JPS62249959A - Novel alpha-dehydroamino acid derivative - Google Patents
Novel alpha-dehydroamino acid derivativeInfo
- Publication number
- JPS62249959A JPS62249959A JP9248186A JP9248186A JPS62249959A JP S62249959 A JPS62249959 A JP S62249959A JP 9248186 A JP9248186 A JP 9248186A JP 9248186 A JP9248186 A JP 9248186A JP S62249959 A JPS62249959 A JP S62249959A
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- dehydrotyrosine
- benzoyl
- formula
- ester
- 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
- 239000002253 acid Substances 0.000 title claims description 10
- -1 trimethylcyclohexyl Chemical group 0.000 claims abstract description 11
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 12
- 229920005989 resin Polymers 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 239000002537 cosmetic Substances 0.000 abstract description 9
- QIAFMBKCNZACKA-UHFFFAOYSA-N N-benzoylglycine Chemical compound OC(=O)CNC(=O)C1=CC=CC=C1 QIAFMBKCNZACKA-UHFFFAOYSA-N 0.000 abstract description 6
- 230000006866 deterioration Effects 0.000 abstract description 5
- 206010015150 Erythema Diseases 0.000 abstract description 4
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 3
- 235000013305 food Nutrition 0.000 abstract description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 abstract description 3
- OKJIRPAQVSHGFK-UHFFFAOYSA-N N-acetylglycine Chemical compound CC(=O)NCC(O)=O OKJIRPAQVSHGFK-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 abstract description 2
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 abstract description 2
- 230000032050 esterification Effects 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract description 2
- 238000007098 aminolysis reaction Methods 0.000 abstract 1
- 238000006482 condensation reaction Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000006096 absorbing agent Substances 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000002250 absorbent Substances 0.000 description 10
- 230000002745 absorbent Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- NPSJHQMIVNJLNN-UHFFFAOYSA-N 2-ethylhexyl 4-nitrobenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C([N+]([O-])=O)C=C1 NPSJHQMIVNJLNN-UHFFFAOYSA-N 0.000 description 6
- 239000004808 2-ethylhexylester Substances 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 5
- 239000012965 benzophenone Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 5
- 229960004889 salicylic acid Drugs 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000010775 animal oil Substances 0.000 description 4
- 239000003925 fat Substances 0.000 description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 description 4
- 235000019871 vegetable fat Nutrition 0.000 description 4
- 239000008158 vegetable oil Substances 0.000 description 4
- IEJPPSMHUUQABK-UHFFFAOYSA-N 2,4-diphenyl-4h-1,3-oxazol-5-one Chemical compound O=C1OC(C=2C=CC=CC=2)=NC1C1=CC=CC=C1 IEJPPSMHUUQABK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000003852 triazoles Chemical class 0.000 description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 206010042496 Sunburn Diseases 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229930016911 cinnamic acid Natural products 0.000 description 2
- 235000013985 cinnamic acid Nutrition 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- 239000010446 mirabilite Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- VWVGLOXKDVGAFA-YVMONPNESA-N (Z)-dehydrotyrosine Chemical compound OC(=O)C(/N)=C/C1=CC=C(O)C=C1 VWVGLOXKDVGAFA-YVMONPNESA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- AZYTZQYCOBXDGY-UHFFFAOYSA-N 2-pyrrolidin-1-ylpyridine Chemical compound C1CCCN1C1=CC=CC=N1 AZYTZQYCOBXDGY-UHFFFAOYSA-N 0.000 description 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 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
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004716 alpha keto acids Chemical class 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- GCFAUZGWPDYAJN-UHFFFAOYSA-N cyclohexyl 3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1C=CC(=O)OC1CCCCC1 GCFAUZGWPDYAJN-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 231100000321 erythema Toxicity 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- RBBOWEDMXHTEPA-UHFFFAOYSA-N hexane;toluene Chemical compound CCCCCC.CC1=CC=CC=C1 RBBOWEDMXHTEPA-UHFFFAOYSA-N 0.000 description 1
- QLNAVQRIWDRPHA-UHFFFAOYSA-N iminophosphane Chemical compound P=N QLNAVQRIWDRPHA-UHFFFAOYSA-N 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/96—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
-
- 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
-
- 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
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
- A61K8/445—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof aromatic, i.e. the carboxylic acid directly linked to the aromatic ring
-
- 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
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
- A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
- A61Q1/06—Lipsticks
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/12—Face or body powders for grooming, adorning or absorbing
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dermatology (AREA)
- Emergency Medicine (AREA)
- Cosmetics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、一般式（τ）仕才テ＃うに）で表わされる新
規α−デヒドロアミノ酸誘導体に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel α-dehydroamino acid derivative represented by the general formula (τ).
