeing medium (1) pH 7 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylene triamine pentasodium salt -pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 g Na2HPO4 0.28 g KH2PO4 0.46 g 59 60

  At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 7 is obtained. Each mixture obtained is applied to locks of gray hair at 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. The shades obtained are shown in the table below: Example 111 112 113 114 115 116 117 observed brown violet brown brown brown blue violet-violet red red intense red intense blue intense intense intense - Examples 118 to 123: dyeing in basic medium 10 The following dye compositions are prepared: Example 118 119 120 121 122 123 Ni-10-3 dihydrochloride 10-3 10-3 10-3 10-3 10-3 (2 ethylbutyl) 2 mole mole mole mole mole mole methylbenzene 1 4 diamine (2p) 5-Amino-2-methyl-phenol 10 moles 1H-Indol-6-ol 3 moles 2-Amino-pyridin-3-ol 3 moles 3,6-Dimethyl-1H-10 3 pyrazolo [5.1-mole e] [1,2,4] triazole 2- (2,4-Diamino-phenoxy) -10 -3-ethanol, hydrochloride mole 3-Amino-2-chloro-6-methyl-3-methylol phenol, hydrochloride Dye carrier (2) (*) (*) (*) (*) (*) (*) Demineralized water qs 100g 100g 100g 100g 100g 100g 15 (*): dyeing medium (2) pH 9.5 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylene triamine pentasodium salt -pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 4.24 g Ammonia at 20% NH.sub.2 2.94 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 is obtained. Each mixture obtained is applied to locks of gray hair at 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

  The shades obtained are given in the table below: Example 118 119 120 121 122 123 Shade observed violet-red-brown red blue violet red red intense intense chromatic Examples 124 to 137: Dyeing composition from the dihydrochloride of N-isobutylbenzene-1 4-diamine (2b) 15 510 - Examples 124 to 130: Tincture in an acid medium The following dye compositions are prepared: Example 124 125 126 127 128 129 130 Dihydrochloride N 10-3 10-3 10-3 10- 3 10-3 10-3 10-3 isobutylbenzene 1 4 diamine mole mole mole mole mole mole mole (2b) Benzene-1,3-diol 10 3 mole 5-Amino-2-methyl-phenol 10 3 mole 1H-Indol- 6-ol 10 3 mole 2-Amino-pyridin-3-ol 3 moles 3,6-Dimethyl-1H-pyrazolo [5.1-10-3 c] [1,2,4] triazole mole 2- ( 2,4-Diamino-phenoxy) - 10-3 ethanol, hydrochloride mole 3-Amino-2-chloro-6-methyl-3-phenol, hydrochloride mole Dye carrier (1) (*) (*) (*) ( *) (*) (*) (*) Demineralized water qs 100g 100g 100g 100g 100g 100g 100g (*): dyeing medium (1) pH 7 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylene triamine pentasodium salt -pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 Na 2 HPO 4 0.28 g KH 2 PO 4 0.46 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 7 is obtained.

