Use for dyeing keratin fibers of a compound of azomethine type bearing a quinoline-derived unit

Abstract

The invention relates to a compound chosen from the compounds of formula (I) below, the optical and geometrical isomers thereof and the tautomers thereof, and also the addition salts thereof with an acid or a base, and the solvates thereof: (I). The invention also relates to the use of these particular compounds and the compositions for dyeing keratin fibers. ##STR00001##

Claims

1. A compound of formula (I) below, an optical isomer thereof, a geometrical isomer thereof, a tautomer thereof, a salt thereof with an acid or a base, or a solvate thereof: ##STR00013## wherein: n represents an integer equal to 0, wherein positions not substituted with a radical R.sub.3 carry a hydrogen atom, R.sub.1 and R.sub.2 represent a hydrogen atom, R.sub.3 represents: a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; K represents a radical corresponding to general formulae (II) to (IV) below: ##STR00014## wherein: m represents an integer equal to 0, 1, 2, 3 or 4, wherein positions not substituted with a radical R.sub.4 carry a hydrogen atom, m′ represents an integer equal to 0, 1, 2, 3 or 4, wherein positions not substituted with a radical R′.sub.4 carry a hydrogen atom, p represents an integer equal to 0, 1, 2, 3 or 4, R.sub.4 represents: a linear or branched C.sub.1-C.sub.6 alkyl radical optionally substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; a linear or branched C.sub.1-C.sub.6 alkoxy radical optionally substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; a halide, R′.sub.4 represents: a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; a linear or branched C.sub.1-C.sub.6 alkoxy radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; a halide, R.sub.5 represents: a hydrogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; a linear or branched C.sub.1-C.sub.6 alkoxy radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−, a halide, a hydroxyl radical, a radical —NR.sub.7R.sub.8, wherein R.sub.7 and R.sub.8 independently represent a hydrogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; R.sub.7 and R.sub.8 may form, together with the nitrogen to which they are attached, a cationic or non-cationic, 4- to 7-membered, heterocycle which may contain one or more nitrogen, oxygen or sulfur atoms and which may itself be substituted with one or more radicals, which may be identical or different, selected from hydroxyl, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino, C.sub.1-C.sub.6 di(hydroxy)alkylamino C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium, C.sub.1-C.sub.6 alkylimidazolium, C.sub.1-C.sub.6 alkylpyridinium or linear or branched C.sub.1-C.sub.6 alkyl, R.sub.6 represents: a hydrogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−, a linear or branched C.sub.1-C.sub.6 alkoxy radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−, a halide, a hydroxyl radical, a radical —NR.sub.9R.sub.10, wherein R.sub.9 and R.sub.10 independently represent a hydrogen atom a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, C.sub.1-C.sub.6 alkylpiperidinium An.sup.−, or linear or branched C.sub.1-C.sub.6 alkyl R.sub.9 and R.sub.10 may form, together with the nitrogen to which they are attached, a cationic or non-cationic, 4- to 7-membered. non-aromatic heterocycle which may contain one or more nitrogen, oxygen or sulfur atoms and which may itself be substituted with one or more radicals, which may be identical or different, selected from hydroxyl, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino, C.sub.1-C.sub.6 di(hydroxy)alkylamino C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium, C.sub.1-C.sub.6 alkylimidazolium, C.sub.1-C.sub.6 alkylpyridinium or linear or branched C.sub.1-C.sub.6 alkyl, X represents: a hydroxyl radical, a linear or branched C.sub.1-C.sub.6 alkoxy radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; a radical —NR.sub.11R.sub.12, wherein R.sub.11 and R.sub.12 independently represent a hydrogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, linear or branched C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−, R.sub.11 and R.sub.12 may form, together with the nitrogen to which they are attached, a cationic or non-cationic, 4- to 7-membered, non-aromatic heterocycle which may contain one or more nitrogen, oxygen or sulfur atoms and which may itself be substituted with one or more radicals, which may be identical or different, selected from hydroxyl, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino, C.sub.1-C.sub.6 di(hydroxy)alkylamino C.sub.1-C.sub.6 alkoxy C.sub.1-C.sub.6 tri(hydroxy)alkylammonium, C.sub.1-C.sub.6 alkylimidazolium, C.sub.1-C.sub.6 alkylpyridinium or linear or branched C.sub.1-C.sub.6 alkyl, wherein when the compound of formula (I) is positively charged, then it comprises as many anionic counterion(s) An.sup.− as cationic charge(s) to achieve the electrical neutrality of the molecule.

