Compositions for dyeing keratinous fibres, containing 3-aminopyrazolo[1,5-a]pyrimidines, method of dyeing, and novel 3-aminopyrazolo[1,5-a]pyrimidines

Abstract

The invention relates to novel compositions for the oxidation dyeing of keratinous fibres, comprising at least one 3-aminopyrazolo[1,5-a]-pyrimidine, to the method of dyeing which employs this composition, to novel 3-aminopyrazolo[1,5-a]pyrimidines and to the process for their preparation.

What is claimed is:  
     
         1 . A composition for the oxidation dyeing of keratinous fibres wherein said composition comprises, in a medium suitable for dyeing, at least one 3-aminopyrazolo[1,5-a]pyrimidine chosen from compounds of formula (I) and acid and base addition salts thereof:  
                   
       in which 
 R 1 , R 2 , R 3  and R 4  are identical or different and represent a hydrogen atom, a halogen atom, a C 1 —C 4  alkyl radical, a C 1 —C 4  trifluoroalkyl radical, a C 1 —C 4  alkoxy radical, an aryl radical, a C 1 —C 4  monohydroxyalkyl radical, a C 2 —C 4  polyhydroxyalkyl radical, a C 1 —C 4  (C 1 —C 4  alkoxy)alkyl radical, a C 1 —C 4  aminoalkyl radical, a C 1 —C 4  (C 1 —C 4  alkyl)aminoalkyl radical, a C 1 —C 4  di(C 1 —C 4  alkyl)aminoalkyl radical, a C 1 —C 4  monohydroxy (C 1 —C 4  alkyl)aminoalkyl radical or a C 1 —C 4  di[hydroxy(C 1 —C 4  alkyl)]aminoalkyl radical.  
 
     
     
         2 . The composition of    claim 1    wherein said keratinous fibers are human keratinous fibers.  
     
     
         3 . The composition of    claim 2    wherein said human keratinous fibers are hair.  
     
     
         4 . The composition of    claim 1   , wherein said at least one 3-aminopyrazolo[1,5-a]-pyrimidine is chosen from: 
 pyrazolo[1,5-a]pyrimidin-3-ylamine;    5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;    5,6,7-trimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;    7-methylpyrazolo[1,5-a]pyrimidin-3-ylamine;    5-methylpyrazolo[1,5-a]pyrimidin-3-ylamine;    7-methoxypyrazolo[1,5-a]pyrimidin-3-ylamine;    5-methoxypyrazolo[1,5-a]pyrimidin-3-ylamine;    7-methoxy-5-methylpyrazolo[1,5-a]pyrimidin-3-ylamine;    2,5,6,7-tetramethylpyrazolo[1,5-a]pyrimidin-3-ylamine;    2-methoxy-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;    5,7-di-tert-butylpyrazolo[1,5-a]pyrimidin-3-ylamine;    5,7-di-trifluoromethylpyrazolo[1,5-a]pyrimidin-3-ylamine;    2,6-dimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;    2-chloro-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;    7-methyl 2-tert-butyl-5- trifluoromethyl-pyrazolo[1,5-a]pyrimidin-3-ylamine; and the acid and base addition salts thereof.    
     
     
         5 . The composition of    claim 1   , wherein said at least one 3-aminopyrazolo[1,5-a]-pyrimidine is chosen from: 
 pyrazolo[1,5-a]pyrimidin-3-ylamine;    5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;    5,6,7-trimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;    2,5,6,7-tetramethylpyrazolo[1,5-a]pyrimidin-3-ylamine;    2-methoxy-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;    5,7-di-trifluoromethylpyrazolo[1,5-a]pyrimidin-3-ylamine;    7-methylpyrazolo[1,5-a]pyrimidin-3-ylamine;    5-methylpyrazolo[1,5-a]pyrimidin-3-ylamine; and acid and base addition salts thereof.    
     
     
         6 . The composition of    claim 1   , wherein said at least one, 3-aminopyrazolo[1,5-a]-pyrimidine represents from 0.0005 to 12% by weight relative to the total weight of the dyeing composition.  
     
