Compositions for dyeing keratinous fibres, containing pyrrolo-azoles; use as couplers; method of dyeing

Abstract

The present invention relates to a composition for the dyeing of keratinous fibres, especially human hair, which comprises, in a medium appropriate for dyeing: as coupler, at least one compound corresponding to one of the formulae: in which R 1 is especially hydrogen, halogen, aryloxy, alkoxy, acyloxy, arylthio, alkylthio, heteroarylthio, heteroaryloxy, etc; R 2 and R 3 are independent and are especially hydrogen, halogen, alkyl, aryl, alkylthio, arylthio, benzylthio, etc; Z a , Z b and Z c are independent and are a nitrogen atom or a carbon atom carrying a radical R 4 , R 5 , R 6 or R 7 ; R 4 , R 6 and R 7 are identical or different and are especially hydrogen, alkyl, aryl, a heterocycle, a halogen, etc; and R 5 is especially hydrogen, halogen, acyl, acyloxy or carbamoyl, etc; and at least one oxidation base.

1 . Composition for the dyeing of keratinous fibres and, in particular, of human keratinous fibres, such as hair, which is characterized in that it comprises, in a medium appropriate for dyeing: 
 as coupler, at least one pyrrolo-azole compound or one of its addition salts with an acid corresponding to one of the following formulae:  
                 
   in which:    R 1  is: a hydrogen atom; a halogen atom; an acetylamido radical; an alkoxy radical; an aryloxy radical; an acyloxy radical; an arylthio radical; an alkylthio radical; a heteroarylthio radical; a heteroaryloxy radical; a thiocyano radical; an N,N-diethylthiocarbonylthio radical; a dodecyloxythiocarbonylthio radical; a benzenesulphonamido radical; an N-ethyltoluenesulphonamido radical; a pentafluorobutanamido radical; a 2,3,4,5,6-pentafluorobenzamido radical; a p-cyanophenylureido radical; an N,N-diethylsulphamoylamino radical; a pyrazolyl radical; an imidazolyl radical; a triazolyl radical; a tetrazolyl radical; a benzimidazolyl radical; a 1-benzyl-5-ethoxy-3-hydantoinyl radical; a 1-benzyl-3-hydantoinyl radical; 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl; a 2-oxy-1,2-dihydro-1-pyridinyl radical; an alkylamido; an arylamido; acetylamido; a radical NR III R IV  where R III  and R IV  are identical or different and are a C 1 -C 4  alkyl; a hydroxyalkyl; a carboxyl; or an alkoxycarboxyl radical;    R 2  and R 3  independently of one another are a hydrogen atom; a halogen atom; a linear or branched C 1 -C 5  alkyl radical which is optionally substituted by one or two halogen, hydroxyl, alkoxy, aryloxy, amino, alkylamino, acyl or acylamino radicals; a C 1 -C 4  alkoxy radical; a C 1 -C 4  alkylthio radical; an arylthio radical; a benzylthio radical; an acyl radical; an acylamino radical; an acyloxy radical; a carbamoyl radical; a phenyl radical which is optionally substituted by one or two halogen, nitro, sulphonyl, C 1 -C 4  alkoxy, C 1 -C 4  alkyl, C 1 -C 3  trifluoroalkyl, amino or alkylamino groups; an alkoxycarbonyl radical; an aryloxycarbonyl radical; a cyano radical; a nitro radical; a dialkylphosphono radical; a diarylphosphono radical; a dialkoxyphospholyl radical; a dialkylphosphinyl radical; a diarylphosphinyl radical; an alkylsulphinyl radical; an arylsulphinyl radical; an arylsulphonyl radical; an alkylsulphonyl radical; a sulphonyloxy radical; an acylthio radical; a sulphamoyl radical; a thiocyanate radical; or a thiocarbonyl radical;    Z a , Z b  and Z c  are independently of one another a nitrogen atom or a carbon atom carrying a radical R 4 , R 5 , R 6  or R 7 ;    R 4 , R 6  and R 7  are identical or different and are a hydrogen atom; a linear or branched C 1 -C 20  alkyl radical which is optionally substituted by 1 or 2 radicals R selected from the group consisting of halogen, nitro, cyano, hydroxyl, alkoxy, aryloxy, amino, alkylamino, acylamino, carbamoyl, sulphonamido, sulphamoyl, imido, alkylthio, arylthio, aryl, alkoxycarbonyl and acyl; an aryl radical which is optionally substituted by 1 or 2 radicals R as defined above; a 5- or 6-membered heterocycle having at least one nitrogen, oxygen or sulphur atom and being optionally substituted by 1 or 2 radicals R as defined above;    when R 4 , R 6  and R 7  are an alkyl radical, an aryl radical or a 5- or 6-membered heterocycle (defined above), the radical or heterocycle may be attached to the carbon atom of the ring system via an oxygen, nitrogen or sulphur atom (in this case, R 4 , R 6  and R 7  become XR 4 , XR 6  or XR 7  where X=O, NH, S);    R 4 , R 6  and R 7  may also be a halogen atom; an acyl radical; a sulphonyl radical; a sulphinyl radical; a phosphonyl radical; a carbamoyl radical; a sulphamoyl radical; a cyano radical; a siloxy radical; an amino radical; an acylamino radical; an acyloxy radical; a carbamoyloxy radical; a sulphonamide radical; an imide radical; a ureido radical; a sulphamoylamino radical; an alkoxycarbonylamino radical; an aryloxycarbonylamino radical; an alkoxycarbonyl radical; an aryloxycarbonyl radical; or a carboxyl radical;    R 5  is hydrogen; halogen; an acyl radical; an acyloxy radical; a carbamoyl radical; an alkoxycarbonyl radical; a cyano radical; a nitro radical; a dialkylphosphono radical; a diarylphosphono radical; a dialkoxyphospholyl radical; a dialkylphosphinyl radical; a diarylphosphinyl radical; an alkylsulphinyl radical; an arylsulphinyl radical; an alkylsulphonyl radical; an arylsulphonyl radical; a sulphonyloxy radical; an acylthio radical; a sulphamoyl radical; a thiocyanate radical; a thiocarbonyl radical; a haloaryloxy radical; a haloalkylamino radical; a haloalkylthio; an aryl which is unsubstituted or substituted by electron-withdrawing groups; or a heterocycle;    and at least one oxidation base.    
     
