Alcoholic or aqueous-alcoholic compositions containing natural essences and benzylidene-camphor derivatives
This application is a continuation of application Ser. No. 573,145, filed Jan. 23, 1984, now abandoned. 
    
    
     The present invention relates to alcoholic or aqueous-alcoholic compositions, in particular of the toilet water, perfume or shaving lotion type, containing natural essences and benzylidenecamphor derivatives. 
     It has been known for a very long time that natural essences such as bergamot oil and lemon oil, contained in various cosmetics, perfumes and toilet water, are involved in certain skin diseases which appear as violent erythemas and eczematoid lesions, followed by non-uniform residual pigmentations. These skin reactions, which require exposure to ultraviolet light, are referred to as &#34;phototoxic reactions&#34;. The compounds responsible for this phototoxicity are furocoumarins, the main representative of this family in bergamot oil being bergaptene, or 5-methoxyfurocoumarin, or alternatively 5-methoxypsoralene (5-MOP), of the formula: ##STR1## 
     This compound is phototoxic, as are the majority of linear furocoumarins such as, for example, furocoumarin itself and 8-methoxyfurocoumarin. 5-Methoxyfurocoumarin is responsible for skin reactions at a concentration of 10 ppm or above, which explains that, to prevent any risk of skin disease, the use of more than 0.1 to 0.3% of bergamot oil on the skin is generally avoided, this oil containing 3000 to 7500 ppm of 5-methoxyfurocoumarin. 
     This shows the advantage of removing the furocoumarins from natural essences such as bergamot oil and lemon oil, in order to protect the health of people induced to using toilet waters or perfumes containing such essences. 
     On account of the economic importance of natural essences, detoxification methods have been proposed, in particular for bergamot oil. These methods employ vacuum distillation of the volatile fraction of the bergamot oils; the distillation residue is then saponified with alcoholic potassium hydroxide in order to convert the furocoumarins to cinnamic acid derivatives by opening of the lactone group, and then extracted with a hydrocarbon after the alcohol has been evaporated off; the extraction solution is neutralised by washing with water, and the residue obtained after the solvent has been evaporated off is incorporated into the volatile fraction. 
     The bergamot oils treated by this process and containing 40 ppm or less of 5-methoxyfurocoumarin are only very slightly phototoxic, as shown in the publication by J. Girard et al. in &#34;Parfums, cosmetiques, aromes&#34; no. 38, April-May 1981, pages 39-44. However, such methods for the detoxification of natural essences are complicated and expensive and have the disadvantage of considerably modifying the olfactory properties of the essences treated. 
     Attempts have therefore been made to find another means of detoxifying natural essences by eliminating the toxic effect due to furocoumarins. 
     It is known that, when furocoumarins absorb ultraviolet light, they are electronically excited. It is the triplet excited level which is the precursor state of all known photobiological reactions. 
     Now, the Applicants have observed that, totally surprisingly, certain benzylidenecamphor derivatives which filter out UV-A radiation are capable of deactivating the triplet level of furocoumarins according the equation: 
     
         Pso.sup.x +Bz-C→Pso+Bz-C.sup.x 
    
     Pso denoting psoralene and Bz-C denoting the benzylidenecamphor derivative. 
     This results in a molecule of furocoumarin in the unexcited ground state and an excited molecule of benzylidenecamphor derivative, which then deactivates itself without any reaction other than a purely intramolecular E-Z isomerization: 
     
         Bz-C.sup.x →1/2Bz-C(E)+1/2Bz-C(Z) 
    