2. The compound as claimed in claim 1, wherein R.sub.4 represents a linear or branched C1-C6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−.

3. The compound as claimed in claim 1, wherein R.sub.4 represents a linear or branched C.sub.1-C.sub.6 .

4. The compound as claimed in claim 1, wherein R′.sub.4 represents: a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino, or di(hydroxy)alkylamino, a linear or branched C.sub.1-C.sub.6 alkoxy radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino, or di(hydroxy)alkylamino; a halide.

5. The compound as claimed in claim 1, wherein R.sub.5 represents a radical −NR.sub.7R.sub.8wherein R7 and R8 independently denote: a hydrogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, C.sub.1-C.sub.6 alkylpiperidinium An.sup.−.

6. The compound as claimed in claim 1, wherein R.sub.5 represents a radical —NR.sub.7R.sub.8 wherein R.sub.7 and R.sub.8 denote a hydrogen atom.

7. The compound as claimed in claim 1, wherein R.sub.6 represents a radical —NR.sub.9R.sub.10 wherein R.sub.9 and R.sub.10 form, together with the nitrogen to which they are attached, a cationic or non-cationic, 4- to 7-membered, non-aromatic heterocycle which may contain one or more nitrogen, oxygen or sulfur atoms and which may itself be substituted with one or more radicals, which may be identical or different, selected from hydroxyl, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino, C.sub.1-C.sub.6 di(hydroxy)alkylamino C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium, C.sub.1-C.sub.6 alkylimidazolium, C.sub.1-C.sub.6 alkylpyridinium, or linear or branched C.sub.1-C.sub.6 alkyl.

8. The compound as claimed in claim 1, wherein R.sub.6 represents a linear or branched C.sub.1-C.sub.6 alkoxy radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−.

9. The compound as claimed in claim 1, wherein X denotes a radical —NR.sub.11R.sub.12 wherein R.sub.11 and R.sub.12 denote: a hydrogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, linear or branched C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkylimidazole, or C.sub.1-C.sub.6 alkylimidazolium An.sup.−.

10. The compound as claimed in claim 1, wherein R.sub.11 and R.sub.12 independently represent a hydrogen atom, a hydroxyethyl radical, an ethyl radical, an isopropyl radical, or a methyl substituted propvlimidazolium An− radical.

11. The compound as claimed in claim 1, wherein X represents a radical —NR.sub.11R.sub.12 wherein R.sub.11 and R.sub.12 form, together with the nitrogen to which they are attached, a cationic or non-cationic. 4- to 7-memberednon-aromatic heterocycle which may contain one or more nitrogen, oxygen or sulfur atoms, and which may itself be substituted with one or more radicals, which may be identical or different, seelcted from hydroxyl, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino, C.sub.1-C.sub.6 di(hydroxy)alkylamino C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium, alkylimidazolium, or C.sub.1-C.sub.6 alkylpyridinium or linear or branched C.sub.1-C.sub.6 alkyl.

12. The compound as claimed in claim 1, wherein X represents a radical −NR.sub.11R.sub.12 wherein R.sub.11 and R12 form, together with the nitrogen to which they are attached, a cationic or non-cationicnon-aromatic heterocycle which may contain one or two nitrogen atoms and which may itself be substituted with one or more radicals, which may be identical or different, selected from hydroxyl, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino, C.sub.1-C.sub.6 di(hydroxy)alkylamino C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium, or linear or branched C.sub.1-C.sub.6 alkyl.

13. The compound as claimed in claim 1, wherein X denotes a hydroxyl radical.

14. The compound as claimed in claim 1, wherein the compound is selected from the formulas below: ##STR00015## ##STR00016## ##STR00017## or salts, isomers, tautomers, orsolvates thereof.

