CZ320899A3 - Novel cationic 4-hydroxyindoles, their use for oxidative dyeing of keratin fibers, dyeing preparations, dyeing procedures and dyeing apparatus - Google Patents

Abstract

The present invention relates to novel compounds derived from 4- hydroxyindole which contain at least one cationic the group Z, wherein Z is a quadruple aliphatic chain containing at least one saturated quadruple cyclic chain and aliphatic a chain containing at least one quaternary unsaturation a cyclic chain, the use of which as a coupling member for oxidative dyeing of keratin fibers, dyes, which contain and methods of oxidative dyeing they use.

Description

NEW CATION 4-HYDROXYINDOLES, THEIR USE FOR OXIDIZING DYEING OF CERATIN FIBERS, DYE PREPARATIONS, DYEING METHODS AND DYEING DEVICES

Field of the invention

The invention relates to novel 4-hydroxyindole-derived compounds containing at least one cationic group Z, wherein Z is a quadruple aliphatic chain, an aliphatic chain comprising at least one saturated quadruple cyclic chain and an aliphatic chain comprising at least one quaternary unsaturated cyclic chain, and their use as a binding member for oxidative dyeing of keratin fibers, coloring compositions containing them, and oxidative dyeing methods using them.

BACKGROUND OF THE INVENTION

A method for dyeing keratin fibers, particularly human hair, with dye preparations containing oxidative dye precursors, especially paraphenylenediamines, ortho- or paraaminophenols, and heterocyclic compounds such as diaminopyrazole derivatives, commonly referred to as oxidizing bases, is known. Oxidative dye precursors or oxidation bases are colorless or only slightly colored compounds which, when mixed with oxidizing agents, have the ability to give rise to colored compounds and dyes by a process called oxidative condensation.

It is also known that by mixing these oxidation bases with different binding members or color modifiers we obtain different shades. The color modifiers are preferably selected from the following compounds: aromatic metadiamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as indole linkers.

A wide variety of molecules that can serve as oxidation bases make it possible to obtain a large number of colors.

The so-called permanent dyeing obtained by the amount of these oxidizing dyes is required, which in addition must meet a certain number of requirements. It must not have any toxicological defects, must be able to obtain the required shade intensity and must be well resistant to external influences (light, harsh weather, washing, permanent waving, perspiration and abrasion).

»♦ · I · · · · ·

The dyes must also cover the white hair and have minimal influence on the properties of the fiber they dye, i.e. the quality of the dyeing must not be different depending on whether the fiber, for example, is damaged or not, must be the same from tip to root.

SUMMARY OF THE INVENTION

The Applicant has now discovered quite surprisingly and unexpectedly that a new class of compounds derived from 4-hydroxyindole of formula I, defined below, containing at least one cationic group Z, wherein Z is a quaternary aliphatic chain, an aliphatic chain containing at least one quaternary saturated cyclic chain, aliphatic chains containing at least one quaternary unsaturated cyclic chain are suitable for use as a binding member for oxidative dyeing and, moreover, allow to obtain dyes having intensive coloring in a very wide range of shades and having excellent resistance to various influences that may affect keratin fibers. Moreover, the synthesis of these compounds is simple.

These discoveries form the basis of the present invention.

The invention thus provides, in particular, compounds derived from 4-hydroxyindole of formula I, cf. below, and their acid addition salts.

where:

R 1 is hydrogen, Z, C 1 -C 4 alkyl radical, C 1 -C 4 monohydroxyalkyl radical, C 2 -C 4 polyhydroxyalkyl radical, (C 1 -C 4 alkoxy) -C 1 -C 4 alkyl radical, hydroxy (C 1 -C 4 alkoxy) -C [- C4 alkyl radical, C1-C4 aminoalkyl radical, C1-C4 aminoalkyl radical whose amine is mono- or disubstituted by C1-C4 alkyl radical, acetyl radical, C1-C4 monohydroxyalkyl radical or C2-C4 polyhydroxyalkyl radical, (C1-C4 alkyl) -C1-C4 thioalkyl radical, monohydroxy (C1-C4 alkyl) - C1-C4 thioalkyl radical, polyhydroxy (C2-C4 alkyl) -C1-C4 alkyl radical, C1-C4 carboxyalkyl radical, (C1-C4 alkoxy) -Ci- C4 thiocarbonylalkyl »*

A radical or C1-C4 acetylaminoalkyl radical, C1-C4 cyanoalkyl radical, C1-C4 trifluoroalkyl radical, C1-C4 haloalkyl radical, C1-C4 phosphoalkyl radical, or C1-C4 sulfoalkyl radical,

R2 and R3, which may be the same or different, represent a hydrogen or halogen atom, Z, -NH-Z, C1-C4 alkyl radical, carboxyl radical, (C1-C4 alkoxy) carbonyl radical or formyl radical,

R 4 and R 5, which may be the same or different, represent a hydrogen or halogen atom, Z, -NH-Z, C 1 -C 4 alkyl radical, C 1 -C 4 alkoxy radical, acetylamino radical, C 1 -C 5 monohydroxyalkyl radical, C2 -C4 polyhydroxyalkyl radical, (C1-C4 alkoxy) -C1-C4 alkyl radical, thiophene radical, furan radical, phenyl radical, aralkyl radical wherein the alkyl radical is C1-C4, phenyl radical or aralkyl radical, wherein the alkyl radical is C1-C4, replaced by a halogen atom, C4-C4 alkyl radical, trifluoromethyl radical, C1-C4 alkoxy radical, aminoradical or aminoradical, which is further mono- or di-substituted by C1-C4 alkyl radical, (C1-C4 alkyl) - A C 1 -C 4 aminoalkyl radical or a di (C 1 -C 4 alkyl) -C 1 -C 4 aminoalkyl radical,

Z is an unsaturated cationic group of formulas II and III below and a saturated cationic group of formula IV also below:

CU _c z ^(R <A N / 'G - - (R) n L - J -—D - N, --- ZG 1 ·: + ?: (R) _m X ’ ^L χ ·

(III) (III) (R10Z

N (iv) * 7

where:

D is a linker which represents an alkyl chain preferably containing from 1 to 14 carbon atoms, which is linear or branched and may be interrupted by one or more heteroatoms such as oxygen, sulfur or nitrogen and which may be substituted by one or more hydroxyl or C1- C 6 alkoxy radicals and may have one or more ketone functional groups, components of the cyclic chain E, G, J, L and M, which are the same or different, represent a carbon, oxygen, sulfur or nitrogen atom, n is an integer from 0 to 4 inclusive, m is an integer from 0 to 5 inclusive, R radicals which are the same or different may represent Z, halogen atom, hydroxyl radical, C 1 -C 6 alkyl radical, C 1 -C 6 monohydroxyalkyl radical, C 2 -C 6 polyhydroxyalkyl radical radical, nitroradical, cyanoradical, C 1 -C 6 cyanoalkyl radical, C 1 -C 6 alkoxy radical, tri (C 1 -C 6 alkyl) silyl-C 1 -C 6 alkyl radical dical, amide radical, aldehyde radical, carboxyl radical, C 1 -C 6 alkylcarbonyl radical, thioradical, C 1 -C 6 thioalkyl radical, (C 1 -C 6 alkyl) thioradical, amine radical, amine radical protected with (C 1 -C 6 alkyl) carbonyl (carbamyl, carbam, (C 1 -C ₆ alkyl) sulfonyl radical, NHR or NRR ''', wherein R and R', which may be the same or different, represent a C 1 -C 6 alkyl radical, a C 1 -C 6 monohydroxyalkyl radical or a C 2 -C 6 polyhydroxyalkyl radical,

R 6 represents a C 1 -C 6 alkyl radical, a C 1 -C 6 monohydroxyalkyl radical, a C 2 -C 6 polyhydroxyalkyl radical, a C 1 -C 6 cynoalkyl radical, a tri (C 1 -C 6 alkyl) silyl-C 1 -C 6 alkyl radical, (C 1 -C 6 alkoxy) - C 1 -C 6 A C 6 -C 6 alkyl radical, a C 1 -C 6 carbamylalkyl radical, a (C 1 -C 6 alkyl) - C 1 -C 6 carboxyalkyl radical, a benzyl radical or a Z group of formula II, III or IV; above,

R 7, R 8 and R 9, which may be the same or different, represent a C 1 -C 6 alkyl radical, a C 1 -C ₆ monohydroxyalkyl radical, a C 2 -C 6 polyhydroxyalkyl radical, a (C 1 -C 6 alkoxy) -C 1 -C 6 alkyl radical, a C 1 -C 6 a cyanoalkyl radical, an aryl radical, a benzyl radical, a C 1 -C 6 amidoalkyl radical, a tri (C 1 -C 6 alkyl) silyl-C 1 -C ₆ alkyl radical or a C 1 -C 6 aminoalkyl radical whose amine is protected by a (C 1 -C 6 alkyl) carbonyl, carbamyl or (C 1 -C 6 alkyl) sulfonyl radical, two of R 7, R 8 and R 9 may also, together with the nitrogen atom to which they are attached, a 5 or 6 membered saturated carbon-containing cyclic chain or one or more heteroatoms such as for example, pyrrolidine 9999 9 9 9 9 9 9 9 9 9 9 9 9 99 99 99 99 99 99 9 9 99 cyclic chain, piperidine cyclic chain, piperazine cyclic chain tězec morpholine or cyclic, the latter being unsubstituted or substituted by a halogen element, hydroxyl radicals, C-Co alkyl radical, CJC monohydroxyalkylovým ₆ radical, C ₂ -C ₆ polyhydroxyalkylovým radical nitroradikálem, kyanoradikálem, Cj-Cg kyanoalkylovým radical, C -C 8 alkoxy radical, tri (C 1 -C ₆ alkyl) silyl-C 1 -C ₆ alkyl radical, amide radical, aldehyde radical, carboxyl radical, C 1 -C 6 ketoalkyl radical, thioradical, C 1 -C 6 thioalkyl radical, (C 1 -C 6 alkyl) ) a thioradical, amine radical or amine radical protected with a (C 1 -C 6 alkyl) carbonyl, carbamyl or (C 1 -C 8 alkyl) sulfonyl radical, one of the radicals R 7, R 8 and R 9 may also represent the other Z, which may be the same or different from the first group Z,

R 10 is a C 1 -C 6 alkyl radical, a C 1 -C 6 monohydroxyalkyl radical, a C ₂ -C 8 polyhydroxyalkyl radical, an aryl radical, a benzyl radical, a C 1 -C 6 aminoalkyl radical or a C 1 -C 6 aminoalkyl radical whose amine is protected by a (C 1 -C 6 alkyl) carbonyl , a carbamyl or (C 1 -C 6 alkyl) sulfonyl radical, a C 1 -C 6 carboxyalkyl radical, a C 1 -C 6 cyanoalkyl radical, a C 1 -C 6 carbamylalkyl radical, a C 1 -C 6 trifluoroalkyl radical, a tri (C 1 -C 6 alkyl) silyl-C 1 -C 6 alkyl radical , C 1 -C 6 sulfonamidoalkyl radical, (C 1 -C 6 alkyl) carboxy- C 1 -C 8 alkyl radical, (C 1 -C ₆ alkyl) sulfinyl- C 1 -C 8 alkyl radical, (C 1 -C ₆ alkyl) sulfonyl- C 1 -C 8 alkyl radical, (C 1 -C 8 alkyl) keto-C 1 -C 8 alkyl radical, N- (C 1 -C 8 alkyl) carbamyl-C 1 -C 8 alkyl radical or N- (C 1 -C 8 alkyl) sulfonamido-C 1 -C 8 alkyl radical, x and y are integers 0 or 1, under the following conditions:

in unsaturated cationic groups of formula II: when x is 0, the linker D is attached to a nitrogen atom,

- if x is equal to 1, the linker D is attached to one of the parts of the cyclic chain E, G, J or L,

- y can only be 1:

(1) when the parts of the cyclic chain E, G, J and L simultaneously represent a carbon atom and when the radical Rg is attached to the nitrogen atom of the unsaturated cyclic chain, or

2) when at least one of the parts of the cyclic chain E, G, J and L represents a nitrogen atom to which the radical R 6 is attached,

- in unsaturated cationic groups of formula III:

- if x is equal to 0, the linker D is attached to the nitrogen atom, if x is equal to 1 the linker D is attached to one of the parts of the cyclic chain E, G, J, L or M,

- y may only have a value of 1 if at least one of the components of the cyclic chain E, G, J, L and M represents a divalent atom and the radical R 6 is attached to the nitrogen atom of the unsaturated cyclic chain,

- in the cationic groups of formula IV, if x is equal to 0, the linker D is attached to the nitrogen atom which carries the radicals R7-R9,

- if x is 1, two of the R7-R9 radicals, together with the nitrogen atom to which they are attached, form a saturated five or six-part cyclic chain as defined above and the linker D is bonded to the carbon atom mentioned above unsaturated cyclic chain,

X represents a monovalent or divalent anion, preferably a halogen element atom such as chlorine, bromine, fluorine or iodine, hydroxyd, hydroxensulfate or C 1 -C 6 alkylsulfate, such as methylsulfate or ethylsulfate, provided that:

the amount of cationic groups Z of formula II, III or IV is at least 1.

