EP1648849A2 - Neue dibenzoylmethanderivativverbindungen, deren verwendung in form von lichtaktivierbaren sonnenfiltern und kosmetische zusammensetzungen, die diese verbindungen enthalten - Google Patents
Neue dibenzoylmethanderivativverbindungen, deren verwendung in form von lichtaktivierbaren sonnenfiltern und kosmetische zusammensetzungen, die diese verbindungen enthaltenInfo
- Publication number
- EP1648849A2 EP1648849A2 EP04767684A EP04767684A EP1648849A2 EP 1648849 A2 EP1648849 A2 EP 1648849A2 EP 04767684 A EP04767684 A EP 04767684A EP 04767684 A EP04767684 A EP 04767684A EP 1648849 A2 EP1648849 A2 EP 1648849A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- linear
- branched
- carbon atoms
- group
- represent
- 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.)
- Withdrawn
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 47
- 239000002537 cosmetic Substances 0.000 title claims abstract description 19
- 239000000203 mixture Substances 0.000 title claims description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 31
- 230000005855 radiation Effects 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 239000012453 solvate Substances 0.000 claims abstract description 17
- 210000004209 hair Anatomy 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 55
- 229920006395 saturated elastomer Polymers 0.000 claims description 27
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical class C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- YBGZDTIWKVFICR-JLHYYAGUSA-N Octyl 4-methoxycinnamic acid Chemical compound CCCCC(CC)COC(=O)\C=C\C1=CC=C(OC)C=C1 YBGZDTIWKVFICR-JLHYYAGUSA-N 0.000 claims description 17
- 229960001679 octinoxate Drugs 0.000 claims description 17
- -1 alkylammonium halide Chemical class 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 230000004224 protection Effects 0.000 claims description 8
- 230000000475 sunscreen effect Effects 0.000 claims description 8
- 239000000516 sunscreening agent Substances 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 7
- 239000002168 alkylating agent Substances 0.000 claims description 7
- 229940100198 alkylating agent Drugs 0.000 claims description 7
- 125000003368 amide group Chemical group 0.000 claims description 6
- 238000005804 alkylation reaction Methods 0.000 claims description 5
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 4
- 230000029936 alkylation Effects 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- HEOCBCNFKCOKBX-SDNWHVSQSA-N enzacamene Chemical compound C1=CC(C)=CC=C1\C=C/1C(=O)C2(C)CCC\1C2(C)C HEOCBCNFKCOKBX-SDNWHVSQSA-N 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 claims description 2
- 230000002035 prolonged effect Effects 0.000 claims description 2
- 239000013543 active substance Substances 0.000 abstract 1
- 239000003223 protective agent Substances 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- 238000002835 absorbance Methods 0.000 description 16
- XNEFYCZVKIDDMS-UHFFFAOYSA-N avobenzone Chemical compound C1=CC(OC)=CC=C1C(=O)CC(=O)C1=CC=C(C(C)(C)C)C=C1 XNEFYCZVKIDDMS-UHFFFAOYSA-N 0.000 description 14
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 14
- UZKBSZSTDQSMDR-UHFFFAOYSA-N 1-[(4-chlorophenyl)-phenylmethyl]piperazine Chemical compound C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)N1CCNCC1 UZKBSZSTDQSMDR-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 239000002609 medium Substances 0.000 description 9
- 230000007423 decrease Effects 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 206010004146 Basal cell carcinoma Diseases 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 210000003491 skin Anatomy 0.000 description 4
- 206010041823 squamous cell carcinoma Diseases 0.000 description 4
- RKDKUKXKVFQJBN-UHFFFAOYSA-N 3-(4-tert-butylphenyl)-3-decoxy-1-(4-methoxyphenyl)prop-2-en-1-one Chemical compound C=1C=C(C(C)(C)C)C=CC=1C(OCCCCCCCCCC)=CC(=O)C1=CC=C(OC)C=C1 RKDKUKXKVFQJBN-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000699670 Mus sp. Species 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- ZTQSADJAYQOCDD-UHFFFAOYSA-N ginsenoside-Rd2 Natural products C1CC(C2(CCC3C(C)(C)C(OC4C(C(O)C(O)C(CO)O4)O)CCC3(C)C2CC2O)C)(C)C2C1C(C)(CCC=C(C)C)OC(C(C(O)C1O)O)OC1COC1OCC(O)C(O)C1O ZTQSADJAYQOCDD-UHFFFAOYSA-N 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 description 2
- QFOHBWFCKVYLES-UHFFFAOYSA-N Butylparaben Chemical compound CCCCOC(=O)C1=CC=C(O)C=C1 QFOHBWFCKVYLES-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001408 amides Chemical group 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 210000004207 dermis Anatomy 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 230000003711 photoprotective effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYGPDIGLEKMQFB-UHFFFAOYSA-N 1-(4-tert-butylphenyl)-2-decyl-3-(4-methoxyphenyl)propane-1,3-dione Chemical compound C=1C=C(C(C)(C)C)C=CC=1C(=O)C(CCCCCCCCCC)C(=O)C1=CC=C(OC)C=C1 OYGPDIGLEKMQFB-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000003512 Claisen condensation reaction Methods 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004909 Moisturizer Substances 0.000 description 1