     
         2 . Composition according to    claim 1   , characterized in that the radicals R 1  of the formulae (I) and (II) are selected from the group consisting of: 
 a hydrogen atom; a C 1 -C 4  alkoxy; phenoxy; phenoxy substituted by a halogen atom, a C 1 -C 4  alkyl, a carboxyl or a trifluoromethyl group; an acyloxy radical; benzyloxy; C 1 -C 4  alkylthio; phenylthio; phenylthio substituted by a halogen atom, a C 1 -C 4  alkyl, a carboxyl or a trifluoromethyl group; a C 1 -C 4  alkylamido; phenylamido; a radical NR III R IV  where R III  and R IV  are identical or different and are a C 1 -C 4  alkyl, a C 1 -C 4  hydroxyalkyl; a carboxyl; and a C 1 -C 4  alkoxycarboxyl radical.    
     
     
         3 . Composition according to    claim 2   , characterized in that the radicals R 1  of the formulae (I) and (II) are selected from the group consisting of: 
 hydrogen; chlorine or bromine; methoxy or ethoxy; phenyloxy; 4-methylphenyloxy; acyloxy; benzyloxy; methylthio or ethylthio; phenylthio; 4-methylphenylthio; 2-tert-butylphenylthio; acetamido; phenylacetamido; dimethylamino; diethylamino; ethylmethylamino; and (β-hydroxyethyl)methylamino.    
     