本発明に係る一般式（Ｉ）零古孝≠４ヰ表示の化合物は
、紫外線吸収剤として用いることができ、日焼は止め、
繊維や樹脂等の黄変防止、容器及び包材や、その内容物
の紫外線からの保護等に有効であり、塗料、樹脂、医薬
、食品、化粧品といった広い分野に対し適応できる。The compound of the general formula (I) according to the present invention can be used as an ultraviolet absorber, prevents sunburn,
It is effective in preventing yellowing of fibers and resins, protecting containers and packaging materials, and their contents from ultraviolet rays, and can be applied to a wide range of fields such as paints, resins, medicines, foods, and cosmetics.
従来の技術
従来、化粧品の分野では紫外線の皮膚に対する有害作用
を防ぐ為、紫外線吸収剤が早くから注目され、数多く開
発されてきた。BACKGROUND OF THE INVENTION Conventionally, in the field of cosmetics, ultraviolet absorbers have long attracted attention and have been developed in large numbers in order to prevent the harmful effects of ultraviolet rays on the skin.
紫外線吸収剤としては、ベンゾフェノン系吸収剤、サリ
チル酸系吸収剤、ケイ皮酸系吸収剤、パラアミノ安息香
酸系吸収剤などが、用いられている。しかしながら、上
述した紫外線吸収剤のうち、効果、安全性、溶解性、安
定性等を兼備するものは非常に少ない。As the ultraviolet absorber, benzophenone absorbent, salicylic acid absorbent, cinnamic acid absorbent, para-aminobenzoic acid absorbent, etc. are used. However, among the above-mentioned ultraviolet absorbers, there are very few that combine effectiveness, safety, solubility, stability, etc.
例えば、ベンゾフェノン系吸収剤は、３２０〜４００ｎ
ｍの長波長紫外線には吸収効果をもつが、火ぶくれなど
の原因と考えられている中波長紫外線（２９０〜３２０
ｎｍ）に対しては、吸収能が相対的に低い。For example, benzophenone absorbent is 320 to 400n
It has an absorption effect on long-wavelength ultraviolet rays (290-320 m), but medium-wavelength ultraviolet rays (290-320 m), which are thought to cause blisters,
nm), the absorption capacity is relatively low.
バラアミノ安息香酸系、ケイ皮酸系吸収剤は、吸収効果
は高いが、安定性に問題があるといわれている。また、
サリチル酸系吸収剤は吸収効果が弱く、大量に配合しな
ければ効果が期待できない。Barraminobenzoic acid-based and cinnamic acid-based absorbents have high absorption effects, but are said to have stability problems. Also,
Salicylic acid-based absorbents have a weak absorption effect and cannot be expected to be effective unless added in large quantities.
上述の紫外線吸収剤の他に紫外線を物理的に反射、散乱
させる機能を有する二酸化チタン、酸化亜鉛、酸化鉄な
どの無機粉体も用いられる。In addition to the above-mentioned ultraviolet absorbers, inorganic powders such as titanium dioxide, zinc oxide, and iron oxide, which have the function of physically reflecting and scattering ultraviolet rays, are also used.
しかし、無機粉体は配合できる化粧品のタイプが限定さ
れ、また多量に配合する際に着色するという問題点があ
る。However, inorganic powders are limited in the types of cosmetics that can be blended with them, and they also have the problem of coloring when blended in large amounts.
一方、樹脂の劣化を防ぐ為、紫外線吸収剤が添加剤とし
てもちいられている。樹脂の添加剤としては、サリチル
酸系、ベンゾフェノン系吸収剤の他、トリアゾール系、
シアノアクリレート系紫外線吸収剤が使用されている。On the other hand, ultraviolet absorbers are used as additives to prevent resin deterioration. As resin additives, in addition to salicylic acid-based and benzophenone-based absorbents, triazole-based,
Cyanoacrylate UV absorbers are used.
しかしながら、サリチル酸系、およびベンゾフェノン
系吸収剤では、ポリエチレンやポリプロピレン、塩化ビ
ニル樹脂に影響をおよぼすといわれている３００〜３２
０ｎｍ付近の吸収が弱く、トリアゾール系吸収剤は安全
衛生上問題があるといわれている。However, salicylic acid-based and benzophenone-based absorbents have a 300 to 32
Triazole-based absorbents are said to have a safety and health problem because of their weak absorption near 0 nm.
