Cosmetic compositions based on 4,5-pyrazolinediones, novel 4,5-pyrazolinediones, process for their preparation and uses thereof

Abstract

The present invention relates to novel cosmetic compositions, in particular for coloring the skin and/or the hair, comprising, in a cosmetically acceptable support, at least one 4,5-pyrazolinedione. The invention also relates to novel 4,5-pyrazolinediones, to processes for their preparation and to their uses in the cosmetics field.

1 . Composition comprising, in a cosmetically acceptable support, at least one 4,5-pyrazolinedione corresponding to formula (I) below:  
       
         
           
           
               
               
           
         
       
       in which R 1  is chosen from: 
 a hydrogen atom; a linear or branched C 1 -C 18  alkyl radical optionally substituted with a hydroxyl (OH), sulphonyl (SO 3 H), carboxyl (COOH) or C 2 -C 4  hydroxyalkyl radical; a cyclohexyl or cyclopentyl radical;  
 a radical  
                     
  in which m is equal to 1, 2 or 3, n is equal to 1, 2 or 3, X is a hydrogen atom or a methyl radical, and Y is a methyl, hydroxyl or linear or branched C 1 -C 5  alkoxy radical;  
 a radical —(CH 2 ) p —OR′ in which R′ represents a substituted or unsubstituted phenyl or naphthyl radical and p is equal to 1 or 2;  
 a radical —(CH 2 ) q —R″ in which q is equal to 1, 2 or 3 and R″ is chosen from: 
 a phenyl radical which is unsubstituted or substituted with not more than 2 radicals chosen from methyl, trifluoromethyl, methoxy or sulphonyl radicals;  
 
 a naphthyl radical, a thienyl radical, a furyl radical, a pyridyl radical or a piperidyl radical;  
 a radical:  
                     
 a radical:  
 a radical:  
 a phenyl radical; a phenyl radical substituted with a nitro radical; a phenyl radical substituted with one to three radicals chosen from: —COOH, —CH 2 COOH, —Cl, —Br, —F, —OH, —SO 3 H, —CH 2 OH, —OCF 3 , —CF 3 , —SO 2 CH 3 , —SO 2 NH 2 , —SO 2 NHC 2 H 5 , —SO 2 NHCH 2 CH 2 OH, —CON(CH 3 ) 2 , —CON(C 2 H 5 ) 2 , —CH 2 N(CH 3 ) 2 , —CH 2 N(C 2 H 5 ) 2 , —NHCOCH 3 , —NHCOC 2 H 5 , a C 1 -C 8  alkyl radical or a radical —ZR 3  in which Z is an oxygen or sulphur atom and R 3  is a hydrogen atom or a linear or branched C 1 -C 18  alkyl radical;  
 a naphthyl radical optionally substituted with an —SO 3 H radical;  
 a benzyl radical; a benzyl radical substituted with a —COOH, —OCH 3  or —SO 3 H radical;  
 a pyridyl radical, a pyrimidinyl radical, a pyrazinyl radical, a triazinyl radical, a benzotriazolyl radical, a benzimidazolyl radical, a thienyl radical, an imidazolyl radical, a thiazolyl radical, a 1,2,4-triazolyl radical, an indazolyl radical, an indolyl radical, a quinolyl radical or an isoquinolyl radical;  
 and R 2  is chosen from:  
 a hydrogen atom; a linear or branched C 1 -C 6  alkyl radical; a C 1 -C 4  hydroxyalkyl radical; a methoxymethyl radical;  
 a phenyl radical; a phenyl radical substituted with a halogen atom, a nitro radical or a trifluoromethyl radical; a phenyl radical substituted with not more than three radicals chosen from C 1 -C 4  alkyl, C 1 -C 4  alkoxy, C 1 -C 4  dialkylamino and C 1 -C 2  alkylthio radicals;  
 a benzyl radical; a benzyl radical substituted with a halogen atom, a C 1 -C 4  alkyl radical, a C 1 -C 4  alkoxy radical, a trifluoromethyl radical or a C 1 -C 4  dialkylamino radical;  
 a radical —(CH 2 ) r —R 4  in which r is equal to 1, 2 or 3 and R 4  is chosen from: 
 an —SO 3 H radical, a C 1 -C 2  alkylthio radical or a benzylthio radical;  
 a methoxycarbonyl or ethoxycarbonyl radical;  
 a phenyl radical;  
 a C 1 -C 4  alkoxy radical or a phenoxy radical optionally substituted with one or more halogen atoms;  
 
