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

Abstract

The present invention relates to a composition for dyeing keratinous fibres, especially human hair, which in a medium appropriate for dyeing comprises: as coupler at least one compound of formula: in which: R 1 is especially hydrogen, alkyl, aryl, a heterocycle, a halogen, etc.; R 2 is especially hydrogen, halogen, aryloxy, alkoxy, acyloxy, arylthio, alkylthio, heteroarylthio, heteroaryloxy, etc.; Z a , Z b and Z c are independently a nitrogen atom or a carbon which carries a radical R 3 or R 4 whose meanings are identical to those of R 1 ; at least one of Z a , Z b and Z c is a nitrogen atom; and R 3 and R 4 may together form an unsubstituted or substituted aromatic ring; and at least one oxidation base.

1 . Composition for dyeing keratinous fibres, and especially human keratinous fibres such as hair, characterized in that it comprises, in a medium appropriate for dyeing: 
 as coupler, at least one pyrazolo-azole compound of the following formula (I) or one of its addition salts with an acid:                          in which    R 1  is: a hydrogen atom; a linear or branched C 1 -C 20  alkyl radical which is optionally substituted by one or two 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 one or two 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 one or two radicals R as defined above;    when R 1  is an alkyl radical, an aryl radical or a 5- or 6-membered heterocycle (as defined above) it can be attached to the carbon atom of the ring system by way of an oxygen, nitrogen or sulphur atom (in this case R 1  becomes XR 1  where X=O, NH, S);    R 1  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 wide radical; a ureido radical; a sulphamoylamino radical; an alkoxycarbonylamino radical; an aryloxycarbonylamino radical; an alkoxycarbonyl radical; an aryloxycarbonyl radical; or a carboxyl radical;    R 2  is: a hydrogen atom; a halogen atom; an acetylamido radical; an alkoxy radical; an aryloxy radical; an acyloxy radical; an arylthio radical; an alkythio 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; 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;    Z a , Z b , and Z c  independently of one another are a nitrogen atom, a carbon atom carrying a radical R 3  or R 4  as defined for the radical R 1 ; with the proviso that at least one of the radicals Z a , Z b  and Z c  is other than a carbon atom; R 3  and R 4  may also together form a substituted or unsubstituted aromatic ring;    and at least one oxidation base.    
     
     
         2 . Composition according to  claim 1 , characterized in that the radicals R 1  of the formula (I) are selected from the group consisting of: 
 a hydrogen atom; a linear or branched C 1 -C 4  alkyl; a phenyl; a phenyl substituted by a halogen atom, a C 1 -C 4  alkyl, a C 1 -C 4  alkoxy, a nitro group, an amino group, a trifluoromethyl group or C 1 -C 4  alkylamino group; a benzyl radical; a benzyl radical substituted by a halogen atom, a C 1 -C 4  alkyl, a C 1 -C 4  alkoxy, a nitro group, an amino group or a trifluoromethyl group; a C 1 -C 4  alkylamino; a heterocycle selected from thiophene, furan and pyridine; a trifluoromethyl radical; a radical (CH 2 ) p -X-(CH 2 ) q -OR′ where p and q are identical or different integers from 1 to 3, R′ is H or methyl and X is an oxygen atom or a group NR″ where R″ is hydrogen or methyl; a C 1 -C 4  hydroxyalkyl; a C 1 -C 4  aminoalkyl; a C 1 -C 4  alkylamino; a C 1 -C 4  dialkylamino; an arylamino; an alkoxy radical selected from methoxy, ethoxy and phenoxy; a halogen selected from fluorine, chlorine and bromine; a carboxyl group; a C 1 -C 4  alkoxycarbonyl; a phenyloxycarbonyl; methylthio; ethylthio; phenylthio; methanesulphonyl; and cyano.    
     
     
         3 . Composition according to  claim 1  or  2 , characterized in that the radicals R 1  of the formula (I) are selected from the group consisting of: 
 hydrogen; an alkyl selected from methyl, ethyl, isopropyl and tert-butyl; a halogen selected from fluorine and chlorine; phenyl; tolyl; 4-chlorophenyl; 4-methoxyphenyl; 3-methoxyphenyl; 2-methoxyphenyl; benzyl; a heterocycle selected from pyridyl, furyl and thienyl; trifluoromethyl; hydroxymethyl; aminomethyl; methoxy or ethoxy; methylamino or ethylamino or dimethylamino; carboxyl; methoxycarbonyl or ethoxycarbonyl; and cyano.  
 