As shown above, the dyeings obtained with the oxidative dye compositions of the present invention are intense and make it possible to obtain shades of a wide range of colors. In addition, they exhibit excellent resistance to various external influences, harsh weather, washing, permanent waving, perspiration, abrasion, these features being particularly remarkable in terms of resistance to light, washing and perspiration.

In formula I, cf. above, the alkyl and alkoxy radicals may be linear or branched. Among the cyclic chains of the unsaturated groups Z of formula II, see. above, mention may be made in particular of the pyrrole imidazole, pyrazole, oxazole, thiazole and triazole cyclic chains.

Among the cyclic chains of unsaturated Z groups of formula III, see. above, mention may be made, for example, of the pyridine, pyrimidine, pyrazine, oxazine and triazine cyclic chains. Of the compounds of formula I, it is worth mentioning:

- 3- (4-hydroxy-1-methyl-1H-indol-5-ylmethyl) -1-methylpyridinium methosulfate,

- 4- (4-hydroxy-1-methyl-1H-indol-5-ylmethyl) -1-methylpyridinium methosulfate,

- 3- [3- (4-hydroxy-5- (1-methylpyridinium) -4-ylmethylindol-1-yl) propyl] -1-methylimidazol-1-ium dimethosulphate, · · ((((((E e e e e e e e e e e e e e e e e e »«

- 4- (4-hydroxy-1- (2-hydroxyethyl) -1H-indol-5-ylmethyl) -1-methylpyridinium methosulfate,

- 3- [3- (4-hydroxy-5- (1-methylpyridinium) -5-ylmethylindol-1-yl) propyl] -1-methylimidazol-1-ium dimethosulfate,

3- [4-hydroxy-5- (1-methylpyridinium) -3-ylmethylindol-1-ylmethyl] -1-methylpyridinium dimethosulfate,

- 3- [3- (5-Benzyl-4-hydroxylindol-1-yl) propyl] -1-methyl-3H-imidazole-1-iummethosulfate,

- [2- (4-hydroxy-1H-indol-3-yl) ethyl] trimethylammonium methosulfate,

- [2- (4-hydroxy-1-methyl-1H-indol-3-yl) ethyl] trimethylammonium methosulfate,

- (4-hydroxy-1-methyl-1H-indol-3-ylmethyl) trimethylammonium methosulfate,

- (4-hydroxy-1H-indol-3-ylmethyl) trimethylammonium methosulfate, {3 - [(4-hydroxy-1H-indole-2-carbonyl) amino] propyl} trimethylammonium methosulfate,

- {3 - [(4-hydroxy-1-methyl-1H-indole-2-carbonyl) amino] propyl} trimethylammonium methosulfate,

- {3 - [(4-hydroxy-5-methyl-1H-indole-2-carbonyl) amino] propyl} trimethylammonium methosulfate,

- {3 - [(4-hydroxy-1,5-dimethyl-1H-indole-2-carbonyl) amino] propyl} trimethylammonium methosulfate,

-3- {3 - [(4-hydroxy-1H-indole-2-carbonyl) amino] propyl} -1-methyl-3H-imidazole-1 -ium methosulfate,

-3- {3 - [(4-hydroxy-1-methyl-1H-indole-2-carbonyl) amino] propyl} -1-methyl-3H-imidazol-1 -ium methosulfate,

-3- {3 - [(4-hydroxy-5-methyl-1H-indole-2-carbonyl) amino] propyl} -1-methyl-3H-imidazol-1 -ium methosulfate,

-3- {3 - [(4-hydroxy-1,5-dimethyl-1H-indole-2-carbonyl) amino] propyl} -1-methyl-3H-imidazol-1 -ium methosulfate,

- {3 - [(4-hydroxy-1H-indole-6-carbonyl) amino] propyl} -trimethylammonium monochloride,

- {3 - [(4-hydroxy-1-methyl-1H-indole-6-carbonyl) amino] propyl} trimethylammonium monochloride, and acid addition salts thereof.

Compounds of formula I in accordance with the invention can be readily obtained by methods well known in the art, such as the preparation process described in FR-A-2 736 640, followed by a conventional final quaternization step.

The invention further provides the use of the compounds of formula I in accordance with the invention as a binding member for the oxidative dyeing of keratin fibers, and in particular human keratin fibers, such as hair.

The invention also provides a composition for the oxidative dyeing of keratin fibers, in particular human keratin fibers, such as hair, characterized in that it contains at least one compound of formula I in accordance with the invention in an environment suitable for dyeing. The compound or compounds of formula I according to the invention and / or its or their addition salt or acid addition salts represent or represent preferably from about 0.0005% to 12% of the total weight of the coloring composition and more preferably from about 0.005% to 5%. % of the total weight of the preparation.

In accordance with a preferred embodiment of the invention, the coloring composition additionally comprises one or more oxidizing bases commonly used in oxidative dyeing, such as, for example, para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases. Examples of para-phenylenediamines include para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para -phenylenediamine, 2,5-dimethyl-paraphenylenediamine, N, N-dimethyl-para-phenylenediamine, Ν, Ν-diethyl-para-phenylenediamine, N, N-dipropyl-para-phenylenediamine, 4-amino-N, N-diethyl-3 -methylaniline, N, N-bis (β-hydroxyethyl) para-phenylenediamine, 4- N, N-bis (β-hydroxyethyl) amino-2-methylaniline, 4- N, N-bis (β-hydroxyethyl) amino -2 -chloroaniline, 2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (β-hydroxypropyl) - para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N , N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-N- (Phydroxyethyl) - para-phenylenediamine, Ν- (β, γ-dihydroxypropyl) -para-phenylenediamine, N- (4'-aminophenyl) -para -phenylenediamine, N-phenyl-para-phenylenediamine, 2-β-hydroxyethyloxy-paraphenylenediamine, 2-p-acetylaminoethyloxy-para-phenylenediamine, N- (β-methoxyethoxy) hyl) - Paraphenylenediamine and their acid addition salts.