63

  Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

  The shades obtained are shown in the table below: Example 124 125 126 127 128 129 130 Shade observed gray violet gray viogris gray blue violet- intense intense violet let- intense violet intense blue intense red intense intense Examples 131 to 137: dyeing medium basic The following dye compositions are prepared: Example 131 132 133 134 135 136 137 N-10-3 dihydrochloride 10-3 10-3 10-3 10-3 10-3 10-3 isobutylbenzene 1.4 mole mole mole mole mole mole diamine (2b) Benzene-1,3-diol 3 mole 5-Amino-2-methyl-phenol 10 mole 1H-Indol-6ol 3 mole 2-Amino-pyridin-3-ol 10 3 mole 3 6-Dimethyl-1H-pyrazolo [5,1-e] [1,2-mole, 4] triazole 2- (2,4-Diamino-phenoxy) -10 -3-ethanol, hydrochloride mole 3-Amino- 2-chloro-6- 3-methylmol phenol, hydrochloride Dye carrier (1) (*) (*) (*) (*) (*) (*) (*) Demineralized water qs 100g 100g 100g 100g 100g 100g 100g 15 (*): dyeing medium (1) pH 9.5 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulphite 0.23 g MA diethylene glycol pentasodium salt triamine-pentaacetic in 40% aqueous solution 0.48 g MA C8-Cio alkyl polyglucoside in 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol with 8 ethylene oxide units 3, 0 g NH4Cl 4.32 g Ammonia at 20% NH3 2.94 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 is obtained. Each mixture obtained is applied to locks of gray hair at 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. The shades obtained are shown in the table below: Example 131 132 133 134 135 136 137 Shade observed brown violet brown gray violet-blue violet- intense intense red red intense red intense blue intense intense intense Examples 138 to 151: Dye composition from 2-Methyl-N- (2-methylbutyl) benzene-1,4-diamine dihydrochloride (2d) Examples 138-144: Acidic acid dyeing The following dye compositions are prepared: Example 138 139 140 141 2-Methyl-3-dihydrochloride 10-3 10-3 10-3 10-3 10-3 10-3 N- (2-methylbutyl) benzene-1,4-mole mole mole mole mole mole mole diamine (2d) Benzene-1,3-diol 10 3 mole 5-Amino-2-methyl-phenol 10 moles 1H-Indol-6-ol 10-3 moles 2-Amino-pyridin-3-ol 10 3 moles 3,6-Dimethyl-1H-pyrazolo [5,1- 10-3 c] [1,2,4] triazole mole 2- (2,4-Diamino-phenoxy) ethanol, hydrochloride mole 3-Amino- 2-chloro-6-methyl-3-phenol, hydrochloride mole Dye support (1) (*) (*) ( *) (*) (*) (*) (*) Demineralized water q.s. 100g 100g 100g 100g 100g 100g 100g (*): dye support (1) pH 7

  96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulphite 0.23 g MA diethylene triamine pentaacetic acid pentasodium salt 40% aqueous solution 0.48 g MA C8-Cio alkyl polyglucoside in 60% aqueous solution 3.6 g MA Benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 g 0.28 g 0.46 g Na2HPO4 KH2PO4 66

  At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 7 is obtained. Each mixture obtained is applied to locks of gray hair at 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. The shades obtained are shown in the table below: Example 138 139 140 141 142 143 144 Shade observed brown violet brown gray gray blue violet intense intense red intense red intense deep intense intense blue 10 Examples 145 to 151: dyeing in basic medium The following dye compositions are prepared: EXAMPLE 145 146 147 148 149 150 151 dihydrochloride of 2- [2- [10-3] 10 -3 10-3 10-3 10-3 10 -3-methyl-N1- (2 mol) mole mole mole mole mole mole methylbutyl) benzene-1,4-diamine (2d) Benzene-1,3-diol 10 mole 5-Amino-2-methyl-phenol 10 mole 1H-Indol-6-ol 10 mole 2- Amino-pyridin-3-ol 3 moles 3,6-Dimethyl-1H-10-3 pyrazolo [5.1-mole e] [1,2,4] triazole 2- (2,4-Diamino-phenoxy) - 10-3 ethanol, hydrochloride mole 3-Amino-2-chloro-6-phenol-3-methylol, hydrochloride Dye support (2) (*) (*) (*) (*) (*) (*) (*) (*) Demineralized water qs 100g 100g 100g 100g 100g 100g 100g 15 (*): dyeing medium (2) pH 9.5 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulphite 0.23 g MA diethylene glycol pentasodium salt triamine-pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3, 0 g NH4Cl 4.32 g Ammonia at 20% NH3 2.94 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 is obtained. Each mixture obtained is applied to locks of gray hair at 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

  The shades obtained are shown in the table below: Example 145 146 147 148 149 150 151 Shade violet brown brown red blue violet- Intense shade red intense red chromatic blue observed intense intense intense intense Examples 152 to 165: Dye composition from the dihydrochloride N- (2-methylbutyl) benzene-1,4-diamine (2q) 20 -Examples 152 to 158: Tincture in an acid medium The following dye compositions are prepared: Example 152 153 154 155 156 157 158 N-dihydrochloride - (2- 10-3 10-3 10-3 10-3 10-3 10-3 10-3 methylbutyl) benzene 1.4 mole mole mole mole mole mole mole diamine (2q) Benzene-1,3-diol 10 3 moles 5-Amino-2-methyl-phenol 3 moles 1H-Indol-6ol 3 moles 2-Amino-pyridin-3-ol 3 moles 3,6-Dimethyl-1H-pyrazolo [5,1-10 -3c] [1,2,4] triazole mole 2- (2,4-Diamino-phenoxy) -10-3 ethanol, hydrochloride mole 3-Amino-2-chloro-6-methyl-3-phenol, hydrochloride mole Dyeing medium (1) (*) (*) (*) (*) (*) (*) (*) Dewatered water q.s. 100g 100g 100g 100g 100g 100g 100g (*): dyeing medium (1) pH 7 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylene triamine pentasodium salt -pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 Na 2 HPO 4 0.28 g KH 2 PO 4 0.46 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 7 is obtained.