本発明が解決しようとする問題点
上述したごとく、化粧品及び樹脂の分野などで種々の紫
外線吸収剤が開発されてはいるが、紫外線吸収能、安全
性、溶剤や樹脂への溶解性、および安定性をすべて満足
するものは未だ見いだされていないというのが実情であ
り、これらを兼備した紫外線吸収剤が望まれている。Problems to be Solved by the Present Invention As mentioned above, various UV absorbers have been developed in the fields of cosmetics and resins, but they lack UV absorbing ability, safety, solubility in solvents and resins, and stability. The reality is that a UV absorber that satisfies all of these properties has not yet been found, and a UV absorber that has both of these properties is desired.
問題点を解決する為の手段
本発明者らは、かかる実情を鑑み；鋭意研究を行なった
結果、前記一般式（Ｔ） ’≠日で表わされる新
規α−デヒドロアミノ酸誘導体が表１に示すように中波
長紫外線領域（２４０〜３６０ｎｍ）に大きな吸収効果
を有し、更に、表２に示すように各種動植物油、油脂、
および、有機溶剤に易溶であることから、これら新規α
−デヒドロアミノ酸誘導体が皮膚の紅斑防止、樹脂の劣
化防止等に有効な紫外線吸収剤であることを見いだし、
本発明を完成した。 一
本発明に係る一般式（Ｉ）表示のα−デヒドロアミノ酸
誘導体は、以下の方法により製造することができる。す
なわち、■芳香属アルデヒドと、アセチルグリシン、ベ
ンゾイルグリシン又はそれらのアズラクトンとの塩基触
媒による縮合、■生成したアズラクトンの加水分解、次
いでエステル化、又はアミド化、もしくはアズラクトン
の直接アルコリシス、アミツリシス、■必要ｔこ応じ、
アミドの窒素原子をアセチル化することにより得ること
ができる。（式１）。アズラクトンのアルコリシスはナ
トリウムアルコラード、カリウムアルコラードなどの金
属アルコラ−１・、水酸化ナトリウム、水酸化カリウム
などの塩基触媒をもちいて行なうことができる。また、
アミドの窒素原子のアセチル化は、ジメチルアミノピリ
ジン、ピロリジノピリジンなどを触媒として行なうこと
ができる。Means for Solving the Problems In view of the above-mentioned circumstances, the present inventors have conducted intensive research and have found novel α-dehydroamino acid derivatives represented by the general formula (T)'≠day as shown in Table 1. It has a large absorption effect in the medium wavelength ultraviolet region (240 to 360 nm), and as shown in Table 2, various animal and vegetable oils, fats and oils,
And, because they are easily soluble in organic solvents, these new α
- Discovered that dehydroamino acid derivatives are effective ultraviolet absorbers for preventing skin erythema and preventing resin deterioration,
The invention has been completed. The α-dehydroamino acid derivative represented by the general formula (I) according to the present invention can be produced by the following method. Namely, (1) base-catalyzed condensation of an aromatic aldehyde with acetylglycine, benzoylglycine, or their azlactones, (2) hydrolysis of the resulting azlactone, followed by esterification or amidation, or (2) direct alcoholysis or amitulysis of the azlactone, (2) necessary. In response,
It can be obtained by acetylating the nitrogen atom of amide. (Formula 1). Alcoholysis of azlactone can be carried out using metal alcohols such as sodium alcoholade and potassium alcoholade, and base catalysts such as sodium hydroxide and potassium hydroxide. Also,
Acetylation of the nitrogen atom of the amide can be carried out using dimethylaminopyridine, pyrrolidinopyridine, or the like as a catalyst.
６一 Ｎ。61 N.
Ｎ ／ Ｎ。N / N.
※ ／
Ｏ
Ｎ ／
ＯＹＲ
ＨＣＺ
（Ｉ） Ｉｔ
０ＹＲ
ＣＨ３ＣＮ ＣＺ
（２） ＋＋ ＋＋
Ｏ
又、α−ケト酸あるいは そのエステルを原料とし、ホ
スフィンイミン（式２）、又はアミド（式３）との縮合
によっても（Ｉ）を得ることができる。* / O N / OYR HCZ (I) It 0YR CH3CN CZ (2) ++ ++ O In addition, α-keto acid or its ester is used as a raw material, and by condensation with phosphinimine (Formula 2) or amide (Formula 3) (I) can also be obtained.