 a C 1 -C 4  alkoxy radical; a trifluoromethyl radical; an acetamido radical; a C 1 -C 4  dialkylamino radical; a carboxyl radical; a methoxycarbonyl radical; an ethoxycarbonyl radical;  
 a thienyl radical, a furyl radical, a pyridyl radical or a pyrazolyl radical.  
 
     
     
         2 . Composition according to  claim 1 , characterized in that R 1  is chosen from: 
 a hydrogen atom; a linear or branched C 1 -C 8  alkyl radical;    a radical —(CH 2 ) 2 —OR′ in which R′ represents a phenyl or naphthyl radical;    a radical —(CH 2 ) q —R″ in which q is equal to 1 or 2 and R″ represents a phenyl radical optionally substituted with a trifluoromethyl radical;    a phenyl radical optionally substituted with a nitro radical, a —Cl radical, a C 1 -C 4  alkyl radical or a C 1 -C 4  alkoxy radical.    
     
     
         3 . Composition according to  claim 1  or  2 , characterized in that R 2  is chosen from: 
 a hydrogen atom; a linear or branched C 1 -C 4  alkyl radical; a C 1 -C 4  hydroxyalkyl radical; a methoxymethyl radical;  
 a phenyl radical optionally substituted with a halogen atom, a nitro radical, a C 1 -C 4  alkyl radical or a C 1 -C 4  alkoxy radical;  
 a C 1 -C 4  alkoxy radical; a trifluoromethyl radical; an acetamido radical; a C 1 -C 4  dialkylamino radical; a carboxyl radical; a methoxycarbonyl radical; an ethoxycarbonyl radical;  
 a thienyl radical, a furyl radical, a pyridyl radical or a pyrazolyl radical.  
 
     
     
         4 . Composition according to  claim 3 , characterized in that R 1  is chosen from: 
 hydrogen and methyl, ethyl, isopropyl, tert-butyl and phenyl radicals;    and R 2  is chosen from:    hydrogen and methyl, phenyl, methoxyphenyl, methoxy, ethoxy, carboxyl, methoxycarbonyl, ethoxycarbonyl, acetamido, dimethylamino, diethylamino, trifluoromethyl, furyl and pyridyl radicals.    
     