69

  Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

  The shades obtained are shown in the table below: Example 152 153 154 155 156 157 158 Shade observed brown gray viogris gray violet- blue violet- intense violet let- red intense red intense blue intense red intense intense intense Examples 159 to 165: dyeing in basic medium The following dye compositions are prepared: Example 159 160 161 162 163 164 165 N- (2- 10-3 10-3 10-3 10 -3 10-3 10-3 10 -3-methylbutyl) benzene dihydrochloride 1.4 mole mole mole mole mole mole mole diamine (2q) Benzene-1,3-diol 10 mole 5-Amino-2-methyl-phenol 10 mole 1H-Indol-6-ol 3 mole 2-Amino pyridin-3-ol 3 mole 3,6-Dimethyl-1H10 3 pyrazolo [5.1mol e] [1,2,4] triazole 2- (2,4-Diamino-phenoxy) -10-3 ethanol , hydrochloride mole 3-Amino-2-chloro-6-methylphenol, hydrochloride Dye carrier (2) (*) (*) (*) (*) (*) (*) (*) Demineralized water qs 100g 100g 100g 100g 100g 100g 100g15 (*): dyeing medium (2) pH 9.5 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylenetriamine pentasodium salt -pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 4.24 g Ammonia at 20% NH.sub.2 2.94 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 is obtained. Each mixture obtained is applied to locks of gray hair at 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. The shades obtained are shown in the table below: Example 159 160 161 162 163 164 165 Shade observed brown violet brown brown violet-blue violet- intense intense red red intense red intense blue intense intense intense Examples 166 to 179: Dye composition from N- (1-ethylpropyl) benzene-1,4-diamine (2r) dihydrochloride. Examples 166 to 172: Acidic acid tincture The following dye compositions are prepared: Example 166 167 168 169 170 171 172 Dihydrochloride N- (1-10-3 10-3 10-3 10-3 10-3 10-3 10-3 ethylpropyl) benzene 1.4 mole mole mole mole mole mole mole diamine (2r) Benzene-1,3- diol 10 3 mol 5-Amino-2-methyl-phenol 10 3 mol 1H-Indol-6-ol 3 mol 2-Amino-pyridin-3-ol 3 moles 3,6-Dimethyl-1H-pyrazolo [5] 1-10-3 c] [1,2,4] triazole mole 2- (2,4-Diamino-phenoxy) -10-3 ethanol, hydrochloride 3-Amino-2-chloro-6-methyl-10-3 phenol, hydrochloride mole Dye carrier (1) (*) (*) (*) (*) (*) (*) (*) Demi water q.s. 100g 100g 100g 100g 100g 100g 100g (*): dyeing medium (1) pH 7 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylene triamine pentasodium salt -pentaacetic 40% aqueous solution 0.48 g MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 0.28 g 0.46 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). We obtain a final pH of 7. Na2HPO4 KH2PO4