     
         4 . Composition according to    claim 2    or    3   , characterized in that the radicals R 1  of the formulae (I) and (II) are selected from the group consisting of: 
 hydrogen; chlorine; ethoxy; phenoxy; benzyloxy; acyloxy; acetamido; and dimethylamino.  
 
     
     
         5 . Composition according to any one of claims  1  to 4, characterized in that the radicals R 2  and R 3  of the formulae (I) and (II) are selected from the group consisting of: 
 acyl; acyloxy; carbamoyl; alkoxycarbonyl; aryloxycarbonyl; cyano; nitro; alkylsulphinyl; arylsulphinyl; alkylsulphonyl; arylsulphonyl; sulphamoyl; haloalkyl; C 1 -C 4  alkyl and hydrogen.  
 
     
     
         6 . Composition according to    claim 5   , characterized in that the radicals R 2  and R 3  of the formulae (I) and (II) are selected from the group consisting of: 
 acyl; alkoxycarbonyl; nitro; cyano; arylsulphonyl; carbamoyl; haloalkyl; hydrogen; and C 1 -C 4  alkyl.    
     
     
         7 . Composition according to    claim 5    or    6   , characterized in that the radicals R 2  of the formulae (I) and (II) are selected from the group consisting of: cyano; hydrogen; methyl; and phenyl and in that the radicals R 3  of the formulae (I) and (II) are selected from the group consisting of: alkoxycarbonyl, such as methoxycarbonyl or ethoxycarbonyl; aryloxycarbonyl; hydrogen; methyl; and cyano.  
     
     
         8 . Composition according to any one of    claims 1    to    7   , characterized in that the radicals R 4 , R 6  and R 7  of the formulae (I) and (II) are selected from the group consisting of: 
 a linear or branched C 1 -C 4  alkyl radical; aryl; phenyl substituted by a halogen, a methoxy radical, a nitro group, a cyano group, a trifluoromethyl group or an amino group; cyano; nitro; acylamino; arylamino; alkylthio; arylthio; carbamoyl; sulphonyl; alkoxycarbonyl; aryloxycarbonyl; acyl and hydrogen.  
 
     
     
         9 . Composition according to    claim 8   , characterized in that the radicals R 4 , R 6  and R 7  of the formulae (I) and (II) are selected from the group consisting of: 
 hydrogen; linear or branched C 1 -C 4  alkyl; aryl; phenyl substituted by a halogen, a methoxy radical, a nitro group, a cyano group, a trifluoromethyl group or an amino group.    
     
     
         10 . Composition according to any one of    claims 1    to    9   , characterized in that the radicals R 5  of the formulae (I) and (II) are selected from the group consisting of: 
 acyl; alkoxycarbonyl; aryloxycarbonyl; nitro; cyano; arylsulphonyl; haloalkyl; and hydrogen.  
 
     
     
         11 . Composition according to any one of    claims 1    to    10   , characterized in that the radicals R 5  are selected from the group consisting of: cyano; alkoxycarbonyl; aryloxycarbonyl; haloalkyl; and a hydrogen.  
     
     
         12 . Composition according to any one of    claims 1    to    11   , characterized in that the compounds of formula (I) are selected from the group consisting of: 
 (i) the pyrrolo[1,2-b]-1,2,4-triazoles of formula:  
                 
 
 (ii) the pyrrolo[2,1-c]-1,2,4-triazoles of formula:  
                 
 
 in which R 1 , R 2 , R 3  and R 4  are as defined in any one of    claims 1    to    11   .  
 
     
     
         13 . Composition according to    claim 12   , characterized in that the compounds of formula (Ia) are those for which: 
 R 1  is hydrogen or chlorine;    R 2  and R 3  are, respectively: cyano and cyano; ethoxycarbonyl and cyano; trifluoromethyl and cyano; phenylsulphonyl and cyano; trifluoromethyl and ethyloxycarbonyl; ethoxycarbonyl and ethoxycarbonyl; methoxycarbonyl and methoxycarbonyl; hydrogen and hydrogen; or hydrogen and methyl; and    R 4  is methyl, ethyl, isopropyl, phenyl or hydrogen.    
     