     
     
         4 . Composition according to  claim 3 , characterized in that the radicals R 1  of the formula (I) are selected from the group consisting of: 
 hydrogen; methyl; ethyl; phenyl; tolyl; 4-chlorophenyl; 4-methoxyphenyl; benzyl; trifluoromethyl; chloro; a methoxy or ethoxy radical; a carboxyl radical; a methylamino or dimethylamino radical; and cyano.    
     
     
         5 . Composition according to any one of  claims 1  to  4 , characterized in that the radicals R 2  of the formula (I) 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 or a C 1 -C 4  hydroxyalkyl; a carboxyl; and a C 1 -C 4  alkoxycarboxyl radical.  
 
     
     
         6 . Composition according to  claim 5 , characterized in that the radicals R 2  of the formula (I) 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.    
     
     
         7 . Composition according to  claim 6 , characterized in that the radicals R 2  of the formula (I) are selected from the group consisting of: 
 hydrogen; chlorine; ethoxy; phenoxy; benzyloxy; acyloxy; acetamido; and dimethylamino.    
     
     
         8 . Composition according to any one of  claims 1  to  7 , characterized in that the radicals R 3  and R 4  of the formula (I) are selected from the group consisting of: 
 a hydrogen atom; a linear or branched C 1 -C 4  alkyl; a trifluoromethyl; a phenyl; a phenyl substituted by one or two groups selected from a halogen, a C 1 -C 4  alkyl, a C 1 -C 4  alkoxy, a hydroxyl, a carboxyl, a nitro group, a C 1 -C 4  alkylthio, a methylenedioxy group, an amino group, a trifluoromethyl group or a C 1 -C 4  alkylamino; a benzyl radical; a benzyl radical substituted by a halogen atom, a methyl or isopropyl, or methoxy; a C 1 -C 4  hydroxyalkyl; a C 1 -C 4  aminoalkyl; a C 1 -C 4  alkylaminoalkyl; an alkoxy radical selected from methoxy, ethoxy and phenoxy; methylthio; ethylthio; phenylthio; methanesulphonyl; and a substituted or unsubstituted aromatic ring formed by R 3  and R 4 .  
 
     
     
         9 . Composition according to  claim 8 , characterized in that the radicals R 3  and R 4  of the formula (I) are selected from the group consisting of: 
 hydrogen; an alkyl selected from methyl, ethyl, isopropyl, n-propyl and tert-butyl; phenyl; tolyl; 2-, 3- or 4-chlorophenyl; 3- or 4-hydroxyphenyl; 3- or 4-aminophenyl; 3- or 4-methoxyphenyl; 4-trifluoromethylphenyl; benzyl; trifluoromethyl; hydroxymethyl; hydroxyethyl; hydroxyisopropyl; aminomethyl or aminoethyl; methoxy or ethoxy; methylthio or ethylthio; and a phenyl ring formed by R 3  and R 4 , such as phenyl.    
     
     
         10 . Composition according to  claim 9 , characterized in that the radicals R 3  and R 4  so the formula (I) are selected from the group consisting of: 
 hydrogen; methyl; ethyl; isopropyl; phenyl; 4-chlorophenyl; 4-methoxyphenyl; 4-aminophenyl; methoxy or ethoxy; methylthio or ethylthio; and a phenyl ring formed by R 3  and R 4 .    
     
     
         11 . Composition according to any one of  claims 1  to  10 , characterized in that the compounds of formula (I) are selected from the group consisting or: 
 i) the pyrazolo[1,5-b]-1,2,4-triazoles of formula:  
                     
 ii) the pyrazolo[3,2-c]-1,2,4-triazoles of formula:  
                     
 iii) the pyrazolotetrazoles of formula:  
                     
 iv) the pyrazolo[1,5-a]imidazoles of formula:  
                     
 v) the pyrazolo[5,1-e]pyrazoles of formula:  
                     
 vi) the pyrazolo[5,1-e]-1,2,3-triazoles of formula:  
                     
 in which R 1 , R 2 , R 3  and R 4  are as defined in any one of  claims 1  to  10 ; and their addition salts with an acid.  
 