72

  Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. The shades obtained are shown in the table below: Example 166 167 168 169 170 171 172 Shade observed gray violet- viogris gray violet- blue violet- intense blue let- violet intense red intense blue intense red intense intense intense Examples 173 to 179: dyeing in basic medium The following dye compositions are prepared: Example 173 174 175 176 177 178 179 N- (1-10-3 10-3 10-3 10-3 10-3 10-3 10-3 ethylpropyl dihydrochloride benzene 1.4 mole mole mole mole mole mole mole diamine (2r) Benzene-1,3-diol 10 mole 5-Amino-2-methyl-phenol 10-3 mole 1H-Indol-6-ol 10 3 mole 2 -Amino-pyridin-3-ol 3 mole 3,6-Dimethyl-1H10 3 pyrazolo [5,1-mole e] [1,2,4] triazole 2- (2,4-Diamino-phenoxy) -10 -3 ethanol, hydrochloride mole 3-Amino-2-chloro-6-methylphenol, hydrochloride Dye carrier (2) (*) (*) (*) (*) (*) (*) (*) (*) ) Demineralized water qs 100g 100g 100g 100g 100g 100g 100g 15 (*): dyeing medium (2) pH 9.5 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulphite 0.23 g MA diethylene glycol pentasodium salt triamine-pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3, 0 g NH4Cl 4.32 g Ammonia at 20% NH3 2.94 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 is obtained. Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. The shades obtained are shown in the table below: Example 173 174 175 176 177 178 179 Shade observed brown violet-brown violet violet-blue violet-intense blue red red intense red intense blue intense intense intense intense 15 Examples 180 to 193: Dye composition from N- (1,2-dimethylpropyl) benzene-1,4-diamine dihydrochloride (2s) - Examples 180 to 186: Acid dyeing The following dye compositions are prepared: Example 180 181 182 183 N- (1,2- 10-3 10-3 10-3 10-3 10-3 10-3 10-3 dimethylpropyl) benzene dihydrochloride 1,4 mole mole mole mole mole mole mole diamine (2s Benzene-1,3-diol 3 mole 5-Amino-2-methyl-phenol 3 moles 1H-Indol-6-ol 3 moles 2-Amino-pyridin-3-ol 3 moles 3,6-Dimethyl -1H-pyrazolo [5.1-10-3c] [1,2,4] triazole mole 2- (2,4-Diamino-phenoxy) -10-3 ethanol, hydrochloride mole 3-Amino-2-chloro 6-methyl-3-phenol, hydrochloride mole Dye carrier (1) (*) (*) (*) (*) (*) (*) (*) Demineralized water q.s. 100g 100g 100g 100g 100g 100g 100g (*): dyeing medium (1) pH 7 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylene triamine pentasodium salt -pentaacetic 40% aqueous solution 0.48 g MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 0.28 g 0.46 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 7 is obtained. Na2HPO4 KH2PO4

75

  Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

  The shades obtained are shown in the table below: Example 180 181 182 183 184 185 186 Shade observed gray purple gray gray purple-blue violet- intense intense violet- purple intense red blue intense red intense intense intense Examples 187 to 193 dyeing medium The following dye compositions are prepared: EXAMPLE 187 188 189 190 191 192 193 N-10-3 dihydrochloride 10-3 10-3 10-3 10-3 10-3 10-3 (1.2 mole mole mole mole mole mole dimethylpropyl) benzene-1,4-diamine (2s) Benzene-1,3-diol 10 moles 5-Amino-2-methyl-phenol 10 moles 1H-Indol-6-ol 10-3 moles -Amino-pyridin-3-ol 3 mole 3,6-Dimethyl-1H-10-3 pyrazolo [5,1-mole e] [1,2,4] triazole 2- (2,4-Diamino-phenoxy) ) - 10-3 ethanol, hydrochloride mole 3-Amino-2-chloro-6-methylphenol, hydrochloride Dye support (2) (*) (*) (*) (*) (*) (*) (*) ) (*) Demineralized water qs 100g 100g 100g 100g 100g 100g 100g 15 (*): dyeing medium (2) pH 9.5 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulphite 0.23 g MA diethylene glycol pentasodium salt triamine-pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3, 0 g NH4Cl 4.32 g Ammonia at 20% NH3 2.94 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 is obtained. Each mixture obtained is applied to locks of gray hair at 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

