JP2612922B2 - Unsaturated 3-benzylidene camphor derivatives and cosmetic compositions - Google Patents
Unsaturated 3-benzylidene camphor derivatives and cosmetic compositionsInfo
- Publication number
- JP2612922B2 JP2612922B2 JP63323845A JP32384588A JP2612922B2 JP 2612922 B2 JP2612922 B2 JP 2612922B2 JP 63323845 A JP63323845 A JP 63323845A JP 32384588 A JP32384588 A JP 32384588A JP 2612922 B2 JP2612922 B2 JP 2612922B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- benzylidenecamphor
- hydrogen atom
- methoxy
- 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.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims description 51
- 239000002537 cosmetic Substances 0.000 title claims description 25
- OIQXFRANQVWXJF-QBFSEMIESA-N (2z)-2-benzylidene-4,7,7-trimethylbicyclo[2.2.1]heptan-3-one Chemical class CC1(C)C2CCC1(C)C(=O)\C2=C/C1=CC=CC=C1 OIQXFRANQVWXJF-QBFSEMIESA-N 0.000 title description 9
- 150000001875 compounds Chemical class 0.000 claims description 52
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 14
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 11
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims 1
- KXTQPNLVIYXTEJ-UHFFFAOYSA-N 3-benzylidene-4-methoxy-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one Chemical compound COC12C(C(C(CC1)(C2(C)C)C)=O)=CC1=CC=CC=C1 KXTQPNLVIYXTEJ-UHFFFAOYSA-N 0.000 claims 1
- 101150065749 Churc1 gene Proteins 0.000 claims 1
- 102100038239 Protein Churchill Human genes 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- 239000003921 oil Substances 0.000 description 20
- 235000019198 oils Nutrition 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 210000003491 skin Anatomy 0.000 description 14
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 230000005855 radiation Effects 0.000 description 13
- -1 alkenyl halide Chemical class 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 235000014113 dietary fatty acids Nutrition 0.000 description 10
- 239000000194 fatty acid Substances 0.000 description 10
- 229930195729 fatty acid Natural products 0.000 description 10
- 210000002615 epidermis Anatomy 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000004166 Lanolin Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 7
- 229940039717 lanolin Drugs 0.000 description 7
- 239000006210 lotion Substances 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 238000002211 ultraviolet spectrum Methods 0.000 description 7
- 239000001993 wax Substances 0.000 description 7
- DSSYKIVIOFKYAU-OIBJUYFYSA-N (S)-camphor Chemical compound C1C[C@]2(C)C(=O)C[C@H]1C2(C)C DSSYKIVIOFKYAU-OIBJUYFYSA-N 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 206010042496 Sunburn Diseases 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 235000019388 lanolin Nutrition 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 150000004678 hydrides Chemical class 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 239000000516 sunscreening agent Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000006071 cream Substances 0.000 description 4
- 239000003925 fat Substances 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 230000000475 sunscreen effect Effects 0.000 description 4
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 206010015150 Erythema Diseases 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 231100000321 erythema Toxicity 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 239000002453 shampoo Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 238000005821 Claisen rearrangement reaction Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 229940110456 cocoa butter Drugs 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- JVTZFYYHCGSXJV-UHFFFAOYSA-N isovanillin Chemical compound COC1=CC=C(C=O)C=C1O JVTZFYYHCGSXJV-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- FBLUJEZNJVZMKK-UHFFFAOYSA-N 3,4-dimethoxy-5-prop-2-enylbenzaldehyde Chemical compound COC1=CC(C=O)=CC(CC=C)=C1OC FBLUJEZNJVZMKK-UHFFFAOYSA-N 0.000 description 1
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 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
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010063493 Premature ageing Diseases 0.000 description 1
- 208000032038 Premature aging Diseases 0.000 description 1
- 206010040954 Skin wrinkling Diseases 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HUTDUHSNJYTCAR-UHFFFAOYSA-N ancymidol Chemical compound C1=CC(OC)=CC=C1C(O)(C=1C=NC=NC=1)C1CC1 HUTDUHSNJYTCAR-UHFFFAOYSA-N 0.000 description 1
- 239000002249 anxiolytic agent Substances 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000019868 cocoa butter Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229940125890 compound Ia Drugs 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000037308 hair color Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 231100000760 phototoxic Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- QMEHFJGLJHMPHU-UHFFFAOYSA-N potassium;toluene Chemical compound [K].CC1=CC=CC=C1 QMEHFJGLJHMPHU-UHFFFAOYSA-N 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000037307 sensitive skin Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 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
- A61K8/35—Ketones, e.g. benzophenone
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
- C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/657—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings
- C07C49/683—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings having unsaturation outside the aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
- C07C49/747—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/753—Unsaturated compounds containing a keto groups being part of a ring containing ether groups, groups, groups, or groups
Description
【発明の詳細な説明】 (産業上の利用分野) 本発明は3−ベンジリデンカンフアーの新規な不飽和
誘導体ならびに人体の表皮および毛髪を日光から保護す
るための、そしてまた光に敏感な成分を含有する化粧品
組成物の安定化のための紫外線吸収剤として化粧品の分
野でこの不飽和誘導体を使用することに関する。本発明
はまた有機硅素化合物の合成のための中間体としてこの
化合物を用いることも企図する。The present invention relates to a novel unsaturated derivative of 3-benzylidenecamphor and a component for protecting the human epidermis and hair from sunlight and also for light-sensitive components. It relates to the use of this unsaturated derivative in the cosmetics field as an ultraviolet absorber for the stabilization of the cosmetic composition containing it. The present invention also contemplates using this compound as an intermediate for the synthesis of organosilicon compounds.
(解決しようとする課題) 280〜400nmの波長範囲の日光輻射線は人体の表皮の褐
色化を惹起しうること、またB−紫外線の名で知られる
波長範囲280〜320nmの光線が紅斑および皮膚の熱傷を惹
き起こし、そのため美しい肌焼きを行うのを阻害するこ
とが知られており、従つてこのB−紫外線は濾光せねば
ならない。(Problems to be Solved) Sunlight radiation in the wavelength range of 280 to 400 nm can cause browning of the epidermis of the human body, and the light in the wavelength range of 280 to 320 nm known as B-ultraviolet light causes erythema and skin. The B-ultraviolet radiation must be filtered out, which is known to cause burns on the skin and thus hinder beautiful skin burning.
波長範囲320〜400nmのA−紫外線は、皮膚の褐色化を
惹起するので、敏感な皮膚または日光輻射線に連続的に
曝露された皮膚の場合は特に皮膚の変性を誘発する可能
性がある。A−紫外線は特に、皮膚の弾性力の低下およ
びしわの発生を惹起し、過早の老化をもたらす。A紫外
線は紅斑反応の開始を促進するか、あるいはある種の患
者にあつては紅斑反応を重くしかつ光毒性または光アレ
ルギー性反応のもとになることさえある。A-ultraviolet radiation in the wavelength range of 320-400 nm causes browning of the skin and can induce skin degeneration, especially in the case of sensitive skin or skin continuously exposed to sunlight radiation. A-ultraviolet radiation in particular causes a reduction in the elasticity of the skin and the development of wrinkles, leading to premature aging. A-UV radiation promotes the onset of the erythema reaction or, in some patients, may exacerbate the erythema reaction and even cause a phototoxic or photoallergic reaction.
従つてA−紫外線およびB−紫外線をともに濾光する
ことができるように広い帯域にわたつて紫外線を吸収す
る化合物を入手することは興味深いことである。It is therefore interesting to have compounds that absorb UV radiation over a wide band so that both A-UV and B-UV light can be filtered.
さらに、化粧品調合物中に含入される成分は、光線に
対する十分な安定性を席にもつとは限らず、日光輻射線
の作用下で劣化することが知られている。Furthermore, it is known that components contained in cosmetic formulations do not always have sufficient stability to light and degrade under the action of sunlight radiation.
従つて、この調合物中に、紫外線を濾光できしかも化
粧品中に通常用いる媒体中で、特に油および脂肪中での
良好な安定性と溶解性とを示す化合物を含入することが
望ましい。It is therefore desirable to include in this formulation a compound which can filter out UV radiation and which has good stability and solubility in the media normally used in cosmetics, especially in oils and fats.
また、特に脱色または色合いの変化を避けるために、
光化学的劣化に対して毛髪を良好に保護することも同様
に望ましい。Also, especially to avoid bleaching or color changes,
Good protection of the hair against photochemical degradation is likewise desirable.
