SPECIFIC 7-AMINO-1,2,3,4-TETRAHYDROQUINOLINES, METHOD, AND COMPOSITION

Abstract

The present patent application relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising a step of applying to said keratin fibers one or more 7-amino-1,2,3,4-tetrahydroquinoline derivatives substituted in position 8, to dye compositions comprising such 7-amino-1,2,3,4-tetrahydroquinolines, and also to the devices using these compounds.

Claims

1. A process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising at least one step i) of applying to said keratin fibers one or more compounds of formula (I) below, and also the organic or mineral acid or base salts thereof, the tautomeric forms thereof, the optical isomers thereof, the geometrical isomers thereof and/or the solvates thereof such as the hydrates thereof: ##STR00027## in which formula (I): A represents: i) a halogen atom, ii) a carboxyl radical COOH or carboxylate radical COO.sup.M.sup.+, iii) a sulfonic radical SO.sub.3H or sulfonate radical SO.sub.3.sup.M.sup.+, or alkylsulfonyl radical S(O).sub.2R with R representing a linear or branched (C.sub.1-C.sub.4)alkyl group, iv) a group C(R.sub.12)(R.sub.13)R.sub.11 or C(R.sub.12)C(R.sub.1)R.sub.13, in which R.sub.11, R.sub.12 and R.sub.13, which may be identical or different, represent: a hydrogen atom, a halogen atom such as fluorine, chlorine, bromine or iodine, preferably fluorine, a hydroxyl radical, a linear or branched C.sub.1-C.sub.14 alkyl or C.sub.2-C.sub.14 alkenyl, in particular C.sub.1-C.sub.8 alkyl or C.sub.2-C.sub.8 alkenyl, preferably C.sub.1-C.sub.6 alkyl or C.sub.2-C.sub.6 alkenyl group, said alkyl or alkenyl group: optionally interrupted with one or more heteroatoms or groups, which may be identical or different, chosen from O, S, S(O), S(O).sub.2, N(H), N(R), NR, RN and C(X) with X representing an oxygen or sulfur atom or NR and with R representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl, or combinations of said heteroatoms or groups, preferably chosen from: OC(O), C(O)O, C(O)N, NC(O), C(O)N(H), N(H)C(O), N(H)C(O)N(H), OC(O)N(H), N(H)C(O)O, N(H)C(NH)N(H), and/or said alkyl or alkenyl group being optionally substituted with one or more radicals, which may be identical or different, chosen from the following radicals: i) hydroxyl, ii) C.sub.1-C.sub.6 (hydroxy)alkoxy, iii) amino NH.sub.2, iv) C.sub.1-C.sub.6 mono and/or di(hydroxy)alkylamino, v) halo such as fluoro F, vi) sulfonic SO.sub.3H, or sulfonate SO.sub.3-M.sup.+, vii) thiol SH, viii) cationic or noncationic (hetero)cycle, said heterocycle being optionally substituted, in particular optionally substituted with one or more radicals, which may be identical or different, chosen from (hydroxy)(C.sub.1-C.sub.6)alkyl radicals such as methyl, ethyl, propyl or 2-hydroxyethyl, hydroxyl radicals, ammonium radicals N.sup.+RRR, An, with R, R and R, which may be identical or different, representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl; ix) an ammonium radical N.sup.+RRR, An, with R, R and R, which may be identical or different, representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl; or else R.sub.11 forms with R.sub.9, the nitrogen atom which bears R.sub.9 and the carbon atoms which bear N(R.sub.9)R.sub.10 and R.sub.11, a 5- to 8-membered cationic or noncationic heterocycle, said heterocycle being optionally substituted with one or more radicals, which may be identical or different, chosen from the following radicals: i) hydroxyl, ii) C.sub.1-C.sub.4 alkyl, iii) C.sub.1-C.sub.4 alkoxy, and iv) an ammonium radical N.sup.+RRR, An, with R, R and R, which may be identical or different, representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl and at least one of the members of said heterocycle possibly representing a divalent oxo radical (C(O), v) a group WR.sub.14 in which: W represents an oxygen or sulfur atom or a divalent group chosen from: N(R.sub.14),S(O) and S(O).sub.2, R.sub.14 and R.sub.14 independently represent: a hydrogen atom, a linear or branched C.sub.1-C.sub.14 alkyl or C.sub.2-C.sub.14 alkenyl group, in particular C.sub.1-C.sub.8, preferably C.sub.1-C.sub.6, said alkyl or alkenyl group being: optionally interrupted with one or more heteroatoms or groups, which may be identical or different, chosen from O, S, S(O), S(O).sub.2, N(H), N(R), NR, RN and C(X) with X representing an oxygen or sulfur atom or NR and with R representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl, or combinations of said heteroatoms or groups, preferably chosen from: OC(O), C(O)O, C(O)N, NC(O), C(O)N(H), N(H)C(O), N(H)C(O)N(H), OC(O)N(H), N(H)C(O)O, N(H)C(NH)N(H), and/or said alkyl or alkenyl group being optionally substituted with one or more radicals, which may be identical or different, chosen from the following radicals: i) hydroxyl, ii) C.sub.1-C.sub.6 (hydroxy)alkoxy, iii) amino NH.sub.2, iv) C.sub.1-C.sub.6 mono and/or di(hydroxy)alkylamino, v) halo such as fluoro F, vi) sulfonic SO.sub.3H, or sulfonate SO.sub.3-M.sup.+, vii) thiol SH, viii) cationic or noncationic (hetero)cycle, said heterocycle being optionally substituted, in particular optionally substituted with one or more radicals, which may be identical or different, chosen from (hydroxy)(C.sub.1-C.sub.6)alkyl radicals such as methyl, ethyl, propyl or 2-hydroxyethyl, hydroxyl radicals, ammonium radicals N.sup.+RRR, An, with R, R and R, which may be identical or different, representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl; ix) an ammonium radical N.sup.+RRR, An, with R, R and R, which may be identical or different, representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl; or else R.sub.14 forms with R.sub.9, the nitrogen atom which bears R.sub.9 and the carbon atoms which bear N(R.sub.9)(R.sub.10) and W, a 5- to 8-membered cationic or noncationic heterocycle, said heterocycle being optionally substituted with one or more radicals, which may be identical or different, chosen from the following radicals: i) hydroxyl, ii) C.sub.1-C.sub.4 alkyl, iii) C.sub.1-C.sub.4 alkoxy, and iv) an ammonium radical N.sup.