  The shades obtained are shown in the table below: Example 187 188 189 190 191 192 193 observed brown violet brown gray violet-blue violet-violet irougentense red intense red intense blue intense intense intense 15 Examples 194 to 207: Dye composition from N- (1,2,2-trimethylpropyl) benzene-1,4-diamine dihydrochloride (2t) - Examples 194 to 200: Acid dyeing The following dye compositions are prepared: Example 194 195 196 197 198 199 200 2t: N-10-3 dihydrochloride 10-3 10-3 10-3 10-3 10-3 10-3 (1,2,2-trimethylpropyl) benzene mole mole mole mole mole mole mole 1,4 (2t) benzene-1,3-diol 10 3 mole 5-Amino-2-methyl-phenol 10 mole 1H-Indol-6-ol 10-3 mole 2-Amino-pyridin-3-ol 10 3 mole 3,6-Dimethyl-1H-pyrazolo [5,1- 10-3 c] [1,2,4] triazole mole 2- (2,4-Diamino-phenoxy) -10-ethanol, hydrochloride mole 3-Amino- 2-chloro-6-methyl-3-phenol, hydrochloride mole Dye carrier (1) (*) (*) (*) (*) (*) (*) (*) ) (*) Demineralized water q.s. 100g 100g 100g 100g 100g 100g 100g (*): dyeing medium (1) pH 7 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylene triamine pentasodium salt -pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 Na2HPO4 0.28 g KH2PO4 0.46 g

  At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 7 is obtained. Each mixture obtained is applied to locks of gray hair at 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. The shades obtained are shown in the table below: EXAMPLE 194 195 196 197 198 199 200 Grades observed gray violet gray viogris gray blue intense violet intense red let- intense violet deep blue intense intense intense red 10 Examples 201 to 207 dyeing in basic medium The following dye compositions are prepared: Example 201 202 203 204 205 206 207 2t: dihydrochloride of the 10-3 10-3 10-3 10-3 10-3 10-3 10-3 N- (1,2,2- mole mole mole mole mole mole mole trimethylpropyl) benzene 1,4-diamine (2t) Benzene-1,3-diol 10 3 mole 5-Amino-2-methyl-phenol 10 3 mole 1H-Indol-6-ol 10 3 mole 2 -Amino-pyridin-3-ol 3 moles 3,6-Dimethyl-1 H-10-3 pyrazolo [5,1-mole e] [1,2,4] triazole 2- (2,4-Diamino-phenoxy) -3 ethanol, hydrochloride mole 3-Amino-2-chloro-6-methylphenol, hydrochloride Dye carrier (2) (*) (*) (*) (*) (*) (*) (*) (*) ) Demineralized water qs 100g 100g 100g 100g 100g 100g 100g (*): dyeing medium (2) pH 9.5 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylene triamine pentasodium salt -pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 4.24 g Ammonia at 20% NH.sub.2 2.94 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 is obtained. Each mixture obtained is applied to locks of gray hair at 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. The shades obtained are shown in the table below: Example 201 202 203 204 205 206 207 Shade observed brown violet brown violet-violet violet blue intense intense red red intense red intense blue intense intense intense Examples 208 to 221: Dye composition to From the dihydrochloride of N- (1-methylpentyl) benzene-1,4-diamine (2u) 20 - Examples 208 to 214: Tincture in an acidic medium The following dye compositions are prepared: Example 208 209 210 211 212 213 214 dihydrochloride N- (1-10-3 10-3 10-3 10-3 10-3 10-3 10-3 methylpentyl) benzene 1.4 mole mole mole mole mole mole mole diamine (2u) 1,3-Benzene 10 mol 3-methyl-2-methyl-phenol 3 mol 1H-Indol-6-ol 3 mol 2-Amino-pyridin-3-ol 3 moles 3,6-Dimethyl-1H-pyrazolo [ 5.1 - 10-3 c] [1,2,4] triazole mole 2- (2,4-Diamino-phenoxy) -10-3 ethanol, hydrochloride mole 3-Amino-2-chloro-6-methyl-10- -3 phenol, hydrochloride mole Dyeing medium (1) (*) (*) (*) (*) (*) (*) (*) Water demineralized q.s. 100g 100g 100g 100g 100g 100g 100g (*): dyeing medium (1) pH 7 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite 0.23 g MA diethylene triamine pentasodium salt -pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3.0 Na 2 HPO 4 0.28 g KH 2 PO 4 0.46 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 7 is obtained.

