[go: up one dir, main page]

WO2000066527A1 - Derives de dibenzoylmethane, leurs procedes de preparation et d'utilisation - Google Patents

Derives de dibenzoylmethane, leurs procedes de preparation et d'utilisation Download PDF

Info

Publication number
WO2000066527A1
WO2000066527A1 PCT/JP2000/002820 JP0002820W WO0066527A1 WO 2000066527 A1 WO2000066527 A1 WO 2000066527A1 JP 0002820 W JP0002820 W JP 0002820W WO 0066527 A1 WO0066527 A1 WO 0066527A1
Authority
WO
WIPO (PCT)
Prior art keywords
iso
tert
butyl
butynole
sec
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.)
Ceased
Application number
PCT/JP2000/002820
Other languages
English (en)
Japanese (ja)
Inventor
Naohiko Fukuoka
Heinosuke Yasuda
Yoshinori Ohmae
Kenichi Fukui
Masao Mitsuda
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemipro Kasei Kaisha Ltd
Original Assignee
Chemipro Kasei Kaisha Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Chemipro Kasei Kaisha Ltd filed Critical Chemipro Kasei Kaisha Ltd
Priority to AU41450/00A priority Critical patent/AU4145000A/en
Publication of WO2000066527A1 publication Critical patent/WO2000066527A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a dibenzoylmethane derivative having excellent ultraviolet absorbing ability and high light stability and hardly causing a coloring reaction even in the presence of metal ion, a method for producing the same, an ultraviolet absorber containing the same, and a cosmetic.
  • UV-B having a wavelength of 290 to 320 nm
  • UV-A having a wavelength of 320 to 400 nm.
  • UV-A region has higher energy than UV-B region and is known to cause skin browning, burns, and aging.
  • Japanese Patent Application Laid-Open Publication Nos. 11-2822734, 11-1-2563, and 11-292748 disclose that dibenzoyl is used as a cosmetic for preventing ultraviolet rays.
  • UV absorbers such as dibenzoylmethane, benzophenone, and triazole have been developed and used to address such problems.
  • a dibenzoylmethane derivative for example, 4-tert-butyl-14'-methoxydibenzoylmethane
  • the dibenzoylmethane derivative is not only degraded and decomposed, but also colored due to interaction with metal ions. There is a problem. Particularly when used as cosmetics, the appearance is impaired by this coloring, which is not preferable.
  • a first object of the present invention is to have a function of effectively absorbing ultraviolet rays in the UV-A region (having a large molecular extinction coefficient) and a function of preventing coloring due to interaction with metal ions.
  • Another object of the present invention is to provide a novel dibenzoylmethane derivative excellent in water resistance and a method for producing the same.
  • a second object of the present invention is to provide an ultraviolet absorber containing the novel dibenzoylmethane derivative utilizing the ultraviolet absorption ability and a cosmetic containing the same. Disclosure of the invention
  • UV—A dibenzoylmethane derivative that effectively absorbs UV light in the A region, such as 4-tert-butyl-1-4'-methoxydibenzoylmethane
  • One possible cause is that the metal ion coordinates and binds to the lone pair of carbonyl groups. Therefore, as a result of intensive studies on the method of suppressing coloring by metal ions, it was found that compounds in which a substituent was introduced at the ortho-position to the carbonyl group bonded to the aromatic ring of the dibenzoylmethane derivative could suppress coloring by metal ions. And completed the present invention.
  • R 1 is a group selected from the group consisting of a hydrogen atom, a linear or branched alkyl group and an alkoxy group
  • R 2 is a hydrogen atom, a linear or branched alkyl group and an alkoxy group
  • R 3 is a group selected from the group consisting of a hydrogen atom, a linear or branched alkyl group and an alkoxy group
  • R 4 is a hydrogen atom or a hydrogen atom.
  • R 4 is an alkoxy group when R 1 is a linear or branched alkyl group;
  • R 5 is a group selected from the group consisting of a hydrogen atom, a linear or branched alkyl group and an alkoxy group
  • R 6 is Hydrogen atom, straight or branched, al A group selected from the group consisting of kill and alkoxy groups, R 'and one of R 4, and from either is not a hydrogen atom groups R 2 and R 5 It was chosen.
  • R 1 is a group selected from the group consisting of a hydrogen atom, a linear or branched alkyl group and an alkoxy group
  • R 2 is a hydrogen atom, a linear or branched alkyl group and an alkoxy group
  • R 3 is a group selected from the group consisting of a hydrogen atom, a linear or branched alkyl group and an alkoxy group
  • R 4 is a hydrogen atom or a hydrogen atom.
  • R 4 is an alkoxy group when R 1 is a linear or branched alkyl group;
  • R 1 is an alkoxy group, it is a linear or branched alkyl group, and
  • R 5 is a hydrogen atom, a linear or branched alkyl group or an alkoxy group.