+RRR, An, with R, R and R, which may be identical or different, representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl and at least one of the members of said heterocycle possibly representing a divalent oxo radical (C(O.sup.), vi) a radical C(X)R.sub.11, preferably carbonyl C(O)R.sub.11, with R.sub.11 as defined previously, vii) a radical C(X)XR.sub.11, preferably ester C(O)OR.sub.11, thioester C(O)SR.sub.11, dithioester C(S)SR.sub.11, with R.sub.11 as defined previously, XC(X)R.sub.11, preferably amide N(R)C(O)R.sub.11 or XC(X)XR.sub.11, preferably carbamate N(R)C(O)OR.sub.11, with X as defined previously, and X and X, which may be identical or different, represent an oxygen or sulfur atom or a group N(R) with R representing a hydrogen atom or a C.sub.1-C.sub.4 alkyl group; preferably, X represents an oxygen atom and X represents an oxygen or sulfur atom or a group N(R) with R representing a hydrogen atom or a C.sub.1-C.sub.4 alkyl group; viii) an optionally substituted cationic or noncationic (hetero)cycle, ix) an ammonium radical N.sup.+RRR, An.sup., with R, R and R, which may be identical or different, representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl, R.sub.1 represents: a hydrogen atom, a saturated or unsaturated, linear or branched C.sub.1-C.sub.6 alkyl radical, said alkyl radical: optionally comprising one or more heteroatoms or groups, which may be identical or different, chosen from O, S, S(O), S(O).sub.2, N(H), N(R), NR, RN and C(X) with R as defined previously, and with X representing an oxygen or sulfur atom or NR, or combinations of said heteroatoms or groups, preferably chosen from: OC(O), C(O)O, C(O)N(H), N(H)C(O), C(O)N, NC(O), N(H)C(O)N(H), OC(O)N(H), N(H)C(O)O, N(H)C(NH)NH, and/or said alkyl radical being optionally substituted with one or more radicals, which may be identical or different, chosen from the following radicals: i) hydroxyl, ii) C.sub.1-C.sub.6 (hydroxy)alkoxy, iii) amino NH.sub.2, iv) C.sub.1-C.sub.6 mono and/or di(hydroxy)alkylamino, v) cationic or noncationic (hetero)cycle; R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.7, which may be identical or different, represent: a hydrogen atom, a hydroxyl radical, a saturated or unsaturated, linear or branched C.sub.1-C.sub.6 alkyl radical, said alkyl radical: optionally comprising one or more heteroatoms or groups, which may be identical or different, chosen from O, S, S(O), S(O).sub.2, N(H), N(R), NR, RN and C(X) with R as defined previously, and with X representing an oxygen or sulfur atom or NR, or combinations of said heteroatoms or groups, preferably chosen from: OC(O), C(O)O, C(O)N(H), N(H)C(O), C(O)N, NC(O), N(H)C(O)N(H), OC(O)N(H), N(H)C(O)O, N(H)C(NH)NH, and/or said alkyl radical being optionally substituted with one or more radicals, which may be identical or different, chosen from the following radicals: i) hydroxyl, ii) C.sub.1-C.sub.6 (hydroxy)alkoxy, iii) amino NH.sub.2, iv) C.sub.1-C.sub.6 mono and/or di(hydroxy)alkylamino, an aromatic or nonaromatic, saturated or unsaturated, 5- to 8-membered (hetero)cycle, optionally substituted with one or more radicals, which may be identical or different, chosen from the following radicals: i) hydroxyl, ii) C.sub.1-C.sub.6 (hydroxy)alkyl, iii) C.sub.1-C.sub.6 (hydroxy)alkoxy, iii) amino NH.sub.2, iv) C.sub.1-C.sub.6 mono and/or di(hydroxy)alkylamino, and at least one of the members of which may represent a divalent oxo radical; R.sub.8 represents: a hydrogen atom, a halogen atom such as fluorine, chlorine, bromine or iodine, preferably chlorine, fluorine or bromine, a hydroxyl radical, a (C.sub.1-C.sub.8)alkylcarbonyl radical, a saturated or unsaturated, linear or branched C.sub.1-C.sub.8 alkyl radical, said alkyl radical: optionally comprising one or more heteroatoms or groups, which may be identical or different, chosen from O, S, S(O), S(O).sub.2, N(H), N(R), NR, RN and C(X) with R as defined previously, and with X representing an oxygen or sulfur atom or NR, or combinations of said heteroatoms or groups, preferably chosen from: OC(O), C(O)O, C(O)N(H), N(H)C(O), C(O)N, NC(O), N(H)C(O)N(H), OC(O)N(H), N(H)C(O)O, N(H)C(NH)NH, and/or said alkyl radical being optionally substituted with one or more radicals, which may be identical or different, chosen from the following radicals: i) hydroxyl, ii) C.sub.1-C.sub.6 (hydroxy)alkoxy, iii) amino NH.sub.2, iv) C.sub.1-C.sub.6 mono and/or di(hydroxy)alkylamino, v) cationic or noncationic (hetero)cycle; R.sub.9 and R.sub.10, which may be identical or different, represent: a hydrogen atom, a saturated or unsaturated, linear or branched C.sub.1-C.sub.6 alkyl radical, said alkyl radical: optionally comprising one or more heteroatoms or groups, which may be identical or different, chosen from O, S, S(O), S(O).sub.2, N(H), N(R), NR, RN and C(X) with R as defined previously, and with X representing an oxygen or sulfur atom or NR, or combinations of said heteroatoms or groups, preferably chosen from: OC(O), C(O)O, C(O)N(H), N(H)C(O), C(O)N, NC(O), N(H)C(O)N(H), OC(O)N(H), N(H)C(O)O, N(H)C(NH)NH, and/or said alkyl radical being optionally substituted with one or more radicals, which may be identical or different, chosen from the following radicals: i) hydroxyl, ii) C.sub.1-C.sub.6 (hydroxy)alkoxy, iii) amino NH.sub.2, iv) C.sub.1-C.sub.6 mono and/or di(hydroxy)alkylamino, v) cationic or noncationic (hetero)cycle; or R.sub.9 and R.sub.10 form, with the nitrogen atom that bears them, a 5- to 8-membered heterocycle, optionally substituted with one or more radicals, which may be identical or different, chosen from the following radicals: i) hydroxyl, ii) C.sub.1-C.sub.10 (hydroxy)alkyl, iii) C.sub.1-C.sub.6 (hydroxy)alkoxy, iv) amino NH.sub.2, v) C.sub.1-C.sub.4 mono and/or di(hydroxy)alkylamino, vi) thiol SH, vii) C.sub.1-C.sub.4 alkylthiol, viii) carboxyl COOH or carboxylate COO.sup., M.sup.+ ix) C.sub.1-C.sub.4 alkylcarbonyl, x) sulfonic SO.sub.3H or sulfonate SO.sub.3.sup., M.sup.+, xi) amido NHC(O)CH.sub.3, and at least one of the members of said heterocycle possibly representing a divalent oxo radical; An.sup. denotes an anion or a mixture of anions for ensuring the electrical neutrality of the molecule, preferably chosen from halide ions such as bromide or chloride, methyl sulfate or toluenesulfonate ions, or a mixture of these ions; M.sup.+ represents a cation or a mixture of cations for ensuring the electrical neutrality of the molecule, preferably chosen from sodium, potassium, calcium and ammonium.