     The experiments carried out by the Applicants have shown that a concentration of benzylidenecamphor derivative of the order of 4.10 -3  mol per liter is sufficient to deactivate 80% of the excited furocoumarin molecules. Under these conditions, the phototoxic activity of a solution containing a furocoumarins and 4.10 -3  mol per liter of benzylidenecamphor derivative would be 5 times lower than the phototoxic activity of an identical solution not containing benzylidenecamphor derivative. 
     The object of the present invention is therefore to reduce the phototoxicity of the furocoumarins contained in natural essences by the addition of benzylidenecamphor derivatives filtering out UV-A radiation, which have the property of picking up the electronic excitation energy of the furocoumarins and degrading it in the form of heat energy after isomerisation. 
     The present invention relates to alcoholic or aqueous-alcoholic compositions containing a phototoxic dose of furocoumarin and at least one benzylidenecamphor derivative filtering out UV-A radiation and chosen from amongst: 
     the 3-p-oxybenzylidenebornan-2-ones of French Pat. No. 2,430,938, having the formula: ##STR2## in which: Z 1  and Z&#39; 1  respectively denote a hydrogen atom, a radical SO 3  H or a salt of this sulphonic acid with an inorganic or organic base, at least one of the two radicals Z 1  or Z&#39; 1  representing a hydrogen atom; 
     R 1  denotes a hydrogen atom, an optionally branched alkyl radical containing 2 to 18 carbon atoms, an alkenyl radical containing 3 to 18 carbon atoms or a radical ##STR3## in which R denotes H, an alkyl radical containing 1 to 8 carbon atoms, --(CH 2 ) 3  --SO 3  H or a salt of this acid with an organic or inorganic base, or alternatively a divalent radical --(CH 2 ) m  or --CH 2  --CHOH--CH 2 , m having the values 1 to 10 and n having the values 1 to 6, and R 3  and R 4  each representing a hydrogen atom or an optionally branched or hydroxylated alkyl radical, or together forming an aminoaliphatic heterocycle with the nitrogen atom; 
     R 2  denotes a hydrogen atom, an alkoxy radical containing 1 to 4 carbon atoms or a divalent radical --O-- joined to the radical R 1  in the case where the latter is also divalent; and 
     q denotes 1 or 2, it being understood that if q has the value 2, R 1  is a divalent radical, and that if R 1  denotes hydrogen, R 2  also denotes hydrogen; moreover, if R 2  denotes alkoxy, R 1  can also denote methyl; 
     the benzylidenecamphors described in Belgian Patent Application No. 211,002, having the formula: ##STR4## in which: R 1  denotes a hydrogen atom or a radical --SO 3 .sup.⊖ M.sup.⊕, in which M denotes a hydrogen atom, an alkali metal or a group N.sup.⊕ (R 3 ) 4 , R 3  denoting a hydrogen atom or a C 1  to C 4  alkyl or hydroxyalkyl radical; 
     n=0, that is to say R 2  denotes a hydrogen atom; and 
     Z represents a group ##STR5## in which R 4  has the same meanings as R 1  and can be equal to R 1  or different from R 1 , or alternatively a group ##STR6## in which R 5  denotes a hydrogen atom, a C 1  to C 4  alkyl radical, an aryl radical optionally substituted by halogen atoms or by C 1  to C 4  alkyl or alkoxy groups, or a group --CN, --COOR 7  or ##STR7## and R 6  denotes a group --COOR 8  or ##STR8## R 7  and R 8 , which are identical or different, being alkyl, alkenyl, cycloalkyl or aralkyl radicals containing at most 20 carbon atoms, which are optionally substituted by hydroxyl, alkoxy, amine or quaternary ammonium groups, and R 9  and R 10 , which are identical or different, denoting a hydrogen atom or alkyl, alkenyl, cycloalkyl or aralkyl radicals containing at most 20 carbon atoms, which are optionally substituted by hydroxyl, alkoxy, amine or quaternary ammonium groups, or alternatively if R 5  denotes a hydrogen atom or an alkyl or optionally substituted aryl radical, R 6  can also represent a radical --COO.sup.⊖ M.sup.⊕, M being defined as above, 
     the two methylidenecamphor radicals, on the one hand, and Z, on the other hand, being attached to the aromatic nucleus A in the para position relative to one another; and 
     the sulphonamides derived from benzylidenecamphor described in Belgian Patent Application No. 211,134, having the formula: ##STR9## in which: X 1  denotes the radical Y; 
     X 2  denotes a radical Z; and 
     X 3  denotes a hydrogen atom, 
     Y denoting the group ##STR10## in which R 1  denotes a hydrogen atom or a C 1  -C 4  alkyl or hydroxyalkyl radical and R 2  denotes a hydrogen atom, a linear or branched alkyl or alkenyl radical or a cycloalkyl, aryl or aralkyl radical, it being possible for these various C 1  -C 20  radicals to be substituted by one or more hydroxyl, alkoxy or dialkylamino groups, it being impossible for R 1  and R 2  simultaneously to denote a hydrogen atom, and Z denoting one of the following groups: 
