FR2509990A1 - ANTI-SOLAR AGENTS - Google Patents
ANTI-SOLAR AGENTS Download PDFInfo
- Publication number
- FR2509990A1 FR2509990A1 FR8212619A FR8212619A FR2509990A1 FR 2509990 A1 FR2509990 A1 FR 2509990A1 FR 8212619 A FR8212619 A FR 8212619A FR 8212619 A FR8212619 A FR 8212619A FR 2509990 A1 FR2509990 A1 FR 2509990A1
- Authority
- FR
- France
- Prior art keywords
- ester
- acid
- methoxycinnamic
- solar
- methoxycinnamic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract 2
- -1 propylene glycol ester Chemical class 0.000 claims description 25
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 15
- AFDXODALSZRGIH-UHFFFAOYSA-N 4-methoxycinnamic acid Chemical compound COC1=CC=C(C=CC(O)=O)C=C1 AFDXODALSZRGIH-UHFFFAOYSA-N 0.000 claims description 14
- AFDXODALSZRGIH-QPJJXVBHSA-N (E)-3-(4-methoxyphenyl)prop-2-enoic acid Chemical compound COC1=CC=C(\C=C\C(O)=O)C=C1 AFDXODALSZRGIH-QPJJXVBHSA-N 0.000 claims description 13
- 239000000516 sunscreening agent Substances 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 230000000475 sunscreen effect Effects 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000002537 cosmetic Substances 0.000 description 6
- 239000002304 perfume Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229960004063 propylene glycol Drugs 0.000 description 6
- 235000013772 propylene glycol Nutrition 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- 239000000546 pharmaceutical excipient Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 3
- CNXZMGRWEYQCOQ-UHFFFAOYSA-N 2-methoxy-3-phenylprop-2-enoic acid Chemical compound COC(C(O)=O)=CC1=CC=CC=C1 CNXZMGRWEYQCOQ-UHFFFAOYSA-N 0.000 description 3
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical class NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229960004889 salicylic acid Drugs 0.000 description 3
- 229940099259 vaseline Drugs 0.000 description 3
- CGOJOQBYEAVATL-QPJJXVBHSA-N (e)-3-(4-methoxyphenyl)prop-2-enoyl chloride Chemical compound COC1=CC=C(\C=C\C(Cl)=O)C=C1 CGOJOQBYEAVATL-QPJJXVBHSA-N 0.000 description 2
- DWYHDSLIWMUSOO-UHFFFAOYSA-N 2-phenyl-1h-benzimidazole Chemical compound C1=CC=CC=C1C1=NC2=CC=CC=C2N1 DWYHDSLIWMUSOO-UHFFFAOYSA-N 0.000 description 2
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZDQWESQEGGJUCH-UHFFFAOYSA-N Diisopropyl adipate Chemical compound CC(C)OC(=O)CCCCC(=O)OC(C)C ZDQWESQEGGJUCH-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 2
- 229940063655 aluminum stearate Drugs 0.000 description 2
- BLFLLBZGZJTVJG-UHFFFAOYSA-N benzocaine Chemical compound CCOC(=O)C1=CC=C(N)C=C1 BLFLLBZGZJTVJG-UHFFFAOYSA-N 0.000 description 2
- 229960005274 benzocaine Drugs 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 2
- 229940031766 diethanolamine cetyl phosphate Drugs 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- GKKMCECQQIKAHA-UHFFFAOYSA-N hexadecyl dihydrogen phosphate;2-(2-hydroxyethylamino)ethanol Chemical compound OCCNCCO.CCCCCCCCCCCCCCCCOP(O)(O)=O GKKMCECQQIKAHA-UHFFFAOYSA-N 0.000 description 2
- VEZIKIAGFYZTCI-UHFFFAOYSA-N methyl ester of p-methoxycinnamic acid Natural products COC(=O)C=CC1=CC=C(OC)C=C1 VEZIKIAGFYZTCI-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229940055577 oleyl alcohol Drugs 0.000 description 2
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 230000037072 sun protection Effects 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- OIQXFRANQVWXJF-QBFSEMIESA-N (2z)-2-benzylidene-4,7,7-trimethylbicyclo[2.2.1]heptan-3-one Chemical compound CC1(C)C2CCC1(C)C(=O)\C2=C/C1=CC=CC=C1 OIQXFRANQVWXJF-QBFSEMIESA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- LALVCWMSKLEQMK-UHFFFAOYSA-N 1-phenyl-3-(4-propan-2-ylphenyl)propane-1,3-dione Chemical compound C1=CC(C(C)C)=CC=C1C(=O)CC(=O)C1=CC=CC=C1 LALVCWMSKLEQMK-UHFFFAOYSA-N 0.000 description 1
- WHQOKFZWSDOTQP-UHFFFAOYSA-N 2,3-dihydroxypropyl 4-aminobenzoate Chemical compound NC1=CC=C(C(=O)OCC(O)CO)C=C1 WHQOKFZWSDOTQP-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- NDNMXRYLRJEZAR-UHFFFAOYSA-N 2-[1-(4-methoxyphenyl)propylidene]octanoic acid Chemical compound CCCCCCC(C(O)=O)=C(CC)C1=CC=C(OC)C=C1 NDNMXRYLRJEZAR-UHFFFAOYSA-N 0.000 description 1
- NFIHXTUNNGIYRF-UHFFFAOYSA-N 2-decanoyloxypropyl decanoate Chemical compound CCCCCCCCCC(=O)OCC(C)OC(=O)CCCCCCCCC NFIHXTUNNGIYRF-UHFFFAOYSA-N 0.000 description 1
- HIPQTCQUXOFTFI-UHFFFAOYSA-N 2-methoxy-1,3-diphenylpropane-1,3-dione Chemical compound C=1C=CC=CC=1C(=O)C(OC)C(=O)C1=CC=CC=C1 HIPQTCQUXOFTFI-UHFFFAOYSA-N 0.000 description 1
- DUAYDERMVQWIJD-UHFFFAOYSA-N 2-n,2-n,6-trimethyl-1,3,5-triazine-2,4-diamine Chemical compound CN(C)C1=NC(C)=NC(N)=N1 DUAYDERMVQWIJD-UHFFFAOYSA-N 0.000 description 1