(課題を解決するための手段) このような次第で、本発明者はその研究の経過から、
不飽和基をもつ3−ベンジリデンカンフアーのある種の
誘導体が波長280〜360nmの広い範囲にわたつて良好な濾
光特性を示すことを驚くべきことに発見した。3−ベン
ジリデンカンフアーの新規な誘導体はこの良好な濾光特
性に加えて優れた化学的および光化学的安定性を示しか
つ毒性も刺激性もなくかつ皮膚に対する完全な無害性を
そなえているという利点をもつ。(Means for Solving the Problems) Due to such circumstances, the present inventor has learned from the course of his research,
It has surprisingly been found that certain derivatives of 3-benzylidenecamphors with unsaturated groups exhibit good filtering properties over a wide range of wavelengths from 280 to 360 nm. The novel derivatives of 3-benzylidenecamphors, in addition to their good filtering properties, exhibit excellent chemical and photochemical stability and are non-toxic, non-irritating and completely harmless to the skin. With.
同様にこの新規な誘導体は優れた油溶性を示し、その
ために化粧品中に用いる油脂媒体、特に紫外線に対して
人体表皮を保護するための組成物、そして一層特定的に
は日焼防止用組成物においてこの誘導体を用いるのが有
利となる。The novel derivatives likewise exhibit excellent oil solubility and are therefore used in cosmetics in oil-and-fat media, in particular compositions for protecting the human epidermis against UV rays, and more particularly compositions for preventing sunburn. It is advantageous to use this derivative.
従つて、本発明は式: 〔式中、R1は水素原子、C1〜C6アルキル基、C1〜C6アル
コキシ基または−(O)n−(CH2)p−C(R4)=CH2
(式中、nは0または1であり、pは1から10望ましく
は1から4の整数を表わし、かつR4は水素原子またはC1
〜C4アルキル基を表わす)を表わし; R2は水素原子、C1〜C6アルキル基、C1〜C6アルコキシ
基または−(CH2)p−C(R4)=CH2(式中、pおよび
R4は上記の意味をもつ)を表わし; R3は水素原子、C1〜C6アルキル基またはC1〜C6アルコ
キシ基を表わすが; たゞしR1またはR2残基の一方はそれぞれ−(O)n−
(CH2)p−C(R4)=CH2または−(CH2)p−C
(R4)=CH2(式中n,pおよびR4は上記した意味をもつ)
を表わすものとする〕の新規な不飽和3−ベンジリデン
カンフアー誘導体を目的とする。Thus, the present invention provides the formula: [Wherein, R 1 is a hydrogen atom, a C 1 -C 6 alkyl group, a C 1 -C 6 alkoxy group, or — (O) n — (CH 2 ) p —C (R 4 ) = CH 2
Wherein n is 0 or 1, p is an integer of 1 to 10, preferably 1 to 4, and R 4 is a hydrogen atom or C 1
-C 4 alkyl group represents a); R 2 is a hydrogen atom, C 1 -C 6 alkyl group, C 1 -C 6 alkoxy or - (CH 2) p -C ( R 4) = CH 2 ( wherein Medium, p and
R 4 has the meaning given above; R 3 represents a hydrogen atom, a C 1 -C 6 alkyl group or a C 1 -C 6 alkoxy group, provided that one of the R 1 or R 2 residues is Each-(O) n-
(CH 2 ) p -C (R 4 ) = CH 2 or-(CH 2 ) p -C
(R 4 ) = CH 2 (wherein n, p and R 4 have the above meanings)
Which represents a new unsaturated 3-benzylidenecamphor derivative.
本発明の好ましい化合物として以下の化合物をあげる
ことができる: ・3′−アリル−4′−メトキシ−3−ベンジリデンカ
ンフアー、 ・3′−アリル−4′,5′−ジメトキシ−3−ベンジリ
デンカンフアー、 ・3′−メタリル−4′−メトキシ−3−ベンジリデン
カンフアー、 ・3′−メタリル−4′,5′−ジメトキシ−3−ベンジ
リデンカンフアー、 ・3′−アリロキシ−4′−メトキシ−3−ベンジリデ
ンカンフアー、 ・3′−メタアリロキシ−4′−メトキシ−3−ベンジ
リデンカンフアー、 ・4′−アリル−3−ベンジリデンカンフアー、 ・4′−メタリル−3−ベンジリデンカンフアー。The following compounds may be mentioned as preferred compounds of the present invention: 3'-allyl-4'-methoxy-3-benzylidenecam, 3'-allyl-4 ', 5'-dimethoxy-3-benzylidenecan 3'-methallyl-4'-methoxy-3-benzylidenecamphor;3'-methallyl-4',5'-dimethoxy-3-benzylidenecamphor;3'-allyloxy-4'-methoxy- 3-benzylidenecamphor, 3'-methallyloxy-4'-methoxy-3-benzylidenecamphor, 4'-allyl-3-benzylidenecamphor, 4'-methallyl-3-benzylidenecamphor.
本発明に従う式(I)の化合物は以下の方法のいづれ
かに従つて製造することができる: 第1の方法 R1が−(O)n−(CH2)p−C(R4)=CH2を表わす
か、あるいはR2は−(CH2)p−C(R4)=CH2を表わす
(これらの式中R1、R2、n、p、R4およびR3は上記に示
した意味をもつ)式(I)の化合物の製造。The compounds of formula (I) according to the present invention can be prepared according to any of the following methods: First Method R 1 is — (O) n — (CH 2 ) p —C (R 4 ) = CH or represents 2, or R 2 is - (CH 2) p -C ( R 4) = CH represents the 2 (in these formulas R 1, R 2, n, p, R 4 and R 3 is in the Preparation of compounds of formula (I).
下記の反応図式に従つて式(II)の芳香族アルデヒド
を合成カンフアー(d,l−カンフアー)または天然カン
フアー(d−カンフアー)と縮合する: この反応は、塩基の存在で、例えばアルカリ金属のア
ミド、水素化物、水酸化物またはアルコレートのような
塩基の存在で、ベンゼン、トルエン、エーテル、ジオキ
サンまたは1,2−ジメトキシエタンのような不活性溶媒
中で0℃から溶媒の沸点までの温度範囲において実施す
る。The aromatic aldehyde of formula (II) is condensed with a synthetic (d, l-camphor) or natural camphor (d-camphor) according to the following reaction scheme: This reaction is carried out in the presence of a base, for example an amide, hydride, hydroxide or alcoholate of an alkali metal, in the presence of a base such as benzene, toluene, ether, dioxane or 1,2-dimethoxyethane. It is carried out in an active solvent in a temperature range from 0 ° C. to the boiling point of the solvent.
a) R1が基−(O)n−(CH2)p−C(R4)=CH
2(たゞしn=1)を表わす式(II)のアルデヒドは、
式(III)のハロゲン化アルケニルを下記の反応図式に
従つて式(II A)のアルデヒドと反応することにより得
ることができる: この反応は塩基の存在下の溶媒中で、例えばアルカリ
もしくはアルカリ土類金属の水酸化物もしくは炭酸塩ま
たはアルカリアミド、アルコレートもしくは水素化物の
ような塩基の存在で、水またはアルコール、ジオキサ
ン、ジメチルスルホキシドもしくはジメチルホルムアミ
ドのような有機溶媒のように塩基の性質に対して親和性
のある溶媒中で、環境温度から溶媒の沸点までの温度範
囲において実施する。a) R 1 is a group — (O) n — (CH 2 ) p —C (R 4 ) = CH
2 An aldehyde of the formula (II) representing (n = 1) is
It can be obtained by reacting an alkenyl halide of the formula (III) with an aldehyde of the formula (II A) according to the following reaction scheme: The reaction is carried out in a solvent in the presence of a base, for example in the presence of a base such as an alkali or alkaline earth metal hydroxide or carbonate or an alkali amide, alcoholate or hydride, with water or alcohol, dioxane, dimethyl. It is carried out in a solvent having an affinity for the nature of the base, such as an organic solvent such as sulfoxide or dimethylformamide, in a temperature range from ambient temperature to the boiling point of the solvent.