Ｘ。X.
〇 ＯＹＲ ＨＣＺ （Ｉ） ＋＋ Ｘ。〇 OYR HCZ (I) ++ X.
〇
Ｃ０ＹＲ
Ｎ）（ＣＺ
（Ｉ） ＋＋
更に（Ｉ）は、Ｎ−ヒドロキシルアミノ酸エステル誘導
体の脱水によっても得ることができる（式４）。〇C0YR N)(CZ (I) ++ Furthermore, (I) can also be obtained by dehydration of an N-hydroxylamino acid ester derivative (Formula 4).
ｙ。y.
ＯＹＲ
ＨＣＺ
（Ｉ） ｎ
（但し、Ｘｔ、 Ｘ２、Ｘ３は水素原子、水酸基、又は
メトキシ基のいずれかであり、このうち二つ、あるいは
三つが同時に同じでも、又、全部が異なっていても良い
。Ｙは酸素原子、又はアミノ基（−ＮＨ−）である。Ｚ
はメチル基、又はフェニル基である。ＲはＣ３〜ＣＡ８
のアルキル基、シクロヘキシル基、もしくは、トリメチ
ルシクロヘキシル基である。）
本発明の一般式（ｒ）帳紅六七に）表示の化合物を例示
するならば、Ｎ−ベンゾイル−〇−メチルーα−デヒド
ロチロシン ラウリルアミド、Ｎ−ベンゾイル−０−メ
チル−α−デヒドロチロシン イソプロピルエステル、
Ｎ−ベンゾイル−０−メチル−α−デヒドロチロシン
ラウリルエステル、Ｎ−ベンゾイル−０−メチル−α−
デヒドロチロシン ステアリルエステル、Ｎ−ベンゾイ
ル−０−メチル−α−デヒドロチロシン ２−エチルヘ
キシルエステル、Ｎ−ベンゾイル−Ｏ−メチル−α−デ
ヒドロチロシン シクロヘキシルエステル、Ｎ−ベンゾ
イル−Ｏ−メチル−α−デヒドロチロシン ３．３．５
−トリメチルシクロヘキシルエステル、Ｎ−アセチル−
０−メチル−α−デヒドロチロシン イソプロピルエス
テル、Ｎ−アセチル−０−メチル−α−デヒドロチロシ
ン２−エチルヘキシルエステル、Ｎ−アセチル−Ｏ−メ
チル−α−デヒドロチロシン ラウリルエステル、Ｎ−
アセチル−Ｏ−メチル−α−デヒドロチロシン ステア
リルエステル、Ｎ−アセチル−Ｎ−ベンゾイル−０−メ
チル−α−デヒドロチロシン エチルエステル、Ｎ−ア
セチル−Ｎ−ベンゾイル−０−メチル−α−デヒドロチ
ロシンイソプロピルエステル、Ｎ−アセチル−Ｎ−ベン
ゾイル−Ｏ−メチル−α−デヒドロチロシン ２−エチ
ルヘキシルエステル、Ｎ−アセチル−Ｎ−ベンゾイル−
０−メチル−α−デヒドロチロシンラウリルエステル、
Ｎ−アセチル−Ｎ−ベンゾイル−０−メチル−α−デヒ
ドロチロシン ステアリルエステル、Ｎ、Ｎ−ジアセチ
ル−〇−メチルーα−デヒドロチロシン エチルエステ
ル、Ｎ％Ｎ−ジアセチル−〇−メチルーα−デヒドロチ
ロシン イソプロピルエステル、Ｎ、Ｎ−ジアセチル−
〇−メチルーα−デヒドロチロシン ２−エチルヘキシ
ルエステル、Ｎ、Ｎ−ジアセチル−〇−メチルーα−デ
ヒドロチロシン ラウリルエステル、Ｎ、Ｎ−ジアセチ
ル−〇−メチル−α−デヒドロチロシン ステアリルエ
ステル等が挙げられる。OYR HCZ (I) n (However, Xt, X2, and X3 are either a hydrogen atom, a hydroxyl group, or a methoxy group, and two or three of these may be the same at the same time, or all may be different. .Y is an oxygen atom or an amino group (-NH-).Z
is a methyl group or a phenyl group. R is C3 to CA8
an alkyl group, a cyclohexyl group, or a trimethylcyclohexyl group. ) Examples of the compounds of the present invention represented by the general formula (r) Chokoku67) include N-benzoyl-0-methyl-α-dehydrotyrosine laurylamide, N-benzoyl-0-methyl-α-dehydrotyrosine isopropyl ester,
N-benzoyl-0-methyl-α-dehydrotyrosine
lauryl ester, N-benzoyl-0-methyl-α-
Dehydrotyrosine stearyl ester, N-benzoyl-0-methyl-α-dehydrotyrosine 2-ethylhexyl ester, N-benzoyl-O-methyl-α-dehydrotyrosine cyclohexyl ester, N-benzoyl-O-methyl-α-dehydrotyrosine 3 .3.5