- TVIMZSOUQXNWHO-UHFFFAOYSA-N 2-tetradecanoylglycerol Chemical compound CCCCCCCCCCCCCC(=O)OC(CO)CO TVIMZSOUQXNWHO-UHFFFAOYSA-N 0.000 description 1
- UKWCVKJHOSEORN-UHFFFAOYSA-N 3-benzylidene-4-tert-butyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one Chemical compound CC1(C)C2(C(C)(C)C)CCC1(C)C(=O)C2=CC1=CC=CC=C1 UKWCVKJHOSEORN-UHFFFAOYSA-N 0.000 description 1
- XIOBZUDJYKXUEL-UHFFFAOYSA-N 4-ethyl-2-[(4-methoxyphenyl)methylidene]octanoic acid Chemical compound CCCCC(CC)CC(C(O)=O)=CC1=CC=C(OC)C=C1 XIOBZUDJYKXUEL-UHFFFAOYSA-N 0.000 description 1
- ZCILGMFPJBRCNO-UHFFFAOYSA-N 4-phenyl-2H-benzotriazol-5-ol Chemical compound OC1=CC=C2NN=NC2=C1C1=CC=CC=C1 ZCILGMFPJBRCNO-UHFFFAOYSA-N 0.000 description 1
- NNJMFJSKMRYHSR-UHFFFAOYSA-M 4-phenylbenzoate Chemical compound C1=CC(C(=O)[O-])=CC=C1C1=CC=CC=C1 NNJMFJSKMRYHSR-UHFFFAOYSA-M 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 206010015150 Erythema Diseases 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- WVMBPWMAQDVZCM-UHFFFAOYSA-N N-methylanthranilic acid Chemical compound CNC1=CC=CC=C1C(O)=O WVMBPWMAQDVZCM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical class NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 1
- XSIFPSYPOVKYCO-UHFFFAOYSA-N benzoic acid butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 1
- KYZHGEFMXZOSJN-UHFFFAOYSA-N benzoic acid isobutyl ester Natural products CC(C)COC(=O)C1=CC=CC=C1 KYZHGEFMXZOSJN-UHFFFAOYSA-N 0.000 description 1
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- WOAZEKPXTXCPFZ-UHFFFAOYSA-N dimethyl(phenyl)azanium;chloride Chemical compound Cl.CN(C)C1=CC=CC=C1 WOAZEKPXTXCPFZ-UHFFFAOYSA-N 0.000 description 1
- 229940113120 dipropylene glycol Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- 231100000321 erythema Toxicity 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical class OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000010512 hydrogenated peanut oil Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- LXTZRIBXKVRLOA-UHFFFAOYSA-N padimate a Chemical compound CCCCCOC(=O)C1=CC=C(N(C)C)C=C1 LXTZRIBXKVRLOA-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- GKPGJMUBFVSCRE-UHFFFAOYSA-N propane-1,2-diol;urea Chemical compound NC(N)=O.CC(O)CO GKPGJMUBFVSCRE-UHFFFAOYSA-N 0.000 description 1
- 239000000473 propyl gallate Substances 0.000 description 1
- 229940116422 propylene glycol dicaprate Drugs 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- ORHBXUUXSCNDEV-UHFFFAOYSA-N umbelliferone Chemical compound C1=CC(=O)OC2=CC(O)=CC=C21 ORHBXUUXSCNDEV-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
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Abstract
LA PRESENTE INVENTION CONCERNE DES AGENTS ANTI-SOLAIRES. CES AGENTS CONTIENNENT UN COMPOSE DE FORMULE (CF DESSIN DANS BOPI) OU R REPRESENTE UN HYDROGENE OU UN ALCOYLE EN C A C, R UN HYDROGENE OU UN ALCOYLE EN C A C, X LE GROUPEMENT (-CH-) OU (-CHOCH-) ET M1-5, N0-4 ET P1-3, SOUS FORME DISSOUTE OU DISPERSEE ET EVENTUELLEMENT D'AUTRES MATIERES HABITUELLES DANS LES AGENTS ANTI-SOLAIRES.THE PRESENT INVENTION CONCERNS ANTI-SUN AGENTS. THESE AGENTS CONTAIN A COMPOUND OF FORMULA (CF DRAWING IN BOPI) OR R REPRESENTS A HYDROGEN OR A CAC ALCOHOL, R A HYDROGEN OR A CAC ALCOHOL, X THE GROUP (-CH-) OR (-CHOCH-) AND M1- 5, N0-4 AND P1-3, IN DISSOLVED OR DISPERSE FORM AND POSSIBLY OTHER MATERIALS USUALLY IN ANTI-SUN AGENTS.
Description
La présente invention concerne de nouveaux agents anti-solaires,The present invention relates to novel anti-solar agents,
caractérisés en ce qu'ils contiennent un composé de formule lCH 3 O CH=CHCOO-CH R 1 Im x I X characterized in that they contain a compound of the formula lCH 3 O CH = CHCOO-CH R 1 Im x I X
CH 30 CH=CH-COO-C R 1 R 2CH 3 CH = CH-COO-C R 1 R 2
-0 1 o R 1 représente un hydrogène ou un alcoyle en C 1 à C 3, en particulier un hydrogène ou un méthyle, R 2 représente un hydrogène ou un aleoyle en C 1 à C 7, en particulier un méthyle, X représente le groupement (-CH 2-)n ou (-CH 2 OCH 2-)pet m = 1 à 5, en particulier 1, N = O à 4, en particulier O et p = 1 à 3, en particulier 1 ou 2, R 1 represents a hydrogen or a C 1 to C 3 alkyl, in particular a hydrogen or a methyl, R 2 represents a hydrogen or a C 1 to C 7 alkyl, in particular a methyl, X represents the group (-CH 2-) n or (-CH 2 OCH 2-), pet m = 1 to 5, in particular 1, N = 0 to 4, in particular O and p = 1 to 3, in particular 1 or 2,
sous forme dissoute ou dispersée L'invention concerne égale- dissolved or dispersed form The invention also relates to
ment l'application des composés de formule I sous forme dis- application of the compounds of formula I in the form of
soute ou dispersée comme agents anti-solaires. bunker or dispersed as anti-solar agents.