- LVDRREOUMKACNJ-BKMJKUGQSA-N N-[(2R,3S)-2-(4-chlorophenyl)-1-(1,4-dimethyl-2-oxoquinolin-7-yl)-6-oxopiperidin-3-yl]-2-methylpropane-1-sulfonamide Chemical compound CC(C)CS(=O)(=O)N[C@H]1CCC(=O)N([C@@H]1c1ccc(Cl)cc1)c1ccc2c(C)cc(=O)n(C)c2c1 LVDRREOUMKACNJ-BKMJKUGQSA-N 0.000 description 1
- 208000000453 Skin Neoplasms Diseases 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 206010041303 Solar dermatitis Diseases 0.000 description 1
- 206010042496 Sunburn Diseases 0.000 description 1
- 239000004904 UV filter Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002535 acidifier Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940067596 butylparaben Drugs 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 231100000673 dose–response relationship Toxicity 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 1
- 229960002216 methylparaben Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001333 moisturizer Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229940031709 peg-30-dipolyhydroxystearate Drugs 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000037368 penetrate the skin Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229940048845 polyglyceryl-3 diisostearate Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009759 skin aging Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000036561 sun exposure Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 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
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
- A61P17/16—Emollients or protectives, e.g. against radiation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/52—Stabilizers
Definitions
- the present invention relates to compounds having good capacities for absorbing ultraviolet radiation, acquiring a part of this capacity under light excitation, and whose absorption properties are photostable. It also relates to their use in cosmetic preparations as a UVA filter, and cosmetic and / or dermatological compositions containing such compounds.
- UV ultraviolet
- visible and infrared The sun emits a set of light rays that reach the earth's surface: ultraviolet, visible and infrared.
- a radiation is characterized by its wavelength and its energy, these two quantities being inversely proportional. Thus a short wavelength is associated with high energy.
- ultraviolet rays are the part of the solar spectrum concerned. These radiations, as a whole, do not exceed 5% of the total energy received on the earth's surface, but their impact on living organisms is very important. The best known of these is “sunburn” and the most sought after is “tanning”.
- Ultraviolet rays are divided into three main areas: UVA, UVB, UVC. UVCs are radiations with a wavelength between 1 90 and 290 nm.
- UVB rays with a wavelength between 290 and 320 nm, represent 2% of UV rays reaching the earth's surface. They partially penetrate the skin, and only 10 to 20% reach the dermis. They are traditionally held responsible for solar erythema but also cause greater damage, particularly at the genomic level. They are therefore attributed carcinogenic properties. UVA represents 98% of UV rays received on the surface of the
- UVA rays penetrate deeper into the skin than UVB rays. Thus 20 to 30% reach the middle dermis. They induce the formation of pigments and are responsible for tanning. In the long term, they have long been attributed a participation in accelerated skin aging, but it is only in the last ten years that we have recognized their carcinogenic potential. It should also be noted that the first generations of sunscreens did not contain UVA filters but only UVB filters. The introduction of UVA filtration has become imperative after the publication of scientific articles showing the capacity of UVA to induce skin cancers in animals (fish and mice).
- UVA photoprotection is only 100 times less effective than UVB in inducing BCC and SCC cancer in mice.
- UVA photoprotection There, for the past ten years, particular attention has been paid to UVA photoprotection.
- One of the most used is, without question, Parsol 1 789 or 4-tertiobutyl-4'- methoxydibenzoylmethane [CAS: 70356-09-1]. This molecule has a high coefficient of molar extinction in UVA with maximum absorption efficiency around 340 nm.
- his photostability is a subject of controversy.