     
     
         12 . Composition according to  claim 11 , characterized in that the compounds of formula (Ia) or (Ib) are selected from those for which: 
 R 1  is hydrogen, methyl, ethylthio, amino, trifluoromethyl, carboxyl, phenyl, ethoxy or cyano;    R 2  is hydrogen or chlorine; and    R 3  is hydrogen, methyl, ethyl, isopropyl, β-aminoethyl, β-hydroxyethyl, phenyl, methylthio or ethoxy.    
     
     
         13 . Composition according to  claim 11 , characterized in that the compounds of formula (Ic) are selected from those for which: 
 R 1  is hydrogen, methyl, trifluoromethyl, carboxyl, phenyl, ethoxy or cyano; and    R 2  is hydrogen or chlorine.    
     
     
         14 . Composition according to  claim 11 , characterized in that the compounds of formula (Id) are selected from those for which: 
 R 1  is hydrogen, methyl, trifluoromethyl, amino, carboxyl, phenyl, ethoxy or cyano;    R 2  is hydrogen or chlorine; and    R 3  and R 4  are respectively hydrogen and hydrogen, hydrogen and methyl, methyl and hydrogen, hydrogen and amino, or hydrogen and phenyl; or together form a phenyl ring.    
     
     
         15 . Composition according to  claim 11 , characterized in that the compounds of formula (Ie) are selected from those for which: 
 R 1  is hydrogen, methyl, trifluoromethyl, carboxyl, phenyl, ethoxy or cyano;    R 2  is hydrogen or chlorine; and    R 3  and R 4  are respectively hydrogen and methyl, methyl and hydrogen, methyl and methyl or hydrogen and phenyl.    
     
     
         16 . Composition according to  claim 11 , characterized in that the compounds of formula (If) are selected from those for which: 
 R 1  is hydrogen, methyl, trifluoromethyl, carboxyl, phenyl, ethoxy or cyano;    R 2  is hydrogen or chlorine; and    R 3  is hydrogen or methyl.    
     
