Patent EA-001248-B1 (EA)
Title: Keratin fibre dye composition containing pyrazolo-azole compounds, use thereof as dye couplers for dying of keratin fibres, method of dying and kit for that
Inventor: VIDAL LAURENT
IPC: A61K8/49
Filed: 1997-03-21
Abstract: 1. Composition for dying keratin fibers, particularly human keratin fibers, such as hair, characterized in that said composition consisting of a medium suitable for use in dying hair: - at least one pyrazolo-azocompound of formula (I) as a dying coupler or one of salts thereof adding with an acid:   wherein  R1 is a hydrogen atom, a radical alkyl C1-C20, linear or branched, optionally substituted by 1 or 2 radicals R, selected from the group consisting of halogen, nitro, cyano, hydroxy, alkoxy, aryloxy, amino, alkylamino, acylamino, carbamoyl, sulfonamido, sulfamoyl, imido, alkylthio, arylthio, aryl, alcoxycarbonyl, acyl; a radical aryl optionally substituted by 1 or 2 radicals R such as defined above; a heterocyclic radical from 5 or 6 links, having at least one nitrogen atom, oxygen or sulfur, optionally substituted by 1 or 2 radicals R, defined above; wherein when R<1> is a radical alkyl, a radical aryl or a heterocychaving 5 or 6 links (defined above), it can be bound with a carbon atom of a ring via an atom of oxygen, nitrogen or sulfur (in this case R1 is XR1 where X = O, NH, S); R1 can also be a halogen atom; a radical acyl; a radical sulfonyl; a radical sulfinyl; a radical phosphonyl, a radical carbamoyl; a radical sulfamoyl; a radical cyano; a radical siloxy, a radical amino; a radical acylamino; a radical acyloxy; a radical carbamoyloxy; a radical sulfonamide; a radical imide; a radical ureido; a radical sulfamoylamino; a radical alkoxycarbonylamino; a radical aryloxycarbonylamino; a radical alcoxycarbonyl; a radical aryloxycarbonyl; a radical carboxyl; R2 is a hydrogen atom, a halogen atom, a radical acetylamido; a radical alkoxy; a radical aryloxy; a radical acyloxy; a radical arylthio; a radical alkylthio; a radical heteralkylthio; a radical heteroaryloxy; a radical thiocyano; a radical N,N-diethylthiocarbonylthio; a radical dodecyloxythiocarbonylthio; a radical benzene-sulfonamido; a radical N-ethyltolunesulfonamido; a radical pentafluorobutanamido; a radical 2,3,4,5,6-penta-fluorobenzamido; a radical p-cyanophenylureido, a radical N,N-diethyl-sulfamoylamino; a radical pyrazolyl; a radical imidazolyl; a radical triazolyl; a radical tetrazolya radical benzimidazolyl; a radical 1-benzyl 5-ethoxy 3-hydantonyl; a radical 1-benzyl 3-hydantonyl; 5,5-dimethyl 2,4-dioxo 3-oxazolidinyl; a radical 2-oxy 1,2-dihydro 1-pyridinyle; an alkylamido; an arylamido; a radical NR<III> R<IV>, where R<III> and R<IV> are the same or different an alkyl C1-C4, a hydroxyalkyl; a carboxyl; a radical alkoxycarboxylic. Each of Za, Zb , Zc are independently a nitrogen atom, a carbon atom with a radical R3 or R4 having the same meaning as R1; provided that at least one of radicals Za, Zb , Zc is different from a carbon atom; R3 and R4 may together form an optionally substituted aromatic ring; and at least one oxidation base. 2. The composition as claimed in claim 1, characterized in that radicals R1 of formula (I) are selected from the group comprising: a hydrogen atom; an alkyl C1-C4, lineair or branched; a phenyl; a phenyl substituted by a halogen atom, an alkyl C1-C4, an alkoxy C1-C4, a group nitro, amino, trifluoromethyl