Comme radicaux alcoyle en C 1 à C 3 il faut mentionner le méthyle, l'éthyle, le propyle ou le i-propyle On préfère le méthyle Les radicaux en C 4 à C 7 peuvent également être à chaîne droite ou ramifiée, donc être p ex un butyle, i-butyle, amyle, hexyle, heptyle, etc. Les composés de formule I préférés sont: L'ester de propylèneglycol-di-(acide pméthoxycinnamique) l'ester de 1,3-butylèneglycol-di-(acide pméthoxycinnamique) As C 1 to C 3 alkyl radicals, mention should be made of methyl, ethyl, propyl or i-propyl. Methyl C 4 to C 7 radicals may also be straight or branched, so be eg, butyl, i-butyl, amyl, hexyl, heptyl, etc. The preferred compounds of formula I are: propylene glycol-di- (pmethoxycinnamic acid) ester 1,3-butylene glycol-di- (pmethoxycinnamic acid) ester
l'ester de triéthylèneglycol-di-(p-acide méthoxycinnamique). triethylene glycol-di- (p-methoxycinnamic acid) ester.
D'autres représentants de la formule I sont: l'ester d'éthylèneglycol-di(acide p-méthoxycinnamique) l'ester de triméthylèneglycol-di-(acide pméthoxycinnamique) l'ester de 2,3-butylèneglycol-di-(acide pméthoxycinnamique) l'ester de dithy 12 neglycol-di-(acide pmthoxycinnamique) l'ester de diéthylèneglycorine-tri-(acide pméthoxycinnamique) l'ester de glycérine-tri-(acide p-méthoxycinnamique) l'ester de dipropyleneglycol-di-(acide p-méthoxycinnamique) Other representatives of formula I are: ethylene glycol-di (p-methoxycinnamic acid) ester trimethylene glycol-di-(methoxycinnamic acid) ester 2,3-butylene glycol-di- (acid) ester pmethoxycinnamic) dithyneglycol-di- (methoxycinnamic acid) ester diethyleneglycorin-tri- (methoxycinnamic acid) ester glycerin-tri- (p-methoxycinnamic acid) ester dipropyleneglycol di-ester (p-methoxycinnamic acid)
l'ester de 2-méthyl-2,4-pentanediol-di-(acide p-méthoxycinna- the ester of 2-methyl-2,4-pentanediol-di- (p-methoxycinnamic acid)
mique) l'ester de 1,4-butanediol-di-(acide p-méthoxycinnamique) l'ester de 1,5-pentanediol-di-(acide p-méthoxycinnamique) l'ester de 1,6hexanediol-di-(acide p-méthoxycinnamique) l'ester de 2,5-hexanediol-di(acdie p-méthoxycinnamique) 1,3-butanediol-di- (p-methoxycinnamic acid) ester of 1,5-pentanediol-di- (p-methoxycinnamic acid) 1,6-hexanediol-di- (acid) ester. p-methoxycinnamic) 2,5-hexanediol-di-ester (p-methoxycinnamic acetic acid)
l'ester de sorbitol-hexa-(acide p-méthoxycinnamique). sorbitol ester-hexa- (p-methoxycinnamic acid).
Les composés de formule I absorbent les rayons solai- The compounds of formula I absorb the sun rays.
res ultra-violets provoquant l'érythème (entre 280 et 320 nm) de façon prononcée, c'est-à-dire qu'ils écartent ces rayons ultraviolet rays causing erythema (between 280 and 320 nm) in a pronounced way, ie they spread these rays
des cellules vivantes de l'épiderme Ciest pourquoi les com- the living cells of the epidermis.
posés de formule I peuvent être utilisés comme agents anti- poses of the formula I can be used as anti-
solaires L'invention concerne également un procédé de pré- The invention also relates to a method for
paration d'un agent anti-solaire, caractérisé en ce qu'on introduit un composé de formule I dans un excipient habituel parative of an anti-solar agent, characterized in that a compound of formula I is introduced into a usual excipient
en cosmétique.in cosmetics.
Comme excipients cosmétiques habituels pour les agents de protection antisolaire au sens de l'invention on peut As usual cosmetic excipients for sunscreen agents within the meaning of the invention, it is possible to
utiliser toute préparation habituelle correspondant aux exi- use any usual preparation corresponding to the requirements
gences cosmétiques, p ex des crèmes, émulsions, onguents, solutions (alcooliques), liquides pulvérisés, bâtons, laits, etc, voir également G A Nowak, Die Kosmetischen Prâparate, cosmetics, eg creams, emulsions, ointments, (alcoholic) solutions, sprayed liquids, sticks, milks, etc., see also G At Nowak, Die Kosmetischen Práparate,
1 édition 1969 2 édition 1975 (Augsbourg), cette réfé- 1 edition 1969 2 edition 1975 (Augsburg), this reference
rence bibliographique décrivant de façon détaillée les solvants (dansle cas présent en particulier les solvants polaires), tiers solvants, émulsifiants, épaississants, bibliographic reference describing in detail the solvents (in this case in particular the polar solvents), third solvents, emulsifiers, thickeners,
parfums, agents de conservation, colorants, et autres adju- perfumes, preservatives, dyes, and other
vants éventuels utilisables dans la préparation de pre- potential for use in the preparation of pre-
parations cosmétiques L'effet de protection contre la lumiè- The protective effect against light
re dépend également naturellement de l'excipient utilisé. It also depends naturally on the excipient used.