     
         5 . Composition according to  claim 4 , characterized in that the 4,5-pyrazolinedione is chosen from: 3-methyl-1-phenyl-4,5-pyrazolinedione; 3-methyl-4,5-pyrazolinedione; 1,3-dimethyl-4,5-pyrazolinedione; 1-ethyl-3-methyl-4,5-pyrazolinedione; 1-isopropyl-3-methyl-4,5-pyrazolinedione; 1-tert-butyl-3-methyl-4,5-pyrazolinedione; 1-methyl-3-phenyl-4,5-pyrazolinedione; 1-methyl-3-(3′-methoxyphenyl)-4,5-pyrazolinedione; 3-(2′-furyl)-1-methyl-4,5-pyrazolinedione; 1-methyl-3-(4′-pyridyl)-4,5-pyrazolinedione; 1-methyl-3-methoxy-4,5-pyrazolinedione; 3-ethoxy-1-methyl-4,5-pyrazolinedione; 3-dimethylamino-1-methyl-4,5-pyrazolinedione; 3-diethylamino-1-methyl-4,5-pyrazolinedione; 3-acetamido-1-methyl-4,5-pyrazolinedione; 1-phenyl-4,5-pyrazolinedione; 1-methyl-4,5-pyrazolinedione; 1-ethyl-4,5-pyrazolinedione; 1-isopropyl-4,5-pyrazolinedione; 1-tert-butyl-4,5-pyrazolinedione; 3-methoxy-1-phenyl-4,5-pyrazolinedione; 3-ethoxy-1-phenyl-4,5-pyrazolinedione; 3-acetamido-1-phenyl-4,5-pyrazolinedione; 3-dimethylamino-1-phenyl-4,5-pyrazolinedione; 3-diethylamino-1-phenyl-4,5-pyrazolinedione; 1-phenyl-3-trifluoromethyl-4,5-pyrazolinedione; 1-methyl-3-trifluoromethyl-4,5-pyrazolinedione; 1-isopropyl-3-trifluoromethyl-4,5-pyrazolinedione; 1-ethyl-3-trifluoromethyl-4,5-pyrazolinedione; 3-trifluoromethyl-4,5-pyrazolinedione; 3-carboxy-1-phenyl-4,5-pyrazolinedione; 3-methoxycarbonyl-1-phenyl-4,5-pyrazolinedione; 3-ethoxycarbonyl-1-phenyl-4,5-pyrazolinedione; 3-methoxy-4,5-pyrazolinedione; 3-ethoxy-4,5-pyrazolinedione; 3-carboxy-1-methyl-4,5-pyrazolinedione; 3-methoxycarbonyl-1-methyl-4,5-pyrazolinedione; 3-ethoxycarbonyl-1-methyl-4,5-pyrazolinedione.  
     
     
         6 . Composition according to any one of  claims 1  to  5 , characterized in that the 4,5-pyrazolinedione is present in the composition at a concentration of between 0.05 and 10% by weight relative to the total weight of the composition.  
     
     
         7 . Composition according to  claim 6 , characterized in that the said concentration is between 0.05 and 5% by weight relative to the total weight of the composition.  
     
     
         8 . Composition according to any one of the preceding claims, characterized in that it is a cosmetic composition for colouring the skin.  
     
     
         9 . Composition according to any one of  claims 1  to  7 , characterized in that it is a cosmetic composition for dyeing the hair.  
     
     
         10 . Cosmetic treatment process for the skin which is intended to artificially tan and/or brown it, characterized in that it consists in applying an effective amount of a composition as defined in any one of  claims 1  to  8  or a 4,5-pyrazolinedione as defined in any one of  claims 1  to  5  to the skin.  
     
     
         11 . Use of a 4,5-pyrazolinedione as defined in any one of  claims 1  to  5  in, or for the manufacture of, compositions intended to artificially tan and/or brown the skin.  
     
     
         12 . Cosmetic treatment process for the hair which is intended to dye it, characterized in that it consists in applying an effective amount of a composition as defined in any one of  claims 1  to  9  or a 4,5-pyrazolinedione as defined in any one of  claims 1  to  5  to the hair.  
     
     
         13 . Use of a 4,5-pyrazolinedione as defined in any one of  claims 1  to  5  in, or for the manufacture of, compositions intended to dye the hair.  
     
     
         14 . Compounds corresponding to the general formula (I′) below:  
       
         
           
           
               
               
           
         
       