15. A composition for dyeing keratin fibers comprising, in a medium that is suitable for dyeing keratin fibers, one or more compounds of formula (I) below, an optical isomer. a geometrical isomer or a tautomer thereof, a salt thereof with an acid or a base, or a solvate thereof: ##STR00018## wherein: n represents an integer equal to 0, wherein positions not substituted with a radical R.sub.3 carry a hydrogen atom, R.sub.1 and R.sub.2 represent a hydrogen atom R.sub.3 represents: a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; K represents a radical corresponding to general formulae (II) to (IV) below: ##STR00019## wherein: m represents an integer equal to 0, 1, 2, 3 or 4, wherein positions not substituted with a radical R.sub.4 carry a hydrogen atom, m′ represents an integer equal to 0, 1, 2, 3 or 4, wherein positions not substituted with a radical R′.sub.4 carry a hydrogen atom, p represents an integer equal to 0, 1, 2, 3 or 4, R.sub.4 represents: a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; a linear or branched C.sub.1-C.sub.6 alkoxy radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; a halide, R′.sub.4 represents: a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; a linear or branched C.sub.1-C.sub.6 alkoxy radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; a halide, R.sub.5 represents: a hydrogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; a linear or branched C.sub.1-C.sub.6 alkoxy radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−, a halide, a hydroxyl radical, a radical —NR.sub.7R.sub.8, wherein R.sub.7 and R.sub.8 independently represent a hydrogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; R.sub.7 and R.sub.8 may form, together with the nitrogen to which they are attached, a cationic or non-cationic, 4- to 7-membered, heterocycle which may contain one or more nitrogen, oxygen or sulfur atoms and which may itself be substituted with one or more radicals, which may be identical or different, selected from hydroxyl, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino, C.sub.1-C.sub.6 di(hydroxy)alkylamino C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium, C.sub.1-C.sub.6 alkylimidazolium, C.sub.1-C.sub.6 alkylpyridinium, or linear or branched C.sub.1-C.sub.6 alkyl, R.sub.6 represents: a hydrogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−, a linear or branched C.sub.1-C.sub.6 alkoxy radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−, a halide, a hydroxyl radical, a radical —NR.sub.9R.sub.10, wherein R.sub.9 and Rio independently represent a hydrogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, C.sub.1-C.sub.6 alkylpiperidinium An.sup.−, or linear or branched C.sub.1-C.sub.6 alkyl R9 and Rio may form, together with the nitrogen to which they are attached, a cationic or non-cationic, 4- to 7-membered, non-aromatic heterocycle which may contain one or more nitrogen, oxygen or sulfur atoms and which may itself be substituted with one or more radicals. which may be identical or different, selected from hydroxyl, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino, C.sub.1-C.sub.6 di(hydroxy)alkylamino C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium, C.sub.1-C.sub.6 alkylimidazolium, C.sub.1-C.sub.6 alkylpyridinium, or linear or branched C.sub.1-C.sub.6 alkyl, X represents: a hydroxyl radical, a linear or branched C.sub.1-C.sub.6 alkoxy radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; a radical —NR.sub.11R.sub.12, wherein R.sub.11 and R.sub.12 independently represent a hydrogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, linear or branched C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−, R.sub.11 and R12 may form, together with the nitrogen to which they are attached, a cationic or non-cationic, 4- to 7-membered, non-aromatic heterocycle which may contain one or more nitrogen, oxygen or sulfur atoms and which may itself be substituted with one or more radicals, which may be identical or different, selected from hydroxyl, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino, C.sub.1-C.sub.6 di(hydroxy)alkylamino C.sub.1-C.sub.6 alkoxy, tri(hydroxy)alkylammonium, C.sub.1-C.sub.6 alkylimidazolium, C.sub.1-C.sub.6 alkylpyridinium, or linear or branched C.sub.1-C.sub.6 alkyl, wherein when the compound of formula (I) is positively charged, then it comprises as many anionic counterion(s) An.sup.− as cationic charge(s) to achieve the electrical neutrality of the molecule.