2. The process as claimed claim 1, characterized in that the ammonium radical N.sup.+RRR according to the definition of the group A is chosen from trimethylammonium, triethylammonium, dimethylethylammonium, diethylmethylammonium, diisopropylmethylammonium, diethylpropylammonium, hydroxyethyldiethylammonium, ,-dihydroxyethylmethylammonium and ,,-trihydroxyethylammonium radicals; preferably from trimethylammonium, triethylammonium, dimethylethylammonium, diethylmethylammonium, diisopropylmethyl ammonium and hydroxyethyldiethylammonium radicals.

3. The process as claimed in claim 1, characterized in that the cationic heterocycle according to the definition of the group A is chosen from imidazoliums, pyridiniums, piperaziniums, pyrrolidiniums, morpholiniums, pyrimidiniums, thiazoliums, benzimidazoliums, benzothiazoliums, oxazoliums, benzotriazoliums, pyrazoliums, triazoliums and benzoxazoliums; preferably from imidazoliums, pyridiniums, piperaziniums, pyrrolidiniums, morpholiniums, pyrimidiniums, thiazoliums and benzimidazoliums, and even more preferentially denotes an imidazolium or a piperazinium.

4. The process as claimed in claim 1, characterized in that the noncationic heterocycle according to the definition of the group A is chosen from imidazoles, pyridines, piperazines, pyrrolidines, morpholines, pyrimidines, thiazoles, benzimidazoles, benzothiazoles, oxazoles, benzotriazoles, pyrazoles, triazoles, benzoxazoles, piperidines, pyrroles and oxazolidinones; preferably from morpholines, piperidines, pyrrolidines, imidazoles, pyrroles, piperazines and 1,3-oxazolidin-2-ones.

5. The process as claimed in claim 1, characterized in that R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.8, which may be identical or different, represent: a hydrogen atom, a saturated or unsaturated, linear or branched C.sub.1-C.sub.6 alkyl radical, said alkyl radical being optionally substituted with one or more radicals, which may be identical or different, chosen from the following radicals: i) hydroxyl, ii) C.sub.1-C.sub.4 alkoxy, iii) amino NH.sub.2, iv) C.sub.1-C.sub.6 mono and/or di(hydroxy)alkylamino.

6. The process as claimed in claim 1, characterized in that R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.8 represent a hydrogen atom.

7. The process as claimed in claim 1, characterized in that R.sub.9 and R.sub.10, which may be identical or different, represent: a hydrogen atom, a saturated or unsaturated, linear or branched C.sub.1-C.sub.6 alkyl radical, said alkyl radical being optionally substituted with one or more radicals, which may be identical or different, chosen from the following radicals: i) hydroxyl, ii) C.sub.1-C.sub.6 (hydroxy)alkoxy, iii) amino NH.sub.2, iv) C.sub.1-C.sub.6 mono and/or di(hydroxy)alkylamino; preferably, R.sub.9 and R.sub.10 are identical and represent a hydrogen atom.

8. The process as claimed in claim 1, characterized in that A represents a group C(R.sub.12)(R.sub.13)R.sub.11 and R.sub.11 forms with R.sub.9, the nitrogen atom which bears R.sub.9 and the carbon atoms which bear N(R.sub.9)R.sub.10 and R.sub.11, a 5- to 8-membered cationic or noncationic heterocycle, said heterocycle being: optionally substituted with one or more radicals, which may be identical or different, chosen from the following radicals: i) hydroxyl, ii) C.sub.1-C.sub.4 alkyl, iii) C.sub.1-C.sub.4 alkoxy and iv) an ammonium radical N.sup.+RRR, An, with R, R and R, which may be identical or different, representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl; optionally at least one of the members of said heterocycle possibly representing a divalent oxo radical C(O); R.sub.12 and R.sub.13 being as defined in claim 1 and preferably denoting a hydrogen atom.

9. The process as claimed in claim 1, characterized in that the compound(s) of formula (I) are chosen from compounds (1) to (45), and also the geometrical or optical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof or the solvates thereof such as hydrates: ##STR00028## ##STR00029## ##STR00030## ##STR00031## ##STR00032## ##STR00033## ##STR00034##

10. The process as claimed in claim 1, comprising at least one step i) of applying to said keratin fibers one or more compounds of formula (I) and one or more oxidation bases.

11. The process as claimed in claim 1, comprising at least one step ii) of applying to said keratin fibers an oxidizing cosmetic composition comprising one or more chemical oxidizing agents, preferably chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes (with the optional cofactors thereof), such as peroxidases, 2-electron oxidoreductases, for instance uricases, and 4-electron oxygenases, for instance laccases; more preferentially, the chemical oxidizing agent is hydrogen peroxide; it being understood that between the step(s) i) and the step(s) ii), said fibers may be rinsed, and/or washed and then optionally dried.

12. The process as claimed in claim 1, comprising at least one step of simultaneously applying to said fibers: one or more compounds of formula (I); one or more chemical oxidizing agents; optionally one or more oxidation bases.