     Z 1  = ##STR11## in which Y has the abovementioned meaning, or Z 2  = ##STR12## 
     A phototoxic dose can be defined as being equal to at least 10 ppm of bergaptene. 
     Experiments carried out on guinea-pigs have made it possible to demonstrate the considerable reduction in erythema or the absence of erythema on the skin to which the composition has been applied, after the animal has been exposed to UV-A radiation. 
     The following may be mentioned as particularly preferred compounds filtering out UV-A radiation which are used according to the invention: 3,3&#39;-terephthalylidenecampho-10,10&#39;-disulphonic acid, 3,3&#39;-terephthalylidenecampho-10-sulphonic acid, 4-(ethyl 2&#39;-carboxyethylacrylate)-benzylidenecamphor, 4&#39;-butoxy-3&#39;-methoxy-3-benzylidenebornanone and also their salts. 
     According to a preferred embodiment of the invention, the alcoholic or aqueous-alcoholic composition containing a phototoxic dose of furocoumarin and at least one benzylidenecamphor derivative filtering out UV-A radiation also contains at least one compound filtering out UV-B radiation which is compatible with the abovementioned UV-A filters. 
     The compounds filtering out UV-B radiation are chosen from amongst: 
     benzylidenecamphor; 
     p-methylbenzylidenecamphor; 
     benzylidenecamphor derivatives containing a quaternary ammonium radical on the benzene nucleus in the para position relative to the bornylidene radical, according to French Pat. No. 2,199,971, having the formula: ##STR13## 
     in which: 
     R represents a hydrogen atom or an alkyl group containing 1 to 12 carbon atoms, 
     Y represents a halogen, a methyl group or a hydrogen atom, and 
     X.sup.⊖ represents a halide, an arylsulphonate, an alkylsulphonate, a camphosulphonate or an alkylsulphate; 
     benzylidenecamphor derivatives sulphonated on the methyl radical in the 10-position of the camphor or in the 3&#39;-position or 4&#39;-position on the benzene nucleus, according to French Pat. No. 2,236,515 and No. 2,282,426, respectively having the formulae: ##STR14## in which R denotes a hydrogen atom, a halogen atom such as Cl or F, or an alkyl radical containing 1 to 4 carbon atoms, and R&#39; and R&#34; each denote a hydrogen atom or a radical --SO 3  M, in which M denotes H, an organic ammonium group or a metal, at least one of the radicals R&#39; and R&#34; not having the meaning H, and ##STR15## in which R&#39; denotes a hydrogen atom or a radical --SO 3  M and R&#34; denotes SO 3  M, in which M denotes H, an organic ammonium group or a metal; 
     p-methylbenzylidenecamphor derivatives substituted on the p-methyl group, according to French Pats. No. 2,383,904, No. 2,402,647 and No. 2,421,878, respectively having the formulae: ##STR16## in which Y and Y&#39; denote H or SO 3  H and the corresponding salts with organic or inorganic bases, at least one of the radicals Y and Y&#39; having the meaning H; and Z&#39; denotes the group --CH 2  R, --CHR&#39;R&#39;, --CHO or --COOR&#34;, in which R=-OR 4 , --OCOR 5 , --SR 6 , --CN or --COOR&#34;, R 4  =H, alkyl, polyoxyethylene or substituted or unsubstituted aryl, R 5  =alkyl, alkenyl, aryl or an aromatic or non-aromatic heterocycle containing 5 to 6 ring members, and R 6  =H, alkyl, carboxyalkyl, aminoalkyl, hydroxyalkyl, aryl or alanin-3-yl, R&#39;=OR&#39; 4  or --SR&#39; 6 , in which R&#39; 4  and R&#39; 6  can respectively have the same meanings as R 4  and R 6 , except for the meaning hydrogen, and R&#34;=hydrogen or alkyl, and ##STR17## in which Y denotes H or SO 3  H and the corresponding salts with organic or inorganic bases; 
     Y&#39; denotes H; and 
     Z&#39; denotes the group --CH 2  I, --CH 2  R, --CHR&#39;R&#39;, --CHO or --COOR&#34;, in which R=--OR 4 , --OCOR 5 , --SR 6 , --CN or --COOR&#34;, R 4  =H, alkyl, polyoxyethylene, substituted or unsubstituted aryl, menthyl or dialkylaminoalkyl, R 5  =alkyl, alkenyl, aryl or an aromatic or non-aromatic heterocycle containing 5 to 6 ring members and R 6  =H, alkyl, carboxyalkyl, aminoalkyl, hydroxyalkyl, aryl or alanin-3-yl, R&#39;=--OR&#39; 4  or --SR&#39; 6 , in which R&#39; 4  and R&#39; 6  can respectively have the same meanings as R 4  and R 6 , except for the meanings hydrogen, polyoxyethylene, hydroxyalkyl, alanin-3-yl and aryl, and R&#34;=hydrogen or alkyl; 
     the benzylidenecamphors described in Belgian Patent Application No. 211,002, having the formula: ##STR18## in which: R 1  denotes a hydrogen atom or a radical --SO 3 .sup.⊖ M.sup.⊕, in which M denotes a hydrogen atom, an alkali metal or group N.sup.⊕ (R 3 ) 4 , R 3  denoting a hydrogen atom or a C 1  to C 4  alkyl or hydroxyalkyl radical; 