- the first already widely used, consists in adding a molecule to the preparation, making it possible to stabilize Parsol 1,789 by various mechanisms not always explained (by way of example, various patents may be cited: FR 2,768 730 A 1, FR 2 747 038 A 1, FR 2 750 335 A1, WO 02 / 49598A2, US 6,444, 1 95 B1 ).
- the second approach much less explored, is that of the chemical modification of the molecule itself. This modification should allow the molecule to retain its UV absorption properties but to limit its propensity for photodegradation.
- the present invention thus relates to new derivatives of dibenzoylmethane, having good capacities for absorbing UV radiation, these capacities being photostable and partly photoactivable, that is to say of which the absorbing power appears in its entirety only when said dibenzoylmethane derivatives are subjected to UV exposure.
- the present invention relates to compounds derived from dibenzoylmethane of formula I,
- R R'i, R 2 ⁇ R ' 2 / R 3 , R' 3, R 4 , R ' 4, identical or different each represent: - a hydrogen atom, - or an alkyl group , linear or branched, comprising from 1 to 4 carbon atoms, - or an alkenyl group, linear or branched, comprising from 1 to 4 carbon atoms, - or an alkynyl group, linear or branched, comprising from 1 to 4 atoms of carbon, - or a C1 to C4 alkoxy group, - or a halogen atom, - or a hydroxy group, - or an amino group, - or a nitro group, - or an amido group, - or a carbonyl group of formula -CO-Y, in which Y represents the group -OH, -OR or -SR (R representing a C1 to C4 alkyl), a halogen atom.
- R 5 and R ' 5 different ⁇ each represent: - a hydrogen atom, - or an alkyl group, linear or branched, comprising from 1 to 4 carbon atoms, - or an alkenyl group, linear or branched, comprising from 1 to 4 carbon atoms, - or an alkynyl group, linear or branched, comprising from 1 to 4 carbon atoms, - or an acyclic carbon chain, linear or branched, saturated or unsaturated, comprising from 5 to 20 carbon atoms, - or an acyclic carbon chain, linear or branched, saturated or unsaturated, functionalized at its end, comprising from 5 to 20 carbon atoms, - or an acyclic carbon chain, linear or branched, saturated or unsaturated, comprising a nitrogen atom of amine or amide function and / or an oxygen atom of ether or carboxylic function. comprising from 5 to 20 carbon atoms, as well as their salts or solvates.
- R RN R 2 , R ' 2 ⁇ R 3 , R' 3, R 4 , and R ' 4 each represent a hydrogen atom.
- R 5 and R ' 5 different each represent: - a hydrogen atom, - or an alkyl group, linear or branched, comprising from 1 to 4 atoms of carbon, - or an acyclic carbon chain, linear or branched, saturated or unsaturated, comprising from 5 to 20 carbon atoms
- R v R ' v R 2 , R' 2 / R 3 , R ' 3 ⁇ R 4 , and R' 4 each represent a hydrogen atom.
- R 5 and R ' 5 different each represent: - a hydrogen atom - or an alkyl group, linear or branched, comprising from 1 to 4 carbon atoms, - or an acyclic carbon chain, linear or branched, saturated or unsaturated, comprising from 5 to 20 carbon atoms
- R 5 and R ' 5 identical or different, each represent: - an alkyl group, linear or branched, comprising from 1 to 4 carbon atoms, or an alkenyl group, linear or branched, comprising from 1 to 4 carbon atoms, - or an alkynyl group, linear or branched, comprising from 1 to 4 carbon atoms, - or an acyclic carbon chain, linear or branched, saturated or unsaturated, comprising from 5 to 20 carbon atoms, - or an acyclic carbon chain, linear or branched, saturated or unsaturated, functionalized at its end, comprising from 5 to 20 carbon atoms, - or an acyclic carbon chain, linear or branched, saturated or unsaturated, comprising a nitrogen atom of amine or amide function and / or an ether or carboxylic oxygen atom.
- R RN R 2 , R ' 2 , R 3 .- R' 3, R and R ' 4 each represent a hydrogen atom.