L'intensité de l'effet de protection contre la lumière dépend en outre, pour le même excipient,de la concentration de substance active Les concentrations appropriées sont The intensity of the light-shielding effect also depends, for the same excipient, on the concentration of active substance. The appropriate concentrations are
p ex entre 1 et 6 %, de préférence entre 2 et 4 %, en parti- p ex between 1 and 6%, preferably between 2 and 4%, in particular
culier environ 3 % d'un composé de formule I dans une about 3% of a compound of formula I in a
préparation cosmétique.cosmetic preparation.
De par leur lipophilie les composés I peuvent être introduits à une concentration suffisante dans les préparations cosmétiques contenant de l'huile et des matières grasses; ils disposent de propriétés optimales de par leur solubilité suffisante dans les matières grasses et leur absorption prononcée du rayonnement UV B C'est pourquoi les composés I ont une bonne compatibilité avec la peau comme By their lipophilicity compounds I can be introduced at a sufficient concentration in cosmetic preparations containing oil and fat; they have optimal properties because of their sufficient solubility in fat and their pronounced absorption of UV B radiation. This is why compounds I have a good compatibility with the skin as
substances neutres.neutral substances.
Les préparations cosmétiques peuvent également contenir encore d'autres corps absorbant la lumière, donc Cosmetic preparations may also contain other light-absorbing bodies, so
p ex d'autres filtres UV A et/ou UVB. eg other UV A and / or UVB filters.
Comme exemples de filtres UV A on peut citer: le 4-isopropyldibenzoylméthane, le 4-( 1,1-diméthyléthyl)-4 '-méthoxydibenzoylméthane, le dianisoylméthane, Examples of UV-A filters that may be mentioned include: 4-isopropyldibenzoylmethane, 4- (1,1-dimethylethyl) -4'-methoxydibenzoylmethane, dianisoylmethane,
une hydroxybenzophénone, p ex la 2,4-dihydroxybenzophénone. a hydroxybenzophenone, eg 2,4-dihydroxybenzophenone.
Comme filtres UV B, c'est-à-dire comme substances à maxima d'absorption compris entre environ 290 et 320 nm, on peut mentionner les filtres UV B habituels, comme par exemple les suivants, composés organiques appartenant aux As UV-B filters, that is to say as substances with an absorption maximum of between about 290 and 320 nm, mention may be made of the usual UV-B filters, for example the following organic compounds belonging to
classes de produits les plus différentes. most different product classes.
1) Dérivés de l'acide p-aminobenzolque, comme p ex le p- 1) Derivatives of p-aminobenzoic acid, as for example p
aminobenzoate d'éthyle et d'autres esters comme le p-amino- ethyl aminobenzoate and other esters such as p-amino
benzoate de propyle, de butyle ou d'isobutyle, le p-diméthyl- propyl, butyl or isobutyl benzoate, p-dimethyl-
aminobenzoate d'éthyle, le p-aminobenzoate de glycéryle, ethyl aminobenzoate, glyceryl p-aminobenzoate,
le p-diméthylaminobenzoate d'amyle. amyl p-dimethylaminobenzoate.
2) Dérivés de l'acide cinnamique, p ex l'ester de l'acide 2) Derivatives of cinnamic acid, eg the ester of the acid
2-éthoxyéthyl-p-méthoxycinnamique, l'ester de l'acide 2- 2-ethoxyethyl-p-methoxycinnamic acid ester 2-
éthylhexyl-p-méthoxycinnamique, les mélanges d'esters d'acide pméthoxycinnamique, les mélanges d'ester d'acide cinnamique, ethylhexyl-p-methoxycinnamic acid, mixtures of pmethoxycinnamic acid esters, cinnamic acid ester mixtures,
les sels d'ammonium de l'acide p-méthoxycinnamique. ammonium salts of p-methoxycinnamic acid.
3) Dibenzalazines.3) Dibenzalazines.
4) Composés azotés hétérocycliques, comme dérivés du 2- 4) Heterocyclic nitrogen compounds, as derivatives of 2-
phénylbenzimidazole, p ex l'acide 2-phénylbenzimidazole- phenylbenzimidazole, eg 2-phenylbenzimidazole
-sulfonique. 5) Dérivés de l'acide salicylique, comme p ex l'ester méthylique de l'acide salicylique, l'ester homomenthyliquede sulfonic. 5) Derivatives of salicylic acid, such as eg methyl ester of salicylic acid, homomethyl ester
l'acide salicylique, l'ester phénylique de l'acide salicyli- salicylic acid, the phenyl ester of salicylic acid
que.than.
6) Dérivés de la benzophénone, comme p ex la 4-phénylbenzo- 6) Derivatives of benzophenone, such as 4-phenylbenzoate
phénone, l'isooctylester de l'acide 4-phénylbenzophénone-2- phenone, the isooctyl ester of 4-phenylbenzophenone-2-
carboxylique, l'acide 2-hydroxy-4-méthoxybenzophénone-5- carboxylic acid, 2-hydroxy-4-methoxybenzophenone-5-
sulfonique. 7) Dérivés de coumarine, comme p ex la 7-oxycoumarine, sulfonic acid. 7) Coumarin derivatives, such as 7-oxycoumarin,
l'acide 9-umbelliféronacétique, là 6,7-dioxycoumarine. 9-umbelliferronacetic acid, there 6,7-dioxycoumarin.
8) Dérivés de l'acide gallique, comme p ex le trioléate 8) Derivatives of gallic acid, such as triolate
de digalloyle.of digalloyl.
9) Arylidènecycloalcanone, p ex le benzylidène-camphre, le p- 9) Arylidenecycloalkanone, eg benzylidenecamphor, p
tert-butylbenzylidène-camphre (préféré) ou le méthylbenzyli- tert-butylbenzylidene camphor (preferred) or methylbenzylide
dène-camphre. 10) Dérivés de l'acide anthranilique, coimme p ex l'ester Dene-camphor. 10) Derivatives of anthranilic acid, coimme p ex ester
méthylique de l'acide anthranilique. Methyl anthranilic acid.
11) Hydroxyphénylbenztriazole.11) Hydroxyphenylbenztriazole.