     
         14 . Composition according to    claim 12   , characterized in that the compounds of formula (Ib) are those for which: 
 R 1  is hydrogen or chlorine;    R 2  and R 3  are simultaneously: cyano or hydrogen; and    R 4  is methyl, ethyl, isopropyl, phenyl or hydrogen.    
     
     
         15 . Composition according to    claim 12   , characterized in that the compounds of formula (I) are selected from: 
 3,4-dicyano-8-methylpyrrolo[1,2-b]-1,2,4-triazole,    3,4-dicyano-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,    3,4-dicyano-8-tert-butylpyrrolo[1,2-b]-1,2,4-triazole,    5-chloro-3,4-dicyano-8-methylpyrrolo[1,2-b]-1,2,4-triazole,    5,6-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole,    7-chloro-5,6-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole,    and their addition salts with an acid.    
     
     
         16 . Composition according to any one of    claims 1    to    11   , characterized in that the compounds of formula (II) are selected from the group consisting of: 
 a) the pyrrolo[1,2-b]-1,2,4-triazoles of formula:  
                 
 
 b) the pyrrolo[2,1-c]-1,2,4-triazoles of formula:  
                 
 
 c) the pyrrolo[1,2-c]imidazoles of formula:  
                 
 
 d) the pyrrolo[1,2-e]tetrazoles of formula:  
                 
 
 e) the pyrrolo[1,2-a]pyrroles of formula:  
                 
 
 f) the pyrrolo[1,2-a]imidazoles of formula:  
                 
 
 g) the pyrrolo[1,2-c]-1,2,3-triazoles of formula:  
                 
 
 in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  are as defined in any one of    claims 1    to    10   .  
 
     
     
         17 . Composition according to    claim 16   , characterized in that the compounds of formula (IIa) are those for which: 
 R 3  is hydrogen or chlorine;    R 2  and R 3  are, respectively: methoxycarbonyl and cyano; ethyloxycarbonyl and cyano; cyano and methoxycarbonyl or ethoxycarbonyl; cyano and trifluoromethyl; cyano and phenylsulphonyl; methyloxycarbonyl and methyloxycarbonyl; hydrogen and hydrogen; hydrogen and methyl; trifluoromethyl and cyano or trifluoromethyl and methyloxycarbonyl; carboxyl and cyano; cyano and cyano; ethyloxycarbonyl and ethyloxycarbonyl; phenyl and cyano; methyl and hydrogen; and    R 4  is methyl, ethyl, isopropyl, phenyl or hydrogen.    
     
     
         18 . Composition according to    claim 16   , characterized in that the compounds of formula (IIb) are those for which: 
 R 1  is hydrogen or chlorine;    R 2  and R 3  are, respectively: cyano and methoxycarbonyl; methoxycarbonyl and cyano; methoxycarbonyl and methoxycarbonyl; hydrogen and hydrogen or hydrogen and methyl; cyano and cyano; ethyloxycarbonyl and ethyloxycarbonyl; phenyl and cyano; tert-butyl and cyano; and    R 4  is methyl, ethyl, isopropyl, phenyl or hydrogen.    
     
     
         19 . Composition according to    claim 16   , characterized in that the compounds of formula (IIc) are those for which: 
 R 1  is acetamido, chlorine or hydrogen;    R 2  and R 3  are, respectively: methoxycarbonyl and cyano; or cyano and cyano;    R 4  is hydrogen; and    R 5  is cyano.    
     
     
         20 . Composition according to    claim 16   , characterized in that the compounds of formula (IId) are those for which: 
 R 1  is hydrogen or chlorine; and    R 2  and R 3  are, respectively: cyano and methoxycarbonyl; cyano and cyano; methoxycarbonyl and cyano; methoxycarbonyl and methoxycarbonyl; hydrogen and hydrogen; or hydrogen and methyl.    
     