- R 5 and R ' 5 identical or different , each represent: - an alkyl group, linear or branched, comprising from 1 to 4 carbon atoms, - or an acyclic carbon chain, linear or branched, saturated or unsaturated, comprising from 5 to 20 carbon atoms
- R 5 and R ' 5 identical or different each represent: - an alkyl group, linear or branched, comprising from 1 to 4 carbon atoms, - or an acyclic carbon chain, linear or branched, saturated or unsaturated, comprising from 5 to 20 carbon atoms
- these dibenzoylmethane derivatives can be obtained from a dibenzoylmethane, optionally substituted, by an alkylation reaction according to a protocol similar to those described by MARZINZIK and FELDER (Tetrahedron Letters, Vol. 37, No. 7, pp 1003-1006, 1996) and CLARK and MILLER (JCS Perkin I, pp 1743-1745, 1977).
- the alkylammonium halide used is either a fluoride, or a chloride, or a bromide, or an alkylammonium iodide, preferably tetrabutylammonium fluoride.
- This tetrabutylammonium halide is present either in aqueous solution or in solution in tetrahydrofuran (THF). Therefore, the preparation of the dibenzoylmethane / tetrabutylammonium halide complex is carried out either in an aqueous medium or in an organic medium, preferably in THF.
- the actual alkylation is carried out in an organic solvent such as tetrahydrofuran (THF), acetonitrile, chloroform, preferably THF.
- THF tetrahydrofuran
- the reaction medium is kept under stirring at room temperature or at reflux, preferably at reflux for 2 to 24 hours, preferably 8 hours.
- the alkylating agent can be an alkane halide such as a fluoroalkane, a chloroalkane, a bromoalkane, an iodoalkane, preferably bromoalkane, having from 1 to 20 carbon atoms, preferably 10.
- the starting dibenzoylmethane derivatives, optionally substituted, that is to say the compounds of formula (I), in which R5 and R'5 each represent a hydrogen can be prepared by known synthetic methods such as Claisen condensation (see Organic Reactions, volume VIII, John Wiley and Sons, 1,954), that is to say the condensation between a compound of general formula AR-X and AR'-Y, in which AR and AR 'identical or different each represent a phenyl group optionally mono or polysubstituted, and X and Y, different each represent a methoxycarbonyl group and an acetyl group.
- This condensation reaction is advantageously carried out in the presence of a strong base, in the presence of an inert solvent.
- the invention also relates also to the process for the preparation of a compound of formula (I) as defined above, characterized in that it comprises: a step of forming a complex in aqueous or organic medium, between a) a molecule of general formula (I) in which R ,, RN R 2 , R ' 2 R 3 , R' 3 R 4 , and R ' 4 each represent a group defined in any one of Claims 1 to 4, and R 5 and R ' 5 , identical each represent a hydrogen atom, and b) an alkylammonium halide, then - a step of substitution of at least one of the hydrogens represented by R 5 or R' 5 , in an organic medium with action of at least one halide of general formula R 5 X or R ' 5 X, in which R 5 and R' 5 , which are identical or different, each represent a group defined above.
- R 5 or R ' 5 is an alkylation by the action of at least one alkylating agent of general formula R 5 X or R ' 5 X, in which R 5 and R' g, which are identical or different, each represent an acyclic carbon chain, linear or branched, saturated or unsaturated, comprising from 1 to 20 carbon atoms
- the dibenzoylmethane derivatives thus obtained have a conjugate system analogous to the reference compound described above, namely Parsol 1789 or 4-tertbutyl, -4'- methoxydibenzoylmethane, they therefore exhibit absorption capacities in the ultraviolet As a 'illustration of these absorption capacities in the ultraviolet, measurements were carried out for two dibenzoylmethane derivatives according to the invention.
- Compound 010 has a strong solvochromy which brings the maximum absorption in the UVA to around 360 nm for organized solvents (for example micellar solutions of sodium dodecyl sulfate). The same is true for compound C10.
- these two compounds subjected to ultraviolet radiation, see their wavelength of maximum absorbance pass from UVB to UVA, thus causing the same effect as the organization of the system. So that the maximum displacement of the absorption bands towards UVA is obtained by placing these compounds in an organized medium under irradiation, as is the case for a sunscreen cosmetic preparation under the normal conditions of its use. The irradiation of the preparation amplifies the phenomenon induced by the medium in which the compounds are found.
- the dibenzoylmethane derivatives according to the invention can thus advantageously be used in cosmetic and or dermatological preparations as sunscreens.
- the present invention therefore also relates to a cosmetic and / or dermatological composition characterized in that it comprises as active ingredient at least, a compound of formula (I), according to claims 1 to 4 or one of its salts or solvates , as defined above. It also relates to a composition as previously defined, characterized in that it also comprises another active principle.