-trimethylcyclohexyl ester, N-acetyl-
0-Methyl-α-dehydrotyrosine isopropyl ester, N-acetyl-0-methyl-α-dehydrotyrosine 2-ethylhexyl ester, N-acetyl-O-methyl-α-dehydrotyrosine lauryl ester, N-
Acetyl-O-methyl-α-dehydrotyrosine stearyl ester, N-acetyl-N-benzoyl-0-methyl-α-dehydrotyrosine ethyl ester, N-acetyl-N-benzoyl-0-methyl-α-dehydrotyrosine isopropyl ester , N-acetyl-N-benzoyl-O-methyl-α-dehydrotyrosine 2-ethylhexyl ester, N-acetyl-N-benzoyl-
0-methyl-α-dehydrotyrosine lauryl ester,
N-acetyl-N-benzoyl-0-methyl-α-dehydrotyrosine stearyl ester, N,N-diacetyl-〇-methyl-α-dehydrotyrosine ethyl ester, N%N-diacetyl-〇-methyl-α-dehydrotyrosine isopropyl ester , N, N-diacetyl-
Examples thereof include 〇-methyl-α-dehydrotyrosine 2-ethylhexyl ester, N,N-diacetyl-〇-methyl-α-dehydrotyrosine lauryl ester, N,N-diacetyl-〇-methyl-α-dehydrotyrosine stearyl ester, and the like.
発明の効果
本発明に用いられる前記一般式（■）鈷＃＃七イ表示の
新規α−デヒドロアミノ酸誘導体は、表１に示すように
、２７０〜３３０ｎｍで、１０４以上の高い分子吸光係
数を有し、皮膚の紅斑の原因と考えられる２９０〜３２
０ｎｍ、およびポリエチレン、ポリプロピレン、ポリ塩
化ビニル等の樹脂の劣化原因と考えられている３００〜
３２０ｎｍの紫外線に対し、高い吸収能を持つ。又、表
２に示すように、一般式（Ｉ）表示の化合物は、Ｒの効
果により、既存の化合物、例えばＮ−ベンゾイル−α−
デヒドロチロシン、０−メチル−Ｎ−ベンゾイル−α−
デヒドロチロシン等に、比へ各種動植物油、油脂、およ
び有機溶剤に対する溶解性が、著しく向上した。又、一
般式（２）表示の化合物では、アミド水素原子がアセチ
ル基で置換されている為、各種動植物油、油脂、および
有機溶剤に対し、更に良い溶解性をしめす。このように
、一般式（’Ｉ） ｔ＃＃ミ瞠表示の化合物は、動植物
油、油脂およびその他の有機溶剤に良く溶解させること
ができ、クリーム、乳液、ファンデーション、ヘアーク
リーム、日焼は止め油等の化粧料に添加した際、安定な
配合物を得ることができる。また、これらの化合物をポ
リエチレン、ポリプロピレン、ポリスチレン、ポリ塩化
ビニル、ＡＢＳ樹脂、ポリカーボネートなどの樹脂に添
加した場合、樹脂との良い相溶性が期待できる。本発明
に用いられる前記一般式（Ｄ ’＃ｉ表示のα−
デヒドロアミノ酸誘導体を市販の紫外線吸収剤（例えば
、ベンゾフェノン系、トリアゾール系、サリチル酸系吸
収剤）と比較した場合、■殊に酸素存在下に於ける紫外
線の作用に対して優れた抑制効果を有する。■熱安定性
、光安定性が高く、効果の持続性が良い。０２〜１０倍
の紫外線分子吸光係数を有する。■各種重合体材料との
相溶性が良好である為、繊維、樹脂などの可塑剤として
使用される一方、黄変防止剤としても用いることができ
る等の効果がある。Effects of the Invention As shown in Table 1, the novel α-dehydroamino acid derivative represented by the general formula (■) ##7i used in the present invention has a high molecular extinction coefficient of 104 or more at 270 to 330 nm. 290-32, which is thought to be the cause of skin erythema.