既知の方法で製造できる式(II A)のアルデヒドにお
いて、またR1が基−(O)−(CH2)p−C(R4)=CH2
を表わす式(II)のアルデヒドにおいて、R2およびR3は
水素原子、C1〜C6アルキル基またはC1〜C6アルコキシ基
を表わす。式(III)の化合物においてXはハロゲン原
子、望ましくは塩素または臭素を表わし、かつX4および
pは上記に記載した意味をもつ。In the aldehydes of the formula (II A) which can be prepared by known methods, also wherein R 1 is a group — (O) — (CH 2 ) p —C (R 4 ) = CH 2
In the aldehyde of the formula (II), R 2 and R 3 represent a hydrogen atom, a C 1 -C 6 alkyl group or a C 1 -C 6 alkoxy group. X is a halogen atom in the compound of formula (III), preferably represents chlorine or bromine, and X 4 and p have the meanings given above.
b) R1が基−(O)n−(CH2)p−C(R4)=CH
2(たゞしn=0である)を表わすあるいはR2が基−(C
H2)p−C(R4)=CH2を表わす式(II)のアルデヒド
は下記の反応図式に従つてエチルオルトフオーミエート
を式(VI)の臭化フエニルマグネシウムと反応し、引続
いて生成するアセタールを加水分解することにより得る
ことができる: この反応は例えばエチルエーテル、ジオキサンまたは
1,2−ジメトキシエタンのような不活性溶媒の存在で、
環境温度から溶媒の沸点までの温度範囲において、QUEL
ETによつて述べられている条件(C.R.Acad.Science 182
巻、1285ページおよびBull.Soc.Chim.Fr.45巻267ページ
参照)にて実施することができる。b) R 1 is a group — (O) n — (CH 2 ) p —C (R 4 ) = CH
2 (where n = 0) or R 2 is a group-(C
H 2) p -C (R 4 ) = aldehyde of formula (II) representing the CH 2 is the Supporting connexion ethyl Orutofuo over ate react with bromide phenylalanine magnesium of the formula (VI) in the reaction scheme below, pull It can be obtained by subsequent hydrolysis of the resulting acetal: The reaction may be, for example, ethyl ether, dioxane or
In the presence of an inert solvent such as 1,2-dimethoxyethane,
In the temperature range from the ambient temperature to the boiling point of the solvent, QUEL
Conditions stated by ET (CRAcad.Science 182
Vol., P. 1285 and Bull. Soc. Chim. Fr. 45, p. 267).
式(II B)および(VI)の化合物において、置換基R1
またはR2の一つは基(CH2)p−C(R4)=CH2(式中の
R4およびpは上記と同じ意味をもつ)を表わし、かつ他
の一つは水素原子、C1〜C6アルキル基またはC1〜C6アル
コキシ基を表わしかつR3は水素原子、C1〜C6アルキル基
またはC1〜C6アルコキシ基を表わす。In the compounds of the formulas (II B) and (VI), the substituent R 1
Or one of R 2 is a group (CH 2 ) p —C (R 4 ) = CH 2 (wherein
R 4 and p have the same meanings as above), and the other one represents a hydrogen atom, a C 1 -C 6 alkyl group or a C 1 -C 6 alkoxy group, and R 3 represents a hydrogen atom, C 1 -C represents an alkyl group or a C 1 -C 6 alkoxy group.
第2の方法 R1が基−(O)n−(CH2)p−C(R4)=CH2(nは
1である)を表わす式(I)の化合物(化合物I A)の
製造。Preparation of compounds of formula (I) (Compound IA) representing the (CH 2) p -C (R 4) = ( where n is 1) CH 2 - The second method R 1 is a group - (O) n.
この化合物は塩基の存在で、例えばアルカリもしくは
アルカリ土類金属の水酸化物もしくは炭酸塩の存在でま
たはアルカリアミド、アルコレートまたは水素化物の存
在で、水またはアルコール、ジオキサン、ジメチルスル
ホキシドもしくはジメチルホルムアミドのような有機溶
媒のように塩基の性質に対して親和性のある溶媒中で、
環境温度から溶媒の沸点までの温度範囲において、下記
の反応図式に従つて式(III)のハロゲン化アルケニル
を式(IV)の3′−ヒドロキシ−3−ベンジリデンカン
フアーと反応することによつて得ることができる: 式(IV)、(III)および(I A)の化合物において、
R2およびR3は水素原子、C1〜C6アルキル基またはC1〜C6
アルコキシ基を表わし、R4およびpは上記した意味をも
ちかつXはハロゲン原子、望ましくは塩素または臭素を
表わす。This compound may be used in the presence of a base, for example in the presence of an alkali or alkaline earth metal hydroxide or carbonate or in the presence of an alkali amide, alcoholate or hydride, of water or of an alcohol, dioxane, dimethylsulfoxide or dimethylformamide. In a solvent that has an affinity for the nature of the base, such as an organic solvent,
By reacting an alkenyl halide of formula (III) with a 3'-hydroxy-3-benzylidenecamphor of formula (IV) in a temperature range from ambient temperature to the boiling point of the solvent according to the following reaction scheme: Obtainable: In compounds of formulas (IV), (III) and (IA)
R 2 and R 3 are a hydrogen atom, a C 1 -C 6 alkyl group or a C 1 -C 6
R 4 and p have the meanings given above and X represents a halogen atom, preferably chlorine or bromine.
式(IV)の化合物は新規な化合物である。 The compound of formula (IV) is a novel compound.
式(IV)の化合物は、R5がC1〜C6アルキル残基、望ま
しくはメチル残基を表わし、かつR2およびR3が水素また
はC1〜C6アルキルもしくはアルコキシ基である式(V)
の化合物を下記の反応図式に従つて酸性加水分解するこ
とによつて得ることができる: この加水分解は例えばピリジンの塩酸塩のような加水
分解剤の存在で反応混合物の沸点近くで実施することが
できる。Compounds of formula (IV), R 5 is C 1 -C 6 alkyl residue, preferably a methyl residue, and R 2 and R 3 is hydrogen or C 1 -C 6 alkyl or alkoxy group wherein ( V)
Can be obtained by acid hydrolysis according to the following reaction scheme: This hydrolysis can be carried out near the boiling point of the reaction mixture in the presence of a hydrolyzing agent, for example the hydrochloride of pyridine.
式(IV)の化合物は式(II A)のアルデヒドを下記の
反応図式に従つて合成カンフアー(d,l−カンフアー)
または天然カンフアー(d−カンフアー)と縮合するこ
とにより製造することもできる。The compound of formula (IV) is prepared by synthesizing an aldehyde of formula (IIA) according to the following reaction scheme (d, l-camphor).
Alternatively, it can also be produced by condensing with natural camphor (d-camphor).
ここでR2およびR3は水素原子、C1〜C6アルキルまたは
アルコキシ基を表わす。 Wherein R 2 and R 3 represents a hydrogen atom, C 1 -C 6 alkyl or alkoxy groups.
この反応は溶媒中の塩基の存在で、例えばジオキサン
または1,2−ジメトキシエタン中の水素化ナトリウムま
たはカリウム第三ブチレートを用いて、環境温度から溶
媒の沸点までの温度において実施する。The reaction is carried out in the presence of a base in the solvent, for example with sodium or potassium tert-butylate in dioxane or 1,2-dimethoxyethane, at a temperature from ambient temperature to the boiling point of the solvent.
第3の方法 R1が基−(O)n−(CH2)p−C(R4)=CH2(たゞ
しn=0かつp=1である)を表わす化合物(化合物I
D)の製造。Third Method A compound (compound I) in which R 1 represents a group — (O) n — (CH 2 ) p —C (R 4 ) = CH 2 (where n = 0 and p = 1)
D) Manufacturing.
この化合物は下記の反応図式に従つて式(I B)の化
合物のCLAISEN転位によつて得ることができる: 化合物(I B)および(I C)において、R3およびR4は
上記した意味をもつ。This compound can be obtained by CLAISEN rearrangement of a compound of formula (IB) according to the following scheme: In the compounds (IB) and (IC), R 3 and R 4 have the meanings described above.
(I B)の化合物は下記の図式に従つて、式(VII)の
4′−ヒドロキシ−3−ベンジリデンカンフアーを、p
=1である式(III)のハロゲン化アルケニルと反応さ
せることにより既知の方法で製造することができる: 上記においてR3およびR4はすでに述べた意味をもち、
かつXはハロゲン望ましくは塩素または臭素である。こ
の反応は塩基例えばアルカリもしくはアルカリ土類金属
の炭酸塩もしくは水酸化物、アルカリアミド、アルコレ
ートまたは水素化物の存在で、水または有機溶媒例えば
アルコール、ジオキサン、ジメチルスルホキシド、また
はジメチルホルムアミドのような塩基の性質に対して親
和性のある溶媒中で、環境温度から溶媒の沸点までの温
度において実施する。The compound of the formula (IB) is prepared by converting the 4'-hydroxy-3-benzylidenecamphor of the formula (VII) to p
Can be prepared in a known manner by reacting with an alkenyl halide of the formula (III) wherein = 1. In the above, R 3 and R 4 have the meaning already mentioned,
And X is a halogen, preferably chlorine or bromine. The reaction is carried out in the presence of a base such as an alkali or alkaline earth metal carbonate or hydroxide, an alkali amide, an alcoholate or a hydride in water or an organic solvent such as an alcohol, dioxane, dimethylsulfoxide or dimethylformamide. In a solvent having an affinity for the above-mentioned properties at a temperature from ambient temperature to the boiling point of the solvent.