Among the aforementioned para-phenylenediamines, particularly preferred is para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2β-hydroxy-ethyloxy-para-phenylenediamine, 2,6- dimethyl-para-phenylenediamine, 2,6-diethyl-paraphenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis (β-hydroxyethyl) -para-phenylenediamine, 2-chloro-para-phenylenediamine, 2-P acetylaminoethyloxy-para-phenylenediamine and their acid addition salts.

····

Bisphenylalkylenediamines include, but are not limited to, Ν, Ν'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diaminopropanol, N, N'-bis (β-hydroxyethyl) -N , N'-bis (4'-amino phenyl) ethylenediamine, N, N'-bis (4'-aminophenyl) tetramethylenediamine, N, N'-bis (p-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-diaminophenoxy) -3,5-dioxaoctane and their acid addition salts.

Particular mention may be made of para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino2 (β-hydroxyethylaminomethyl) phenol, 4-amino-2-fluorophenol and their acid addition salts. Among the ortho-aminophenols, mention may be made in particular of 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-aminophenol and their acid addition salts.

Among heterocyclic bases, mention may be made, for example, of compounds derived from pyridine, pyrimidine and pyrazole.

Among pyridine-derived substances, mention may be made, for example, of the compounds described, for example, in GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine,

2- (4-methoxyphenyl) amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2- (p-methoxyethyl) amino-3-amino-6-methoxypyridine, 3,4-diaminopyridine and their addition salts with acid. Among the pyrimidine-derived compounds, mention may be made in particular of the compounds described, for example, in German patent DE 2 359 399 or Japanese patents JP 88-169 571 and JP 91-10659 or in patent application WO 96/15765, such as 2,4,5,6 -tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and pyrazolopyrimidine-derived substances, such as those disclosed in patent application FR-A-2 750 048, of which pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5-dimethylpyrazolo [1,5a] pyrimidine may be mentioned -3,7-diamine, pyrazolo [1,5-a] pyrimidine-3-5-diamine, 2,7-dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine, 3-aminopyrazolo [1,5] -a] pyrimidin-7-ol, 3-aminopyrazolo [1,5-a] pyrimidin-5-ol, 2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol, 2 - [( 3-Aminopyrazolo [1,5a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol, 2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol, 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5, N7, N7-tetramethylpyrazolo [1,5-a] pyrimidine-3,7-diamine and their other salts and tautomers, if any, and their acid addition salts.

Among the pyrazole-derived compounds, mention may be made in particular of the compounds described in the patents

DE 3,843,892, DE 4,133,957 and in patent applications WO 94/08969, WO 94/08970, FRA-2 733 749 and DE 195 43 988, such as 4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1- methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tertbutyl-1-methylpyrazole, 4,5- diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1 (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1 -ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl -1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4 , 5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4- (β-hydroxyethyl) amino-1-meth hylpyrazole and their acid addition salts.

When used, these oxidation bases preferably comprise from about 0.0005% to 12% of the total weight of the coloring composition, more preferably from about 0.0005% to 6% of the total weight of the composition.

In addition to the compounds of formula I, cf. supra, the coloring compositions of the present invention may contain one or more additional binding members that are commonly used in oxidative dyeing, and may include meta-phenylenediamines and heterocyclic binders such as indole, indoline, pyridine and pyrazolone derivatives and their acid addition salts.

Such binding members are, in particular, 2-methyl-5-aminophenol, 5-N- (p-hydroxyethyl) amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro, 3-dihydroxybenzene, 2,4-diamino-1- (P-hydroxyethyloxy) -benzene, 2-amino-4- (Phydroxyethylamino) -1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis (2,4 -diaminophenoxy) propane, sesamol, α-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one , 1-phenyl-3-methylpyrazol-5-one, and their acid addition salts.

• · ·

If present, these binding members preferably comprise from about 0.0001% to 10% of the total weight of the coloring composition, and more preferably from about 0.005% to 5% of the total weight of the coloring composition.

Generally speaking, acid addition salts that can be used in the coloring compositions of the present invention (compositions of Formula I, oxidizing bases and other binding members) are primarily hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates and acetates.

The dye (or vehicle) suitable for dyeing usually consists of water, or a mixture of water with at least one organic diluent, to dissolve compounds that would not be sufficiently soluble in water. These organic diluents may be, for example, C1-C4 lower alkanols, for example ethanol and isopropanol, glycerol, glycols and glycol ethers, for example 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monomethyl ether, and aromatic alcohols such as benzyl alcohol or phenoxyethanol mixtures.

The diluents may be present in the coloring composition in amounts of between about 1% and 40% of its total weight, more preferably between about 5% and 30%.

The pH of the dye composition of the present invention is generally between about 3 and 12, more preferably between about 5 and 11. It can be adjusted to the desired value using suitable pH adjusting agents commonly used in dyeing keratin fibers. Among the acidifying agents which may be mentioned are, for example, mineral acids or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid and lactic and sulphate acids.

Among these acid-enhancing agents are, for example, ammonia, alkali metal carbonates, alkanolamines such as mono-, di- and triethanolamines and derivatives thereof, sodium hydroxide or potassium hydroxide, and compounds of formula V, cf. below:

r \ -W-N /

R ₁₂ (A)

..............

wherein W is a propylene radical which may be optionally substituted by a hydroxyl group or a C 1 -C ₆ alkyl radical and R 11, R 12, R 13 and R 14, which may be the same or different, represent a hydrogen atom or a C 1 -C 6 alkyl or C 1 -C 6 hydroxyalkyl radical.

The oxidative dye compositions of the present invention may also contain at least one spot color to adjust their shades or enrich them with gloss.

The dye compositions of the present invention may also contain various adjuvants commonly used in hair dye products such as anionic, cationic, anionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, anionic, amphoteric or zwitterionic polymers or mixtures thereof , mineral or organic thickeners, antioxidants, penetrants, sequestrants, perfumes, buffers, dispersants and conditioners such as volatile or non-volatile silicones, film formers, ceramides, and preservatives.

Of course, those skilled in the art will select such additive compounds so that the desired properties of the oxidative dye compositions of the present invention are not, at least not significantly negatively affected, by these supplements.