     
         7 . The composition of    claim 6   , wherein said at least one 3-aminopyrazolo[1,5-a]-pyrimidine represents from 0.005 to 6% by weight relative to the total weight of the dyeing composition.  
     
     
         8 . The composition of    claim 1   , wherein said medium suitable for dyeing comprises water, a water/alcohol mixture or a mixture of water and at least one organic solvent chosen from C 1 —C 4  lower alkanols, glycerol, glycols and glycol ethers, aromatic alcohols, and mixtures thereof.  
     
     
         9 . The composition of    claim 8   , wherein said at least one organic solvent is present in proportion ranging from 1 to 40% by weight approximately relative to the total weight of the dye composition.  
     
     
         10 . The composition of    claim 9   , wherein said at least one organic solvent is present in proportions ranging from 5 to 30%.  
     
     
         11 . The composition of    claim 1   , where said composition has a pH ranging from 3 to 12.  
     
     
         12 . The composition of    claim 11   , wherein said composition has a pH ranging from 5 to 11.  
     
     
         13 . The composition of    claim 1   , wherein said composition contains at least one coupler.  
     
     
         14 . The composition of    claim 13   , wherein said at least one coupler is chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic couplers.  
     
     
         15 . The composition of    claim 14   , wherein said at least one coupler is chosen from 2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxy-benzene, 2,4-diamino-1-(β-hydroxyethoxy)benzene, 2-amino-4-(β-hydroxyethylamino)-1 -methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol, α-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy4-methylpyridine, 1 H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, and the addition salts thereof.  
     
     
         16 . The composition of    claim 13   , wherein said at least one coupler represents from 0.0001 to 10% by weight relative to the total weight of the dyeing composition.  
     
     
         17 . The composition of    claim 16   , where said at least one coupler represents from 0.005 to 5% by weight relative to the total weight of the dyeing composition.  
     
     
         18 . The composition of    claim 1   , wherein said composition additionally contains at least one additional oxidation base.  
     
     
         19 . The composition of    claim 18   , wherein said additional oxidation base is chosen from para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases which are different from the 3-aminopyrazolo[1,5-a]pyrimidines of formula (I).  
     
     
         20 . The composition of    claim 19   , wherein said para-phenylenediamines are chosen from para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylene-diamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline, 2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(β-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N,N-(ethyl,β-hydroxyethyl)-para-phenylenediamine, N-(β,γ-dihydroxypropyl)-para-phenylenediamine, N-(4′-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2-β-acetylaminoethyloxy-para-phenylenediamine, N-(β-methoxyethyl)-para-phenylenediamine and the acid addition salts thereof.  
     
     
         21 . The composition of    claim 20   , wherein said para-phenyldiamines are chosen from para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine, 2-β-acetylaminoethyloxy-para-phenylenediamine, and the acid addition salts thereof.  
     
     
         22 . The composition of    claim 19   , wherein said bisphenylalkylenediamines are chosen from N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol, N,N′-bis(β-hydroxyethyl)-N,N ′-bis(4′-aminophenyl)ethylenediamine, N,N′-bis(4-aminophenyl)-tetramethylenediamine, N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine, N,N ′-bis(4-methylaminophenyl)tetramethylenediamine, N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)-ethylenediamine, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and the acid addition salts thereof.  
     
     
         23 . The composition of    claim 19   , wherein said para-aminophenols are chosen from para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxyethylaminomethyl)phenol, 4-amino-2-fluorophenol, and the acid addition salts thereof.  
     
     
         24 . The composition    claim 19   , wherein said ortho-aminophenols are chosen from 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-aminophenol, and the acid addition salts thereof.  
     
     
         25 . The composition of    claim 19   , where said other heterocyclic bases are chosen from pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.  
     
     
         26 . The composition of    claim 18   , wherein said at least one additional oxidation base represents from 0.0005 to 12% by weight of the total weight of the dyeing composition.  
     