CLAISEN転位は、場合によつては溶媒の存在で式(I
B)の化合物を少くとも約170℃に加熱することにより、
TARBELLによつて述べられた条件(ニユーヨークのJohn
Wiley社刊のOrganic Reactions第2巻(1944年)(1ペ
ージ参照)の下で実施できる。The CLAISEN rearrangement, optionally in the presence of a solvent, has the formula (I
By heating the compound of B) to at least about 170 ° C,
The conditions stated by TARBELL (John New York)
It can be carried out under Wiley's Organic Reactions Volume 2 (1944) (see page 1).
このようにして得る式(I C)の化合物は、塩基例え
ばアルカリ土類金属の炭酸塩の存在で、ジメチルホルム
アミドのような溶媒中で、あるいは1,2−ジメトキシエ
タン中のアルカリ金属の水素化物の存在で、C1〜C6のハ
ロゲン化アルキルとの反応によつて、R2がC1〜C6アルコ
キシ基を表わす式(I D)の化合物へと下記の反応図式
に従つて転換する: 化合物(I D)において、R2はC1〜C6アルコキシ基を
表わしかつR3およびR4は上記と同じ意味をもつ。The compound of formula (IC) thus obtained can be obtained by reacting the hydride of the alkali metal in a solvent such as dimethylformamide or in 1,2-dimethoxyethane in the presence of a base, for example an alkaline earth metal carbonate. In the presence, by reaction with a C 1 -C 6 alkyl halide, R 2 is converted into a compound of formula (ID) in which R 2 represents a C 1 -C 6 alkoxy group according to the following reaction scheme: In the compound (ID), R 2 is and R 3 and R 4 represents a C 1 -C 6 alkoxy group has the same meaning as above.
化合物(I C)は、式(I)の化合物と同様に紫外線
吸収特性をもつ新規な化合物である。Compound (IC) is a novel compound having ultraviolet absorption properties like the compound of formula (I).
本発明は式(IV): (式中R2およびR3は水素原子またはC1〜C6アルキルもし
くはアルコキシ基を表わす)の新規な化合物もまた目的
とする。The present invention provides a compound of formula (IV): Also of interest are novel compounds of the formula wherein R 2 and R 3 represent a hydrogen atom or a C 1 -C 6 alkyl or alkoxy group.
本発明はまた式(I C): (式中、R4は水素原子またはC1〜C4アルキル基を表わ
し、かつR3は水素原子、C1〜C6アルキルもしくはアルコ
キシ基を表わす)の新規な化合物ならびにこれを紫外線
濾光剤として使用することも企図する。The present invention also provides a compound of formula (IC): Wherein R 4 represents a hydrogen atom or a C 1 -C 4 alkyl group, and R 3 represents a hydrogen atom, a C 1 -C 6 alkyl or alkoxy group; It is also contemplated to be used as
その油溶性のために、上記の式(I)の不飽和3−ベ
ンジリデンカンフアー誘導体は少くとも一つの油脂相を
含む標準的な化粧品媒体中に分散しかつ有効な保護膜を
つくるために皮膚または毛髪上に適用することができ
る。Due to its oil solubility, the unsaturated 3-benzylidenecamphor derivatives of the above formula (I) are dispersed in a standard cosmetic medium containing at least one grease phase to form an effective protective film on the skin. Or it can be applied on the hair.
従つて本発明は、少くとも一つの油脂相を含む化粧品
として許容できる媒体中に、上記の式(I)の3−ベン
ジリデンカンフアーの不飽和誘導体を少くとも一つ有効
量含有する化粧品組成物もまた目的とする。Accordingly, the present invention relates to a cosmetic composition comprising at least one effective amount of the unsaturated derivative of 3-benzylidenecamphor of the above formula (I) in a cosmetically acceptable medium containing at least one fat phase. Also aims.
本発明はまた、少くとも一つの油脂相を含む化粧品と
して許容できる媒体中に、上記の式(I C)の不飽和3
−ベンジリデンカンフアー誘導体を少くとも一つ有効量
含有する化粧品組成物もまた企図する。The present invention also relates to a cosmetically acceptable medium containing at least one grease phase, wherein the unsaturated 3
Cosmetic compositions containing at least one effective amount of a benzylidenecam derivative are also contemplated.
本発明の化粧品組成物は人体の表皮もしくは毛髪の保
護用組成物としてまたは日焼防止用組成物として用いる
ことができる。The cosmetic composition of the present invention can be used as a composition for protecting human epidermis or hair or as a composition for preventing sunburn.
本発明はまた、少くとも一つの油脂相を含有する化粧
品として許容できる媒体中に含まれる少くとも一つの式
(I)の化合物を有効量、皮膚または毛髪に適用するこ
とからなる、皮膚または自然のまゝのもしくは鋭敏化し
た毛髪を日光輻射線から保護する方法も目的とする。The present invention also provides a method of treating a skin or natural skin comprising applying to a skin or hair an effective amount of at least one compound of formula (I) contained in a cosmetically acceptable medium containing at least one fat phase. A method of protecting raw or sensitized hair from sunlight radiation is also an object.
「損傷した毛髪」とはパーマネント、染色または脱色
をうけた毛髪のことである。"Damaged hair" is permanent, dyed or bleached hair.
本発明はまた、上記の式(I)の3−ベンジリデンカ
ンフアー誘導体を少くとも一つ有効量含有する、光線に
対して安定化された、着色したまたは着色されていない
化粧品組成物も目的とする。The invention also relates to a light-stabilized, colored or uncolored cosmetic composition comprising at least one effective amount of a 3-benzylidenecamphor derivative of the above formula (I). I do.
人体の表皮を紫外線から保護するための組成物として
本発明の化粧品組成物を用いる場合、この組成物はこの
種の組成物のために通常用いる種々な形をとることがで
きる。特に、本組成物は油性もしくはアルコール油性ロ
ーシヨン、クリームもしくは乳液のような乳濁液、アル
コール油性、アルコール性またはアルコール水性ゲル、
固形棒状物の形をとつてよくあるいはエアロゾルとして
包装されてよい。When the cosmetic composition according to the invention is used as a composition for protecting the epidermis of the human body from UV radiation, this composition can take various forms usually used for such compositions. In particular, the composition may be an oily or alcoholic oily lotion, an emulsion such as a cream or emulsion, an alcoholic, alcoholic or alcoholic aqueous gel,
It may be in the form of a solid bar or packaged as an aerosol.
本組成物は、この種の組成物中で通常用いる化粧品補
助剤例えば、増粘剤、緩和剤、湿潤剤、界面活性剤、保
存剤、発泡防止剤、香料、油、ろう、ラノリン、推進
剤、組成物そのものまたは皮膚を着色するための機能を
もつ染料および(または)顔料または化粧品中で通常用
いる他のあらゆる成分を含有してよい。The composition is a cosmetic adjuvant commonly used in such compositions, such as thickeners, emollients, wetting agents, surfactants, preservatives, foam inhibitors, fragrances, oils, waxes, lanolin, propellants. May contain dyes and / or pigments which function to color the composition itself or the skin or any other ingredients commonly used in cosmetics.
式(I)の化合物は、人体表皮を保護するための化粧
品組成物の全重量に対して0.25〜3重量%の範囲の重量
割合で存在する。The compounds of the formula (I) are present in a proportion by weight in the range from 0.25 to 3% by weight relative to the total weight of the cosmetic composition for protecting the human epidermis.
溶解化溶媒として、油、ろうおよび一般的にあらゆる
形の脂肪物質、低級の1価もしくは多価アルコールまた
はこれらの混合物を用いることができる。特に好ましい
1価もしくは多価アルコールはエタノール、イソプロパ
ノール、プロピレングリコール、グリセリンおよびソル
ビトールである。Oils, waxes and generally all forms of fatty substances, lower monohydric or polyhydric alcohols or mixtures thereof can be used as solubilizing solvents. Particularly preferred monohydric or polyhydric alcohols are ethanol, isopropanol, propylene glycol, glycerin and sorbitol.
本発明の一実施態様は、式(I)の化合物に加えて脂
肪族アルコール、脂肪酸エステル特に脂肪酸トリグリセ
リド、脂肪酸、ラノリン、天然もしくは合成的な油もし
くはろうおよび乳化剤を水の存在で含有する保護用のク
リームまたは乳液の形の乳濁液である。One embodiment of the present invention relates to a protective composition comprising, in addition to a compound of the formula (I), an aliphatic alcohol, a fatty acid ester, in particular a fatty acid triglyceride, a fatty acid, lanolin, a natural or synthetic oil or wax and an emulsifier in the presence of water. Is an emulsion in the form of a cream or emulsion.