The dye compositions of the present invention may be presented in a variety of forms, for example, in the form of liquids, creams, gels or any other form suitable for dyeing keratin fibers, and in particular human hair.

The invention also provides a method for oxidative dyeing of keratin fibers, and in particular human keratin fibers, such as hair, using the dye preparations described above.

According to this method, at least one coloring agent as defined above is applied to the fibers, wherein the color is expressed at an acidic, neutral or basic pH, with the aid of an oxidizing agent which is added to the coloring composition at the time of use or is part of the oxidizing agent. which is applied simultaneously or sequentially.

According to a preferred use of the staining method of the present invention, the staining composition described above should be mixed at the time of use with an oxidizing composition comprising at least one oxidizing agent which is in a suitable medium in amounts suitable for staining. The resulting mixture is then applied to the keratin fibers and allowed to act for about 3 to 50 minutes, more preferably for about 5 to 30 minutes, after which the fibers are rinsed, washed with shampoo, rinsed again and dried.

The oxidizing agent may be commonly used for the oxidative dyeing of keratin fibers such as hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and enzymes such as peroxidases, laccainases and dual electron oxidoreductases. Most preferred is hydrogen peroxide.

The pH of the oxidizing agent composition as described above is such that upon mixing with the coloring agent, the pH of the resulting composition, which is applied to the keratin fibers, is between about 3 and 12, more preferably between about 5 and 11. the intended value is adjusted with the pH-modifying agents mentioned above, which are commonly used in dyeing keratin fibers.

The oxidation formulations defined above may also contain a number of excipients commonly used in hair coloring formulations, which are also mentioned above.

The composition which is applied to the kerationic fibers may be presented in various forms, for example in the form of liquids, creams, gels or any other form suitable for coloring keratin fibers, in particular human hair.

The present invention also provides a multi-component coloring device or kit or any other packaging system having two or more compartments, the first comprising a coloring agent as defined above and the second an oxidizing agent as defined above. These devices may be provided with means that allow the resulting composition to be applied to the hair, such as those described in patent FR-2,586,913.

The following examples are intended to illustrate the invention without limiting it.

DETAILED DESCRIPTION OF THE INVENTION

Examples of preparation:

Example 1: Synthesis of 3- (4-hydroxy-1-methyl-1H-indol-5-ylmethyl) -1-methylpyridinium methosulfate

a) Preparation of 1-methyl-5-pyridin-3-ylmethyl-1H-indol-4-ol

500 cm ^{3 of} 2-methyl-2-propanol, 75 g of pyridine-3-carboxaldehyde and 100 g of 1-methyl-1,5,6,7-tetrahydroindol-4-one were charged to a 1 liter reactor equipped with a mechanical stirrer, condenser and thermometer. After stirring for 10 minutes, 157 g of potassium tert-butoxide was added in small portions over fifteen minutes, then the temperature was maintained at 75 ° C for one hour. The mixture was then allowed to cool to room temperature and neutralized (ph = 6) with 20% hydrochloric acid. It was poured into 2 kg of ice water. The precipitate obtained was filtered off with suction, washed with diisopropyl ether, petroleum ether. It was then dried under vacuum at 30 ° C.

This gave 120 g of 1-methyl-5-pyridin-3-ylmethyl-1H-indol-4-ol in 74% yield.

b) Preparation of 3- (4-hydroxy-1-methyl-1H-indol-5-ylmethyl) -1-methylpyridinium methosulfate 95 g of 1-methyl-5-pyridin-3-ylmethyl-1H-indol-4-ol in 500 cm ^{3 of} ethyl acetate and 53 g of dimethyl sulfate were charged to a one liter reactor equipped with a mechanical stirrer, condenser and thermometer. The mixture was refluxed for two hours, then allowed to cool to room temperature and the precipitate collected by filtration. The precipitate was then washed with ethyl acetate and petroleum ether and then dried under vacuum at 30 ° C.

This gave 140 g of 3- (4-hydroxy-1-methyl-1H-indol-5-ylmethyl) -1-methylpyridinium methosulfate in a yield of 96%. This product was then recrystallized from methanol (2.5 cm ³ / g) (yield 80%).

Elemental analysis calculated for C16H17N2O.CH3O4S (MW = 364.42 g) resulted in:

% C H N O WITH Calculated 56.03 5.53 7.69 21.95 8.80 Detected 56.68 5.54 7.63 21.96 8.83

Examples of use:

• ·

Examples 1 to 4 - staining in alkaline medium

The following dye preparations of the present invention (amounts in grams) were prepared:

EXAMPLE 1 2 3 4 3- (4-Hydroxy-1-methyl-1H-indol-5-ylmethyl) -1- methylpyridinium metho sulfate (Binder of Formula I) 1,093 1,093 1,093 1,093 para-aminophenol (oxidation base) 0.327 - - - 2-p-acetylaminoexthoxy-para-phenylenediamine, 2HCl (oxidation base) 0,798 3-methyl-4-aminophenol (oxidation base) 0.369 para-phenylenediamine (oxidation base) 0.327 Conventional Oxidation Vehicle # 1 (*) (*) (*) (*) Demineralized water 100 g 100 g 100 g 100 g

(*) Common staining vehicle # 1:

- 96 ° ethanol 18 g

- 35% aqueous sodium metabisulphite solution 0,68 g

- pentasodium salt of diethylenetriaminepentaacetic acid 1.1 g

- 20% ammonia 10,0 g

All of the above dye preparations were mixed with a 6% hydrogen peroxide solution of spH 3. The resulting mixture was applied to a curl of permanently perfused gray hair, with 90% white hair for 30 minutes. The hair was then rinsed, washed with conventional shampoo, rinsed again and dried.