16. The composition as claimed in claim 15, comprising one or more oxidizing agents.

17. A process for dyeing keratin fibers, comprising applying to these fibers a composition comprising a compound of formula (I) below, an optical isomer, a geometrical isomer or tautomers thereof, a salt thereof with an acid or a base, or a solvate thereof: ##STR00020## wherein: n represents an integer equal to 0, wherein positions not substituted with a radical R.sub.3 carry a hydrogen atom, R.sub.1 and R.sub.2 represent a hydrogen atom R.sub.3 represents: a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; K represents a radical corresponding to general formulae (II) to (IV) below: ##STR00021## wherein: m represents an integer equal to 0, 1, 2, 3 or 4, wherein positions not substituted with a radical R.sub.4 carry a hydrogen atom, m′ represents an integer equal to 0, 1, 2, 3 or 4, wherein positions not substituted with a radical R′.sub.4 carry a hydrogen atom, p represents an integer equal to 0, 1, 2, 3 or 4, R.sub.4 represents: a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; a linear or branched C.sub.1-C.sub.6 alkoxy radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; a halide, R′.sub.4 represents: a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−, a linear or branched C.sub.1-C.sub.6 alkoxy radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; a halide, R.sub.5 represents: a hydrogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; a linear or branched C.sub.1-C.sub.6 alkoxy radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.-−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−, a halide, a hydroxyl radical, a radical —NR.sub.7R.sub.8, wherein R.sub.7 and R.sub.8 independently represent a hydrogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; R.sub.7 and R.sub.8 may form, together with the nitrogen to which they are attached, a cationic or non-cationic, 4- to 7-membered, heterocycle which may contain one or more nitrogen, oxygen or sulfur atoms and which may itself be substituted with one or more radicals, which may be identical or different, selected from hydroxyl, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino, C.sub.1-C.sub.6 di(hydroxy)alkylamino C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium, C.sub.1-C.sub.6 alkylimidazolium, C.sub.1-C.sub.6 alkylpyridinium, or linear or branched C.sub.1-C.sub.6 alkyl, R.sub.6 represents: a hydrogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−, a linear or branched C.sub.1-C.sub.6 alkoxy radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−, a halide, a hydroxyl radical, a radical —NR.sub.9R.sub.10, wherein R.sub.9 and R.sub.10 independently represent a hydrogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, C.sub.1-C.sub.6 alkylpiperidinium An.sup.−, or linear or branched C.sub.1-C.sub.6 alkyl, R.sub.9 and R.sub.10 may form, together with the nitrogen to which they are attached, a cationic or non-cationic, 4- to 7-membered. non-aromatic heterocycle which may contain one or more nitrogen, oxygen or sulfur atoms and which may itself be substituted with one or more radicals, which may be identical or different, selected from hydroxyl, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino, C.sub.1-C.sub.6 di(hydroxy)alkylamino C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium, C.sub.1-C.sub.6 alkylimidazolium, C.sub.1-C.sub.6 alkylpyridinium, or linear or branched C.sub.1-C.sub.6 alkyl, X represents: a hydroxyl radical, a linear or branched C.sub.1-C.sub.6 alkoxy radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−; a radical —NR.sub.11R.sub.12, wherein R.sub.11 and R.sub.12 independently represent a hydrogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical which may be substituted with one or more radicals, which may be identical or different, selected from hydroxyls, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino or di(hydroxy)alkylamino, linear or branched C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkylimidazole, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium An.sup.−, C.sub.1-C.sub.6 alkylimidazolium An.sup.−, C.sub.1-C.sub.6 alkylpyridinium An.sup.−, or C.sub.1-C.sub.6 alkylpiperidinium An.sup.−, R.sub.11 and R.sub.12 may form, together with the nitrogen to which they are attached, a cationic or non-cationic, 4- to 7-membered, non-aromatic heterocycle which may contain one or more nitrogen, oxygen or sulfur atoms and which may itself be substituted with one or more radicals, which may be identical or different, selected from hydroxyl, amino, C.sub.1-C.sub.6 mono(hydroxy)alkylamino, C.sub.1-C.sub.6 di(hydroxy)alkylamino C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 tri(hydroxy)alkylammonium, C.sub.1-C.sub.6 alkylimidazolium, C.sub.1-C.sub.6 alkylpyridinium, or linear or branched C.sub.1-C.sub.6 alkyl, wherein when the compound of formula (I) is positively charged, then it comprises as many anionic counterion(s) An.sup.− as cationic charge(s) to achieve the electrical neutrality of the molecule.

Description

EXAMPLES

Example 1

Synthesis of 6-[(Z)-4-Amino-2,3-dimethylphenylimino]-2,3,4,6-tetrahydroquinolin-7-ylamine hydrochloride (1)

(1) ##STR00010##

(2) In a 500 ml round-bottomed flask, 9.91 g of 2,3-dimethylbenzene-1,4-diamine dihydrochloride (commercial) (a) and 10.48 g of 1,2,3,4-tetrahydroquinolin-7-ylamine dihydrochloride (commercial) (b) are added to 250 ml of water and the pH is adjusted to 9.5 with 20% aqueous ammonia. After 72 hours of stirring, the gum formed is purified by silica column chromatography.

(3) 2.98 g of product are recovered with a purity of 92%. After washing of the powder with acetonitrile, 2.35 g of 6-[(Z)-4-amino-2,3-dimethylphenylimino]-2,3,4,6-tetrahydroquinolin-7-ylamine (1) are obtained with a purity of 95%.