0nm, and 300~ which is considered to be the cause of deterioration of resins such as polyethylene, polypropylene, and polyvinyl chloride.
It has high absorption ability for 320nm ultraviolet light. Furthermore, as shown in Table 2, the compound represented by general formula (I) can be used to synthesize existing compounds such as N-benzoyl-α-
Dehydrotyrosine, 0-methyl-N-benzoyl-α-
Compared to dehydrotyrosine, the solubility in various animal and vegetable oils, fats and oils, and organic solvents was significantly improved. Furthermore, in the compound represented by the general formula (2), since the amide hydrogen atom is substituted with an acetyl group, it exhibits better solubility in various animal and vegetable oils, fats and oils, and organic solvents. As described above, the compound represented by the general formula ('I)t##mizu can be well dissolved in animal and vegetable oils, fats and oils, and other organic solvents, and can be used in creams, milky lotions, foundations, hair creams, and sunscreens. When added to cosmetics such as oils, stable formulations can be obtained. Furthermore, when these compounds are added to resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, ABS resin, polycarbonate, etc., good compatibility with the resin can be expected. The general formula used in the present invention (α- expressed as D'#i)
When dehydroamino acid derivatives are compared with commercially available ultraviolet absorbers (for example, benzophenone-based, triazole-based, and salicylic acid-based absorbers), they have an excellent suppressive effect on the effects of ultraviolet light, especially in the presence of oxygen. ■High thermal stability and photostability, and long-lasting effects. It has an ultraviolet molecular extinction coefficient of 0.2 to 10 times. ■Since it has good compatibility with various polymer materials, it can be used as a plasticizer for fibers, resins, etc., and can also be used as an anti-yellowing agent.
上述したごとく、本発明の用途範囲は、香粧品工業、プ
ラスチック工業、有機薬品工業、写真工業、食品工業、
繊維工業などであり、極めて広い。As mentioned above, the scope of application of the present invention is the cosmetics industry, the plastics industry, the organic medicine industry, the photography industry, the food industry,
The textile industry is extremely wide.
殊に、紫外線吸収波長が、２４０〜３６０ ｎｍ（最大
吸収波長 ３００〜３４０ｎｍ）にあり、香粧品に用い
た場合は、他に比類のない選択的吸収性をもった日焼け
、紅斑防止化粧品となり、また、ポリエチレン、ポリプ
ロピレン、ポリ塩化ビニルなど、重合体中に、混入した
場合、紫外線による劣化を、著しく軽減する。In particular, the ultraviolet absorption wavelength is 240 to 360 nm (maximum absorption wavelength 300 to 340 nm), and when used in cosmetics, it becomes a sunburn and erythema prevention cosmetic with unparalleled selective absorption. Furthermore, when mixed into polymers such as polyethylene, polypropylene, and polyvinyl chloride, deterioration caused by ultraviolet rays is significantly reduced.
次に、本発明に係る代表的な化合物について、最大吸収
波長ならびに、その他の物性値を実施例１としてまとめ
て表１に示す。また実施例２に代表的な製法を示す。又
、有機溶剤に対する溶解性を実施例３として表２に示す
が、本発明はこれらの実施例によって限定されるもので
はない。Next, the maximum absorption wavelength and other physical property values of typical compounds according to the present invention are summarized in Table 1 as Example 1. Further, Example 2 shows a typical manufacturing method. Further, the solubility in organic solvents is shown in Table 2 as Example 3, but the present invention is not limited by these Examples.
実施例２
合成例１
２−フェニル−４−（４−メトキシベンジリデン）−５
−オキサシロン の合成
アニスアルデヒド ２０ ｍ ｌ 、無水酢酸５０ ｍ
ｌ、馬尿酸 ３３．７ｇおよび酢酸ナトリウム６．７ｇ
を、よく混合し、水浴で３０分加熱した。Example 2 Synthesis Example 1 2-phenyl-4-(4-methoxybenzylidene)-5
-Synthesis of oxacylone Anisaldehyde 20 ml, acetic anhydride 50 ml
l, hippuric acid 33.7g and sodium acetate 6.7g
were mixed well and heated in a water bath for 30 minutes.