13. A compound of formula (I), and also the organic or mineral acid or base salts thereof, the tautomeric forms thereof, the optical isomers thereof, the geometrical isomers thereof and/or the solvates thereof, as defined in claim 1, characterized in that: A represents: an iodine atom or a fluorine atom, a carboxyl radical COOH or carboxylate radical COO.sup., M.sup.+, a sulfonic radical SO.sub.3H or sulfonate radical SO.sub.3.sup.M.sup.+, or alkylsulfonyl radical S(O).sub.2R with R representing a linear or branched (C.sub.1-C.sub.4)alkyl group, a group C(R.sub.12)(R.sub.13)R.sub.11 or C(R.sub.12)C(R.sub.11)R.sub.13, in which: R.sub.11, R.sub.12 and R.sub.13, which may be identical or different, represent: a hydrogen atom, a halogen atom such as fluorine, chlorine, bromine or iodine, preferably fluorine, a hydroxyl radical, a linear or branched C.sub.1-C.sub.14 alkyl or alkenyl group, in particular C.sub.1-C.sub.8, preferably C.sub.1-C.sub.6, said alkyl or alkenyl group: optionally comprising one or more heteroatoms or groups, which may be identical or different, chosen from O, S, S(O), S(O).sub.2, N(H), N(R), NR, RN and C(X) with X representing an oxygen or sulfur atom or NR and with R representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl, or combinations of said heteroatoms or groups, preferably chosen from: OC(O), C(O)O, C(O)N, NC(O), C(O)N(H), N(H)C(O), N(H)C(O)N(H), OC(O)N(H), N(H)C(O)O, N(H)C(NH)NH, and/or said alkyl or alkenyl group being optionally substituted with one or more radicals, which may be identical or different, chosen from the following radicals: i) hydroxyl, ii) C.sub.1-C.sub.6 (hydroxy)alkoxy, iii) amino NH.sub.2, iv) C.sub.1-C.sub.6 mono and/or di(hydroxy)alkylamino, v) fluoro F, vi) sulfonic SO.sub.3H, or sulfonate SO.sub.3-M.sup.+, vii) thiol SH, viii) cationic or noncationic (hetero)cycle, said heterocycle being optionally substituted, in particular optionally substituted with one or more radicals, which may be identical or different, chosen from (hydroxy)(C.sub.1-C.sub.6)alkyl radicals such as methyl, ethyl, propyl or 2-hydroxyethyl, hydroxyl radicals, ammonium radicals N.sup.+RRR, An, with R, R and R, which may be identical or different, representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl; ix) an ammonium radical N.sup.+RRR, An, with R, R and R, which may be identical or different, representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl; it being understood that R.sub.11, R.sub.12 and R.sub.13 cannot simultaneously denote a hydrogen atom, or R.sub.11 forms with R.sub.9, the nitrogen atom which bears R.sub.9 and the carbon atoms which bear N(R.sub.9)(R.sub.10) and R.sub.11, a 5- to 8-membered cationic or noncationic heterocycle, said heterocycle being optionally substituted with one or more radicals, which may be identical or different, chosen from the following radicals: i) hydroxyl, ii) C.sub.1-C.sub.4 alkyl, iii) C.sub.1-C.sub.4 alkoxy, and iv) an ammonium radical N.sup.+RRR, An, with R, R and R, which may be identical or different, representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl and at least one of the members of said heterocycle possibly representing a divalent oxo radical (C(O.sup.), it being understood that if R.sub.10, R.sub.12 and R.sub.13 denote a hydrogen atom, R.sub.9 and R.sub.11 cannot constitute a divalent radical (CH.sub.2).sub.3; a group W(R.sub.14) in which: W represents an oxygen or sulfur atom, R.sub.14 represents: a hydrogen atom, a linear or branched C.sub.2-C.sub.14 alkyl or alkenyl group, in particular C.sub.2-C.sub.8, preferably C.sub.2-C.sub.6, said alkyl or alkenyl group: optionally interrupted with one or more heteroatoms or groups, which may be identical or different, chosen from O, S, S(O), S(O).sub.2, N(H), N(R), NR, RN and C(X) with X representing an oxygen or sulfur atom or NR and with R representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl, or combinations of said heteroatoms or groups, preferably chosen from: OC(O), C(O)O, C(O)N, NC(O), C(O)N(H), N(H)C(O), N(H)C(O)N(H), OC(O)N(H), N(H)C(O)O, N(H)C(NH)N(H), and/or said alkyl or alkenyl group being optionally substituted with one or more radicals, which may be identical or different, chosen from the following radicals: i) hydroxyl, ii) C.sub.1-C.sub.6 (hydroxy)alkoxy, iii) amino NH.sub.2, iv) C.sub.1-C.sub.6 mono and/or di(hydroxy)alkylamino, v) fluoro F, vi) sulfonic SO.sub.3H, or sulfonate SO.sub.3.sup.M.sup.+, vii) thiol SH, viii) cationic or noncationic (hetero)cycle, said heterocycle being optionally substituted, in particular optionally substituted with one or more radicals, which may be identical or different, chosen from (hydroxy)(C.sub.1-C.sub.6)alkyl radicals such as methyl, ethyl, propyl or 2-hydroxyethyl, hydroxyl radicals, ammonium radicals N.sup.+RRR, An.sup., with R, R and R, which may be identical or different, representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl; or R.sub.14 forms with R.sub.9, the nitrogen atom which bears R.sub.9 and the carbon atoms which bear N(R.sub.9)(R.sub.10) and W, a 5- to 8-membered cationic or noncationic heterocycle, said heterocycle being optionally substituted with one or more radicals, which may be identical or different, chosen from the following radicals: i) hydroxyl, ii) C.sub.1-C.sub.4 alkyl, iii) C.sub.1-C.sub.4 alkoxy, and iv) an ammonium radical N.sup.+RRR, An, with R, R and R, which may be identical or different, representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl and at least one of the members of said heterocycle possibly representing a divalent oxo radical (C(O.sup.), a group N(R.sub.15)R.sub.15 in which R.sub.15 and R.sub.15 independently represent: a hydrogen atom, a linear or branched C.sub.1-C.sub.14 alkyl or alkenyl group, in particular C.sub.1-C.sub.8, preferably C.sub.1-C.sub.6, said alkyl or alkenyl group: optionally interrupted with one or more heteroatoms or groups, which may be identical or different, chosen from O, S, S(O), S(O).sub.2, N(H), N(R), NR, RN and C(X) with X representing an oxygen or sulfur atom or NR and with R representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl, or combinations of said heteroatoms or groups, preferably chosen from: OC(O), C(O)O, C(O)N, NC(O), C(O)N(H), N(H)C(O), N(H)C(O)N(H), OC(O)N(H), N(H)C(O)O, N(H)C(NH)NH, and/or said alkyl or alkenyl group being optionally substituted with one or more radicals, which may be identical or different, chosen from the following radicals: i) hydroxyl, ii) C.sub.1-C.sub.6 (hydroxy)alkoxy, iii) amino NH.sub.2, iv) C.sub.1-C.sub.6 mono and/or di(hydroxy)alkylamino, v) fluoro F, vi) sulfonic SO.sub.3H, or sulfonate SO.sub.3.sup.M.sup.+, vii) thiol SH, viii) cationic or noncationic (hetero)cycle, said heterocycle being optionally substituted, in particular optionally substituted with one or more radicals, which may be identical or different, chosen from (hydroxy)(C.sub.1-C.sub.6)alkyl radicals such as methyl, ethyl, propyl or 2-hydroxyethyl, hydroxyl radicals, ammonium radicals N.sup.+RRR, An, with R, R and R, which may be identical or different, representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl; ix) an ammonium radical N.sup.+RRR, An, with R, R and R, which may be identical or different, representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl; it being understood that R.sub.15 and R.sub.15 cannot simultaneously denote a hydrogen atom; or R.sub.15 forms with R.sub.9, the nitrogen atom which bears R.sub.9 and the carbon atoms which bear N(R.sub.9)(R.sub.10) and N(R.sub.15), a 5- to 8-membered cationic or noncationic heterocycle, said heterocycle being optionally substituted with one or more radicals, which may be identical or different, chosen from the following radicals: i) hydroxyl, ii) C.sub.1-C.sub.4 alkyl, iii) C.sub.1-C.sub.4 alkoxy, and iv) an ammonium radical N.sup.+RRR, An.sup., with R, R and R, which may be identical or different, representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl and at least one of the members of said heterocycle possibly representing a divalent oxo radical (C(O.sup.), a carbonyl radical C(O)R.sub.11, with R.sub.11 as defined in claim 1, an ester radical C(O)OR.sub.111, a thioester radical C(O)SR.sub.111 or a dithioester radical C(S)SR.sub.11, with R.sub.11 as defined in claim 1, an optionally substituted cationic or noncationic (hetero)cycle, an ammonium radical N.sup.+RRR, An, with R, R and R, which may be identical or different, representing a (C.sub.1-C.sub.4)alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl, propyl or 2-hydroxyethyl; with M.sup.+ as defined in claim 1, it being understood that the compounds of formula (I) are other than: 7-amino-8-fluoro-1,2,3,4-tetrahydroquinoline ##STR00035## 7-amino-8-hydroxy-1,2,3,4-tetrahydroquinoline ##STR00036##

14. The compound as claimed in claim 13, chosen from compounds (1), (4), (8), (9), (10), (11), (12), (13), (14), (15), (16), (18), (19), (20), (21), (22), (23), (24), (25), (26), (27), (28), (29), (30), (31), (32), (33), (34), (35), (36), (37), (38), (39), (40), (41), (42), (43), (44) and (45) and also the organic or mineral acid or base salts thereof, the tautomeric forms thereof, the optical isomers thereof, the geometrical isomers thereof and/or the solvates thereof such as the hydrates thereof.

15. A cosmetic composition comprising: one or more compounds of formula (I) as defined in claim 1; and one or more oxidation bases.

16. The composition as claimed in claim 15, characterized in that it comprises one or more chemical oxidizing agents, preferably chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes (with the optional cofactors thereof), such as peroxidases, 2-electron oxidoreductases, for instance uricases, and 4-electron oxygenases, for instance laccases; more preferentially, the chemical oxidizing agent is hydrogen peroxide.

17. A multi-compartment device, or dyeing kit, comprising a first compartment containing one or more compounds of formula (I) as defined in claim 1, and a second compartment comprising one or more chemical oxidizing agents.