- composition as defined above, characterized in that the other active principle is a filter chosen from the group consisting of PARSOL 1,789, 2,4,6-tris [p- (2'-ethylhexyl -1 '-oxycarbonyl) anilino] -1, 3,5-triazine, 4- (t-butyl) -4'- methoxy-dibenzoylmethane, 2-hydroxy-4-methoxy-benzophenone, and 3- (4'-methylbenzylidene) -camphor.
- the other active principle is a filter chosen from the group consisting of PARSOL 1,789, 2,4,6-tris [p- (2'-ethylhexyl -1 '-oxycarbonyl) anilino] -1, 3,5-triazine, 4- (t-butyl) -4'- methoxy-dibenzoylmethane, 2-hydroxy-4-methoxy-benzophenone, and 3- (4'-methylbenzylidene) -
- composition according to the invention characterized in that it contains from 0.5 to 30% by weight relative to the total weight of the composition, preferably from 1 to 10%, of said active principle.
- compositions according to the invention may also contain conventional cosmetic adjuvants in particular chosen from fatty substances, organic solvents, ionic or nonionic thickeners, softeners, antioxidants, opacifiers, stabilizers, emollients, silicones, defoamers, moisturizers, vitamins, fragrances, preservatives, surfactants, fillers, inorganic or organic pigments, sequestrants, polymers, propellants, alkalizing or acidifying agents, colorants, or any other ingredient usually used in cosmetics, in particular for the manufacture of sunscreen compositions in the form of emulsions. They can also contain one or more complementary sunscreens active in UVA and / or UVB, hydrophilic or lipophilic.
- the present invention also relates to the use of a compound of formula (I) according to the invention or one of its salts or solvates, as an agent for protecting the skin or the hair against UV radiation.
- the invention also relates to a cosmetic and / or dermatological product characterized in that it comprises, as active principle, a compound of formula (I) according to the invention or one of its salts or solvates.
- Example 1 1 - (4-methoxyphenyl) -3- (4-tertbutylphenyl) -propane-1, 3-dione
- reaction medium is maintained at ambient temperature, with magnetic stirring for 26 hours.
- a viscous orange residue is obtained after filtration and evaporation of the solvent.
- a succession of open columns are then produced in order to remove the excess of reagents ( alkylating agent, C 10 H 21 Br and TBAF) and separate the three molecules present in the medium: the unreacted starting molecule, the molecule having for R 5 the acyclic carbon chain, linear saturated, comprising 10 carbon atoms and an H for HR 'R 2 , R' 2 R 3 , R ' 3 R 4 , R' 4 , R ' 5 , and the molecule having for R' 5 the acyclic carbon chain, linear saturated, comprising 10 carbon atoms and an H for R.
- reagents alkylating agent, C 10 H 21 Br and TBAF
- reaction medium is maintained at reflux, with magnetic stirring for 8 hours.
- a viscous orange residue is obtained after filtration and evaporation of the solvent.
- a succession of open columns are then produced in order to remove the excess of reagents (alkylating agent C 10 H 21 Br and TBAF) and to separate the three molecules present in the medium: the unreacted starting molecule, the molecule having for R 5 the acyclic carbon chain, linear saturated, comprising 10 carbon atoms and an H for R 1 f R ',, R 2 , R' 2 / R 3 , R ' 3, R 4 , R' 4 and R ' 5 , and the molecule having for R' 5 the acyclic carbon chain, linear saturated, comprising 10 atoms carbon and an H for R ,, RN R 2 , R ' 2 ⁇ R 3 , R' 3, R 4 , R ' 4 , and R 5.
- the open columns are made in the same way way as before. Separation in HPLC; column C1 8;
- Parsol 1 789 gives 2.59 g of compound C10 and 2.47 g of compound 010, ie respective yields of 34 and 36%.
- the NMR spectra were performed with a Bruker ARX 400 MHz device.
- the UV absorption spectra were performed on an HP 8452 A Diode Array Spectrometer.
- the infrared spectra were performed on a Perkin-Elmer 1,760 X device.
- Stability tests against UV radiation For example, changes under irradiation of a basic preparation (water in oil emulsion) containing the compounds obtained in the previous examples, namely compound C10 and compound 010, are compared to that of the same preparation containing Parsol 1,789 (% by mass equivalent for each filter).