他の実施態様は天然のまたは合成的な油およびろう、
ラノリンならびに脂肪酸エステル特に脂肪酸トリグリセ
リドを基体とするローシヨンから、あるいはエタノール
のような低級アルコールまたはプロピレングリコールの
ようなグリコールおよび(または)グリセリンのような
多価アルコールならびに油、ろうおよび脂肪酸トリグリ
セリドのような脂肪酸エステルを基体とするアルコール
油性ローシヨンからなる。Other embodiments are natural or synthetic oils and waxes,
From lanolin and fatty acid esters, especially lotions based on fatty acid triglycerides, or from lower alcohols such as ethanol or glycols such as propylene glycol and / or polyhydric alcohols such as glycerin and oils, waxes and fatty acids such as fatty acid triglycerides. It consists of an ester-based alcoholic oil lotion.
固形棒状物は天然のもしくは合成的なろうおよび油、
脂肪族アルコール、脂肪酸エステル、ラノリンおよび他
の脂肪物質からなる。Solid bars are natural or synthetic waxes and oils,
Consists of fatty alcohols, fatty acid esters, lanolin and other fatty substances.
エアロゾルとして包装した組成物の場合、アルカン、
フルオロアルカンおよびクロロフルオロアルカンのよう
な標準的な推進剤を用いる。For compositions packaged as aerosols, alkanes,
Standard propellants such as fluoroalkanes and chlorofluoroalkanes are used.
本発明はまた、式(I)の化合物を少くとも一つ含み
かつ他のB−紫外線および(または)A−紫外線を含有
してよい日焼防止用化粧品も企図する。The invention also contemplates sunscreen cosmetics which contain at least one compound of formula (I) and may contain other B-UV and / or A-UV radiation.
この場合、日焼防止用組成物すなわち式(I)の化合
物および場合によつては他の濾光剤中に存在する濾光剤
の全量は、この組成物の全重量に対して0.5〜15重量%
の範囲内にある。In this case, the total amount of the sunscreen composition, i.e. the compound of the formula (I) and optionally the filter agent present in the other filter agent is from 0.5 to 15%, based on the total weight of the composition. weight%
Within the range.
この日焼防止用組成物は人体の表皮を保護する組成物
について上記に示した形をとる。The sunscreen composition takes the form described above for the composition for protecting the human epidermis.
本発明の化粧品組成物が自然のまゝのまたは損傷した
毛髪を紫外線から保護するためのものである場合、この
組成物はシヤンプー、ローシヨン、シヤンプーの前また
は後、染色または脱色の前または後、パーマネントの前
または後に適用すべきすゝぎ洗い用のゲルまたは乳濁
液、整髪または手当て用のローシヨンまたはゲル、ブラ
シ掛けまたはセツトのためのローシヨンまたはゲル、毛
髪用ラツカー、毛髪のパーマネント、染色または脱色用
組成物の形をとつてよい。この組成物は本発明の化合物
に加えて、界面活性剤、増粘剤、重合体、緩和剤、保存
剤、泡沫安定剤、電解質、有機溶媒、硅素化誘導体、
油、ろう、抗脂肪剤、組成物そのものまたは毛髪を着色
する機能をもつ染料および(または)顔料あるいは毛髪
の分野で通常用いる他のあらゆる成分のような、この種
の組成物中に用いる種々の補助剤を含有してよい。When the cosmetic composition of the present invention is for protecting natural or damaged hair from ultraviolet light, the composition may be used before or after shampoo, lotion, shampoo, before or after dyeing or bleaching, Gel or emulsion for rinsing, to be applied before or after permanent, lotion or gel for styling or treatment, lotion or gel for brushing or setting, lacquer for hair, permanent of hair, dyeing or bleaching It may take the form of a composition for use. This composition contains, in addition to the compound of the present invention, a surfactant, a thickener, a polymer, a relaxant, a preservative, a foam stabilizer, an electrolyte, an organic solvent, a silicified derivative,
Various oils used in this type of composition, such as oils, waxes, anti-fat agents, the composition itself or dyes and / or pigments having the function of coloring the hair or any other ingredients commonly used in the field of hair Auxiliaries may be included.
本組成物は式(I)の化合物を0.25〜3重量%含有す
る。The composition contains 0.25 to 3% by weight of the compound of formula (I).
本発明はまた、毛髪用ラツカー、場合によつては処理
または梳毛用のセツトローシヨン、染色シヤンプー、毛
髪用染色組成物のような毛髪用組成物からなる、あるい
はマニキユア、表皮を手当するためのクリームおよび
油、フアンデーシヨン、棒状口紅、入浴用の油またはク
リームのような皮膚手入用組成物、ならびにその成分の
ために保存の際に光線に対する安定性に問題のありうる
他のあらゆる化粧品組成物からなる、紫外線に対する保
護剤として式(I)の化合物を少くとも一つ含む化粧品
組成物もまた企図する。The invention also comprises a hair wrapper, optionally a hair composition such as a set-up, a dyeing shampoo, a hair-coloring composition for treating or combing, or for treating manicure, epidermis. Skin care compositions such as creams and oils, foundations, stick lipsticks, bath oils or creams, and any other cosmetics which may have problems with light stability during storage due to their ingredients Cosmetic compositions comprising at least one compound of formula (I) as a protective agent against ultraviolet radiation, comprising the composition, are also contemplated.
このような組成物は式(I)の化合物を0.25〜3重量
%含有する。Such compositions contain from 0.25 to 3% by weight of the compound of formula (I).
本発明はまた、化粧品組成物中に式(I)の化合物を
少くとも一つ有効量含入することからなる、紫外線から
化粧品組成物を保護する方法も企図する。The invention also contemplates a method of protecting a cosmetic composition from ultraviolet light, comprising the inclusion of at least one effective amount of a compound of formula (I) in the cosmetic composition.
本発明の式(I)の不飽和3−ベンジリデンカンフア
ー誘導体はさらに合成用中間体として特に興味深い。例
えばこれをSiH基を含む有機硅酸化合物と反応すること
ができる。The unsaturated 3-benzylidenecamphor derivatives of the formula (I) according to the invention are further of particular interest as intermediates for synthesis. For example, it can be reacted with an organosilicate compound containing SiH groups.
従つて本発明は、有機硅酸化合物の製造における中間
体として式(I)の3−ベンジリデンカンフアーの新規
な誘導体を使用することも目的とする。The invention therefore also aims at the use of the novel derivatives of 3-benzylidenecamphor of the formula (I) as intermediates in the preparation of organosilicic compounds.
本発明は下記の実施例によつて一層よく例解されよう
が、これらによつて限定されるものではない。The invention will be better illustrated, but not limited, by the following examples.