81

  Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. The shades obtained are shown in the table below: Example 208 209 210 211 212 213 214 Tense observed gray violet brown viogris gray blue intense violet intense red let- intense violet deep blue intense intense red intense 10 Examples 215 to 221 dyeing in basic medium The following dye compositions are prepared: EXAMPLE 215 N- (1-10-3 10-3 10-3 10-3 10-3 10-3 10-3 methylpentyl) benzene mole mole dihydrochloride mole mole mole mole 1,4-diamine (2u) Benzene-1,3-diol 10 3 mole 5-Amino-2-methyl-phenol 10 mole 1H-Indol-6ol 3 mole 2-Amino-pyridin-3 ol 3 mole 3,6-Dimethyl-1H-pyrazolo [5,1-mole e] [1,2,4] triazole 2- (2,4-Diamino-phenoxy) -10-3 ethanol, hydrochloride mole 3-Amino-2-chloro-6- 10-3 methylmol phenol, hydrochloride Dye carrier (2) (*) (*) (*) (*) (*) (*) (*) Demineralized water qs 100g 100g 100g 100g 100g 100g 100g 15 (*): dyeing medium (2) pH 9.5 96% ethyl alcohol 20.8 g 35% aqueous sodium metabisulphite 0.23 g MA diethylene glycol pentasodium salt triamine-pentaacetic solution 0.48 g 40% aqueous MA C8-Cio alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 ethylene oxide units 3, 0 g NH4Cl 4.32 g Ammonia at 20% NH3 2.94 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 is obtained. Each mixture obtained is applied to locks of gray hair 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. The shades obtained are shown in the table below: Example 215 216 217 218 219 220 221 Shade observed gray purple brown gray purple-blue violet- intense intense red vio- red intense blue intense red intense intense intense

Claims (18)