析出した結晶を、温水で洗浄後、ろ過した。ベンゼンよ
り再結晶し、乾燥することで、２−フェニル−４−（４
−メトキシベンジリデン）−５−オキサシロン４０ｇを
得た。収率８３％
合成例２
Ｎ−ベンゾイル−〇−メチルーα−デヒドロチロシン
２−エチルヘキシルエステルの合成合成例１で得られた
２−フェニル−４−（４−メトキシベンジリデン）−５
−オキサシロン１ｋｇを、トルエン１０１に懸濁させ、
２−エチル−１−ヘキサノール０．９３３ｋｇ、水酸化
ナトリラム０．０２９ｋｇを添加した。２５℃で４時間
攪拌した後、酢酸エチル４０１、水 ４０１を、加え攪
拌する。有機層を分離し、芒硝で乾燥、減圧濃縮した後
、残渣をトルエン−ヘキサンで再結晶することで、Ｎ−
ベンゾイル０−メチル−α−デヒドロチロシン ２−エ
チルヘキシルエステル、１．０ｋｇを得た。（収率６８
．２％）合成例３
Ｎ−ベンゾイル−〇−メチルー〇−デヒドロチロシン
ｎ−ラウリルエステルの合成
ｎ−ラウリルアルコール１５４ｍ１に金属ナトリウム２
ｇを加え、加熱溶解する。この溶液に、合成例１で得ら
れた２−フェニル−４−（４−メトキシベンジリデン）
−５−オキサシロン１１８゜６ｇおよび、トルエン３０
０ ｍ ｌを加え、２５℃で８時間、攪拌する。反応液
に酢酸エチル２１を加えた後、ＩＮ塩酸１．５１．５％
炭酸水素ナトリウム水溶液１．５１水１．５１で洗浄、
芒硝で乾燥する。減圧濃縮後、残渣をｎ−ヘキサンで再
結晶することにより、Ｎ−ベンゾイル−〇−メチルーα
−デヒドロチロシン ｎ−ラウリルエステル１６３．５
ｇを得た。く収率８２．７％）合成例４
Ｎ−アセチル−Ｎ−ベンゾイル−０−メチル−α−デヒ
ドロチロシン ｎ−ラウリルエステルの合成
合成例３で得たＮ−ベンゾイル−〇−メチルーα−デヒ
ドロチロシン ｎ−ラウリルエステル１０ｇをピリジン
１００ｍ１に溶解し、無水酢酸２０ ｍ ｌ 、ジメチ
ルアミノピリジン０．５ｇを加え、２５°Ｃで１４時間
、攪拌する。反応液を減圧濃縮し、残渣を酢酸エチル３
００ ｍ ｌに溶解する。水２５０ ｍ ｌで４回洗浄
した後、再び減圧濃縮する。The precipitated crystals were washed with warm water and then filtered. By recrystallizing from benzene and drying, 2-phenyl-4-(4
40 g of -methoxybenzylidene)-5-oxacilone was obtained. Yield 83% Synthesis Example 2 N-benzoyl-〇-methyl-α-dehydrotyrosine
Synthesis of 2-ethylhexyl ester 2-phenyl-4-(4-methoxybenzylidene)-5 obtained in Synthesis Example 1
- 1 kg of oxacylone is suspended in 101 toluene,
0.933 kg of 2-ethyl-1-hexanol and 0.029 kg of sodium hydroxide were added. After stirring at 25°C for 4 hours, 401 parts of ethyl acetate and 40 parts of water were added and stirred. The organic layer was separated, dried over Glauber's salt, concentrated under reduced pressure, and the residue was recrystallized from toluene-hexane to obtain N-
1.0 kg of benzoyl 0-methyl-α-dehydrotyrosine 2-ethylhexyl ester was obtained. (Yield 68
．． 2%) Synthesis Example 3 N-benzoyl-〇-methyl-〇-dehydrotyrosine
Synthesis of n-lauryl ester 154 ml of n-lauryl alcohol and 2 ml of sodium metal
Add g and heat to dissolve. 2-phenyl-4-(4-methoxybenzylidene) obtained in Synthesis Example 1 was added to this solution.
-5-oxacylone 118°6g and toluene 30
Add 0 ml and stir at 25°C for 8 hours. After adding ethyl acetate 21% to the reaction solution, IN hydrochloric acid 1.51.5%
Washing with 1.51 parts of sodium bicarbonate aqueous solution and 1.5 parts of water,
Dry with Glauber's salt. After concentration under reduced pressure, the residue was recrystallized from n-hexane to obtain N-benzoyl-〇-methyl-α.