Description

EXAMPLES OF SYNTHESIS

Examples 1: Synthesis of 8-ethyl-1,2,3,4-tetrahydroquinolin-7-amine dihydrochloride (See Synthesis, 6 (1992) 571-576 for the First Two Steps)

[0285] ##STR00018##

1. 6.06 g of 7-nitrotetrahydroquinoline and 417 mg of 4-dimethylaminopyridine are placed in 23 ml of N,N-diisopropylethylamine in a 250 ml round-bottomed flask equipped with a magnetic bar. While cooling, a solution of 3.0 ml of chloromethanesulfonyl chloride in 34 ml of anhydrous dichloromethane is added dropwise to the reaction medium and the mixture is then left stirring at room temperature for 5 hours. Saturated ammonium chloride solution is then added slowly to the reaction medium to quench the reaction. After shaking and separation of the two phases, the aqueous phase is extracted three times with dichloromethane. The combined organic phases are washed with water and then with saturated sodium chloride solution, and then dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue is purified by flash chromatography on a column of silica gel (eluent: 20/80 ethyl acetate/heptane) to give the expected substituted product obtained in the form of a dark yellow powder.
2. 2.6 g of 1-chloromethanesulfonyl-7-nitro-1,2,3,4-tetrahydroquinoline are placed in 14 ml of dimethyl sulfoxide in a 100 ml round-bottomed flask equipped with a magnetic bar, this solution is added dropwise to another flask which contains 5.16 g of sodium hydroxide in 38 ml of dimethyl sulfoxide, and the reaction medium is then left stirring at room temperature for 70 minutes. The reaction medium is then added to a mixture of 20 ml of ammonium chloride and 100 ml of dichloromethane. The aqueous phase is extracted three times with dichloromethane and the combined organic phases are washed with water and then with saturated sodium chloride solution. After drying over anhydrous sodium sulfate, the solvent is evaporated off under reduced pressure and the residue is purified by standard flash column chromatography (eluent: 30/70 ethyl acetate/heptane). After removing the solvent, 1.57 g of the cyclized product are obtained in the form of a yellow powder.
3. 502 mg of the cyclized intermediate, 2.06 g of potassium carbonate and 7.1 mg of 18-crown-6 (0.01 eq.) are placed in 12 ml of acetonitrile in a 50 ml round-bottomed flask equipped with a magnetic bar. 0.11 ml of dimethyl sulfate is then added dropwise to the solution obtained, with stirring, and the reaction medium is then refluxed for 4 hours. The reaction medium is then added with stirring to a mixture of water and ethyl acetate. The aqueous phase is also extracted three times with dichloromethane and the combined organic phases are washed with water and then with saturated sodium chloride solution. After drying over anhydrous sodium sulfate, the solvent is evaporated off under reduced pressure and the residue is purified by standard flash column chromatography (eluent: 35/65 ethyl acetate/heptane). The methylated tricycle is then obtained in the form of a brown solid.

##STR00019##

4. 0.88 g of the methylated tricycle is placed in 25 mL of tert-butylbenzene in a 100 ml round-bottomed flask equipped with a magnetic bar, and the reaction medium is then maintained at 165 C. for 22 hours. The reaction medium is purified directly by standard flash column chromatography (eluent: 20/80 dichloromethane/heptane and then 15/85 ethyl acetate/heptane) to give the expected 7-nitro-8-vinyl-1,2,3,4-tetrahydroquinoline intermediate in the form of an orange-yellow oil.
5. Hydrogenation is then performed in an H-cube on 0.46 g of 7-nitro-8-vinyl-1,2,3,4-tetrahydroquinoline under the following conditions: Concentration: 0.01 mol/L in methanol, Pressure: 40 bar, Temperature: 70 C., Hydrogen production: 90%, Cartridge: 10% Pd/C, Flow rate: 3 mL/min.
6. In the last step, the product is salified with 12 ml of hydrochloric acid solution (5-6M) in 200 ml of isopropanol, the solution is then concentrated and the final product dried. 8-Ethyl-1,2,3,4-tetrahydroquinolin-7-amine dihydrochloride is thus obtained in the form of a beige-colored powder.

Examples 2: Synthesis of 8-methoxy-1,2,3,4-tetrahydroquinolin-7-amine dihydrochloride (see J. Chem. Soc., Perkin Trans. 1, (2000) 1259-1264 for the Second Step)

[0286] ##STR00020##

1. 10 g of 7-nitroquinoline are placed in 770 ml of dichloromethane in a 1 L three-necked round-bottomed flask equipped with a thermometer and a magnetic bar, followed by addition of 26 g of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone. After stirring for 4 hours, the reaction medium is filtered and the filtrate is then evaporated under vacuum and then dried under vacuum. The product is obtained in the form of an orange powder.
2. 9.9 g of 7-nitroquinoline are placed in 220 ml of tetrahydrofuran in a 1 L round-bottomed flask equipped with a thermometer and a magnetic bar, followed by dropwise addition of 100 ml of sodium methoxide. After stirring for 18 hours at room temperature, water is added and the mixture is then neutralized to pH 7. The resulting mixture is filtered under vacuum and the filtrate is then concentrated on a rotary evaporator and 200 ml of ethyl acetate are added. After shaking and separation of the two phases, the aqueous phase is extracted four times with ethyl acetate. The combined organic phases are washed twice with water and once with saturated sodium chloride solution. After drying over anhydrous magnesium sulfate, the organic phase is concentrated under reduced pressure. The crude product is obtained in the form of a brown powder, which is purified by standard flash column chromatography (eluent: 25/75 ethyl acetate/heptane) to give 8-methoxy-7-nitroquinoline in the form of yellow crystals.
3. A reduction is then performed with an H-cube on the product obtained in the preceding step under the following conditions: Concentration: 0.02 mol/L in methanol, Pressure: 60 bar, Temperature: 70 C., Hydrogen production: 80%, Cartridge: 10% Pd/C, Flow rate: 3 mL/min.
4. The reduced product is then salified in an identical manner to that of step 6 of example 1. 8-Methoxy-1,2,3,4-tetrahydroquinolin-7-amine dihydrochloride is obtained in the form of a white powder.

Examples 3: Synthesis of 1,2,3,4,7,8,9,10-octahydro-1,7-phenanthroline dihydrochloride (see Monatshefte fr Chemie, 119 (1988) 761-780 for the First Step)

[0287] ##STR00021##

1. A reduction is performed with an H-cube starting with 1,7-phenanthroline under the following conditions: Concentration: 0.02 mol/L in methanol, Pressure: 60 bar, Temperature: 70 C., Hydrogen production: 80%, Cartridge: 10% Pd/C, Flow rate: 3 mL/min.
2. The reduced product is then salified in an identical manner to that of step 6 of example 1. Recrystallization is then performed after evaporating off the excess acid. The product is obtained in the form of a white powder.