or alkylamino C1-C4; a radical benzyl; a radical benzyl substituted by a halogen atom, an alkyl C1-C4, an alkoxy C1-C4, a group nitro, amino, trifluoromethyl; an alkylamino C1-C4; a heterocycselected from thiophene, furane or pyridine; a radical trifluoromethyl; a radical (CH2)p-X-(CH2)q-OR', where p and q are integers from 1 to 3, the same or different, R' is H or methyl and X is an oxygen atom or a group NR", where R" is hydrogen or methyl; a hydroxyalkyl C1-C4; a aminoalkyl C1-C4; an alkylamino C1-C4; a dialkylamino C1-C4; an arylamino; a radical alkoxy selected from methoxy, ethoxy et phenoxy; a halogen selected from fluorine, chloine and bromine; a carboxyl group; an alkoxycarbonyl C1-C4; a phenyloxycarbonyl; methylthio; ethylthio; phenylthio; methanesulfonyl; cyano. 3. The composition as claimed in claim 1 or 2, characterized in that radicals R1 of formula (I) are selected from the group, comprising: hydrogen; an alkyl, selected from methyl, ethyl, isopropyl, ter-butyl; a halogen selected from fluorine and chlorine; phenyl; toluyle; 4-chlorophenyl; 4-methoxyphenyl; 3-methoxyphenye; 2-methoxyphenyl; benzyl; a heterocycselected from pyridyl, furyl or thienyl; trifluoromethyl; hydroxymethyl; aminomethyl; methoxy or ethoxy; methylamino or ethylamino or dimethylamino ; carboxyl; methoxycarbonyl or ethoxycarbonyl; cyano. 4. The composition as claime in claim 1 or 2, characterized in that radicals R1 of formula (I) are selected from the group, comprising: hydrogen; methyl; ethyl; phenyl; toluyl; 4-chlorophenyl; 4-methoxyphenyl; benzyl; trifluoromethyl; chlorine; a radical methoxy or ethoxy; a radical carboxyl; a radical methylamino or dimethylamino; cyano. 5. The composition as claimed in claim 1 to 4, characterized in that radical R2 of formula (I) are selected from the group, comprising: a hydrogen atom; an alkoxy C1-C4; phenoxy; phenoxy substituted by a halogen atom, an alkyl C1-C4, a carboxyl, a group trifluoromethyl; a radical acyloxy; benzyloxy; alkylthio C1-C4; phenylthio; phenylthio substituted by a halogen atom, an alkyl C1-C4, a carboxyl, a trifluoromethyl group;an alkylamido C1-C4; phenylamido; a radical NR<III>R<IV>, where R<III> and R<iv> are the same or different, an alkyl C1-C4, a hydroxyalkyl C1-C4; a carboxyl; an alkoxycarboxylic radical C1-C4. 6. The composition as claimed in claim 5, characterized in that radicals R2 of formula (I) are selected from the group, comprising: hydrogen; chlorine or bromine; methoxy or ethoxy; phenyloxy; 4-methylphenyloxy; acyloxy; benzyloxy; methylthio or ethylthio; phenylthio; 4-methylphenylthio; 2-tertio-butylphenylthio; acetamido; phenylacetamido; dimethylamino; diethylamino; ethylmethylamino; (β-hydroxyethyl)methylamino. 7. The composition as claimed in claim 6, characterized in that radicals R2 of formula (I) are selected from the group, comprising: hydrogen; chlorine; ethoxy; phenoxy; benzyloxy; acyloxy; acetamido; dimethylamino. 8. The composition as claimed in any of claims 1 to 7, characterized in that radicals R3 and R4 of formula (I) are selected from the group, comprising: a hydrogen atom; an alkyl C1-C4, lineair or branched; a trifluoromethyl; a phenyl; a phenyl substituted by one or two groups selected from halogen, an alkyl C1-C4, an alkoxy C1-C4, a hydroxy, a carboxyl, as nitro group, an alkylthio C1-C4, a methylenedioxy group, an amino group, an trifluoromethyl group or an alkylamino C1-C4; a radical benzyl; a radical benzyl substituted by a halogen atom, a methyl or isopropyl, methoxy; a hydroxyalkyl C1-C4; an aminoalkyl C1-C4; an alkylaminoalkyl C1-C4; a radical alkoxy selected from methoxy, ethoxy and phenoxy; methylthio; ethylthio; phenylthio; methanesulfonyl; an aromatic cycle, substituted or unsubstituted, formed by R3 and R4. 