製造例 例1 3′−アリル−4′−メトキシ−3−ベンジリデンカン
フアーの製造 第1段階 3′−アリル−4′−ヒドロキシ−3−ベンジリデンカ
ンフアーの製造 フランス特許第2,430,938号明細書の例8に従つて得
られる4′−アリロキシ−3−ベンジリデンカンフアー
296g(1モル)を185℃において撹拌下で24時間加熱す
る。冷却した反応混合物をエチルエーテル中で再結晶す
る。このようにして、下記の特性をもつ3′−アリル−
4′−ヒドロキシ−3−ベンジリデンカンフアー270gを
得る: ・融点:150℃ ・1H核磁気共鳴スペクトル(CDCl3):所期の構造に合
致するスペクトル ・紫外線スペクトル(エタノール):λmax=327nm ε=22600 元素分析: 計算値(%):C 81.04 H 8.16 実測値(%):C 81.11 H 8.18 第2段階 3′−アリル−4′−メトキシ−3−ベンジリデンカン
フアーの製造 上記の第1段階において得た3′−アリル−4′−ヒ
ドロキシ−3−ベンジリデン9g(0.03モル)を、分子篩
上で予め乾燥した1,2−ジメトキシエタン150cm3中に溶
解する。水素化ナトリウム2.56をゆつくりと添加しかつ
60℃に加熱する。沃化メチル8.52g(0.06モル)を少量
ずつ導入し、次いで2時間にわたつて還流する。溶媒を
蒸発しかつ残留物を水50cm3およびエチルエーテル200cm
3によつて回収する。エーテル相を2度水洗し、次いで
硫酸ナトリウム上で乾燥する。溶媒の蒸発後、下記の特
性をもつ白色結晶の形の3′−アリル−4′−メトキシ
−3−ベンジリデンカンフアー8.8gを回収する: ・融点:58℃ ・1H核磁気スペクトル(CDCl3):所期の構造に合致す
るスペクトル ・紫外線スペクトル(95゜エタノール):λmax=321nm ε=24200 元素分析: 計算値(%):C 81.25 H 8.44 O 10.31 実測値(%):C 81.35 H 8.60 O 10.51 例2 3′−メタアリロキシ−4′−メトキシ−3−ベンジリ
デンカンフアーの製造 第1段階 3′−ヒドロキシ−4′−メトキシ−3−ベンジリデン
カンフアーの製造 分子篩上で乾燥した1,2−ジメトキシエタン300cm3中
のd,l−カンフアー83.7g(0.55モル)および水素化ナト
リウム26.4g(1.1モル)の混合物を撹拌下かつ窒素下で
80℃にする。乾燥した1,2−ジメトキシエタン200cm3中
のイソバニリン76g(0.5モル)を30分にわたつて添加し
かつ4時間にわたつて還流下で加熱する。冷却した反応
混合物を氷500gおよび濃塩酸100cm3中に注意して注ぎ込
む。生成する沈澱を濾過し、水洗しかつイソプロピルエ
ーテル中で再結晶する。下記の特性をもつ淡黄色の粉末
の形の3′−ヒドロキシ−4′−メトキシ−3−ベンジ
リデンカンフアー79g(収率55%)を得る: ・融点:125℃ ・1H核磁気共鳴スペクトル(CDCl3):所期の構造に合
致するスペクトル ・紫外線スペクトル(エタノール):λmax=334nm ε=19650 元素分析: 計算値(%):C 75.50 H 7.74 実測値(%):C 75.43 H 7.77 第2段階 3′−メタアリロキシ−4′−3−ベンジリデンカンフ
アーの製造 第1段階で得た3′−ヒドロキシ−4′−メトキシ−
3−ベンジリデンカンフアー30g(0.105モル)とジメチ
ルホルムアミド100cm3中の炭酸カリウム21.8g(0.16モ
ル)との混合物を65〜70℃にする。塩化メタリル17cm3
(0.16モル)を少量づつ添加しかつ3.5時間にわたつて7
0℃に保つ。反応混合物を氷水中に注入する。得られる
沈澱を濾過し、次いで水洗する。下記の特性をもつ淡黄
色粉末の形の3′−メタアリロキシ−4′−メトキシ−
3−ベンジリデンカンフアー34gを得る: ・融点:66℃ ・1H核磁気共鳴スペクトル(CDCl3):所期の構造に合
致するスペクトル ・紫外線スペクトル(エタノール):λmax=330nm ε=19750 元素分析: 計算値(%):C 77.61 H 8.29 O 14.10 実測値(%):C 77.37 H 8.26 O 14.36 本発明の化合物(I)は下記の化粧品組成物中に用い
ることができる。PREPARATION EXAMPLES Example 1 Preparation of 3'-allyl-4'-methoxy-3-benzylidenecam 1st Stage Preparation of 3'-allyl-4'-hydroxy-3-benzylidenecamphor Example of French Patent 2,430,938 4'-allyloxy-3-benzylidenecamphor obtained according to 8
296 g (1 mol) are heated at 185 ° C. with stirring for 24 hours. The cooled reaction mixture is recrystallized in ethyl ether. Thus, 3'-allyl- having the following properties:
270 g of 4'-hydroxy-3-benzylidenecamphor are obtained: Melting point: 150 ° C. 1 H nuclear magnetic resonance spectrum (CDCl 3 ): spectrum matching the expected structure UV spectrum (ethanol): λ max = 327 nm ε = 22600 Elemental analysis: Calculated value (%): C 81.04 H 8.16 Observed value (%): C 81.11 H 8.18 Second step Preparation of 3'-allyl-4'-methoxy-3-benzylidenecamphor First step described above 9 g (0.03 mol) of 3'-allyl-4'-hydroxy-3-benzylidene obtained in 1) are dissolved in 150 cm 3 of 1,2-dimethoxyethane which has been dried on a molecular sieve. Add 2.56 sodium hydride slowly and
Heat to 60 ° C. 8.52 g (0.06 mol) of methyl iodide are introduced in small portions and then refluxed for 2 hours. The solvent is evaporated and the residue is treated with 50 cm 3 of water and 200 cm of ethyl ether.
Collect by 3 . The ether phase is washed twice with water and then dried over sodium sulfate. After evaporation of the solvent, to recover a white crystalline form 3'-allyl-4'-methoxy-3-benzylidene cans Sulfur 8.8g having the following characteristics: Melting point: 58 ° C.-IH Nuclear Magnetic Spectrum (CDCl 3) : Spectrum that matches the expected structure ・ Ultraviolet spectrum (95 ° ethanol): λ max = 321 nm ε = 24200 Elemental analysis: Calculated value (%): C 81.25 H 8.44 O 10.31 Actual value (%): C 81.35 H 8.60 O 10.51 Example 2 Preparation of 3'-Metaallyloxy-4'-methoxy-3-benzylidenecam 1st Stage Preparation of 3'-Hydroxy-4'-methoxy-3-benzylidenecamphor 1,2-dried on molecular sieve A mixture of 83.7 g (0.55 mol) of d, l-camphor and 26.4 g (1.1 mol) of sodium hydride in 300 cm 3 of dimethoxyethane was stirred and stirred under nitrogen.
Bring to 80 ° C. 76 g (0.5 mol) of isovanillin in 200 cm 3 of dry 1,2-dimethoxyethane are added over 30 minutes and heated under reflux for 4 hours. The cooled reaction mixture is carefully poured into 500 g of ice and 100 cm 3 of concentrated hydrochloric acid. The precipitate formed is filtered, washed with water and recrystallized in isopropyl ether. 79 g (55% yield) of 3'-hydroxy-4'-methoxy-3-benzylidenecamphor are obtained in the form of a pale yellow powder with the following properties: Melting point: 125 DEG C. 1H nuclear magnetic resonance spectrum (CDCl 3 ): A spectrum that matches the expected structure. ・ Ultraviolet spectrum (ethanol): λ max = 334 nm ε = 19650 Elemental analysis: Calculated value (%): C 75.50 H 7.74 Actual value (%): C 75.43 H 7.77 2nd Step 3 Preparation of 3'-Metaallyloxy-4'-3-benzylidenecamphor 3'-Hydroxy-4'-methoxy- obtained in the first step
A mixture of 30 g (0.105 mol) of 3-benzylidenecam and 21.8 g (0.16 mol) of potassium carbonate in 100 cm 3 of dimethylformamide is brought to 65-70 ° C. Methallyl chloride 17cm 3
(0.16 mol) in small portions and add 7 over 3.5 hours.
Keep at 0 ° C. The reaction mixture is poured into ice water. The resulting precipitate is filtered and then washed with water. 3'-Metaallyloxy-4'-methoxy- in the form of a pale yellow powder having the following properties:
34 g of 3-benzylidenecamphor are obtained: Melting point: 66 ° C. 1 H nuclear magnetic resonance spectrum (CDCl 3 ): spectrum conforming to the expected structure Ultraviolet spectrum (ethanol): λ max = 330 nm ε = 19750 Elemental analysis: Calculated value (%): C 77.61 H 8.29 O 14.10 Actual value (%): C 77.37 H 8.26 O 14.36 The compound (I) of the present invention can be used in the following cosmetic compositions.