  • R 6 is a group selected from the group consisting of a hydrogen atom, a linear or branched alkyl group and an alkoxy group, and one of R 1 and R 4 , and R 2 and R Any of 5 is selected from groups that are not hydrogen atoms.
  • R 1 is a group selected from the group consisting of a hydrogen atom, a linear or branched alkyl group and an alkoxy group
  • R 2 is a hydrogen atom, a linear or branched alkyl group and an alkoxy group
  • R 3 is a group selected from the group consisting of a hydrogen atom, a straight-chain or branched alkyl group and an alkoxy group
  • R 4 is a hydrogen atom or a straight-chain atom.
  • R 4 is an alkoxy group when R 1 is a linear or branched alkyl group, and R 1 is In the case of an alkoxy group, it is a linear or branched alkyl group
  • R 5 is a hydrogen atom, a group selected from the group consisting of a linear or branched alkyl group and an alkoxy group
  • R 6 is a hydrogen atom, Straight or branched
  • a cosmetic comprising a dibenzoylmethane derivative represented by the formula:
  • a fourth aspect of the present invention is to provide the following general formula (2)
  • R 4 , R 5 and R 6 are the same as described above, and R 7 is a linear or branched alkyl group.
  • R 7 is a linear or branched anolequinole group.
  • R 1 examples include a straight-chain or branched alkyl group, and particularly preferably those having 1 to 8 carbon atoms. Specifically, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butynole, sec-butyl, tert-butyl, n-pentyl, iso-pentinole Group, sec-pentynole group, tert-octynole group, 2-ethylhexyl group and the like.
  • R 2 examples include a linear or branched alkyl group and an alkoxy group, and preferably have 1 to 8 carbon atoms.
  • alkyl groups include methyl group, ethyl group, n-propyl group, iso-pro- Pinole, n-butyl, iso-butynole, sec-butyl, tert-butynole, n-pentynole, iso-pentynole, sec-pentyl, tert-octyl, 2-ethylhexyl And the like.
  • Alkoxy groups include methoxy, ethoxy, n -propoxy, iso-propoxy, n -butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, iso — Pentynoleoxy group, sec —pentynoleoxy group, tert-octynoleoxy group, 2-ethylhexyloxy group and the like.
  • R 3 , R 4 , R 5, and R 6 include a hydrogen atom or a linear or branched alkyl group and an alkoxy group, and preferably have 1 to 8 carbon atoms.
  • alkyl groups include methyl group, ethynole group, n-propynole group, iso-propyl group, n-butynole group, iso-butynole group, sec-butyl group, tert-butyl group, n-pentynole group, iso-pentynole group, sec-pentynole group, tert-octynole group, 2-ethylhexyl group and the like.
  • Alkoxy groups include methoxy, ethoxy, n -propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n- Pentyloxy group, iso-pentyloxy group, sec-pentyloxy group, tert-octyloxy group, 2-ethylhexyloxy group and the like.
  • Examples of the linear or branched alkyl group for R 7 include a methyl group, an ethynole group, an n-propynole group, an iso-propynole group, an n-butyl group, and an iso-butyl group.
  • the number of carbon atoms is preferably 1 to 3.
  • the acetophenone derivative and the aromatic ester derivative represented by the general formulas (2) and (3) or (2 ′) and (3 ′) are reacted in the presence of a suitable condensing agent described below. Under normal pressure or reduced pressure, 10 to 150 ° C, preferably
  • a solvent an organic solvent is usually used.
  • examples of the solvent include an aliphatic ether, an aliphatic cyclic ether, an alkyl halide, and an aromatic compound.
  • the solvent include, for example, getyl ether, dipropanolene ether, tetrahydrofuran, 1,4-dioxane, dichloroethylene, chlorophonolem, tosoleen, xylene and the like.
  • Examples of the condensing agent include sodium amide, potassium amide, lithium amide, sodium alkoxide, sodium alkoxide, sodium hydride, sodium hydroxide, and water. Oxidizing power can be used.
  • Specific examples of the dibenzoylmethane derivative represented by the general formula (1) of the present invention include the following compounds.