     
         27 . The composition of    claim 26   , wherein said at least one additional oxidation base represents from 0.005 to 6% by weight of the total weight of the dyeing composition.  
     
     
         28 . The composition of    claim 1   , wherein said acid addition salts are chosen from hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates and acetates.  
     
     
         29 . The composition of    claim 1   , wherein said base addition salts are chosen from sodium hydroxide solution, potassium hydroxide solution, aqueous ammonia, and amines.  
     
     
         30 . The composition of    claim 1   , wherein said composition additionally contains at least one direct dye.  
     
     
         31 . The composition of    claim 30   , wherein said at least one direct dye is chosen from the nitro derivatives of benzene.  
     
     
         32 . The composition of    claim 1   , wherein said composition additionally contains at least one adjuvant chosen from anionic, cationic, nonionic, amphoteric and zwitterionic surfactants, anionic, cationic, nonionic, amphoteric and zwitterionic polymers, organic and inorganic thickeners, antioxidants, penetration agents, sequestrants, fragrances, buffers, dispersants, conditioners, film forming agents, ceramides, preserving agents and opacifiers.  
     
     
         33 . The composition of    claim 32   , wherein said conditioners are chosen from modified and unmodified, volatile and nonvolatile silicones.  
     
     
         34 . A method for dyeing keratinous fibres, comprising the steps of contacting said fibres for a time sufficient to achieve color development, with a dye composition of    claim 1    or a salt thereof.  
     
     
         35 . The method of    claim 34    wherein said keratinous fibers are human keratin fibers.  
     
     
         36 . The method of    claim 35    wherein said human keratinous fibers are hair.  
     
     
         37 . The method of    claim 34   , wherein said dye composition is mixed at the time of use with an oxidizing composition comprising, in a medium suitable for dyeing, at least one oxidizing agent present in an amount sufficient for color development.  
     
     
         38 . The method of    claim 34   , wherein said dye composition additionally contains at least one oxidation catalyst.  
     
     
         39 . The method of    claim 37   , wherein said at least one oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, and enzymes.  
     
     
         40 . The method of    claim 39   , wherein said persalts are chosen from perborates and persulphates.  
     
     
         41 . The method of    claim 39   , wherein said enzymes are chosen from peroxidases and oxidoreductases with 2 unpaired electrons.  
     
     
         42 . The method of    claim 37   , wherein said oxidizing composition is added simultaneously, sequentially, or separately at the time the dye composition is employed.  
     
     
         43 . The method of    claim 34   , wherein said time ranges from 3 to 50 minutes.  
     
     
         44 . The method of    claim 43   , wherein said time ranges from 5 to 30 minuts.  
     
     
         45 . The method of    claim 37   , wherein said oxidizing composition has a pH ranging from 3 to 12.  
     
     
         46 . The method of    claim 45   , wherein said oxidizing composition has a pH ranging from 5 to 11.  
     
     
         47 . The method of    claim 37   , wherein said oxidizing composition additionally contains at least one adjuvant chosen from anionic, cationic, nonionic, amphoteric and zwitterionic surfactants, anionic, cationic, nonionic, amphoteric and zwitterionic polymers, organic and inorganic thickeners, antioxidants, penetration agents, sequestrants, fragrances, buffers, dispersants, conditioners, film forming agents, ceramides, preserving agents and opacifiers.  
     
     
         48 . The method of    claim 34   , wherein said color development occurs at an acidic, neutral or alkaline pH.  
     
     
         49 . The composition of    claim 1   , wherein said composition further comprises an oxidizing composition comprising, in a medium suitable for dyeing, at least one oxidizing agent present in an amount sufficient for color development of said keratinous fibers.  
     
     
         50 . The composition of    claim 49   , wherein said oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, and enzymes.  
     
     
         51 . The composition of    claim 50   , wherein said persalts are chosen from perborates and persulphates.  
     