(4) The NMR and mass analyses are in accordance with the expected structure (1) .

Example 2

Synthesis of 4-{3-[7-Amino-3,4-dihydro-2H-quinolin-(6E)-ylideneamino]pyrazolo[1,5-a]pyridin-2-yl}-1,1-dimethylpiperazin-1-ium chloride (2)

(5) ##STR00011##

(6) 0.722 g of 4-(3-aminopyrazolo [ 1,5-a]pyridin-2-yl)-1,1-dimethylpip erazin-l-ium chloride hydrochloride (described in FR3022454) (c) and 0.502 g of 1,2,3,4-tetrahydroquinolin-7-ylamine dihydrochloride (commercial) (b) are added to 15 ml of water and then the pH is adjusted to 9.5 with 20% aqueous ammonia. After 24 hours of stirring, 100 ml of isopropanol are added and the reaction medium is evaporated to dryness. 20 ml of methanol are added to the resulting powder and, after the insoluble material (ammonium chloride) has been filtered off, the filtrate is concentrated 788 mg of compound (2) are thus obtained in the form of a blue-black powder.

(7) The NMR and mass analyses are in accordance with the expected structure (2) .

Example 3

Synthesis of 3-Amino-2-[7-amino-3,4-dihydro-2H-quinolin-(6E)-ylideneamino]-6,7-dihydro-5 H-pyrazolo[1,2-a]pyrazol-1-one chloride (3)

(8) ##STR00012##
0.288 mmol of 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo [1,2-a] pyrazol-1-one dimethanesulfonate (100 mg, 1 equivalent) (commercial) (d) and 0.288 mmol of 1,2,3,4-tetrahydroquinolin-7-amine dihydrochloride (63.8 mg, 1 equivalent) (commercial) (b) are introduced into a 25 ml round-bottomed flask containing 5 ml of water, 1 ml of 20% aqueous ammonia and 0.5 ml of 6% aqueous hydrogen peroxide. The reaction medium is stirred at ambient temperature for 2 hours and then concentrated in a rotary evaporator so as to give 170 mg of a black solid.

(9) Normal-phase chromatography of the black solid on silica, carried out with an eluent constituted of dichloromethane and methanol, makes it possible to obtain 14.5 mg of (6E)-7-amino-6-[(3-amino-1-oxo-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-2-yl)imino]-2,3,4,6-tetrahydroquinolinium chloride (3) in the form of a black powder with a yield of 16%.

(10) The NMR and mass analyses are in accordance with the expected structure (3) .

Example 4

Dyeing Compositions

(11) The following dye compositions are prepared from the ingredients indicated in the table below:

(12) TABLE-US-00001 Composition 1 Composition 2 Compound 1 (according 500 mg to example 1) Compound 2 (according 500 mg to example 2) water 80 g 80 g ethanol 15 g 15 g Benzyl alcohol  5 g  5 g
1.25 g of each composition 1 and 2 are applied to a lock of 0.25 g of gray hair containing 90% white hairs. After a leave-on time of 30 minutes at ambient temperature, the lock is rinsed, washed with a standard shampoo and then dried.

(13) The colors of the locks thus obtained were evaluated in the CIE L*a*b* system, by means of a Minolta CM-3610d colorimeter , the values being exploited with the Spectra Magix NX software.

(14) In this L*a*b* system, the three parameters denote, respectively, L*: the color intensity, a*: the green/red color axis, and b*: the blue/yellow color axis. For the intensity, the lower the value, the darker and more intense the color.

(15) The variation in coloring or gain in color build-up is the difference in color between the locks of hair treated with the composition according to the invention, and the untreated locks, and is measured by (ΔE) according to the following equation:
ΔE=√{square root over ((L*−L.sub.o*).sup.2+(a*−a.sub.o*).sup.2+(b* −b.sub.o*).sup.2)}
In this equation, L*, a* and b* represent the values measured on NG dyed hair according to the invention, and L.sub.0*, a.sub.0* and b.sub.0* represent the values measured on the untreated locks.

(16) The higher the value of ΔE, the greater the gain in color build-up.

(17) The results are indicated in the table below.

(18) TABLE-US-00002 Composition 1 Composition 2 Color of the locks Blue Blue-green (colorimetric data)   L = 18.87   L = 24.35   a = −1.13   a = −5.75   b = −8.90    b = −13.02 ΔE = 46.96 ΔE = 47.89