On préfère les composés cités en 2), tout particu- The compounds mentioned in 2 are preferred, especially
lièrement l'ester de l'acide 2-éthylhexyl-p-méthoxycinnami- firstly the ester of 2-ethylhexyl-p-methoxycinnamic acid
que.than.
Les composés de formule I sont connus ou peuvent être préparés selon des procédés connus Pour ce faire on estérifie l'acide p-méthoxycinnamique, en pratique sous la forme d'un dérivé réactif, p ex de chlorure, avec le polyalcool On utilise alors en pratique des quantités stoechiométriques d'acide et d'alcool Ondissout le dérivé d'acide en pratique dans un solvant, p ex un hydrocarbure chloré, comme le chloroforme, et on verse goutte à goutte l'alcool, de préférence dissous dans une amine, comme la diméthylaniline, comme solvant, à des températures d'environ The compounds of formula I are known or can be prepared according to known processes. To this end, p-methoxycinnamic acid is esterified, in practice in the form of a reactive derivative, eg of chloride, with polyalcohol. Practicing stoichiometric amounts of acid and alcohol dissolves the acid derivative in practice in a solvent, eg a chlorinated hydrocarbon, such as chloroform, and the alcohol, preferably dissolved in an amine, is added dropwise, as dimethylaniline, as a solvent, at temperatures of about
O à 20 C Il est préférable de chauffer ensuite pour complé- O to 20 C It is better to warm up later to
ter la réaction.ter the reaction.
On verse ensuite en pratique le produit brut sur de la glace et on le purifie par réextraction et lavage ainsi que par recristallisation. On peut également obtenir des composés de formule I par des réactions de trans-estérification A cet effet on fait réagir un alcoyle inférieurester de l'acide p-méthoxycinnamique, p ex le méthyl ou éthylester, avec le polyaleool désiré, p ex l'éthylèneglycol ou la gly cérine, etc, en présence d'un catalyseur Les catalyseurs appropriés sont des bases, comme le méthylate de sodium ou l'éthylate de sodium On choisit en pratique la température de la réaction de manière à pouvoir enlever par distillation à la pression atmosphérique l'alcool méthylique ou l'aleool The crude product is then poured into practice on ice and purified by reextraction and washing as well as by recrystallization. It is also possible to obtain compounds of formula I by trans-esterification reactions. For this purpose, a lower alkyl ester of p-methoxycinnamic acid, eg methyl or ethyl ester, is reacted with the desired polyalcohol, eg ethylene glycol. or glycerine, etc., in the presence of a catalyst Suitable catalysts are bases, such as sodium methoxide or sodium ethoxide. The reaction temperature is chosen in practice so that it can be removed by distillation under pressure. atmospheric methyl alcohol or aleool
éthylique formé.Ethyl formed.
ExemplesExamples
A Préparation des substances actives A Preparation of active substances
Exemple 1Example 1
Dans un ballon rond de I litre à 4 goulots équimé d'un agitateur, d'un thermomètre) d'un réfrigérait à reflmx et d'un tube à brome on verse 100 g de chlorure -e l'acide p-méthoxycinnamique lpréparé selon Farmacia (Bucarest} 9 ( 1961) 345-50; C A 56 8312 il et 200 ml de chloroforme _ On refroidit à 100 C et on verse goutte à goutte pendant 1 h à cette température tout en agitant un mélange de b D 5 g de diméthylaniline et de 19,1 g de propylèneglycol On In a 4-liter round-bottom flask equilibrated with stirrer, thermometer, reflux condenser and bromine tube, 100 g of p-methoxycinnamic acid chloride prepared according to Farmacia (Bucharest) 9 (1961) 345-50, CA 56 8312 and 200 ml of chloroform were cooled to 100 ° C. and poured dropwise for 1 h at this temperature while stirring a mixture of bD 5 g of dimethylaniline and 19.1 g of propylene glycol
complète la réaction en chauffant pendant 2 h à la tempé- complete the reaction by heating for 2 hours at room temperature
rature de reflux Après refroidissement on verse le mélange réactionnel sur de la glace On absorbe dans 250 ml de chloroforme et on extrait par lavage le chlorhydrate de diméthylaniline avec de l'acide chlorhydrique à 10 % puis on After cooling, the reaction mixture is poured onto ice. It is taken up in 250 ml of chloroform and the dimethylaniline hydrochloride is extracted with hydrochloric acid at 10% by washing.
lave avec de l'eau jusqu'au point neutre. wash with water until neutral point.
On fait évaporer le solvant et on recristallise le résidu ( 90 g de produit brut) à partir de l'acétonezeau 4:1 On obtient 50,1 g d'ester de propylèneglyco JL-di-{acide The solvent is evaporated and the residue is recrystallized (90 g of crude product) from acetonezeau 4: 1. 50.1 g of propyleneglycol ester JL-di- (acid) are obtained.
p-méthoxycinnamique); Pf 97-99 C;e 310 = 46100 E = 1163. p-methoxycinnamic); Mp 97-99 ° C; 310 = 46100 E = 1163.
Rendement: 50,5 % de la quantité théorique. Yield: 50.5% of the theoretical amount.
Exemple 2Example 2
Dans un ballon rond d'1 litre muni d'un agitateur et d'une soupape de robinet on met 173 g d'ester méthylique de l'acide p-méthoxycinnamique, 38 g de propylèmeglycol, g de méthylate de sodium et 300 ml de xylène sec -s chauffe en agitant et on retire lentement par distillation le méthanol apparu ( 32 g) On maintient encore pendant 5 h In a 1-liter round flask equipped with a stirrer and a tap valve, 173 g of p-methoxycinnamic acid methyl ester, 38 g of propylene glycol, g of sodium methoxide and 300 ml of Dry xylene is heated with stirring and the resulting methanol is slowly distilled off (32 g). The mixture is then kept for 5 hours.