Examples 4: Synthesis of 8-(morpholin-4-yl)-1,2,3,4-tetrahydroquinolin-7-amine dihydrochloride

[0288] ##STR00022##

1. The synthesis is performed starting with 7-nitrotetrahydroquinoline. 15 g of 7-nitrotetrahydroquinoline are placed in 300 ml of acetonitrile in a 500 ml three-necked round-bottomed flask equipped with a thermometer and a magnetic bar, followed by addition of 11.3 g of N-chlorosuccinimide. The reaction medium is then refluxed for 4 hours 30 minutes. The medium is transferred into a 1 L round-bottomed flask containing 50 ml of water and 300 ml of ethyl acetate. The mixture is concentrated on a rotary evaporator and 200 ml of ethyl acetate and 100 ml of water are then added. After stirring and separation of the two phases, the aqueous phase is extracted twice with ethyl acetate. The combined organic phases are washed twice with water and once with saturated sodium chloride solution. After drying over anhydrous magnesium sulfate, the organic phase is concentrated under reduced pressure. Purification by standard flash column chromatography (eluent: 10/90 dichloromethane/heptane) is then performed, and the chloro product is obtained in the form of an orange-colored powder.
2. 650 mg of 8-chloro-7-nitrotetrahydroquinoline are placed with stirring in 25 ml of dichloromethane in a 100 ml three-necked round-bottomed flask equipped with a thermometer and a magnetic bar. 1.38 mg of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone are then added. After stirring for 6 hours, the reaction medium is filtered and the filtrate is evaporated under vacuum on a rotary evaporator. The product is purified by standard flash column chromatography (eluent: 30/70 ethyl acetate/heptane) and 8-chloro-7-nitroquinoline is obtained in the form of a yellow powder.

##STR00023##

3. 500 mg of the intermediate obtained previously are placed in 25 ml of ethanol in a 100 ml three-necked round-bottomed flask equipped with a thermometer and a magnetic bar, and 630 l of morpholine are added. The mixture is then refluxed for 8 hours and the reaction medium is then evaporated to dryness under vacuum. 100 ml of ethyl acetate and 100 ml of water are added. After stirring and separation of the two phases, the aqueous phase is extracted with ethyl acetate. The combined organic phases are washed twice with water and then once with saturated sodium chloride solution. After drying over anhydrous magnesium sulfate, the organic phase is concentrated under reduced pressure. Purification by standard flash column chromatography (eluent: 10/90 ethyl acetate/heptane) is then performed, and 610 mg of the expected product are thus obtained.
4. A reduction is then performed with an H-cube under the following conditions: Concentration: 0.02 mol/L in methanol, Pressure: 60 bar, Temperature: 70 C., Hydrogen production: 80%, Cartridge: 10% Pd/C, Flow rate: 3 mL/min.
5. The reduced product is then salified in an identical manner to that of step 6 of example 1. 200 mg of 8-(morpholin-4-yl)-1,2,3,4-tetrahydroquinolin-7-amine dihydrochloride are obtained in the form of a white powder.

Examples 5: Synthesis of 2,2-[(7-amino-1,2,3,4-tetrahydroquinolin-8-yl)imino]diethanol dihydrochloride

[0289] ##STR00024##

1. The synthesis is performed starting with the intermediate 8-chloro-7-nitroquinoline, as described in the synthesis of example 4. 13.0 g of 8-chloro-7-nitroquinoline are placed in 500 ml of 1-butanol in a 1 L three-necked round-bottomed flask equipped with a thermometer and a magnetic bar. 18 ml of diethanolamine are then added to the solution obtained, with stirring, and the reaction medium is then refluxed for 16 hours. After evaporating off the solvent under vacuum, dichloromethane and water are added to the residue. After shaking and separation of the two phases, the aqueous phase is extracted three times with dichloromethane. The combined organic phases are washed three times with water and then once with saturated sodium chloride solution. After drying over anhydrous magnesium sulfate, the organic phase is concentrated under reduced pressure and then taken up in diethyl ether and the mixture is stirred for 2 hours until an orange precipitate appears. After removing the solvent, the nitro precursor of the expected product is isolated in the form of an orange-colored powder.
2. 7.0 g of 8-diethanolamine-7-nitroquinoline and 0.7 g of Pd/C (10% by weight) are placed in 250 ml of ethanol in a 1 L autoclave. The autoclave is then sealed and purged with nitrogen, and then filled with 20 bar of H.sub.2. After stirring for 48 hours at room temperature, the reaction medium is filtered through Celite, the solvent is then removed under reduced pressure and the residue is purified by standard flash column chromatography (eluent: 10/90 methanol/dichloromethane).
3. The product is then salified with 19 ml of hydrochloric acid solution in isopropanol.
After filtration and removal of the solvent, the expected product is isolated in the form of a light brown powder.

Examples 6: Synthesis of 1-(7-amino-1,2,3,4-tetrahydroquinolin-8-yl)-3-methyl-1H-imidazol-3-ium chloride hydrochloride

[0290] ##STR00025##

1. The synthesis is performed starting with the intermediate 8-chloro-7-nitroquinoline, as described in the synthesis of example 4. 7.0 g of 8-chloro-7-nitroquinoline are placed in 250 ml of toluene in a 500 ml three-necked round-bottomed flask equipped with a thermometer and a magnetic bar. 8 ml of 1-methylimidazole are then added to the solution obtained, with stirring, and the reaction medium is then refluxed for 16 hours. A brown precipitate appears, which is filtered off and then washed with diethyl ether. The precipitate is then taken up in acetonitrile and the mixture is refluxed for 10 minutes. After cooling to room temperature, the precipitate obtained is filtered off to give the nitro precursor of the expected product in the form of a light brown powder.
2. 6.0 g of 8-(1-methylimidazolium)-7-nitroquinoline chloride and 0.6 g of Pd/C (10% by weight) are placed in 250 ml of ethanol in a 1 L autoclave. The autoclave is then sealed and purged with nitrogen, and then filled with 20 bar of H.sub.2. Since the reaction is incomplete after 3 days of stirring at room temperature, a further 0.6 g of Pd/C (10% by weight) is added and the reduction is continued for a further 2 days. The reaction medium is filtered through Celite, the solvent is then removed under reduced pressure and the residue is purified by standard flash column chromatography (eluent: 20/80 methanol/dichloromethane).
3. The product is then salified with 3 eq. of hydrochloric acid solution in isopropanol. After removal of the solvent, the 1-(7-amino-1,2,3,4-tetrahydroquinolin-8-yl)-3-methyl-1H-imidazol-3-ium chloride hydrochloride is isolated in the form of a pale yellow powder.

Examples 7: Synthesis of 8-(1H-pyrrol-1-yl)-1,2,3,4-tetrahydroquinolin-7-amine hydrochloride

[0291] ##STR00026##

1. The synthesis is performed starting with the intermediate 8-chloro-7-nitroquinoline, as described in example 4. 15 g of 8-chloro-7-nitroquinoline are placed in 150 ml of acetonitrile in a 500 ml three-necked round-bottomed flask equipped with a thermometer and a magnetic bar. 25 ml of pyrrole and 70 g of cesium carbonate are then added to the solution obtained, with stirring. The flask is then purged with nitrogen, and 1.36 g of copper (I) iodide are then added. The reaction medium is refluxed under nitrogen for 16 hours, and the reaction is monitored by liquid-phase chromatography coupled to mass spectrometry. The reaction medium is then filtered through silica and eluted with ethyl acetate, the filtrate is then concentrated under reduced pressure and the residue is purified by standard flash column chromatography (eluent: 20/80 ethyl acetate/petroleum ether) to give 8-pyrrole-7-nitroquinoline.
2. 7.3 g of 8-pyrrole-7-nitroquinoline and 0.73 g of Pd/C (10% by weight) are placed in 250 ml of ethanol in a 1 L autoclave. The autoclave is then sealed and purged with nitrogen, and then filled with 15 bar of H.sub.2. After stirring for 4 days at room temperature, since the reaction is incomplete, 0.6 g of Pd/C (10% by weight) is added and the reaction is continued under 20 bar of H.sub.2 for 3 days. The reaction medium is then filtered through Celite, the solvent is then removed under reduced pressure and the residue is purified twice by standard flash column chromatography (eluent: 65/35 dichloromethane/petroleum ether).
3. The product is then salified with 3 eq. of hydrochloric acid solution in isopropanol. After removal of the solvent, the 8-(1H-pyrrol-1-yl)-1,2,3,4-tetrahydroquinolin-1-amine hydrochloride is isolated in the form of a yellow powder.