例3 3′−メタリル−4′−メトキシ−3−ベンジリデンカ
ンフアーの製造 第1段階 4′−ヒドロキシ−3′−メタリル−3−ベンジリデン
カンフアーの製造 4′−メタアリロキシ−3−ベンジリデンカンフアー
10g(0.032モル)を撹拌下で19時間180℃に加熱する。
冷却した反応混合物をジクロロメタン中に回収する。こ
の有機相を10%ソーダで処理する。油状の中間体相が表
面に生成する。これを単離しかつシリカ60のクロマトグ
ラフカラムによつて精製する(溶離剤はCH2Cl2)。以上
のようにして下記の特性をもつ4′−ヒドロキシ−3′
−メタリル−3−ベンジリデンカンフアー4.5gを得る: ・融点:111〜113℃ ・1H核磁気共鳴スペクトル(CDCl3):所期の構造に合
致するスペクトル ・紫外線スペクトル(96%エタノール):λmax=324nm ε=20850 元素分析: 計算値(%):C 81.25 H 8.44 O 10.31 実測値(%):C 81.44 H 8.43 O 10.49 第2段階 3′−メタリル−4′−メトキシ−3−ベンジリデンカ
ンフアーの製造 上記の第1段階で得た4′−ヒドロキシ−3′−メタ
リル−3−ベンジリデンカンフアー1.5g(0.005モル)
とジメチルホルムアミド20cm3中の炭酸カリウム1.4g
(0.01モル)との混合物を40℃にする。沃化メチル1.4g
(0.01モル)を少量づつ添加しかつ40℃に4時間保つ。
反応混合物を氷水中に注入する。得られる沈澱を濾過
し、次いで水洗する。下記の特性をもつ白色粉末の形の
3′−メタリル−4′−メトキシ−3−ベンジリデンカ
ンフアー1.5g(収率95%)を得る: 融点:33〜34℃ ・1H核磁気共鳴スペクトル(CDCl3):所期の構造に合
致するスペクトル ・紫外線スペクトル(CH2Cl2):λmax=318nm ε=23900 元素分析: 計算値(%):C 81.44 H 8.70 O 9.86 実測値(%):C 81.34 H 8.69 O 10.01 例4 3′−アリル−4′,5′−ジメトキシ−3−ベンジリデ
ンカンフアーの製造 樟脳(4.4g、0.029モル)と分子篩上で乾燥したトル
エン15cm3中のカリウム0.3gとの混合物を撹拌下で80℃
にする。3−アリル−4,5−ジメトキシ−ベンズアルデ
ヒド3g(0.0145モル)を30分にわたつて添加しかつ4時
間にわたつて還流下で加熱する。共沸により水を除去す
る。冷却した反応混合物を氷水中に注入しかつジクロロ
メタンにより抽出する。得られる油をシリカ60のカラム
上でクロマトグラフイーにより精製し(溶離剤は50/50
のCH2Cl2/トルエンである)かつ純エタノール中で再結
晶する。下記の特性をもつ白色粉末状の3′−アリル−
4′,5′−ジメトキシ−3−ベンジリデンカンフアー1.
2g(収率25%)を得る: ・融点:104〜105℃ ・1H核磁気共鳴スペクトル(CDCl3):所期の構造に合
致するスペクトル ・紫外線スペクトル(96%エタノール):λmax=312nm ε=18200 元素分析: 計算値(%):C 77.61 H 8.29 O 14.10 実測値(%):C 77.41 H 8.33 O 14.31 適用例 例A−日焼防止用油 場合によつては均質化するために40〜45℃に加熱する
ことにより下記の成分を混合する: ・カカオバター 2.5 g ・3′−アリル−4′−メトキシ−3−ベンジリデンカ
ンフアー 1.5 g ・ブチルヒドロキシアニソール 0.05g ・香料 十分な量 ・植物油 全体を100gとする量 例B−日焼防止油 下記の成分から上記と同様に日焼防止用油を調製す
る: ・ラノリン 2.5 g ・3′−メタアリロキシ−4′−メトキシ−3−ベンジ
リデンカンフアー 3 g ・ブチルヒドロキシアニソール 0.05g ・香料 十分な量 ・C8〜C12脂肪酸のトリグリセリド 全体を100gとする量 例C−日焼防止用アルコール油性ローシヨン ・ラノリン 2.5 g ・C8〜C12脂肪酸のトリグリセリド 40 g ・香料 十分な量 ・3′−アリル−4′−ヒドロキシ−3−ベンジリデン
カンフアー 2 g ・ブチルヒドロキシトルエン 0.05g ・96゜アルコール 全体を100gとする量 例D−日焼防止用油 ・3′−メタアリル−4′−メトキシ−3−ベンジリデ
ンカンフアー 1.5 g ・カカオバター 2.5 g ・ブチルヒドロキシアニソール 0.05g ・日まわり油 全体を100gとする量 例E−日焼防止用油 ・3′−アリル−4′,5′−ジメトキシ−3−ベンジリ
デンカンフアー 3 g ・ラノリン 2.5g ・保存剤、香料 十分な量 ・C8〜C12脂肪酸のトリグリセリド 全体を100gとする量Example 3 Preparation of 3'-methallyl-4'-methoxy-3-benzylidenecam 1st step Preparation of 4'-hydroxy-3'-methallyl-3-benzylidenecamphor 4'-methallyloxy-3-benzylidenecamphor
10 g (0.032 mol) are heated to 180 ° C. under stirring for 19 hours.
The cooled reaction mixture is recovered in dichloromethane. This organic phase is treated with 10% soda. An oily intermediate phase forms on the surface. It is isolated and purified by chromatography on a silica 60 column (eluent is CH 2 Cl 2 ). As described above, 4'-hydroxy-3 'having the following properties:
- methallyl -3-benzylidene Kang Sulfur 4.5 g: - melting point: 111 to 113 ° C., IH nuclear magnetic resonance spectrum (CDCl 3): spectrum ultraviolet spectrum that matches the desired structure (96% ethanol): lambda max = 324 nm ε = 20850 Elemental analysis: Calculated value (%): C 81.25 H 8.44 O 10.31 Observed value (%): C 81.44 H 8.43 O 10.49 Second stage 3'-methallyl-4'-methoxy-3-benzylidenecamphor Preparation of 1.5 g (0.005 mol) of 4'-hydroxy-3'-methallyl-3-benzylidenecamphor obtained in the first step above
And potassium carbonate 1.4 g in dimethylformamide 20 cm 3
(0.01 mol) to 40 ° C. 1.4 g of methyl iodide
(0.01 mol) are added in portions and kept at 40 ° C. for 4 hours.
The reaction mixture is poured into ice water. The resulting precipitate is filtered and then washed with water. 1.5 g (95% yield) of 3'-methallyl-4'-methoxy-3-benzylidenecam in the form of a white powder having the following properties are obtained: Melting point: 33-34 ° C. 1H nuclear magnetic resonance spectrum (CDCl 3 ): Spectrum conforming to the expected structure. ・ Ultraviolet spectrum (CH 2 Cl 2 ): λ max = 318 nm ε = 23900 Elemental analysis: Calculated value (%): C 81.44 H 8.70 O 9.86 Actual measured value (%): C 81.34 H 8.69 O 10.01 example 4 3'-allyl-4 ', 5'-dimethoxy-3-benzylidene cans Sulfur manufacturing camphor (4.4 g, 0.029 mol) and potassium toluene 15cm 3 were dried over molecular sieves 0.3g The mixture is stirred at 80 ° C
To 3 g (0.0145 mol) of 3-allyl-4,5-dimethoxy-benzaldehyde are added over the course of 30 minutes and heated under reflux for 4 hours. Water is removed by azeotropic distillation. The cooled reaction mixture is poured into ice water and extracted with dichloromethane. The resulting oil is purified by chromatography on a column of silica 60 (eluent 50/50
CH 2 Cl 2 / toluene) and recrystallize in pure ethanol. 3'-allyl in the form of a white powder having the following characteristics:
4 ', 5'-Dimethoxy-3-benzylidenecam 1.
2 g (yield 25%) are obtained: Melting point: 104-105 ° C. 1 H nuclear magnetic resonance spectrum (CDCl 3 ): spectrum matching the expected structure UV spectrum (96% ethanol): λ max = 312 nm ε = 18200 Elemental analysis: Calculated value (%): C 77.61 H 8.29 O 14.10 Observed value (%): C 77.41 H 8.33 O 14.31 Application examples Example A-sunburn preventing oil In some cases, 40 to homogenize Mix the following ingredients by heating to ~ 45 ° C: cocoa butter 2.5 g 3'-allyl-4'-methoxy-3-benzylidenecam 1.5 g butylhydroxyanisole 0.05 g fragrance sufficient amount Vegetable oil Amount to total 100 g Example B-Sunscreen oil Prepare sunscreen oil in the same manner as above from the following ingredients:-Lanolin 2.5 g-3'-Metalallyloxy-4'-methoxy-3-benzylidenecan Fur 3 g ・ Butyl hydroxyanisole 0.05 g・ Sufficient amount of fragrance ・ Amount of 100 g of triglyceride of C 8 to C 12 fatty acids as a whole Example C-alcoholic oily lotion for preventing sunburn ・ 2.5 g of lanolin ・ 40 g of triglyceride of C 8 to C 12 fatty acids・ 3′-allyl-4′-hydroxy-3-benzylidenecamphor 2 g ・ butylhydroxytoluene 0.05 g ・ 96 ゜ Alcohol to make the total amount 100 g Example D-sunburn preventing oil ・ 3'-methallyl-4 ' -Methoxy-3-benzylidene camphor 1.5 g-Cocoa butter 2.5 g-Butylhydroxyanisole 0.05 g-Daily oil 100 g of total oil Example E-Sunburn preventing oil-3'-allyl-4 ', 5' - dimethoxy-3-benzylidene cans Sulfur 3 g · lanolin 2.5 g · preservative, the amount of the entire triglyceride perfume sufficient · C 8 -C 12 fatty acid and 100g
Claims (7)
コキシ基または−(O)n−(CH2)p−C(R4)=CH2
(nは0または1であり、pは1から10を表し、かつR4
は水素原子またはC1〜C4アルキルを表す)を表し、 R2は水素原子、C1〜C6アルキル基、C1〜C6アルコキシ基
または−(CH2)p−C(R4)=CH2(pおよびR4は上記
の意味をもつ)を表し、 R3は水素原子、C1〜C6アルキル基またはC1〜C6アルコキ
シ基を表すが、 ただしR1は−(O)n−(CH2)p−C(R4)=CH2であ
るかまたはR2は−(CH2)p−C(R4)=CH2(n,pおよ
びR4は上記した意味をもつ)を表すものとする〕を有す
る化合物。(1) Expression [Wherein, R 1 is a hydrogen atom, a C 1 -C 6 alkyl group, a C 1 -C 6 alkoxy group, or — (O) n — (CH 2 ) p —C (R 4 ) = CH 2
(N is 0 or 1, p represents 1 to 10, and R 4
Represents a hydrogen atom or C 1 -C 4 alkyl), and R 2 represents a hydrogen atom, a C 1 -C 6 alkyl group, a C 1 -C 6 alkoxy group or — (CH 2 ) p —C (R 4 ) CHCH 2 (p and R 4 have the above meanings), R 3 represents a hydrogen atom, a C 1 -C 6 alkyl group or a C 1 -C 6 alkoxy group, provided that R 1 is — (O ) n - (CH 2) p -C (R 4) = CH 2 as or R 2 is - (CH 2) p -C ( R 4) = CH 2 (n, p and R 4 meaning given above Which has the following formula :).