à la température de reflux Après refroidissement on neutra- at reflux temperature After cooling, neutralize
lise avec 5,5 g d'acide acétique, on absorbe dans l'éther et on lave à l'eau Après séchage sur sulfate de sodium on enlève l'éther par distillation On obtient 177 g de produit brut Après recristallisation à partir du méthanol cnobtient After drying with sodium sulphate, the ether is removed by distillation. 177 g of crude product are obtained. After recrystallization from methanol, the mixture is dissolved in ether and washed with water (5.5 g of acetic acid). cnobtient
l'ester de propylèneglycol-di-(acide p-méthoxycinnamique). propylene glycol-di- (p-methoxycinnamic acid) ester.
Pf = 96-980 C.Mp = 96-980C.
Exemple 3Example 3
Dans un ballon rond de 1 litre à 4 goulots, équipé d'un agitateur, d'un thermomètre, d'un réfrigérant reflux et d'un tube à brome on met 100 g de chlorure de l'acide p-méthoxycinnamique et 200 ml de chloroforme On refroidit à 10 C et on verse goutte à goutte à cette In a round flask of 1 liter to 4 necks, equipped with a stirrer, a thermometer, a reflux condenser and a bromine tube is placed 100 g of p-methoxycinnamic acid chloride and 200 ml. chloroform is cooled to 10 ° C. and poured dropwise into this mixture.
température tout en agitant un mélange de 60,5 g de diméthyl- temperature while stirring a mixture of 60.5 g dimethyl
aniline et de 15,5 g de glycérine pendant h On complète aniline and 15.5 g of glycerine for 1 hour
la réaction en agitant au reflux pendant 1 h Après refroidis- the reaction with stirring under reflux for 1 hour after cooling.
sement on verse le mélange réactionnel sur de la glace. The reaction mixture is poured onto ice.
On absorbe dans 200 ml de chloroforme et on extrait la diméthyl- It is taken up in 200 ml of chloroform and the dimethyl
aniline par lavage avec de l'acide chlorhydrique à 10 % puis on lave avec de l'eau Jusqu'à neutralité On fait évaporer le solvant et on recristallise le résidu solide ( 113 g de produit brut) à partir de 200 ml de toluène On obtient aniline by washing with 10% hydrochloric acid and then washing with water until neutrality The solvent is evaporated and the solid residue (113 g of crude product) is recrystallized from 200 ml of toluene gets
51,1 g d'ester de glycérine-tri-(acide p-méthoxycinnamique). 51.1 g of glycerin-tri- (p-methoxycinnamic acid) ester.
Pf = 104-105 C;e 310 = 67970; E = 1187; rendement: 52,5 % Mp = 104-105 C; e 310 = 67970; E = 1187; yield: 52.5%
de la quantité théorique.of the theoretical quantity.
Exemple 4Example 4
Selon le procédé décrit dans les exemples 1 et 3 According to the process described in Examples 1 and 3
on obtient à partir de 100 g de chlorure de l'acide p- 100 g of p-acid chloride are obtained
méthoxycinnamique et de 37,5 g de triéthylèneglycol en présence de 60,5 g de diméthylaniline dans le chloroforme 81 g d'ester de triéthylèneglycoldi(acide p-méthoxycinnamique); Pf = 82-83 C; e 310 = 46900 E = 995 Rendement: 69 % de methoxycinnamic acid and 37.5 g of triethylene glycol in the presence of 60.5 g of dimethylaniline in chloroform 81 g of triethyleneglycoldi ester (p-methoxycinnamic acid); Mp = 82-83 ° C; e 310 = 46900 E = 995 Yield: 69% of
la quantité théorique.the theoretical quantity.
De manière analogue on prépare les esters suivants: Ester d'éthylèneglycol-di-(acide p-méthoxycinnamique); In a similar manner, the following esters are prepared: Ethylene glycol-di (p-methoxycinnamic acid) ester;
Pf 147-149 o C;e 310 = 44932 E = 1175. Mp 147-149 ° C; e 310 = 44932 E = 1175.
Ester de triméthylèneglycol-di-(acide p-méthoxyoinnamique); Trimethylene glycol-di- (p-methoxyoinnamic acid) ester;
Pf = 140-141 a C; S 31 = 45150 E = 1139. Mp 140-141 to C; S 31 = 45150 E = 1139.
Ester de 1,3-but Ylèneglycol-di-(acide p-méthoxycinnamique); 1,3-butene-diol ester (p-methoxycinnamic acid);
Pf= 97,5-99,50 C;c 310 = 144780 E = 1090. Mp = 97.5-99.50 C, c 310 = 144780 E = 1090.
Ester de 2,3-but Ylèneglycol-Di-<acide p-méthoxycinnamique>; 2,3-butene-2,3-butene-di-β-methoxycinnamic acid ester;
Pf= 154-1560 C; E 1 ú 46260 E= 1127. Mp 154-1560 ° C; E 1 ú 46260 E = 1127.
Ester de 2-méthyl-2,14-pentanediol-di-(acide p-méthoxy- Ester of 2-methyl-2,14-pentanediol-di- (p-methoxy acid)
cinnamique);cinnamic);
Pf = 100-1010 C; e 1 = 143368 E= 989. Mp = 100-1010 ° C; e 1 = 143368 E = 989.
Ester de 1,5-pentanediol-Di-(acide p-méthoxycinnamique>; 1,5-Pentanediol-Di- (p-methoxycinnamic acid) ester;
Pf= 76,5-780 C: e 310 = 47250 E = 1115. Mp = 76.5-780 C: E 310 = 47250 E = 1115.
Ester de 1,6-hexanediol-di-<acide p-méthoxycinnamique); 1,6-hexanediol-di-β-methoxycinnamic acid ester;
Pr= 92,5-93,501 C; ú 310 = 47300 E= 1080 - Pr = 92.5-93.501 ° C; 310 = 47300 E = 1080 -
Ester de 2,5-hexanediol-di-(acide p-méthoxycinnamique); 2,5-hexanediol-di- (p-methoxycinnamic acid) ester;
Pf = 126; 5-128,50 C; c 30 = 144700 E= 1020. Pf = 126; 5-128.50 ° C; c = 144700 E = 1020.