- the preparations chosen may be composed as follows: Glycasil L 0.19%, butylparaben 0.3%, beeswax 4%, PEG-30 dipolyhydroxystearate 3%, dicapryl carbonate 10%, polyglyceryl-3- diisostearate 1 .5%, water 78.64%, xanthan gum 1%, Na 2 EDTA 0.2%, NaCl 1%; methylparaben 0.17%
- the compounds C10 or O10 or Parsol 1789 in% by mass equivalent may be composed as follows: Glycasil L 0.19%, butylparaben 0.
- the two compounds tested therefore exhibit better photostability than Parsol 1 789.
- their molar extinction coefficient is lower than that of Parsol 1 789 by about 30% (when the maximum absorption is reached by irradiation). It may thus be possible to use the dibenzoylmethane derivatives according to the invention in combination with other filters such as Parsol 1 789, the dibenzoylmethane derivatives according to the invention protecting Parsol 1 789 by screen effect. This association makes it possible to use a minimum mass of filter for a maximum filtering effect.
- a preparation similar to the previous ones containing 1% by mass of filters in total, including 32.5% of Parsol 1,789, 35% of compound C10 and 32.5% of compound O10 (molar%) was irradiated with sun under the same conditions as above and its evolution was compared to that of a preparation containing 1% by mass of Parsol 1 789.
- the mixed preparation retains its initial absorbance (or greater absorbance) in UVA for 1 h and that- this decreases by 33% after 2 hours.
- the preparation containing only Parsol 1 789 sees its absorbance decrease regularly from the start of the exposure. This decrease reaches 51% in 1 hour and 73% in 2 hours.
- a preparation similar to the previous ones containing 1% by mass of filters in total, including 10% of Parsol 1789, 30% of compound C10 and 60% of compound O 1 0 (molar%) was irradiated in the sun in the same conditions as above and its development was compared to that of a preparation containing 1% by mass of Parsol 1,789.
- the mixed preparation retains its initial absorbance (or greater absorbance) in UVA for 2 h 30 min.
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR0308736A FR2857663B1 (fr) | 2003-07-17 | 2003-07-17 | Nouveau composes derives de dibenzoylmethane, utilisation en tant que filtres solaires photoactivables et compositions cosmetiques les contenant |
PCT/FR2004/001859 WO2005009938A2 (fr) | 2003-07-17 | 2004-07-15 | Composés dérivés de dibenzoylméthane, utilisation en tant que filtres solaires photoactivables et compositions cosmétiques les contenant |
Publications (1)
Publication Number | Publication Date |
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EP1648849A2 true EP1648849A2 (de) | 2006-04-26 |
Family
ID=33548215
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EP04767684A Withdrawn EP1648849A2 (de) | 2003-07-17 | 2004-07-15 | Neue dibenzoylmethanderivativverbindungen, deren verwendung in form von lichtaktivierbaren sonnenfiltern und kosmetische zusammensetzungen, die diese verbindungen enthalten |
Country Status (8)
Country | Link |
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US (1) | US7446230B2 (de) |
EP (1) | EP1648849A2 (de) |
JP (1) | JP2007516208A (de) |
KR (1) | KR20060052830A (de) |
CN (1) | CN1823028A (de) |
CA (1) | CA2532197A1 (de) |
FR (1) | FR2857663B1 (de) |
WO (1) | WO2005009938A2 (de) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102015211792A1 (de) | 2015-06-25 | 2016-12-29 | Beiersdorf Ag | Sonnenschutzmittel mit Ausgangsstoff für die Bildung von 4-(tert.-Butyl)-4'-methoxydibenzoylmethan |