     
         21 . Composition according to    claim 16   , characterized in that the compounds of formula (IIe) are those for which: 
 R 1  is hydrogen or chlorine;    R 2  and R 3  are, respectively: cyano and methoxycarbonyl;    R 5  is trifluoromethyl;    R 6  is phenyl or methyl; and    R 7  is methyl.    
     
     
         22 . Composition according to    claim 16   , characterized in that the compounds of formula (IIf) are those for which: 
 R 1  is hydrogen or chlorine; and    R 2 , R 3 , R 6  and R 7  are, respectively: 
 methoxycarbonyl/cyano/cyano/phenyl;  
 cyano/methoxycarbonyl/cyano/phenyl;  
 cyano/methoxycarbonyl/methoxycarbonyl/phenyl;  
 hydrogen/hydrogen/hydrogen/hydrogen; or  
 hydrogen/hydrogen/methyl/methyl.  
   
     
     
         23 . Composition according to    claim 16   , characterized in that the compounds of formula (IIg) are those for which: 
 R 1  is hydrogen or chlorine;    R 2  is cyano;    R 3  is methoxycarbonyl; or ethyloxycarbonyl; and    R 5  is cyano.    
     
     
         24 . Composition according to    claim 16   , characterized in that the compounds of formula (II) are selected from: 
 5-cyano-4-ethoxycarbonyl-8-methylpyrrolo[1,2-b]-1,2,4-triazole,    5-cyano-4-carboxy-8-methylpyrrolo[1,2-b]-1,2,4-triazole,    4,5-dicyano-8-methylpyrrolo[1,2-b]-1,2,4-triazole,    5-cyano-8-methyl-4-phenylpyrrolo[1,2-b]-1,2,4-triazole,    4,8-dimethylpyrrolo[1,2-b]-1,2,4-triazole,    4,5-di(ethyloxycarbonyl)-8-methylpyrrolo[1,2-b]-1,2,4-triazole,    3-chloro-5-cyano-4-ethoxycarbonyl-8-methylpyrrolo-[1,2-b]-1,2,4-triazole,    5-cyano-4-ethoxycarbonyl-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,    5-cyano-4-carboxy-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,    4,5-dicyano-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,    4,5-di(ethyloxycarbonyl)-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,    3-chloro-5-cyano-4-ethoxycarbonyl-8-phenylpyrrolo-[1,2-b]-1,2,4-triazole,    4-cyano-5-carboxy-8-(2-nitro-5-hydroxyphenyl)pyrrolo-[1,2-b]-1,2,4-triazole,    6,7-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole,    5-chloro-6,7-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole,    6,7-di(ethyloxycarbonyl)-3-methylpyrrolo[2,1-c]-1,2,4-triazole,    7-cyano-3-methyl-6-phenylpyrrolo[2,1-c]-1,2,4-triazole,    7-cyano-3-methyl-6-tert-butylpyrrolo[2,1-c]-1,2,4-triazole,    6,8-dicyano-5-ethoxycarbonylpyrrolo[1,2-c]imidazole,    4-chloro-6,8-dicyano-5-ethoxycarbonylpyrrolo[1,2-c]-imidazole,    6,7-dicyanopyrrolo[1,2-e]tetrazole,    6-cyano-7-ethoxycarbonylpyrrolo[1,2-e]tetrazole,    5-chloro-6,7-dicyanopyrrolo[1,2-e]tetrazole,    2,3,7-tricyano-6-methylpyrrolo[1,2-a]imidazole,    2,3,7-tricyano-6-trifluoromethylpyrrolo[1,2-a]-imidazole,    2,3,7-tricyano-6-tert-butylpyrrolo[1,2-a]imidazole,    2,3,7-tricyano-6-phenylpyrrolo[1,2-a]imidazole,    2,3,7-tricyano-6-ethoxycarbonylpyrrolo[1,2-a]-imidazole,    5-chloro-2,3,7-tricyano-6-tert-butylpyrrolo[1,2-a]-imidazole,    5-chloro-2,3,7-tricyano-6-phenylpyrrolo[1,2-a]-imidazole,    7-cyano-6-ethoxycarbonylpyrrolo[1,2-a]benzimidazole,    7-cyano-6-phenylpyrrolo[1,2-a]benzimidazole,    5,6,8-tricyanopyrrolo[1,2-c]-1,2,3-triazole,    7-amido-6-ethoxycarbonylpyrrolo[1,2-a]benzimidazole,    5,8-dicyano-6-ethoxycarbonylpyrrolo[1,2-c]-1,2,3-triazole,    4-chloro-5,8-dicyano-6-ethoxycarbonylpyrrolo[1,2-c]-1,2,3-triazole,    and their addition salts with an acid.    
     