-dehydrotyrosine n-lauryl ester 163.5
I got g. (Yield: 82.7%) Synthesis Example 4 N-Acetyl-N-benzoyl-0-methyl-α-dehydrotyrosine Synthesis of n-lauryl ester N-benzoyl-〇-methyl-α-dehydrotyrosine obtained in Synthesis Example 3 10 g of n-lauryl ester is dissolved in 100 ml of pyridine, 20 ml of acetic anhydride and 0.5 g of dimethylaminopyridine are added, and the mixture is stirred at 25°C for 14 hours. The reaction solution was concentrated under reduced pressure, and the residue was dissolved in ethyl acetate 3
Dissolve in 00 ml. After washing 4 times with 250 ml of water, it is concentrated again under reduced pressure.
Claims (1)
誘導体。 ▲数式、化学式、表等があります▼（ I ） （但し、ＢはＨ又は▲数式、化学式、表等があります▼ であり、 Ｘ＿１、Ｘ＿２、Ｘ＿３は水素原子、水酸基、又はメト
キシ基のいずれかであり、このうち二つあるいは三つが
同時に同じであっても、又、全部が異なっていても良い
。Ｙは酸素原子、又はアミノ基（−ＮＨ−）である。Ｚ
はメチル基、又はフェニル基である。ＲはＣ＿３〜Ｃ＿
１＿８のアルキル基、シクロヘキシル基、もしくは、ト
リメチルシクロヘキシル基である。）[Claims] An α-dehydroamino acid derivative represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, B is H or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and X_1, X_2, X_3 are either hydrogen atoms, hydroxyl groups, or methoxy groups and two or three of these may be the same at the same time, or all may be different.Y is an oxygen atom or an amino group (-NH-).Z
is a methyl group or a phenyl group. R is C_3~C_
1_8 alkyl group, cyclohexyl group, or trimethylcyclohexyl group. )
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61092481A JPH0776200B2 (en) | 1986-04-22 | 1986-04-22 | Novel α-dehydroamino acid derivative |
| US07/038,364 US4797493A (en) | 1986-04-22 | 1987-04-14 | Benzylidene compounds |
| DE19873713094 DE3713094A1 (en) | 1986-04-22 | 1987-04-16 | BENZYLIDE COMPOUNDS AND THEIR CONTAINING COSMETIC PREPARATIONS AND ULTRAVIOLET ABSORBERS |
| FR878705711A FR2597476B1 (en) | 1986-04-22 | 1987-04-22 | BENZYLIDENIC COMPOUNDS, COMPOSITIONS CONTAINING THE SAME, AND ULTRAVIOLET RADIATION ABSORBING AGENTS MADE THEREFROM. |
| US07/242,166 US5000945A (en) | 1986-04-22 | 1988-09-08 | Method of stabilizing a UVB absorbing compound, a stabilized UV absorber, and a cosmetic composition containing the same |
| US07/259,257 US4985237A (en) | 1986-04-22 | 1988-10-18 | Benzylidene compounds, cosmetic compositions containing the same and ultraviolet absorber comprising the same |
| US07/509,765 US5087729A (en) | 1986-04-22 | 1990-04-17 | Benzylidene compounds, cosmetic compositions containing the same and ultraviolet absorber comprising the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61092481A JPH0776200B2 (en) | 1986-04-22 | 1986-04-22 | Novel α-dehydroamino acid derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62249959A true JPS62249959A (en) | 1987-10-30 |
| JPH0776200B2 JPH0776200B2 (en) | 1995-08-16 |
Family
ID=14055498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61092481A Expired - Lifetime JPH0776200B2 (en) | 1986-04-22 | 1986-04-22 | Novel α-dehydroamino acid derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0776200B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007332084A (en) * | 2006-06-16 | 2007-12-27 | Shiseido Co Ltd | Benzilidene malonamide and its salt, ultraviolet absorber and external preparation for skin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4879782A (en) * | 1972-01-29 | 1973-10-25 |
-
1986
- 1986-04-22 JP JP61092481A patent/JPH0776200B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4879782A (en) * | 1972-01-29 | 1973-10-25 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007332084A (en) * | 2006-06-16 | 2007-12-27 | Shiseido Co Ltd | Benzilidene malonamide and its salt, ultraviolet absorber and external preparation for skin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0776200B2 (en) | 1995-08-16 |
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