DE102015211793A1 (de) | 2015-06-25 | 2016-12-29 | Beiersdorf Ag | Alkandiol-haltige Sonnenschutzmittel mit Ausgangsstoff für die Bildung von 4-(tert.-Butyl)-4'-methoxydibenzoylmethan |
WO2016206961A1 (de) | 2015-06-25 | 2016-12-29 | Beiersdorf Ag | Sonnenschutzmittel mit pre-avobenzon |
DE102015216959A1 (de) | 2015-09-04 | 2017-03-09 | Beiersdorf Ag | Parfümiertes Sonnenschutzmittel mit Ausgangsstoff für die Bildung von 4-(tert.-Butyl)-4'-methoxydibenzoylmethan |
DE102015225570A1 (de) | 2015-12-17 | 2017-06-22 | Beiersdorf Ag | Allerneustes Sonnenschutzmittel mit Ausgangsstoff für die Bildung von 4-(tert.-Butyl)-4'-methoxy-di-ben-zoylmethan |
DE102015225567A1 (de) | 2015-12-17 | 2017-06-22 | Beiersdorf Ag | Neues Sonnenschutzmittel mit Ausgangsstoff für die Bildung von 4-(tert.-Butyl)-4'-methoxydibenzoylmethan |
WO2017102301A1 (de) | 2015-12-17 | 2017-06-22 | Beiersdorf Ag | Sonnenschutzmittel mit 4-(tert.-butyl)-4 -methoxydibenzoylmethan vorstufe |
DE102016000800A1 (de) | 2016-01-27 | 2017-07-27 | Beiersdorf Ag | Sonnenschutzmittel mit Tricyclodecanmethylisononanoat |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2467122A2 (de) * | 2009-08-21 | 2012-06-27 | Blueshift Pharma GmbH | Lichtreaktive sonnenschutzzusammensetzung |
US9580678B2 (en) | 2013-06-21 | 2017-02-28 | The Regents Of The University Of California | Microfluidic tumor tissue dissociation device |
US10722540B1 (en) | 2016-02-01 | 2020-07-28 | The Regents Of The University Of California | Microfluidic device and method for shear stress-induced transformation of cells |
JP2024508123A (ja) | 2021-02-26 | 2024-02-22 | サン ケミカル コーポレイション | ジベンゾイルメタン副構造を有する光開始剤樹脂 |
WO2023118482A1 (en) | 2021-12-24 | 2023-06-29 | Sun Chemical Corporation | Amine synergists with uv-a absorption |
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NL190101C (nl) * | 1978-11-13 | 1993-11-01 | Givaudan & Cie Sa | Dibenzoylmethaanverbinding en tegen licht beschermend preparaat. |
FR2506156A1 (fr) * | 1981-05-20 | 1982-11-26 | Oreal | Compositions cosmetiques contenant des derives hydroxyles du dibenzoylmethane et leur utilisation pour la protection de l'epiderme humain contre les rayons ultraviolets |
FR2526658B2 (fr) * | 1981-05-20 | 1986-05-23 | Oreal | Compositions cosmetiques contenant des derives hydroxyles du dibenzoylmethane et leur utilisation pour la protection de l'epiderme humain contre les rayons ultraviolets, nouveaux derives hydroxyles du dibenzoylmethane utilises et leur procede de preparation |
JPH0695184A (ja) * | 1992-09-10 | 1994-04-08 | Hitachi Ltd | 有機非線形光学材料とそれを用いた光機能素子 |
FR2747038B1 (fr) | 1996-04-05 | 1998-05-22 | Oreal | Composition filtrante photostable comprenant un derive de dibenzoylmethane et un alkylether de polysaccharide et ses utilisations |
FR2750335B1 (fr) | 1996-07-01 | 1998-07-31 | Oreal | Compositions comprenant du 4-tert-butyl-4'- methoxydibenzoylmethane, un derive de 1, 3, 5-triazine et un (alpha-cyano)-beta, beta'-diphenylacrylate d'alkyle et utilisations |
FR2768730B1 (fr) | 1997-09-25 | 1999-12-31 | Jean Noel Thorel | Procede de photostabilisation du 4-(ter.butyl) 4'-methoxy dibenzoylmethane, compositions filtrantes ainsi obtenues et leurs utilisations |
FR2818130A1 (fr) | 2000-12-18 | 2002-06-21 | Oreal | Compositions cosmetiques antisolaires a base d'un melange synergetique de filtres et utilisations |
BR0006583A (pt) * | 2000-12-22 | 2002-07-30 | Unicamp | Obtenção de novos derivados de dibenzoilmetano que apresentam atividade antineoplásica e de aplicação potencial como protetores solares |
US6444195B1 (en) | 2001-06-18 | 2002-09-03 | Johnson & Johnson Consumer Companies, Inc. | Sunscreen compositions containing a dibenzoylmethane derivative |