     
         25 . Composition according to any one of the preceding claims, characterized in that the acid addition salts of the compounds of formula (I) or (II) are selected from hydrochlorides, hydrobromides, tartrates, tosylates, benzenesulphonates, sulphates, lactates and acetates.  
     
     
         26 . Composition according to any one of the preceding claims, characterized in that the compound or compounds of formula (I) or (II) make up from 0.0005 to 12% by weight of the total weight of the dyeing composition.  
     
     
         27 . Composition according to    claim 26   , characterized in that the compound or compounds of formula (I) or (II) make up from 0.0005 to 6% by weight of the total weight of the dyeing composition.  
     
     
         28 . Composition according to any one of the preceding claims, characterized in that the oxidation base or bases are selected from para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols, terocyclic bases, and their addition salts with an acid.  
     
     
         29 . Composition according to any one of the preceding claims, characterized in that the oxidation base or bases make up from 0.0005 to 12% by weight, approximately, of the total weight of the dyeing composition.  
     
     
         30 . Composition according to    claim 29   , characterized in that the oxidation base or bases make up from 0.005 to 6% by weight, approximately, of the total weight of the dyeing composition.  
     
     
         31 . Composition according to any one of the preceding claims, characterized in that it also includes one or more additional couplers other than the compounds of formula (I) or (II) and/or one or more direct dyes.  
     
     
         32 . Composition according to any one of the preceding claims, characterized in that the medium appropriate for dyeing (or vehicle) consists of water or of a mixture of water and at least one organic solvent selected from C 1 -C 4  lower alkanols, glycerol, glycols and glycol ethers, aromatic alcohols, similar products, and mixtures thereof.  
     
     
         33 . Composition according to any one of the preceding claims, characterized in that it has a pH of between 3 and 12.  
     
     
         34 . Composition according to any one of the preceding claims, characterized in that it is in the form of liquids, creams, gels or any other form appropriate for dyeing keratinous fibres, and especially human hair.  
     
     
         35 . Use of the compounds of formula (I) or (II) or their acid addition salts as defined in any one of    claims 1    to    25    as couplers in compositions for the oxidation dyeing of keratinous fibres and, in particular, of human keratinous fibres, such as hair, in combination with at least one oxidation base.  
     
     
         36 . Method of oxidation-dyeing keratinous fibres and, in particular, human keratinous fibres, such as hair, characterized in that at least one dyeing composition as defined in any one of    claims 1    to    34    is applied to these fibres, the colour being developed at an acidic, neutral or alkaline pH with the aid of an oxidizing agent which is added just at the moment when the dyeing composition is employed or which is present in an oxidizing composition which is applied simultaneously or sequentially and separately.  
     
     
         37 . Method according to    claim 36   , characterized in that the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, and persalts, such as perborates and persulphates.  
     
     
         38 . Multi-compartment device, or multi-compartment dyeing kit, a first compartment of which contains a dyeing composition as defined in any one of    claims 1    to    34   , and a second compartment of which contains an oxidizing composition.