DYEING EXAMPLES

Example 1: Dyeing Evaluation of the Couplers

[0292] a) Composition

[0293] Composition (A) according to the present invention was prepared using the ingredients of which the contents, expressed as mass percentages of active material relative to the total weight of the composition, are indicated in the table below.

TABLE-US-00001 Composition A 96 ethyl alcohol 20.8 Aqueous 35% sodium metabisulfite solution 0.23 Pentasodium salt of diethylenetriaminepentaacetic 0.48 acid as an aqueous 40% solution C.sub.8-C.sub.10 alkyl poly glucoside as an aqueous 60% 3.6 solution Benzyl alcohol 2.0 Polyethylene glycol containing 8 units of ethylene 3.0 oxide NH.sub.4C1 4.32 Aqueous ammonia containing 20% NH.sub.3 2.94 Coupler 10.sup.3 mol Oxidation base 10.sup.3 mol Water qs 100

[0294] Composition (A) was prepared with each of the oxidation bases below.

TABLE-US-00002 Oxidation base Composition para-Aminophenol A1 4-Aminophenylamine dihydrochloride A2 2-Methylbenzene-1,4-diamine sulfate A3 2-[(4-Aminophenyl)(2-hydroxyethyl)amino]ethanol sulfate A4 3-(2,5-Diaminophenyl)propan-1-ol dihydrochloride A5 2-(4,5-Diamino-lH-pyrazol-1-yl)ethanol sulfate A6 2,3-Diamino-6,7-dihydro-1H,5H-pyrazolo[1,2- A7 a]pyrazol-1-one dimethanesulfonate 2-[(3-Aminopyrazolo[1,5-a]pyridin-2- A8 yl)oxy]ethanol hydrochloride 4-(3-Aminopyrazolo[1,5-a]pyridin-2-yl)- A9 1,1-dimethylpiperazin-1-ium chloride hydrochloride

[0295] Seven series (S1), (S2), (S3), (S4), (S5), (S6) and (S7) of compositions (A1) to (A9) were thus prepared.

[0296] Each of the compositions (A1) to (A9) of series (S1) comprises 8-ethyl-1,2,3,4-tetrahydroquinolin-7-amine dihydrochloride as coupler.

[0297] Each of the compositions (A1) to (A9) of series (S2) comprises 8-methoxy-1,2,3,4-tetrahydroquinolin-7-amine dihydrochloride as coupler.

[0298] Each of the compositions (A1) to (A9) of series (S3) comprises 1,2,3,4,7,8,9,10-octahydro-1,7-phenanthroline dihydrochloride as coupler.

[0299] Each of the compositions (A2) to (A9) of series (S4) comprises 8-(morpholin-4-yl)-1,2,3,4-tetrahydroquinolin-7-amine dihydrochloride as coupler.

[0300] Each of the compositions (A2) to (A9) of series (S5) comprises 2,2-[(7-amino-1,2,3,4-tetrahydroquinolin-8-yl)imino]diethanol dihydrochloride as coupler.

[0301] Each of the compositions (A1) to (A9) of series (S6) comprises 1-(7-amino-1,2,3,4-tetrahydroquinolin-8-yl)-3-methyl-1H-imidazol-3-ium hydrochloride as coupler.

[0302] Each of the compositions (A2) to (A9) of series (S7) comprises 8-(1H-pyrrol-1-yl)-1,2,3,4-tetrahydroquinolin-7-amine hydrochloride as coupler.

[0303] b) Procedure

[0304] At the time of use, each of the compositions (A1) to (A9) is mixed with 20-volumes aqueous hydrogen peroxide solution (6% by weight) in a 1:1 ratio. The final pH of each of the mixtures is equal to 9.5.

[0305] Each mixture thus obtained is applied to a lock of gray hair containing 90% white hairs. After a leave-on time of 30 minutes, the locks are rinsed, washed with a standard shampoo and then rinsed again. The locks are then dried. [0306] c) Results

[0307] The color results are given in the tables below:

[0308] Summary of the dyeing evaluations for (S1) to (S7)

TABLE-US-00003 S1 S2 S3 S4 S5 S6 S7 A1 Red Red Red Matt yellow A2 Blue Blue Blue Blue Blue Green Blue-green A3 Blue Blue Blue Blue Blue Green Blue-green A4 Blue-green Blue-green Blue-green Blue-green Green-blue Green Green A5 Blue Blue Blue-green Blue Blue Green Green A6 Red-violet Violet-red Red-violet Red-violet Red-violet Red-violet Violet-red A7 Red Red Red Red Coppery red Red Mahogany red A8 Violet-red Violet-red Violet-red Violet Violet Violet Violet A9 Green Green Green Green Green Green Green

Example 2: Evaluation of the Persistence with Respect to Shampooing and to Light, and the Chromaticity of the Dyeing Results

[0309] The intensity of the coloring obtained for each of the compositions was evaluated in the CIE L* a* b* system, using a Minolta Spectrophotometer CM3610D colorimeter. In this L* a* b* system, the three parameters respectively denote the intensity of the color (L*), the green/red color axis (a*) and the blue/yellow color axis (b*).

[0310] The comparative evaluation was performed with the same dye support (A) as described in example 1 and under the same operating conditions.

[0311] The couplers are numbered as follows: [0312] C1 is 8-ethyl-1,2,3,4-tetrahydroquinolin-7-amine dihydrochloride (Invention); [0313] C2 is 8-methoxy-1,2,3,4-tetrahydroquinolin-7-amine dihydrochloride (Invention); [0314] C3 is 1,2,3,4,7,8,9,10-octahydro-1,7-phenanthroline dihydrochloride (Invention); [0315] C4 is 8-(morpholin-4-yl)-1,2,3,4-tetrahydroquinolin-7-amine dihydrochloride (Invention); [0316] C5 is 2,2-[(7-amino-1,2,3,4-tetrahydroquinolin-8-yl)imino]diethanol dihydrochloride (Invention); [0317] C6 is 1-(7-amino-1,2,3,4-tetrahydroquinolin-8-yl)-3-methyl-1H-imidazol-3-ium chloride hydrochloride (Invention); [0318] C7 is 8-(1H-pyrrol-1-yl)-1,2,3,4-tetrahydroquinolin-7-amine hydrochloride (Invention); and [0319] D is 1,2,3,4-tetrahydroquinolin-7-amine dihydrochloride (Comparative).

[0320] The oxidation bases are numbered as follows: [0321] B1 is 4-aminophenylamine dihydrochloride; [0322] B2 is 2-methylbenzene-1,4-diamine sulfate; and [0323] B3 is 4-aminophenol.

[0324] Evaluation of the Persistence with Respect to Shampooing of the Dyeing Results

[0325] At the time of use, each of the compositions is mixed with 20-volumes aqueous hydrogen peroxide solution (6% by weight) in a 1:1 ratio. The final pH of each of the mixtures is equal to 9.5.