       in which R′ 1  and R′ 2  have the same meanings as those given in formula (I) of  claim 1  for R 1  and R 2  with, however, the following provisos: 
 (i) when R′ 1  represents a phenyl radical, then R′ 2  is other than a hydrogen atom, a methyl radical, a tert-butyl radical, a phenyl radical, a p-methylphenyl radical, a p-nitrophenyl radical or a p-methoxyphenyl radical,  
 (ii) when R′ 2  represents a methyl radical, R′ 1  is other than a p-nitrophenyl radical, a 2-phenoxyethyl radical, a 2-naphthyloxyethyl radical, a methyl radical, an m-trifluoromethylbenzyl radical, a 1-phenylethyl radical, a 1-cyclohexylethyl radical or a 1-(3′,4′-dichlorophenyl)ethyl radical,  
 (iii) when R′ 1  represents a 2-naphthyloxyethyl radical, R′ 2  is other than an n-propyl radical or a hydroxymethyl radical,  
 (iv) when R′ 1  represents a 2-phenoxyethyl radical, R′ 2  is other than a tert-butyl radical,  
 (v) when R′ 2  represents a methoxymethyl radical, R′ 1  is other than a 2-naphthyloxyethyl radical or a 1-(3′,4′-dichlorophenyl)ethyl radical,  
 (vi) when R′ 1  represents a hydrogen atom, R′ 2  is other than a methyl radical.  
 
     
     
         15 . Compounds according to  claim 14 , characterized in that R′ 1  is chosen from: 
 a hydrogen atom; a linear or branched C 1 -C 8  alkyl radical;  
 a radical —(CH 2 ) 2 —OR′ in which R′ represents a phenyl or naphthyl radical;  
 a radical —(CH 2 ) q   13  R″ in which q is equal to 1 or 2 and R″ represents a phenyl radical optionally substituted with a trifluoromethyl radical;  
 a phenyl radical optionally substituted with a nitro radical, a —Cl radical, a C 1 -C 4  alkyl radical or a C 1 -C 4  alkoxy radical.  
 
     
     
         16 . Compounds according to  claim 14  or  15 , characterized in that R′ 2  is chosen from: 
 a hydrogen atom; a linear or branched C 1 -C 4  alkyl radical; a C 1 -C 4  hydroxyalkyl radical; a methoxymethyl radical;  
 a phenyl radical optionally substituted with a halogen atom, a nitro radical, a C 1 -C 4  alkyl radical or a C 1 -C 4  alkoxy radical;  
 a C 1 -C 4  alkoxy radical; a trifluoromethyl radical; an acetamido radical; a C 1 -C 4  dialkylamino radical; a carboxyl radical; a methoxycarbonyl radical; an ethoxycarbonyl radical;  
 a thienyl radical, a furyl radical, a pyridyl radical or a pyrazolyl radical.  
 
     
     
         17 . Compounds according to  claim 16 , characterized in that R′ 1  is chosen from: 
 hydrogen and methyl, ethyl, isopropyl, tert-butyl and phenyl radicals;  
 and R′ 2  is chosen from:  
 hydrogen and methyl, phenyl, methoxyphenyl, methoxy, ethoxy, carboxyl, methoxycarbonyl, ethoxycarbonyl, acetamido, dimethylamino, diethylamino, trifluoromethyl, furyl and pyridyl radicals.  
 
     
     
         18 . Compound according to  claim 17 , characterized in that it is chosen from: 1-ethyl-3-methyl-4,5-pyrazolinedione; 1-isopropyl-3-methyl-4,5-pyrazolinedione; 1-tert-butyl-3-methyl-4,5-pyrazolinedione; 1-methyl-3-phenyl-4,5-pyrazolinedione; 1-methyl-3-(3′-methoxyphenyl)-4,5-pyrazolinedione; 3-(2′-furyl)-1-methyl-4,5-pyrazolinedione; 1-methyl-3-(4′-pyridyl)-4,5-pyrazolinedione; 1-methyl-3-methoxy-4,5-pyrazolinedione; 3-ethoxy-1-methyl-4,5-pyrazolinedione; 3-dimethylamino-1-methyl-4,5-pyrazolinedione; 3-diethylamino-1-methyl-4,5-pyrazolinedione; 3-acetamido-1-methyl-4,5-pyrazolinedione; 1-methyl-4,5-pyrazolinedione; 1-ethyl-4,5-pyrazolinedione; 1-isopropyl-4,5-pyrazolinedione; 1-tert-butyl-4,5-pyrazolinedione; 3-methoxy-1-phenyl-4,5-pyrazolinedione; 3-ethoxy-1-phenyl-4,5-pyrazolinedione; 3-acetamido-1-phenyl-4,5-pyrazolinedione; 3-dimethylamino-1-phenyl-4,5-pyrazolinedione; 3-diethylamino-1-phenyl-4,5-pyrazolinedione; 1-phenyl-3-trifluoromethyl-4,5-pyrazolinedione; 1-methyl-3-trifluoromethyl-4,5-pyrazolinedione; 1-isopropyl-3-trifluoromethyl-4,5-pyrazolinedione; 1-ethyl-3-trifluoromethyl-4,5-pyrazolinedione; 3-trifluoromethyl-4,5-pyrazolinedione; 3-carboxy-1-phenyl-4,5-pyrazolinedione; 3-methoxycarbonyl-1-phenyl-4,5-pyrazolinedione; 3-ethoxycarbonyl-1-phenyl-4,5-pyrazolinedione; 3-methoxy-4,5-pyrazolinedione; 3-ethoxy-4,5-pyrazolinedione; 3-carboxy-1-methyl-4,5-pyrazolinedione; 3-methoxycarbonyl-1-methyl-4,5-pyrazolinedione; 3-ethoxycarbonyl-1-methyl-4,5-pyrazolinedione.  
     