9. The composition as claimed in claim 8, characterized in that radicals R3 and R4 of formula (I) are selected from the group, comprising: hydrogen; an alkyl selected from methyl, ethyl, isopropyl, n-propyl, ter-butyl; phenyl; toluyl; 2-, 3- or 4-chlorophenyl; 3- or 4-hydroxyphenyl; 3- or 4-aminophenyl; 3- or 4-methoxyphenyl; 4-trifluoromethylphenyl; benzyl; trifluoromethyl; hydroxymethyl; hydroxyethyl; hydroxy-isopropyl; aminomethyl or aminoethyl; methoxy or ethoxy; methylthio or ethylthio; an aromatic cycformed by R3 and R4 such as phenyl. 10. The composition as claimed in claim 8, characterized in that radicals R3 and R4 of formula (I) are selected from the group, comprising: hydrogen; methyl; ethyl; isopropyl; phenyl; 4-chlorophenyl; 4-methoxy-phenyl; 4-aminophenyl; methoxy or ethoxy; methylthio or ethylthio; a phenyl cycle, formed by R3 and R4. 11. The composition as claimed in any of claims 1 to 10, characterized in that the compounds of formula (I) are selected from the group, comprising:  (i) pyrazolo-[1,5-b]-1,2,4-triazoles of formula:    (ii) pyrazolo [3,2-c]-1,2,4-triazoles of formula:    (iii) pyrazolo tetrazoles of formula:    (iv) pyrazolo-[1,5-a]-imidazoles of formula:    (v) pyrazolo-[5,1-a]-pyrazoles of formula:    (vi) pyrazolo-[5,1-e]-1,2,3-triazoles of formula:    in which R1, R2, R3 and R4 have the same designations as defined in one of claims 1 to 10, and the salts thereof adding with acid. 12. The composition as claimed in claim 8, characterized in that the compounds of formula (Ia) or (Ib) are selected from the compounds, in which: - R1 is hydrogen, methyl, ethylthio, amino, trifluoromethyl, carboxyl, phenyl, ethoxy or cyano  - R2 is hydrogen or chlorine;  - R3 is hydrogen, methyl, ethyl, isopropyl, .beta.-aminoethyle, β-hydroxyethyl, phenyl, methylthio or ethoxy. 13. The composition as claimed in claim 11, characterized in that the compounds of formula (Ic) are selected from the compounds, in which: - R1 is hydrogen, methyl, trifluoromethyl, carboxyl, phenyl, ethoxy or cyano; - R2 is hydrogen or chlorine. 14. The composition as claimed in claim 11, characterized in that, the compounds of formula (Id) are selected from compounds, where: - R1 is hydrogen, methyl, trifluoromethyl, amino, carboxyl, phenyl, ethoxy or cyano  - R2 is hydrogen or chlorine;  - R3 and R4 are correspondingly hydrogen and hydrogen, hydrogen and methyl, methyl and hydrogen, hydrogen and amino, hydrogen and phenyl; or form between each other a phenyl cycle. 15. The composition as claimed in claim 11, characterized in that the compounds of formula (Ie) are selected from compounds, where: - R1 is hydrogen, methyl, trifluoromethyl, carboxyl, phenyl, ethoxy or cyano  - R2 is hydrogen or chlorine;  - R3 and R4 are correspondingly hydrogen and hydrogen, methyl and methyl, hydrogen and phenyl. 16. The composition as claimed in claim 11, characterized in that the compounds of formula (If) are selected from compounds, where: - R1 is hydrogen, methyl, trifluoromethyl, carboxyl, phenyl, ethoxy or cyano  - R2 is hydrogen