     R 2  denotes a linear or branched C 1  to C 4  alkyl radical or a C 1  to C 4  alkoxy radical, n being an integer ranging from 0 to 4; if n≧2, the radicals R 2  can be identical or different; and Z represents a group ##STR19## in which R 4  has the same meanings as R 1  and can be equal to R 1  or different from R 1 , or alternatively a group ##STR20## in which R 5  denotes a hydrogen atom, a C 1  to C 4  alkyl radical, an aryl radical optionally substituted by halogen atoms or by C 1  to C 4  alkyl or alkoxy groups, or a group --CN, --COOR 7  or ##STR21## and R 6  denotes a group --COOR 8  or ##STR22## R 7  and R 8 , which are identical or different, being alkyl, alkenyl, cycloalkyl or aralkyl radicals containing at most 20 carbon atoms, which are optionally substituted by hydroxyl, alkoxy, amine or quaternary ammonium groups, and R 9  and R 10 , which are identical or different, denoting a hydrogen atom or alkyl, alkenyl, cycloalkyl or aralkyl radicals containing at most 20 carbon atoms, which are optionally substituted by hydroxyl, alkoxy, amine or quaternary ammonium groups, or alternatively if R 5  denotes a hydrogen atom or an alkyl or optionally substituted aryl radical, R 6  can also represent a radical --COO.sup.⊖ M.sup.⊕, M being defined as above, 
     the two methylidenecamphor radicals, on the one hand, and Z, on the other hand, being attached to the aromatic nucleus A in the meta position relative to one another; they can be attached in the para position if n≠0; and 
     the sulphonamides derived from benzylidenecamphor described in Belgian Patent Application No. 211,134, having the formula: ##STR23## in which X 1  denotes a hydrogen atom or the radical Y; X 2  denotes a hydrogen or halogen atom, a C 1  -C 4  alkyl or alkoxy radical or a radical Y or Z; and X 3  denotes a hydrogen or halogen atom, a C 1  -C 4  alkyl or alkoxy radical or a radical Y or Z, or alternatively X 2  and X 3  together form an alkylenedioxy group in which the alkylene group contains 1 or 2 carbon atoms, Y denoting the group ##STR24## in which R 1  denotes a hydrogen atom or a C 1  -C 4  alkyl or hydroxyalkyl radical and R 2  denotes a hydrogen atom, a linear or branched alkyl or alkenyl radical or a cycloalkyl, aryl or aralkyl radical, it being possible for these various C 1  -C 20  radicals to be substituted by one or more hydroxyl, alkoxy or dialkylamino groups, it being impossible for R 1  and R 2  simultaneously to denote a hydrogen atom, and Z denoting one of the following groups: 
     Z 1  = ##STR25## in which Y has the abovementioned meaning, or Z 2  = ##STR26## or Z 3  = ##STR27## in which R 3  denotes a hydrogen atom or a group --CN or --COR 5  and R 4  denotes a group --COR 6 , R 5  and R 6 , which are identical or different, being C 1  -C 20  alkoxy or alkylamino groups, 
     with the proviso that one of the symbols X 1 , X 2  and X 3  is different from the other two and that 
     (a) when X 1  denotes a hydrogen atom, X 2  and X 3  are different from one another and cannot take the meanings Z 2  and Z 3 , one of the two necessarily having the meaning Y or Z 1 , and 
     (b) when X 1  has the meaning Y, X 2  and X 3  are different from Y and cannot simultaneously take the meaning Z 1 , Z 2  or Z 3 , and, moreover, if X 2  =Z 1  or Z 2 , X 3  does not denote a hydrogen atom. 
     The following may be mentioned as particularly preferred compounds filtering out UV-B radiation: benzylidenecamphor, 4-[(2-oxo-3-bornylidene)-methyl]phenyltrimethylammonium methyl-sulphate, p-methylbenzylidenecamphor, N-(2-ethylhexyl)-3-benzylidenecampho-10-sulphonamide, 3-benzylidene-2-oxobornane-10-sulphonic acid, 3-(2-oxo-3-bornylidenemethyl)-benzenesulphonic acid, 2-methyl-5-(2-oxo-3-bornylidenemethyl)benzenesulphonic acid and also their salts. 
     The alcoholic or aqueous-alcoholic composition according to the invention can consist of an eau de cologne, a toilet water, a perfume or a pre-shave or after-shave lotion containing natural essences such as bergamot oil and lemon oil. 
     It generally contains 0.01 to 2% and preferably 0.1 to 1% by weight of benzylidenecamphor derivative(s). 
     The pre-shave or after-shave lotions, eaux de cologne and toilet waters are presented in the form of an aqueous-alcoholic solution containing, apart from the natural essence and the benzylidenecamphor or one of its derivatives, a lower alkanol containing 1 to 4 carbon atoms, preferably ethanol or isopropanol and, if appropriate, n-propanol, and glycols such as ethylene glycol or propylene glycol, and comprising the adjuvants normally used, such as softeners, for example glycerol, and cicatrising agents, as well as preservatives. 
     The composition according to the invention can also be an alcoholic or aqueous-alcoholic gel comprising, in addition to natural essences, one or more lower alcohols such as ethanol, propylene glycol or glycerol, and a thickener, if appropriate in the presence of water. 
    