The shades obtained are shown in the following table:

EXAMPLE Staining pH Achieved shade 1 10 ± 0.2 glossy red 2 10 ± 0.2 blue 3 10 ± 0.2 glossy red 4 10 ± 0.2 dark purple blue

PATENT CLAIMS

Claims (26)

Compounds according to claim 1, characterized in that the cyclic chains of the unsaturated groups Z of formula II are pyrrole, imidazole, pyrazole, oxazole, thiazole or triazole cyclic chains. (1) when the parts of the cyclic chain E, G, J and L simultaneously represent a carbon atom and when the radical Rg is attached to the nitrogen atom of the unsaturated cyclic chain, or Compounds characterized in that they correspond to the general formula I, cf. below, and their acid addition salts: where: R1 is hydrogen, Z, C1-C4 alkyl radical, C1-C4 monohydroxyalkyl radical, C2-C4 polyhydroxyalkyl radical, (C1-C4 alkoxy) -C1-C4 alkyl radical, hydroxy (C1-C4 alkoxy) -C1-C4 alkyl radical, C1-C4 aminoalkyl radical, C1-C4 aminoalkyl radical whose amine is mono- or disubstituted by C1-C4 alkyl radical, acetyl radical, C1-C4 monohydroxyalkyl radical or C2-C4 polyhydroxyalkyl radical, (C1-C4 alkyl) - C 1 -C 4 thioalkyl radical, monohydroxy (C 1 -C 4 alkyl) - C 1 -C 4 thioalkyl radical, polyhydroxy (C 2 -C 4 alkyl) -C 1 -C 4 thioalkyl radical, C 1 -C 4 carboxyalkyl radical, (C 1 -C 4 alkoxy) -C 1 -C 4 a carbonylalkyl radical or a C1-C4 acetylaminoalkyl radical, a C1-C4 cyanoalkyl radical, a C1-C4 trifluoroalkyl radical, a C1-C4 haloalkyl radical, a C1-C4 phosphoalkyl radical or a C1-C4 sulfoalkyl radical, R2 and R3, which may be the same or different, represent hydrogen or halogen o an element, Z, -NH-Z, C 1 -C 4 alkyl radical, carboxyl radical, (C 1 -C 4 alkoxy) carbonyl radical or a form radical, R 4 and R 5, which may be the same or different, represent a hydrogen atom or halogen, Z, -NH-Z, C1-C4 alkyl radical, C1-C4 alkoxy radical, acetylamino radical, C1-C5 monohydroxyalkyl radical, C2-C4 polyhydroxyalkyl radical, (C1-C4 alkoxy) -C1-C4 an alkyl radical, a thiophene radical, a furan radical, a phenyl radical, an aralkyl radical in which the alkyl radical is a C1-C4 radical, a phenyl radical or an aralkyl radical in which the alkyl radical is a C1-C4 radical, each replaced by a halogen atom, C1-C4 alkyl radical, with trifluoromethyl radical, C1-C4 alkoxy radical, an amino radical or an amino radical which is • · · · further mono- or di- substituted by C1 -C4 akylovým radical, (C1-C4 alkyl) -C -C ₄ aminoalkyl radical or a di ( C1-C Z is an unsaturated cationic group according to formulas II and III below and a saturated cationic group of formula IV also below: (RJx N? ' G ' ⁺ , y - (R) _n L - J X '( ^R 10) x _ \ / ^E N, - ZG -!>; < (f%) _y (R) 'dl' (lil) -D (R, 0l _x R / N * -R _o (IV) R. where: D is a linker which represents an alkyl chain preferably containing from 1 to 14 carbon atoms, which is linear or branched and may be interrupted by one or more heteroatoms such as oxygen, sulfur or nitrogen and which may be substituted by one or more hydroxyl or C1- C 8 alkoxy radicals and may have one or more ketone functional groups, the components of the cyclic chain E, G, J, L and M, which are the same or different, represent a carbon, oxygen, sulfur or nitrogen atom, n is an integer from 0 to 4 inclusive, m is an integer from 0 to 5 inclusive, R radicals which are the same or different may represent Z, halogen, hydroxyl, C 1 -C 6 alkyl radical, C 1 -C 6 monohydroxyalkyl radical, C 2 -C 6 polyhydroxyalkyl radical, nitroradical, cyanoradical, C 1 -C 6 cyanoalkyl radical, C 1 -C 6 alkoxy radical, tri (C 1 -C 6 alkyl) • silyl-C 1 -C ₆ alkyl radical, amide radical, aldehyde radical, carboxyl radical, C 1 -C 6 alkylcarbonyl radical, thioradical, C 1 -C 6 thioalkyl radical, (C 1 -C ₆ alkyl) thioradical, amine radical, protected (C 1 -C 6 alkyl) radical a carbonyl, carbamyl or (C 1 -C 6 alkyl) sulfonyl radical, an NHR or NRR ' _{5 group} wherein R and R "', which may be the same or different, represent a C 1 -C 6 alkyl radical, a C 1 -C ₆ monohydroxyalkyl radical or C ₂ C6 polyhydroxyalkyl radical, Rg represents a C alkyl radical CD, CD C monohydroxyalkyl radical, C ₂ -C ₆ polyhydroxyalkyl radical, a C-Co kynoalkylový radical, a tri (Cl-Co alkyl) silyl-Ci-C6 alkyl radical, a (C (C 6 alkoxy) - C 1 -C 6 alkyl radical, C 1 -C 6, carbamylalkyl radical, (C 1 -C 6 alkyl) - C 1 -C ₆ carboxyalkyl radical, benzyl radical or a group of the formulas II, III or IV, cf. above, R 7, R 8 and R 9, which may be the same or different, represent a C ₁ -C ₆ alkyl radical, a C ₁ -C ₆ monohydroxy alkyl radical, a C ₂ -C ₆ polyhydroxy alkyl radical, a (C 1 -C 6 alkoxy) -C 1 -C 6 alkyl radical , C 1 -C 6 cyanoalkyl radical, aryl radical, benzyl radical, C 1 -C 6 amidoalkyl radical, tri (C 1 -C 6 alkyl) silyl-C 1 -C 6 alkyl radical or C 1 -C 6 aminoalkyl radical whose amine is protected (C 1 -C 6 alkyl) carbonyl, carbamyl or (C 1 -C 6 alkyl) sulfonyl radical, wherein two of the radicals R 7, R 8 and R 9 may also, together with the nitrogen atom to which they are attached, form a 5 or 6 membered saturated carbon-containing cyclic chain or one or more heteroatoms, which may be unsubstituted or substituted by a halogen element, a hydroxyl radical, a C 1 -C 6 alkyl radical, a C 1 -C 6 monohydroxyalkyl radical, a C ₂ C 6 polyhydroxyalkyl radical, a nitroradical, cyan an oradical, a C 1 -C 6 cyanoalkyl radical, a C 1 -C 6 alkoxy radical, a tri (C 1 -C 6 alkyl) silyl-C 1 -C 6 alkyl radical, an amide radical, an aldehyde radical, a carboxyl radical, a C 1 -C 6 ketoalkyl radical, a C 1 -C 6 a radical, (C 1 -C 6 alkyl) thioradical, amine radical or amine radical protected with a (C 1 -C 6 alkyl) carbonyl, carbamyl or (C 1 -C 6 alkyl) sulfonyl radical, one of the radicals