ジリデンカンファー、3′−アリル−4′,5′−ジメト
キシ−3−ベンジリデンカンファー、3′−メタリル−
4′−メトキシ−3−ベンジリデンカンファー、3′−
メタリル−4′,5′−ジメトキシ−3−ベンジリデンカ
ンファー、3′−アリロキシ−4′−メトキシ−3−ベ
ンジリデンカンファー、3′−メタリルオキシ−4′−
メトキシ−3−ベンジリデンカンファー、4′−アリル
−3−ベンジリデンカンファー、および4′−メタリル
−3′−ベンジリデンカンファーのうちから選択する、
請求項1記載の化合物。2. 3'-allyl-4'-methoxy-3-benzylidenecamphor, 3'-allyl-4 ', 5'-dimethoxy-3-benzylidenecamphor, 3'-methallyl-
4'-methoxy-3-benzylidenecamphor, 3'-
Methallyl-4 ', 5'-dimethoxy-3-benzylidenecamphor, 3'-allyloxy-4'-methoxy-3-benzylidenecamphor, 3'-methallyloxy-4'-
Selected from methoxy-3-benzylidene camphor, 4'-allyl-3-benzylidene camphor, and 4'-methallyl-3'-benzylidene camphor;
A compound according to claim 1.
つR3は水素原子、C1〜C6アルキル基またはC1〜C6アルコ
キシ基を表す)を有する化合物。3. The formula: (Wherein R 4 represents a hydrogen atom or a C 1 -C 4 alkyl group and R 3 represents a hydrogen atom, a C 1 -C 6 alkyl group or a C 1 -C 6 alkoxy group).
ンジリデンカンファーである、請求項3に記載の化合
物。4. The compound according to claim 3, which is 3'-allyl-4'-hydroxy-3-benzylidenecamphor.
として許容できる媒体中に、請求項1〜4に記載する式
(I)又は(I C)の化合物を少なくとも一つ含有する
ことを特徴とする、化粧品組成物。5. A cosmetically acceptable medium containing at least one fatty phase, characterized in that it contains at least one compound of the formula (I) or (IC) according to claims 1 to 4. , Cosmetic compositions.
C)の化合物を0.25〜3重量%含有する請求項5に記載
の化粧品組成物。6. The compound of formula (I) or (I) according to claim 1, wherein
6. The cosmetic composition according to claim 5, comprising 0.25 to 3% by weight of the compound (C).
C)の化合物の量は0.5〜15重量%である請求項5に記載
の化粧品組成物。7. The compound of formula (I) or (I) according to claim 1, wherein
The cosmetic composition according to claim 5, wherein the amount of the compound (C) is 0.5 to 15% by weight.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
LU87093 | 1987-12-23 | ||
LU87093A LU87093A1 (en) | 1987-12-23 | 1987-12-23 | NOVEL UNSATURATED BENZYLIDENE-3 CAMPHOR DERIVATIVES, PROCESS FOR THEIR PREPARATION AND THEIR USE AS ABSORBERS OF ULTRA-PURPLE RADIATION IN COSMETICS AND AS INTERMEDIATES OF SYNTHESIS OF ORGANO-SILICON COMPOUNDS |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01211546A JPH01211546A (en) | 1989-08-24 |
JP2612922B2 true JP2612922B2 (en) | 1997-05-21 |
Family
ID=19731006
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63323845A Expired - Fee Related JP2612922B2 (en) | 1987-12-23 | 1988-12-23 | Unsaturated 3-benzylidene camphor derivatives and cosmetic compositions |
Country Status (9)
Country | Link |
---|---|
JP (1) | JP2612922B2 (en) |
BE (1) | BE1002221A4 (en) |
CH (1) | CH678180A5 (en) |
DE (1) | DE3843325C2 (en) |
FR (1) | FR2625195B1 (en) |
GB (1) | GB2212048B (en) |
IT (1) | IT1234233B (en) |
LU (1) | LU87093A1 (en) |
NL (1) | NL8803129A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4027980A1 (en) * | 1990-09-04 | 1992-03-05 | Merck Patent Gmbh | DIALKOXYBENZYLIDENKAMPFER DERIVATIVES |
EP2422763A1 (en) | 2010-08-27 | 2012-02-29 | Colomer Beauty and Professional Products, S.L. | Process and kit for treating hair |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
LU67061A1 (en) * | 1973-02-19 | 1974-09-25 | ||
JPS53116360A (en) * | 1977-03-15 | 1978-10-11 | Oreal | Novel benzylidene camphor process for preparing same and cosmetic composition containig sae |
FR2430938A1 (en) * | 1978-07-11 | 1980-02-08 | Oreal | NOVEL BORNANONE OXYBENZYLIDENES, PROCESS FOR THEIR PREPARATION, AND COSMETIC COMPOSITIONS CONTAINING THEM |
LU85139A1 (en) * | 1983-12-14 | 1985-09-12 | Oreal | NOVEL 3-BENZYLIDENE CAMPHOR DERIVATIVES, PROCESS FOR THEIR PREPARATION AND THEIR USE AS PROTECTIVE AGENTS AGAINST UV RAYS AND AS MEDICAMENTS |
LU85138A1 (en) * | 1983-12-14 | 1985-09-12 | Oreal | PHARMACEUTICAL COMPOSITIONS CONTAINING CAMPHO-METHYLIDENE CINNAMIC ACID DERIVATIVES |
-
1987
- 1987-12-23 LU LU87093A patent/LU87093A1/en unknown
-
1988
- 1988-12-20 CH CH4703/88A patent/CH678180A5/fr not_active IP Right Cessation
- 1988-12-21 FR FR8816931A patent/FR2625195B1/en not_active Expired - Fee Related
- 1988-12-21 NL NL8803129A patent/NL8803129A/en not_active Application Discontinuation
- 1988-12-22 IT IT8868141A patent/IT1234233B/en active
- 1988-12-22 DE DE3843325A patent/DE3843325C2/en not_active Expired - Fee Related
- 1988-12-23 GB GB8830181A patent/GB2212048B/en not_active Expired - Fee Related
- 1988-12-23 JP JP63323845A patent/JP2612922B2/en not_active Expired - Fee Related
- 1988-12-23 BE BE8801432A patent/BE1002221A4/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
GB2212048B (en) | 1991-07-17 |
NL8803129A (en) | 1989-07-17 |
IT8868141A0 (en) | 1988-12-22 |
JPH01211546A (en) | 1989-08-24 |
IT1234233B (en) | 1992-05-13 |
GB2212048A (en) | 1989-07-19 |
FR2625195B1 (en) | 1990-06-15 |
LU87093A1 (en) | 1989-07-07 |
BE1002221A4 (en) | 1990-10-16 |
DE3843325A1 (en) | 1989-07-06 |
DE3843325C2 (en) | 2000-05-18 |
FR2625195A1 (en) | 1989-06-30 |
CH678180A5 (en) | 1991-08-15 |
GB8830181D0 (en) | 1989-02-22 |
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