-
2003
- 2003-07-17 FR FR0308736A patent/FR2857663B1/fr not_active Expired - Lifetime
-
2004
- 2004-07-15 KR KR1020067001164A patent/KR20060052830A/ko not_active Application Discontinuation
- 2004-07-15 CN CNA200480020285XA patent/CN1823028A/zh active Pending
- 2004-07-15 WO PCT/FR2004/001859 patent/WO2005009938A2/fr active Application Filing
- 2004-07-15 JP JP2006519962A patent/JP2007516208A/ja active Pending
- 2004-07-15 EP EP04767684A patent/EP1648849A2/de not_active Withdrawn
- 2004-07-15 US US10/564,888 patent/US7446230B2/en not_active Expired - Fee Related
- 2004-07-15 CA CA002532197A patent/CA2532197A1/fr not_active Abandoned
Non-Patent Citations (1)
Title |
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See references of WO2005009938A2 * |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102015211792A1 (de) | 2015-06-25 | 2016-12-29 | Beiersdorf Ag | Sonnenschutzmittel mit Ausgangsstoff für die Bildung von 4-(tert.-Butyl)-4'-methoxydibenzoylmethan |
DE102015211793A1 (de) | 2015-06-25 | 2016-12-29 | Beiersdorf Ag | Alkandiol-haltige Sonnenschutzmittel mit Ausgangsstoff für die Bildung von 4-(tert.-Butyl)-4'-methoxydibenzoylmethan |
WO2016206963A1 (de) | 2015-06-25 | 2016-12-29 | Beiersdorf Ag | Alkandiol-haltige sonnenschutzmittel mit ausgangsstoff für die bildung von 4-(tert.-butyl)-4'-methoxydibenzoylmethan |
WO2016206962A1 (de) | 2015-06-25 | 2016-12-29 | Beiersdorf Ag | Sonnenschutzmittel mit ausgangsstoff für die bildung von 4-(tert.-butyl)-4'-methoxydibenzoylmethan |
WO2016206961A1 (de) | 2015-06-25 | 2016-12-29 | Beiersdorf Ag | Sonnenschutzmittel mit pre-avobenzon |
DE102015211790A1 (de) | 2015-06-25 | 2016-12-29 | Beiersdorf Ag | Ethanolisches Sonnenschutzmittel mit Ausgangsstoff für die Bildung von 4-(tert.-Butyl)-4'-methoxydibenzoylmethan |
DE102015216959A1 (de) | 2015-09-04 | 2017-03-09 | Beiersdorf Ag | Parfümiertes Sonnenschutzmittel mit Ausgangsstoff für die Bildung von 4-(tert.-Butyl)-4'-methoxydibenzoylmethan |
DE102015225570A1 (de) | 2015-12-17 | 2017-06-22 | Beiersdorf Ag | Allerneustes Sonnenschutzmittel mit Ausgangsstoff für die Bildung von 4-(tert.-Butyl)-4'-methoxy-di-ben-zoylmethan |
DE102015225567A1 (de) | 2015-12-17 | 2017-06-22 | Beiersdorf Ag | Neues Sonnenschutzmittel mit Ausgangsstoff für die Bildung von 4-(tert.-Butyl)-4'-methoxydibenzoylmethan |
WO2017102301A1 (de) | 2015-12-17 | 2017-06-22 | Beiersdorf Ag | Sonnenschutzmittel mit 4-(tert.-butyl)-4 -methoxydibenzoylmethan vorstufe |
WO2017102302A1 (de) | 2015-12-17 | 2017-06-22 | Beiersdorf Ag | Sonnenschutzmittel enthaltend einen precursor von avobenzon |
WO2017102300A1 (de) | 2015-12-17 | 2017-06-22 | Beiersdorf Ag | Neues sonnenschutzmittel mit ausgangsstoff für die bildung von 4-(tert.-butyl)-4'-methoxy-dibenzoylmethan |
DE102015225568A1 (de) | 2015-12-17 | 2017-06-22 | Beiersdorf Ag | Neustes Sonnenschutzmittel mit Ausgangsstoff für die Bildung von 4-(tert.-Butyl)-4'-methoxydibenzoylmethan |
DE102016000800A1 (de) | 2016-01-27 | 2017-07-27 | Beiersdorf Ag | Sonnenschutzmittel mit Tricyclodecanmethylisononanoat |
Also Published As
Publication number | Publication date |
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FR2857663A1 (fr) | 2005-01-21 |
KR20060052830A (ko) | 2006-05-19 |
JP2007516208A (ja) | 2007-06-21 |
US20070025930A1 (en) | 2007-02-01 |
WO2005009938A2 (fr) | 2005-02-03 |
US7446230B2 (en) | 2008-11-04 |
WO2005009938A3 (fr) | 2005-04-14 |
CN1823028A (zh) | 2006-08-23 |
FR2857663B1 (fr) | 2007-12-21 |
CA2532197A1 (fr) | 2005-02-03 |
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