     
         17 . Composition according to  claim 11 , characterized in that the compounds of formula (I) are selected from: 
 2-methylpyrazolo[1,5-b]-1,2,4-triazole,    2-ethylpyrazolo[1,5-b]-1,2,4-triazole,    2-isopropylpyrazolo[1,5-b]-1,2,4-triazole,    2-phenylpyrazolo[1,5-b]-1,2,4-triazole,    2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,    6-methyl-2-ethylpyrazolo [1,5-b]-1,2,4-triazole,    6-methyl-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole,    6-methyl-2-phenylpyrazolo[1,5-b]-1,2,4-triazole,    6-carboxy-2-methylpyrazolo[1,5-b]-1,2,4-triazole,    6-carboxy-2-ethylpyrazolo[1,5-b]-1,2,4-triazole,    6-carboxy-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole,    6-carboxy-2-phenylpyrazolo[1,5-b]-1,2,4-triazole,    6-phenyl-2-methylpyrazolo[1,5-b]-1,2,4-triazole,    6-phenyl-2-ethylpyrazolo[1,5-b]-1,2,4-triazole,    6-phenyl-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole,    6-phenyl-2-phenylpyrazolo[1,5-b]-1,2,4-triazole,    6-amino-2-methylpyrazolo[1,5-b]-1,2,4-triazole,    6-amino-2-ethylpyrazolo[1,5-b]-1,2,4-triazole,    6-amino-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole,    6-amino-2-phenylpyrazolo[1,5-b]-1,2,4-triazole,    6-ethylthio-2-methylpyrazolo[1,5-b]-1,2,4-triazole,    6-ethylthio-2-ethylpyrazolo[1,5-b]-1,2,4-triazole,    6-ethylthio-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole,    6-ethylthio-2-phenylpyrazolo[1,5-b]-1,2,4-triazole,    6-ethoxy-2-methylpyrazolo[1,5-b]-1,2,4-triazole,    6-ethoxy-2-ethylpyrazolo[1,5-b]-1,2,4-triazole,    6-ethoxy-2-isopropyloyrazolo[1,5-b]-1,2,4-triazole,    6-ethoxy-2-phenylpyrazolo[1,5-b]-1,2,4-triazole,    6-methyl-2-(2′-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole,    6-carboxy-2-(2′-aminoethyl)pyrazolo[1,5-b]-1,2, 4-triazole,    6-phenyl-2-(2′-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole,    6-ethylthio-2-(2′-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole,    2-(2′-aminoethyl) pyrazolo[1,5-b]-1,2,4-triazole,    2-(2′-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole,    6-methyl-2- (2′-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole,    6-ethylthio-2-(2′-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole,    6-carboxy-2-(2′-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole,    6-phenyl-2-(2′-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole,    7-chloro-2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,    7-bromo-2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,    3-methylpyrazolo[3,2-c]-1,2,4-triazole,    3-methylsulphinyl-6-phenylpyrazolo[3,2c]-1,2,4-triazole,    3-ethylpyrazolo[3,2-c]-1,2,4-triazole,    3-isopropylpyrazolo[3,2-c]-1,2,4-triazole,    3-phenylpyrazolo[3,2-c]-1,2,4-triazole,    3-(2′-aminoethyl)pyrazolo[3,2-c-]1,2,4-triazole,    3-(2′-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole,    6-methyl-3-ethylpyrazolo[3,2-c]-1,2,4-triazole,    3,6-dimethylpyrazolo[3,2-c]-1,2,4-triazole,    6-methyl-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole,    6-methyl-3-phenylpyrazolo[3,2-c]-1,2,4-triazole,    6 -methyl-3-(2′-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole,    6-methyl-3-(2′-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole,    6-methyl-3-methylthiopyrazolo[3,2-c]-1,2,4-triazole,    6-phenyl-3-methylpyrazolo[3,2-c]-1,2,4-triazole,    6-phenyl-3-ethylpyrazolo[3,2-c]-1,2,4-triazole,    6-phenyl-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole,    6-phenyl-3-phenylpyrazolo[3,2-c]-1,2,4-triazole,    6-phenyl-3-(2′-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole,    6-phenyl-3-(2′-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole,    6-phenyl-3-methylthiopyrazolo[3,2-c]-1,2,4-triazole,    6-ethylthio-3-methylpyrazolo[3,2-c]-1,2,4-triazole,    6-ethylthio-3-ethylpyrazolo[3,2-c]-1,2,4-triazole,    6-ethylthio-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole,    6-ethylthio-3-phenylpyrazolo[3,2-c]-1,2,4-triazole,    6-ethylthio-3-(2′-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole,    6-ethylthio-3-(2′-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole,    6-trifluoromethyl-3-methylthiopyrazolo[3,2-c]-1,2,4-triazole,    6-trifluoromethylpyrazolo[3,2-c]-1,2,4-triazole,    6-carboxy-3-methylpyrazolo[3,2-c]-1,2,4-triazole,    6-carboxy-3-ethylpyrazolo[3,2-c]-1,2,4-triazole,    6-carboxy-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole,    6-carboxy-3-phenylpyrazolo[3,2-c]-1,2,4-triazole,    6-carboxy-3-(2′-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole,    6-carboxy-3-(2′-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole,    7-chloro-3,6-dimethylpyrazolo[3,2-c]-1,2,4-triazole,    7-methoxycarbonyl-3,6-dimethylpyrazolo[3,2-c]-1,2,4-triazole,    pyrazolo[5,1-e]tetrazole,    6-methylpyrazolo[5,1-e]tetrazole,    6-phenylpyrazolo[5,1-e]tetrazole,    6-carboxypyrazolo[5,1-e]tetrazole,    7-chloro-6-methylpyrazolo[5,1-e]tetrazole,    pyrazolo[1,5-a]imidazole,    2-methylpyrazolo[1,5-a]imidazole,    2-phenylpyrazolo[1,5-a]imidazole,    pyrazolo[1,5-a]benzimidazole,    6-methylpyrazolo[1,5-a]imidazole,    2,6-dimethylpyrazolo[1,5-a]imidazole,    6-methyl-2-phenylpyrazolo[1,5-a]imidazole,    6-methylpyrazolo[1, 5-a]benzimidazole,    6-phenylpyrazolo[1,5-a]imidazole,    6-phenyl-2-methylpyrazolo[1,5-a]imidazole,    2,6-diphenylpyrazolo[1,5a]imidazole,    6-phenylpyrazolo[1,5-a]benzimidazole,    6-carboxypyrazolo[1,5-a]imidazole,    6-carboxy-2-methylpyrazolo[1,5-a]imidazole,    6-carboxy-2-phenylpyrazolo[1,5-a]imidazole,    6-carboxypyrazolo[1,5-a]benzimidazole,    6-ethoxypyrazolo[1,5-a]imidazole,    6-ethoxy-2-methylpyrazolo[1,5-a]imidazole,    6-ethoxy-2-phenylpyrazolo[1,5-a]imidazole,    6-trifluoromethylpyrazolo[1,5-a]benzimidazole,    6-aminopyrazolo[1,5-a]imidazole,    6-amino-2-methylpyrazolo[1,5-a]imidazole,    6-amino-2-phenylpyrazolo[1,5-a]imidazole,    6-aminopyrazolo[1,5-a]benzimidazole,    6-ethylthiopyrazolo[1,5-a]imidazole,    6-ethylthio-2-methylpyrazolo[1,5-a]imidazole,    6-ethylthio-2-phenylpyrazolo[1,5-a]imidazole,    7-chloro-6-methylpyrazolo[1,5-a]imidazole,    7-chloro-6-methylpyrazolo[1,5-a]benzimidazole,    8-amino-4-methylpyrazolo[5,1-e]pyrazole,    8-amino-5-chloro-4-methylpyrazolo[5,1-e]pyrazole,    5-methylpyrazolo[5,1-e]-1,2,3-triazole,    5-methyl-6-chloropyrazolo[5,1-e]-1,2,3-triazole,    5-phenylpyrazolo[5,1-e]-1,2,3-triazole,    and their addition salts with an acid.    
     