  1. A compound characterized in that it is a secondary paraphenylenediamine of general formula (I): H, N, Ak R1 wherein: Ak represents an unsubstituted linear or branched C4-C10 alkyl chain; R1 represents an unsubstituted alkyl radical; an unsubstituted alkoxy radical; or its addition salts or solvates with the exception of the following compounds: H NACH2) 5Me OMe NH2NH2HN1, Me   2. Compound according to claim 1, characterized in that the Ak group of formula (I) represents a 2-methylbutyl, 2-ethylbutyl, 1,3-dimethylbutyl or isobutyl group.   3. Compound according to claim 1 or 2, characterized in that the R1 group of the formula (I) represents a methyl group or a methoxy group.   4. Compound according to claim 1, wherein the compound of formula (I) is chosen from the following compounds: NH, HNHN 2-ethylbutyl) -2-methylbenzene-1,4-N4- (2-ethylbutyl) -2-methylbutyl) benzene 1,4 NH2 diamine methylbenzene-1,4-diamine diamine HN HN HN N-1- (1,3-Dimethyl) -butyl) -3-methyl-N-1-Isobutyl-2-methyl-NH2-benzene-1,4-diamine benzene-1,4-NH2-NH2-diamine N-1- (1,3-Dimethyl-butyl) -2 methyl-benzene-1,4-diamine HN MeO N-1-Isobutyl-2-MeO N-1-Isobutyl-3-NH 2 -methoxy-benzene-1,4-methoxy-benzene-1,4-diamine HN HN NH 2 -NH 2 diamine N-1-Isobutyl-3-methylbenzene-1,4-diamine and their addition salts and solvates.   5. Compound according to any one of claims 1 to 4, characterized in that the addition salts of the secondary para-phenylenediamines of general formula (I) are chosen from hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.   6. Nitrogen compound characterized in that it has the following structure (II): H, N, Ak HN HN NH 2 N-1- (1,3-Dimethyl-butyl) -2-methoxy-benzene-1,4-diamine NH 2 N-1- (1,3-Dimethylbutyl) -3-methoxybenzene-1,4-diamine MeO MeO R1 NO2 wherein: Ak represents an unsubstituted C4-C10 linear or branched alkyl chain; R1 represents an unsubstituted alkyl radical; an unsubstituted alkoxy radical; or its addition salts or its solvates, with the exception of the following compounds: H, N, nBu H, N (CH2) 5MeH, N ~ (CH2) 9Me OMe NO2 NO2 NO2H, N ~ tBu NO2H, N, nBu NO2 Me   7. Process for the preparation of the compound of formula (I) as defined in any one of claims 1 to 5, characterized in that a reduction step of a nitro compound of formula (II) is carried out such that defined in claim 6.   8. Use of at least one compound of formula (III) below: H, N, Ak NH 2 (III) in which: Ak represents an unsubstituted linear or branched C 4 -C 10 alkyl chain; R represents a hydrogen atom, a C1-C6 alkyl radical, a C1-C6 alkoxy, a (C1-C6) alkoxy) C1-C6 alkyl, a C1-C6 hydroxyalkoxy, a mono- or poly) hydroxy C 1 -C 6 alkyl n represents an integer ranging from 0 to 2; Or its addition salts or solvates as an oxidation base for capillary oxidation dyeing.   9. Cosmetic composition for dyeing keratinous fibers, preferably human keratin fibers, such as the hair, comprising, in a medium suitable for dyeing, at least one compound of general formula (III), as defined in claim 8 and at least one oxidation coupler.   10. Composition according to the preceding claim, characterized in that the compound of formula (III) is chosen from the following compounds and their salts and solvates: HN HN NH NH 2 NH 2 N- (3-methyl-butyl) benzene N- isobutylbenzene-1,4-N- (1,3-1,4-diamino diamine dimethylbutyl) benzene 1,4-diamine N NH2 Hz NH2HNHN2-methyl-N1- (2- N- (1-N4-) (2-ethylbutyl) -2-methylbutyl) benzene-1,4-diamine methylpentyl) benzene-methylbenzene-1,41,4-diamine diamineHN HN NH 2 NH 2 NH N -octylbenzene-1,4N-hexylbenzene-1,4-diamine diamine N (sec butyl) benzene 1,4-diamine HZN NH HN HN / NH 2 Np entylb enzene-1,4-diamine N- (1,5-NH 2 dimethylhexyl) benzene-N (2 1,4-diamine ethylhexyl) b enzene 1,4-diamino HNNH N H N H N NH 2 NH 2 N -butylbenzene-1,4-N- (1-N- (2-ethylbutyl) enzene-1,4-diamine diamine methylheptyl) benzene-1 4-diamine HN HN NH 2 N- (2 NHzNH 2 methylbutyl) b-enzene-N- (1-methylhexyl) b-enzene-1,4-N- (2-ethylbutyl) -2-1,4-diamine diamine m 1,4-diamino-ethyl-1,4-diamine HNHN-NH 2 NH 2 NH 2 N- (1,2-N- (1,2,2-N- (1-ethylpropyl) benzene-1,4-dimethylpropyl) benzene trimethylpropyl) benzene diamine -1 4-diamine-1,4-diamine HN N-Heptylbenzene-1,4-diamine HN N- (7-methyloctyl) -NH- (2,2-dimethylpropyl) -benzene-1, 4- NH 2 NH 2 benzene-1,4-diamine NH 2 diamine HN n C 9 H 19 HN N- (3,3-Dimethyl-butyl) -NH 2 benzene-1,4-diamine NH 2 N-decyl-benzene-1,4-diamine   11. Composition according to the preceding claim, characterized in that the compound of formula (III) is chosen from the following compounds: 5HN NH 2 N-isobutylbenzene-1,4-diamine HN NH 2 N- (1,3-dimethylbutyl) benzene-1, 4-diamine and their salts and solvates.   12. Composition according to any one of claims 9 to 11, characterized in that the concentration of the compound of general formula (III) is between 0.0001 and 20%, preferably between 0.005 and 6% by weight relative to total weight of the composition.   13. Composition according to any one of claims 9 to 12, characterized in that the oxidation coupler is selected from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts.   14. Composition according to any one of claims 9 to 13, characterized in that the concentration of the coupler or couplers is between 0.0001 and 20% by weight, preferably between 0.005 and 6% by weight, relative to the weight total of the composition.   15. Composition according to any one of claims 9 to 14, characterized in that the medium suitable for dyeing is constituted by water or a mixture of water and at least one organic solvent selected from alcohols C1-C4 lower, branched or unbranched; polyols and polyol ethers; aromatic alcohols and mixtures thereof.   16. Composition according to any one of the preceding claims further comprising at least one oxidizing agent.   17. A process for dyeing keratin fibers, characterized in that at least one composition according to any one of claims 9 to 16 is applied to said fibers for a time sufficient to develop the desired coloration in the presence of an agent. oxidant.   18. Multi-compartment device wherein the first compartment contains a dye composition for dyeing keratinous fibers as defined in any one of claims 9 to 15 and a second compartment contains an oxidizing agent.