    
     The alcoholic or aqueous-alcoholic composition according to the invention will be illustrated more clearly by the non-limiting examples which follow. 
     EXAMPLE 1 
     
         ______________________________________                                    
Perfume                                                                   
______________________________________                                    
Natural essence containing 5% of                                          
                     25        g                                          
bergamot oil                                                              
Triethanolamine salt of 3,3&#39;-tere-                                        
                     0.5       g                                          
phthalylidenedicampho-10,10&#39;-di-                                          
sulphonic acid                                                            
Distilled water      0.2       g                                          
96.2° strength alcohol q.s.                                        
                     100       cm.sup.3                                   
______________________________________                                    
 
    
     The perfume formulated in this way contains 43.7 ppm of 5-MOP. 
     EXAMPLE 2 
     
         ______________________________________                                    
Perfume                                                                   
______________________________________                                    
Natural essence containing 5% of                                          
                     20.5      g                                          
bergamot oil                                                              
Triethanolamine salt of 3,3&#39;-tere-                                        
                     0.3       g                                          
phthalylidenedicampho-10-sulphonic                                        
acid                                                                      
Benzylidenecamphor   0.1       g                                          
Distilled water      0.2       g                                          
96.2° strength alcohol q.s.                                        
                     100       cm.sup.3                                   
______________________________________                                    
 
    
     The perfume formulated in this way contains 35.8 ppm of 5-MOP. 
     EXAMPLE 3 
     
         ______________________________________                                    
Toilet water                                                              
______________________________________                                    
Natural essence containing 30% of                                         
                       8        g                                         
bergamot oil                                                              
Triethanolamine salt of 3,3&#39;-tere-                                        
                       0.55     g                                         
phthalylidenedicampho-10,10&#39;-di-                                          
sulphonic acid                                                            
N--(2-ethylhexyl)-3-benzylidene-10-                                       
                       0.4      g                                         
camphosulphonamide                                                        
Distilled water        4.3      g                                         
96.2° strength alcohol q.s.                                        
                       100      cm.sup.3                                  
______________________________________                                    
 
    
     The toilet water formulated in this way contains 84 ppm of 5-MOP. 
     EXAMPLE 4 
     
         ______________________________________                                    
Eau de cologne                                                            
______________________________________                                    
Natural essence containing 50% of                                         
                         1.5     g                                        
bergamot oil                                                              
4&#39;-butoxy-3&#39;-methoxy-3-benzylidene-                                       
                         0.2     g                                        
bornanone                                                                 
4-[(2-oxo-3-bornylidene)-methyl]-                                         
                         0.2     g                                        
phenyltrimethylammonium methyl-sulphate                                   
Distilled water          28.3    g                                        
96.2° strength alcohol q.s.                                        
                         100     cm.sup.3                                 
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     This eau de cologne contains 26.25 ppm of 5-MOP.