R 7, R 8 and R 9 may also represent a second group Z, which may be the same or different from the first group Z, R 10 is a C 1 -C 6 alkyl radical, a C 1 -C 6 monohydroxyalkyl radical, a C 2 -C 6 polyhydroxyalkyl radical, an aryl radical, a benzyl radical, a C 1 -C 6 aminoalkyl radical or a C 1 -C 6 aminoalkyl radical, whose amine is protected (C 1 -C 6 alkyl) · · · »· ♦ · · · · · · · · · · · Ci Ci · Ci Ci Ci · ······ · · · Carbonyl, carbamyl or (C 1 -C 6 alkyl) sulfonyl radical, C 1 -C 6 carboxyalkyl radical, C 1 -C ₆ cyanoalkyl radical, C] -C ₆ carbamylalkyl, C 1 -C 6 trifluoroalkyl radical, tri (C 1 -C ₆ alkyl) silyl-C 1 -C 6 alkyl radical, C 1 -C 6 sulfonamidoalkyl radical, (C 1 -C 6 alkyl) carboxy-C 1 -C ₆ alkyl radical , (C 1 -C 6 alkyl) sulfinyl-C 1 -C 6 alkyl radical, (C 1 -C 6 alkyl) sulfonyl- C 1 -C 6 alkyl radical, (C 1 -C 6 alkyl) keto-C 1 -C 6 alkyl radical, N (C 1 -C 6 alkyl) ) carbamyl-C1- _C6 alkyl radical or N- (C1-C6 alkyl) sulfonamido-C1-C6 alkyl radical, x and y are integers equal to 0 or 1, under the following conditions: in unsaturated cationic groups of formula II: - if x is equal to 0, the linker D is attached to a nitrogen atom, - if x is equal to 1, the linker D is attached to one of the parts of the cyclic chain E, G, J or L, - y can only be 1: - [2- (4-hydroxy-1-methyl-1H-indol-3-yl) ethyl] trimethylammonium methosulfate, - [2- (4-hydroxy-1H-indol-3-yl) ethyl] trimethylammonium methosulfate, Compounds according to claim 1, characterized in that the cyclic chains of the unsaturated groups Z of formula III are pyridine, pyrimidine, pyrazine, oxazine and triazine chains. (2) when at least one of the cyclic chain moieties E, G, J and L represents a nitrogen atom to which the radical Rg is attached, - in unsaturated cationic groups of formula III: if x is equal to 0, linker D is attached to the nitrogen atom, if x is equal to 1 linker D is attached to one of the parts of the cyclic chain E, G, J, L, or M, - y may only have a value of 1 if at least one of the components of the cyclic chain E, G, J, L and M represents a divalent atom and when the R 6 radical is attached to the unsaturated cyclic nitrogen atom in the cationic groups of formula IV: when x is 0, the linker D is attached to the nitrogen atom which carries the radicals R7 to R9, - if x is 1, two of the radicals R 7 to R 9 together with the nitrogen atom to which they are attached form a five or six membered saturated cyclic chain as defined above and the linker D is attached to the carbon atom of said unsaturated cyclic chain X represents a monovalent or divalent anion, provided that: the amount of cationic groups Z of formula II, III or IV is at least 1 - {3 - [(4-hydroxy-1H-indole-6-carbonyl) amino] propyl} trimethylammonium monochloride, - {3 - [(4-hydroxy-1-methyl-1H-indole-6-carbonyl) amino] propyl} trimethylammonium monochloride, and their acid addition salts. -3- {3 - [(4-hydroxy-1,5-dimethyl-1H-indole-2-carbonyl) amino] propyl} -1-methyl-3Himidazol-1-ium methosulfate, -3- {3 - [(4-hydroxy-5-methyl-1H-indole-2-carbonyl) amino] propyl} -1-methyl-3H-imidazole-1-ium methosulfate, -3- {3 - [(4-hydroxy-1-methyl-1H-indole-2-carbonyl) amino] propyl} -1-methyl-3H-imidazol-1-ium methosulfate, -3- {3 - [(4-Hydroxy-1H-indole-2-carbonyl) amino] propyl} -1-methyl-3H-imidazol-1 -ium methosulfate, - {3 - [(4-hydroxy-1,5-dimethyl-1H-indole-2-carbonyl) amino] propyl} trimethylammonium methosulfate, - {3 - [(4-hydroxy-5-methyl-1H-indole-2-carbonyl) amino] propyl} trimethylammonium methosulfate, - {3 - [(4-hydroxy-1H-indole-2-carbonyl) amino] propyl} trimethylammonium methosulfate, {3 - [(4-hydroxy-1-methyl-1H-indole-2-carbonyl) amino] propyl} trimethylammonium methosulfate, - 3- [3- (5-Benzyl-4-hydroxylindol-1-yl) propyl] -1-methyl-3H-imidazol-1-ium methosulfate, - 3- [4-hydroxy-5- (1-methylpyridinium) -3-ylmethylindol-1-ylmethyl] -1-methylpyridinium dimethosulphate, - 3- [3- (4-hydroxy-5- (1-methylpyridinium) -5-ylmethylindol-1-yl) propyl] -1-methylimidazol-1-ium dimethosulfate, - 3- [3- (4-hydroxy-5- (1-methylpyridinium) -4-ylmethylindol-1-yl) propyl] -1-methylimidazol-1-ol dimethosulfate, - 3- (4-hydroxy-1-methyl-1H-indol-5-ylmethyl) -1-methylpyridinium methosulfate, Compounds according to any one of the preceding claims, characterized in that two of the radicals R 7, R 8 and R 9 form a pyrrolidine ring, a piperidine ring, a piperazine ring or a morpholine ring, which ring may be unsubstituted or substituted by an atom. a halogen element, a hydroxyl radical, a C 1 -C 6 alkyl radical, a C 1 -C 6 monohydroxyalkyl radical, a C 2 -C 6 polyhydroxyalkyl radical, a nitroradical, a cyanoradical, a C 1 -C 6 cyanoalkyl radical, a C 1 -C 6 alkoxy radical, a C 1 -C 6 alkoxy radical, -C 6 alkyl radical, amide radical, aldehyde radical, carboxyl radical, C 1 -C 6 alkylcarbonyl radical, thioradical, C 1 -C 6 thioalkyl radical, (C 1 -C 6 alkyl) thioradical, amine radical or amino (C 1 -C 6 alkyl) radical ₍ Alkyl) carbonyl, carbamyl or (C 1 -C 6 alkyl) sulfone yl radical. - (4-hydroxy-1H-indol-3-ylmethyl) trimethylammonium methosulfate, - (4-hydroxy-1-methyl-1H-indol-3-ylmethyl) trimethylammonium methosulfate, -4- (4-hydroxy-1- (2-hydroxyethyl) -1H-indol-5-ylmethyl) -1-methylpyridinium methosulfate; 9 9 » - 4- (4-hydroxy-1-methyl-1H-indol-5-ylmethyl) -1-methylpyridinium methosulfate, Compounds according to any one of the preceding claims, characterized in that X is a halogen atom, hydroxide, hydrogen sulphate or C 1 -C 6, alkyl sulphate. Compounds according to any one of the preceding claims, characterized in that they are: Compounds according to any one of the preceding claims, characterized in that the acid addition salts are hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates and acetates. «· Use of compounds according to formula I as defined in any one of claims 1 to 7 as a binding member for the oxidative dyeing of keratin fibers, in particular human keratin fibers, such as hair. A composition for the oxidative dyeing of keratin fibers, in particular human keratin fibers, such as hair, comprising, in a medium suitable for dyeing, at least one compound of formula I as defined in any one of claims 1 to 7 . The composition of claim 9, wherein the compound or compounds of formula I represents or represent from 0.0005% to 12% of the total weight of the coloring composition. 