Ester de diéthylèneglycol-di-<acide p-méthoxycinnamique); Diethylene glycol-di- (p-methoxycinnamic acid) ester;
Pf= 77,5-789 '50 C; ú 310 = 145000 E = 1055. Mp = 77.5-789 ° C; 310 = 145000 E = 1055.
B FormulationsB Formulations
Exemple 5Example 5
Crème de protection solaire, semi-grasse (H E): Fractions pondérales Sunscreen cream, semi-fat (H E): Weight fractions
A) 14-( 1,1-diméthyléthyl)-414-A) 14- (1,1-dimethylethyl) -414-
méthoxy-dibenzoylméthane, 5methoxy dibenzoylmethane, 5
Ester de propylèneglycol di-Propylene glycol ester di-
<acide p-méthoxycinnamique) 3,0 Acide stéarique, 3 rois comprimé 10,0 Alcool cétylique 1,0 Monomyristate de glycérine 5,0 Adipate d'isopropyle 7,0 Alcool oléYlique 4,0 <p-methoxycinnamic acid) 3.0 Stearic acid, 3 times tablet 10.0 Cetyl alcohol 1.0 Glycerine monomer 5.0 Isopropyl adipate 7.0 Oleyl alcohol 4.0
Acide méthyl et propyl-p-amino-Methyl and propyl-p-amino acid
benzolque ( 70/30} 0,25 B) Cétylphosphate de diéthanolamine C) Eau distillée Propylèneglycol D) Parfum 3,0 59,25 6,0 q.s. On chauffe les composants A réunis sur un bain d'eau à 85 C, puis on ajoute B à cette température On chauffe C Benzol (70/30) 0.25 B) Diethanolamine cetylphosphate C) Distilled water Propylene glycol D) Fragrance 3.0 59.25 6.0 q.s. The combined components A are heated on a water bath at 85 ° C., then B is added at this temperature.
à 75 C et on l'ajoute à A + B On agite le mélange apparu. at 75 ° C and added to A + B The resulting mixture is stirred.
Après refroidissement à 35 C on compense les pertes d'eau After cooling to 35 C the water losses are compensated
éventuelles et on ajoute D -possible and we add D -
Exemple 6Example 6
Lait de protection solaire (H/E): Fractions A) Alcool cétylique Monomyristate de glycérine Huile d'arachide hydrogénée pharmacop. Adipate d'isopropyle Sunscreen (O / W): Fractions A) Cetyl Alcohol Glycerin Monomyristate Hydrogenated Peanut Oil Pharmacop. Isopropyl adipate
Ester de propylèneglycol-di-Propylene glycol-di-ester
(acide p-méthoxycinnamique B) Cétylphosphate de diéthanolamine C) Eau distillée Propylèneglycol Urée D) Parfum Agent de conservation pondérales 2,0 4,0 2,0 ,0 (p-methoxycinnamic acid B) Diethanolamine cetylphosphate C) Distilled water Propylene glycol Urea D) Fragrance Preservative Weight 2.0 4.0 2.0, 0
2,0-5,02.0-5.0
3,03.0
74,0-68; 574.0 to 68; 5
3,0 ,0 q.s. q s. On chauffe le mélange A sur un bain d'eau à 85 C, puis on ajoute B à cette température On chauffe à 75 C 3.0, q q.s. q s. The mixture A is heated on a water bath at 85 ° C., then B is added at this temperature. It is heated to 75 ° C.
les composants de C réunis puis on ajoute à A + B On compen- components of C combined and then added to A + B
se les pertes d'eau après refroidissement à 25-30 C, puis on procède à l'addition de D On continue d'agiter jusqu'à ce que la température atteigne 250 C. the water losses after cooling to 25-30 C, then proceed to the addition of D It continues to stir until the temperature reaches 250 C.
Exemple 7Example 7
Crème de protection solaire pour sportifs (E H): Fractions pondérales Sports sunscreen cream (E H): Weight fractions
A) Ester de propylèneglycol-di-A) Propylene glycol-di-ester
(acide p-méthoxycinnamique) 1,5(p-methoxycinnamic acid) 1.5
4-( 1,1-diméthyléthyl)-4 '-méthoxy- 4- (1,1-dimethylethyl) -4'-methoxy-
dibenzoylméthane 1,0 Sesquioléate de sorbityle 9,0 Lanoline 1,0 Huile de paraffine 8,0 dibenzoylmethane 1.0 Sorbityl sesquioleate 9.0 Lanolin 1.0 Paraffin oil 8.0
Ester d'acide méthyl et propyl-Ester of methyl and propyl
p-aminobenzoique ( 70/30) 0,25 B) Myristate d'isopropyle 10,0 Stéarete d'aluminium 0,1 C) Sulfate de magnésium 0,3 Propylèneglycol 3,0 Eau distillée 67,35 Parfum 0,5 On mélange avec soin le stéarate d'aluminium avec le myristate d'isopropyle et on ajoute le mélange B p-aminobenzoic acid (70/30) 0.25 B) Isopropyl myristate 10.0 Aluminum stearate 0.1 C) Magnesium sulphate 0.3 Propylene glycol 3.0 Distilled water 67.35 Fragrance 0.5 Mixed aluminum stearate with isopropyl myristate carefully and mix B is added
apparu aux composants de A rassemblés chauffés à 80 C. appeared to the assembled A components heated to 80 C.
Au mélange A + B chaud on ajoute lentement la solution C To the hot mixture A + B, solution C is slowly added.
chauffée à 75 C On refroidit A + B + C tout en agitant. heated to 75 ° C. A + B + C is cooled while stirring.
A 40 C on compense les pertes d'eau et on ajoute le parfum. At 40 C the water losses are compensated and the perfume added.
On homogénéise ensuite.Then homogenize.