     
         18 . Composition according to any one of  claims 1  to  11 , characterized in that it comprises at least one compound of formula:  
       
         
           
           
               
               
           
         
       
     
     
         19 . Composition according to any one of the preceding claims, characterized in that the acid addition salts of the compounds of formula (I) are selected from hydrochlorides, hydrobromides, sulphates, tartrates, benzenesulphonates, lactates, tosylates and acetates.  
     
     
         20 . Composition according to any one of the preceding claims, characterized in that the compound or compounds of formula (I) represent 0.0005 to 12% by weight of the total weight of the dyeing composition.  
     
     
         21 . Composition according to  claim 20 , characterized in that the compound or compounds of formula (I) represent from 0.005 to 6% by weight of the is total weight of the dyeing composition.  
     
     
         22 . Composition according to any one of the preceding claims, characterized in that the oxidation base or bases are selected from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, and their addition salts with an acid.  
     
     
         23 . Composition according to any one of the preceding claims, characterized in that the oxidation base or bases represent from 0.0005 to 12% by weight, approximately, of the total weight of the dyeing composition.  
     
     
         24 . Composition according to  claim 23 , characterized in that the oxidation base or bases represent from 0.005 to 6% by weight, approximately, of the total weight of the dyeing composition.  
     
     
         25 . Composition according to any one of the preceding claims, characterized in that it also comprises one or more additional couplers other than the compounds of formula (I) and/or one or more direct dyes.  
     
     
         26 . 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 lower C 1 -C 4  alcohols, glycerol, glycols and glycol ethers, aromatic alcohols, similar products, and mixtures thereof.  
     
     
         27 . Composition according to any one of the preceding claims, characterized in that it has a pH of between 3 and 12.  
     
     
         28 . 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 which is appropriate for producing a dye for keratinous fibres and especially human hair.  
     
     
         29 . Use of the compounds of formula (I) or of their addition salts with an acid, as defined in any one of  claims 1  to  19 , as couplers in compositions for the oxidation dyeing of keratinous fibres, and especially human keratinous fibres such as hair, in combination with at least one oxidation base.  
     
     
         30 . Method of oxidation-dyeing keratinous fibres, and especially human keratinous fibres such as hair, characterized in that at least one dyeing composition as defined in any one of  claims 1  to  28  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 right at the time when the dyeing composition is employed or which is present in an oxidizing composition which is applied simultaneously or sequentially and separately.  
     
     
         31 . Method according to  claim 30 , characterized in that the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, and persalts, such as perborates and persulphates.  
     
     
         32 . Multi-compartment device, or multi-compartment dyeing kit, a first compartment of which contains a dyeing composition as defined in any one or  claims 1  to  28  and a second compartment of which contains an oxidizing composition.