9 9 9 9 * ♦ e · · · ♦ · · · · 9 9 9 9 999999 99 9 · 9 9 9 The composition of claim 9, wherein the compound or compounds of formula I represents or represent from 0.005% to 6% of the total weight of the coloring composition. Composition according to any one of claims 9 to 11, characterized in that it contains one or more oxidizing bases which are para-phenylenediamines, bisphenylalkylenediamines, paraaminophenols, ortho-aminophenols and heterocyclic bases. A composition according to claim 12, wherein the para-phenylenediamines are paraphenylenediamines, para-tolylenediamines, 2-chloro-para-phenylenediamines, 2,3-dimethyl-paraphenylenediamines, 2,6-dimethyl-para-phenylenediamines, 6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, Ν, Ν-dimethyl-para-phenylenediamine, N, N-diethyl-paraphenylenediamine, Ν, Ν-dipropyl-para-phenylenediamine, 4-amino- N, N-diethyl-3-methylaniline, N, N-bis (p-hydroxyethyl) para-phenylenediamine, 4-N, N-bis (p-hydroxyethyl) amino-2-methylaniline, 4- N, N-bis (P-hydroxyethyl) amino-2-chloroaniline, 2-P-hydroxyethyl-paraphenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (P-hydroxypropyl) -a-phenylenediamine, 2-hydroxymethyl - para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-N- (β-hydroxyethyl) - para-phenylenediamine, N- (4'-aminophenyl) -para-phenylenediamine, N-phenyl-paraphenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2-β-ac ethyl-aminoethyloxy-xypara-phenylenediamine, N- (p-methoxyethyl) para-phenylenediamine and their acid addition salts. A composition according to claim 12, wherein the bisphenylalkylenediamines are Ν, Ν'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diaminopropanol, Ν, Ν'- bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, Ν, Ν'-bis (4'-aminophenyl) tetramethylenediamine, Ν, Ν'-bis (β-hydroxyethyl) -N, N '-bis (4'-aminophenyl) tetramethylenediamine, Ν, Ν'-bis (4'-methylaminophenyl) tetramethylenediamine, Ν, Ν'-bis (ethyl) - Ν, Ν'bis (4'-amino-3'-methylphenyl) ) ethylenediamine, 1,8-bis (2,5-diaminophenoxy) -3,5-dioxaoctane and their acid addition salts. A composition according to claim 12, wherein the para-aminophenols are para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2 (β-hydroxyethylaminomethyl) phenol, 4-amino-2-fluorophenol and their acid addition salts. 15. A composition according to claim 12, wherein the ortho-amino phenols are 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-aminophenol and their acid addition salts. . The composition of claim 12, wherein the heterocyclic bases are derived from pyridine, pyrimidine and pyrazole. Composition according to any one of claims 12 to 17, characterized in that the oxidation base represents or represents from 0.0005% to 12% of the total weight of the coloring composition. The composition of claim 18, wherein the oxidation base represents, or represents, from 0.005% to 6% of the total weight of the coloring composition. • · · · • · · A composition according to any one of claims 9 to 19 comprising one or more binding members which are meta-phenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic linkers. 20. The composition of claim 20, wherein the binding members are 2-methyl-5-aminophenol, 5-N- (p-hydroxyethyl) amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3- dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1- (β-hydroxyethyloxy) -benzene, 2-amino-4- (β-hydroxyethylamino) -1-methoxy-benzene, 1,3-diaminobenzene, 1,3-bis (2,4-diaminophenoxy) propane, sesamol, α-naphthol, 6-hydroxy-indole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy- 4-methylpyridine, 1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, and acid addition salts thereof. The composition of claim 20 or 21, wherein the binding member or members represent or represent from about 0.0001% to 10% of the total weight of the colorant. The composition of claims 20 or 21, wherein the binding member or members represent or represent from about 0.005% to 5% of the total weight of the colorant. Composition according to any one of claims 9 to 23, characterized in that the acid addition salts are hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates and acetates. A method of dyeing keratin fibers, in particular human keratin fibers, such as hair, characterized in that at least one dye composition as defined in any one of claims 9 to 24 is applied to said fibers and in that the color is transferred at an acidic, neutral or a basic pH by means of an oxidizing agent which is added to the coloring agent at the time of its use, or which is part of the oxidizing agent, which is applied simultaneously or sequentially and separately. • · • · The method of claim 25, wherein the oxidizing agent is hydrogen peroxide, urea peroxide, alkali metal bromate, persulfate such as perborate or persulfate, and an enzyme such as peroxidase, lactase or dual electron oxidoreductase. A multi-compartment coloring device or kit, wherein the first compartment comprises a coloring composition as defined in any one of claims 9-24 and the second compartment comprises an oxidizing agent.