     
         52 . The composition of    claim 50   , wherein said enzymes are chosen from peroxidases and oxidoreductases with 2 unpaired electrons.  
     
     
         53 . The composition of    claim 49   , wherein said oxidizing composition has a pH ranging from 3 to 12.  
     
     
         54 . The composition of    claim 53   , wherein said oxidizing composition has a pH ranging from 5 to 11.  
     
     
         55 . The composition of    claim 49   , wherein said oxidizing composition additionally contains at least one adjuvant chosen from anionic, cationic, nonionic, amphoteric and zwitterionic surfactants, anionic, cationic, nonionic, amphoteric and zwitterionic polymers, organic and inorganic thickeners, antioxidants, penetration agents, sequestrants, fragrances, buffers, dispersants, conditioners, film forming agents, ceramides, preserving agents and opacifiers.  
     
     
         56 . The composition of    claim 1   , wherein said composition contains at least one oxidation catalyst.  
     
     
         57 . The composition of    claim 1   , said composition being in the form of a liquid, a cream, a gel or any other form suitable for dyeing keratinous fibers.  
     
     
         58 . A method of making at least one 3-aminopyrazolo[1,5-a]pyrimidine chosen from compounds of formula (I) or an acid or base addition salt thereof:  
                   
       in which 
 R 1 , R 2 , R 3  and R 4  are identical or different and represent a hydrogen atom, a halogen atom, a C 1 —C 4  alkyl radical, a C 1 —C 4  trifluoroalkyl radical, a C 1 —C 4  alkoxy radical, an aryl radical, a C 1 —C 4  monohydroxyalkyl radical, a C 2 —C 4  polyhydroxyalkyl radical, a C 1 —C 4  (C 1 —C 4  alkoxy)alkyl radical, a C 1 —C 4  aminoalkyl radical, a C 1 —C 4  (C 1 —C 4  alkyl)aminoalkyl radical, a C 1 —C 4  di(C 1 —C 4  alkyl)aminoalkyl radical, a C 1 —C 4  monohydroxy (C 1 —C 4  alkyl)aminoalkyl radical or a C 1 —C 4  di[hydroxy(C 1 —C 4  alkyl)]aminoalkyl radical comprising the steps of:  
 (a) carrying out a cyclocondensation reaction between a 3(5)-amino-4-nitropyrazole derivative and a β-keto ester, or a β-diketone or a β-keto aldehyde to form a nitro derivative pyrazolo[1,5-a]pyrimidine; and  
 (b) reducing the nitro derivative of (a) to give a 3-amino-pyrazolo[1 ,5-a]pyrimidine of formula (I) or  
 (c) nitrating the nitro derivative of (a) followed by reducing to give the 3-amino-pyrazolo.  
 
     
     
         59 . A multi-compartment dyeing device or kit for dyeing keratin fibers, comprising at least two compartments, wherein 
 a first compartment contains a dyeing composition according to    claim 1    and    a second compartment contains an oxidizing composition.    
     
     
         60 . A 3-Aminopyrazolo[1,5-a]pyrimidine chosen from: 
 pyrazolo[1,5-a]pyrimidin-3-ylamine;    5,6,7-trimethylpyrazolo[1,5-a]pyrimidin-3-ylamine;    7-methylpyrazolo[1,5-a]pyrimidin-3-ylamine;    5-methylpyrazolo[1,5-a]pyrimidin-3-ylamine;    7-methoxypyrazolo[1,5-a]pyrimidin-3-ylamine;    5-methoxypyrazolo[1,5-a]pyramid-3-ylamine;    7-methoxy-5-methylpyrazolo[1,5-a]pyrimidin-3 -ylamine;    2,5,6,7-tetramethylpyrazolo[1,5-a]pyrimidin-3-ylamine;    5,7-di-tert-butylpyrazolo[1,5-a]pyrimidin-3-ylamine;    5,7-di-trifluoromethylpyrazolo[1,5-a]pyrimidin-3-ylamine; and the acid and base addition salts thereof.