[0326] Each mixture thus obtained is applied to a lock of gray hair containing 90% white hairs. After a leave-on time of 30 minutes, the locks are rinsed, washed with a standard shampoo and then rinsed again. The locks are then dried.

[0327] The difference in color build-up before and after cycles of one shampoo wash and three rinses were calculated by applying the formula below:

DE={square root over ((LL*).sup.2+(aa*).sup.2+(bb*).sup.2)}

L*, a* and b*, as defined previously, are the values measured before shampooing but after dyeing; L, a and b are the values measured after dyeing and after shampooing (DOP50%, 6 cycles of 1 shampoo wash +3 rinses, on a Pall transparent plate) or (DOP2% 6 shampoo washes).

TABLE-US-00004 Bases Couplers B1 B2 B3 D (10.sup.3 mol) comparative 7.76 8.15 11.43 C1 (10.sup.3 mol) 2.36 1.65 6.35 C2 (10.sup.3 mol) 3.19 C4 (10.sup.3 mol) 3.34 4.49 5.31 C5 (10.sup.3 mol) 4.02 4.39 6.57 C6 (10.sup.3 mol) 4.72 4.32 3.34 C7 (10.sup.3 mol) 4.67 5.00 5.14

[0328] Evaluation of the Persistence with Respect to Light of the Dyeing Results

[0329] At the time of use, each of the compositions is mixed with 20-volumes aqueous hydrogen peroxide solution (6% by weight) in a 1:1 ratio. The final pH of each of the mixtures is equal to 9.5.

[0330] Each mixture thus obtained is applied to a lock of gray hair containing 90% white hairs. After a leave-on time of 30 minutes, the locks are rinsed, washed with a standard shampoo and then rinsed again. The locks are then dried.

[0331] The difference in color build-up-up before and after exposure to light was calculated by applying the formula below:

DE={square root over ((LL*).sup.2+(aa*).sup.2+(bb*).sup.2)}

[0332] L*, a* and b* as defined previously, are the values measured before exposure to light but after dyeing; L, a and b are the values measured after dyeing and after exposure to light (Xenon-1600W, exposure for 2 h 26 min, equivalent to 1 month of normal life).

TABLE-US-00005 Bases Couplers B1 B3 D (10.sup.3 mol) comparative 10.55 11.51 C1 (10.sup.3 mol) 4.41 6.44 C2 (10.sup.3 mol) 6.19 6.60 C3 (10.sup.3 mol) 3.41 4.62 C5 (10.sup.3 mol) 6.66 C6 (10.sup.3 mol) 5.25 3.92

[0333] Evaluation of the Chromaticity of the Dyeing Results

[0334] At the time of use, each of the compositions is mixed with 20-volumes aqueous hydrogen peroxide solution (6% by weight) in a 1:1 ratio. The final pH of each of the mixtures is equal to 9.5.

[0335] Each mixture thus obtained is applied to a lock of gray hair containing 90% white hairs. After a leave-on time of 30 minutes, the locks are rinsed, washed with a standard shampoo and then rinsed again. The locks are then dried.

[0336] The chromaticity of the color after dyeing was calculated by applying the formula below:

c*={square root over (a*.sup.2+b*.sup.2)}

a* and b* as defined previously, are the values measured after dyeing.

TABLE-US-00006 Bases Couplers B1 B2 D (10.sup.3 mol) 8.71 8.99 C1 (10.sup.3 mol) 11.96 12.96 C2 (10.sup.3 mol) 13.58 12.73 C3 (10.sup.3 mol) 10.8 13.15

[0337] It is seen from the above results of the dyeing process according to the invention which uses couplers of 7-aminotetrahydroquinoline type substituted in position 8, relative to the dyeing process which uses a coupler of 7-aminotetrahydroquinoline type not substituted in position 8, that the colorings obtained with the process of the invention are significantly more persistent with respect to shampooing and to light and more chromatic than the comparative.

Example 3: Comparative Evaluation of the Build-Up, the Intensity and the Chromaticity of the Dyeing Results

[0338] The comparative evaluation was performed with the dye compositions prepared from the following ingredients:

TABLE-US-00007 Compositions Amount Oxidation base 0.05 mmol Oxidation coupler 0.05 mmol Water 7.0 ml Ethanol 2.0 mL Aqueous ammonia containing 20% NH.sub.3 1.0 mL 20-volumes aqueous hydrogen peroxide 1.0 mL solution

[0339] Each composition obtained is applied to 1 g locks of natural Caucasian hair containing 90% white hairs. After a leave-on time of 30 minutes at 27 C., the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

[0340] The oxidation couplers are numbered as follows: [0341] C2 is 8-methoxy-1,2,3,4-tetrahydroquinolin-7-amine dihydrochloride (Invention); [0342] D2 is 8-methoxy-1,2,3,4-tetrahydroquinolin-5-amine (Comparative)

[0343] The oxidation bases are numbered as follows: [0344] A6 is 2-(4,5-diamino-1H-pyrazol-1-yl)ethanol sulfate; [0345] A7 is 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one dimethanesulfonate; and [0346] A8 is 2-[-aminopyrazolo[1,5-a]pyridin-2-yl)oxy]ethanol hydrochloride.

L, A, b Results:

[0347] The colorimetric data for each of the locks are then measured with a Minolta CM-3610d spectrophotometer. In this L* a* b* system, L* represents the lightness, a* indicates the green/red color axis and b* indicates the blue/yellow color axis. The higher the value of L, the lighter or less intense the color. Conversely, the lower the value of L, the darker or more intense the color. The higher the value of a*, the redder the shade, and the higher the value of b*, the yellower the shade.
The color build-up on hair thus corresponds to the variation in coloring between the locks of dyed NG hair (natural gray hair containing 90% white hairs) and the non-dyed (i.e. untreated) NG hair, which is measured by (E) according to the following equation:

E={square root over ((LL.sub.0*).sup.2+(aa.sub.0*).sup.2+(bb.sub.0*).sup.2)}

In this equation, L*, a* and b* represent the values measured after dyeing of the NG hair, and L.sub.0*, a.sub.0* and b.sub.0* represent the values measured before dyeing of the NG hair. The higher the E value, the better the build-up of the coloring.

[0348] Evaluation of the Build-Up of the Dyeing Results (E)

TABLE-US-00008 Couplers D2 C2 Bases (Comparative) (Invention) A6 43.76 55.68 A8 35.32 49.18

[0349] Evaluation of the Intensity of the Dyeing Results (L*)

TABLE-US-00009 Couplers D2 C2 Bases (Comparative) (Invention) A8 33.13 21.04
The chromaticity is calculated according to the following formula:

C*={square root over ((a*).sup.2+(b*).sup.2)}

The higher the chromaticity value C*, the more chromatic the color of the treated keratin fibers.

[0350] Evaluation of the Chromaticity of the Dyeing Results (C*)

TABLE-US-00010 Couplers D2 C2 Bases (Comparative) (Invention) A6 20.22 31.59 A7 24.56 32.49

[0351] It is seen from the above results that the colorings obtained with the dyeing process according to the invention using couplers of 7-aminotetrahydroquinoline type substituted in position 8 are significantly more intense, more chromatic and with a better color build-up than the colorings obtained via a comparative dyeing process using couplers of 5-aminotetrahydroquinoline type substituted in position 8.