Exemple 8Example 8
Huile de protection solaire: Fractions pondérales Sun protection oil: Weight fractions
Ester de propylèneglycol-di-Propylene glycol-di-ester
(acide p-méthoxycinnamique) 4,0 Dicaprylate et dicaprate de propylèneglycol 26,0 (p-methoxycinnamic acid) 4.0 Dicaprylate and Propylene Glycol Dicaprate 26.0
huile de vaseline (d = 0,849-Vaseline oil (d = 0.849-
0,866) 70,00.866) 70.0
Colorant soluble dans l'huile q s.Oil soluble dye q s.
Parfum ( 0,5-1 %) q s.Perfume (0.5-1%) q s.
On chauffe les composants réunis à 80 C Ensuite The combined components are heated to 80 ° C.
on refroidit et on parfume.we cool and perfume.
Exemple 9Example 9
Bâton de protection solaire: Fractions pondérales Sun protection stick: Weight fractions
4-( 1,1-diméthyléthyl)-4 '-méthoxy- 4- (1,1-dimethylethyl) -4'-methoxy-
dibenzoylméthane 2,0 Ester de propylèneglycol-di-(acide pméthoxycinnamique) 5,0 Alcool oléylique (Satol) 17,0 Huile de ricin hydrogénée craquée 19,0 Cire microcristalline 30,0 Huile de vaseline 10,0 dibenzoylmethane 2.0 Propyleneglycol-di- (methoxycinnamic acid) ester 5.0 Oleyl alcohol (Satol) 17.0 Cracked hydrogenated castor oil 19.0 Microcrystalline wax 30.0 Vaseline oil 10.0
Ester d'acide méthyl et propyl-p-Ester of methyl and propyl-p-
aminobenzo Ique ( 70/30) 0,25 Vaseline 16,75 Parfum 0,5 On fond ensemble les composants réunis et on Aminobenzo Ique (70/30) 0.25 Vaseline 16.75 Perfume 0.5 The combined components are melted together and
parfume On verse ensuite dans des moules. perfume Then poured into molds.
Claims (9)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH478381A CH648753A5 (en) | 1981-07-22 | 1981-07-22 | Light protection. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR2509990A1 true FR2509990A1 (en) | 1983-01-28 |
| FR2509990B1 FR2509990B1 (en) | 1985-08-09 |
Family
ID=4282465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR8212619A Expired FR2509990B1 (en) | 1981-07-22 | 1982-07-20 | ANTI-SOLAR AGENTS |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5824512A (en) |
| CH (1) | CH648753A5 (en) |
| DE (1) | DE3227250A1 (en) |
| FR (1) | FR2509990B1 (en) |
| GB (1) | GB2105190B (en) |
| NL (1) | NL8202949A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2486026A4 (en) * | 2009-10-09 | 2015-07-01 | Alexander Macgregor | Derivatives of di(phenylpropanoid) glycerol for the treatment of cancer |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6248612A (en) * | 1985-08-27 | 1987-03-03 | Narisu Keshohin:Kk | Cosmetic |
| JP3537622B2 (en) * | 1996-02-26 | 2004-06-14 | 株式会社資生堂 | UV absorbing composition |
| US8968452B2 (en) * | 2011-04-27 | 2015-03-03 | Xerox Corporation | Phase change inks containing crystalline trans-cinnamic diesters and amorphous isosorbide oligomers |
| US8906150B2 (en) * | 2011-04-27 | 2014-12-09 | Xerox Corporation | Phase change inks containing crystalline trans-cinnamic diesters and polyterpene resins |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2190917A (en) * | 1938-04-07 | 1940-02-20 | Dow Chemical Co | Ethylene dicinnamate |
| BE662111A (en) * | 1965-04-06 | 1965-08-02 | ||
| FR2453132A1 (en) * | 1979-04-02 | 1980-10-31 | Shiseido Co Ltd | ULTRAVIOLET RADIATION ABSORBING AGENT BASED ON METHOXY CINNAMIC ACID |
| EP0056189A1 (en) * | 1980-12-26 | 1982-07-21 | Ss Pharmaceutical Co., Ltd. | 2,3-Butanediol diester derivatives, process for producing the same, and an antiulcer drug containing the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2744326A1 (en) * | 1977-10-01 | 1979-04-12 | Henkel Kgaa | Antiinflammatory agents for cosmetics - esp. sunscreen compsns., comprises hydroxy-cinnamic acid ester(s) |
-
1981
- 1981-07-22 CH CH478381A patent/CH648753A5/en not_active IP Right Cessation
-
1982
- 1982-07-20 FR FR8212619A patent/FR2509990B1/en not_active Expired
- 1982-07-21 DE DE19823227250 patent/DE3227250A1/en not_active Withdrawn
- 1982-07-21 GB GB08221133A patent/GB2105190B/en not_active Expired
- 1982-07-21 JP JP12744982A patent/JPS5824512A/en active Pending
- 1982-07-21 NL NL8202949A patent/NL8202949A/en not_active Application Discontinuation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2190917A (en) * | 1938-04-07 | 1940-02-20 | Dow Chemical Co | Ethylene dicinnamate |
| BE662111A (en) * | 1965-04-06 | 1965-08-02 | ||
| FR2453132A1 (en) * | 1979-04-02 | 1980-10-31 | Shiseido Co Ltd | ULTRAVIOLET RADIATION ABSORBING AGENT BASED ON METHOXY CINNAMIC ACID |
| EP0056189A1 (en) * | 1980-12-26 | 1982-07-21 | Ss Pharmaceutical Co., Ltd. | 2,3-Butanediol diester derivatives, process for producing the same, and an antiulcer drug containing the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2486026A4 (en) * | 2009-10-09 | 2015-07-01 | Alexander Macgregor | Derivatives of di(phenylpropanoid) glycerol for the treatment of cancer |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2105190B (en) | 1985-07-17 |
| GB2105190A (en) | 1983-03-23 |
| JPS5824512A (en) | 1983-02-14 |
| CH648753A5 (en) | 1985-04-15 |
| DE3227250A1 (en) | 1983-02-10 |
| NL8202949A (en) | 1983-02-16 |
| FR2509990B1 (en) | 1985-08-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| ST | Notification of lapse |