     
         19 . Process for the preparation of the novel compounds of formula (I′), characterized in that it comprises the following steps, the meanings of R′ 1  and R′ 2  being as defined in claim  14 : 
 i) a 5-pyrazolinone (1) is reacted with an aromatic nitroso compound (2) in order to obtain the corresponding 4-arylimino-5-pyrazolinone (3):  
                     
 this reaction being carried out in a lower alcohol, at reflux, at a temperature of between 65° C. and 85° C.,  
 ii) the 4-arylimino-5-pyrazolinone (3) is then hydrolysed, in strong acid medium, in order to obtain the corresponding 4,5-pyrazolinedione derivative of formula (I′):  
                     
 
     
     
         20 . Process according to  claim 19 , characterized in that the lower alcohol used in step (i) is chosen from methanol, ethanol and isopropanol.  
     
     
         21 . Process according to  claim 19  or  20 , characterized in that step (i) is carried out in the presence of a catalytic amount of a weak base such as a carbonate or a bicarbonate.  
     
     
         22 . Process according to any one of  claims 19  to  21 , characterized in that the aromatic nitroso derivative of step (i) is a p-nitrosodialkylaniline of formula (2)′ below:  
       
         
           
           
               
               
           
         
       
       in which R 5  and R 6  represent a linear or branched C 1 -C 4  alkyl radical.  
     
     
         23 . Process according to any one of  claims 19  to  22 , characterized in that the acid hydrolysis of step (ii) is carried out with dilute sulphuric acid or aqueous hydrochloric acid at room temperature, in the presence of a co-solvent for the 4,5-pyrazolinedione, which is immiscible with water.  
     
     
         24 . Process according to  claim 23 , characterized in that the said co-solvent is an ether chosen from diethyl ether and diisopropyl ether.  
     
     
         25 . Process for the preparation of the novel compounds of formula (I′), characterized in that it comprises the following steps, the meanings of R′ 1  and R′ 2  being as defined in claim  14 : 
 i) bromine is reacted with a 5-pyrazolinone of formula (1) in order to obtain the corresponding 4,4-dibromo-5-pyrazolinone of formula (4) (step a),  
 ii) lead diacetate is then reacted so as to form the corresponding diacetate of formula (5), this product being an unstable intermediate which leads spontaneously, by elimination of acetic anhydride, to the 4,5-pyrazolinedione derivative of formula (I′) (step b), these two steps being carried out according to the following reaction scheme:  
                     
 
     
     
         26 . Process according to  claim 25 , characterized in that step a is carried out in aqueous medium in the presence of two equivalents of bromine at room temperature.  
     
     
         27 . Process according to  claim 25  or  26 , characterized in that step b is carried out at the reflux point of acetic acid for a few hours.