  • 4 1 iso-butynole 1 4 '— n-butinole 2 — methoxydibenzoyl methane, 4 — tert monobutyl _ 4' 1 n-butyl-2, methoxydibenzoyl methane, 4 '— n — butynole 1 2 —Methoxy 4 — tert —Occhinorezibenzoinoremetan,
  • 2,4-zy iso-propynole 1 2'-methyl 1 4'-methoxydibenzoylmethane, 2 ', 4-dimethyl-1 2-iso_propynole 1 4'-methoxydibenzoinolemethane, 2 — Iso — Propinole 2 ′ —methyl-1-ethyl 4- ′ — methoxydibenzoylmethane, 2 — iso —propyl 1 2 — —methyl_4_n—propyl-1 4′-methoxydibenzo Ilmetane, 2—iso—propinole 2′—methyl 1—n—butyl—4′—methoxydibenzoinolemethane, 2—iso—propinole 2′—methinole 1—iso—butinole 4 ′ -Methoxydibenzoinolemethane, 2-iso-propyl-1 2 '-methyl-4-sec -but
  • 2,4 zy iso—Propyl mono 2 ', 4'—Dimethoxydibenzoylmethane, 4-Methyl mono 2—iso—Propyl mono 2', 4'—Dimethoxy benzodibenzoinolemethane, 2—iso —Pro-Pinole 4 4-Echinole 1 2 ', 4' —Dimethoxydibenzoylmethane, 2 — iso —Propyl-1 4 _n —Pup pill—2 ', 4' —Dimethoxydibenzoylmethane, 2— iso — pulp pill 1 4 — n — butyl-2 ', 4' — dimethoxydibenzoylmethane, 2 — iso — propyl-1 4 iso — butynoley 2 ', 4' — dimethoxydibenzylmetane, 2 — Iso — propylinole
  • 2,4-zy is ⁇ —Butyl-6 —Methylenol 2 ', 4'Dimethoxydibenzoylmethane, 4,6 —Dimethyl-2 —iso —Butyl-2', 4 '—Dimethoxydibenzoylmethane, 2 —iso—Butyl-1 6 — methyl 1 4 — n — propyl 1 2 ', 4' dimethoxydibenzoynolemethane, 2 — iso — butinole 1 6 — methinole 4 — iso — propinole 2 ', 4' — dimethoxydibe Mesylmethane, 2 — iso —butyl-1 6 —methyl-4 — n —butyl-2 ′, 4 ′ —dimethoxydibenzoinolemethane, 2 — iso —butynole 6 — methinole 14 1 sec —
  • 2,4—Gee tert—Butinole 6 Metal-2 ′, 4′—Dimethyl benzodibenzoinolemethane, 4, 6—Dimethyltinole 2—tert Butinole 1 2 ′ 4′—Dimethoxy benzodibenzoinolemethane, 2 — tert — Butynole 6 — Methyl 4-ethyl 1 2 ′, 4 ′ Dimethoxydibenzoylmethane, 2 — tert-Butyl 6 — Methinole 4 1 n — Pro-Pinolelet 2 ′, 4 ′ Dimethoxydibenzoinoleme Tan, 2 — tert-butyl 6 — methinolate 4
  • 2 ', 4'-Gee iso-Propyl 6'-Dimethyl 2,4-Dimethoxydibenzoinolemethane, 4', 6'-Dimethyl 2'-Iso-Pu-pinola 2,4—Dimethoxydibenzo Dimethyl, 2'-iso-propyl-6'-methyl-1,4'-ethyl-2,4 dimethyldibenzoinolemethane, 2'-iso-propyl-6'-methyl-4'-n-propyl — 2,4 dimethoxydibenzoylmethanethane, 2 '— iso—Propyl 1 6' —methyl-4 '1 n-butyl-2,4—Dimethoxydibenzoylmethane, 2' — iso—Propinolay 6 '— Methyl mono 4 '— iso — butyl — 2,4 — dimethoxydibenzoinolemethane, 2
  • R 2 or R 5 is a hydrogen atom
  • specific examples of the compound represented by the general formula (2) or (2 ′) include the following compounds.
  • R 2 or R 5 is not a hydrogen atom
  • the following compounds may be exemplified. it can.
  • 2'-iso-butynoleic 4' metalhinoleacet tophenone, 2 ', 4'-di-iso-butynolease tophenonone, 2'-iso-butinoleic 4'—ethinolease tophenonone, 2'-iso-butinole-1 4' — N—Propiracetophenonone, 2 '— iso—butinoleone 4' — n—butynolease tophenone, 2 '— iso—butinoleone 4' — sec — Butinolease tophenone, 2 ' ⁇ iso —butynole 4 ′ — tert —butynolease tophenone, 2 ′ — iso —butynole 1 4'-tert —octinolease tophenon,
  • 2'-iso-butyl-4 ', 6'-dimethylacetophenone, 2', 4'-iso-butyl-1-6'-methylacetophenone, 2'-iso-butyl-4'-ethylino-6'-methylacetophenone, 2 '— is o —Butyl 4 ′ — n—Propyl 1 6 ′ —Methylacetophenone, 2 ′ — iso—butynole 1 4 ′ — n—Butinole 6 ′ —Methinolacettophenon, 2 ′ — Iso—butinole 4 ′ — sec — Butinore 1 6 '—Methinoreacetphenone, 2' — iso—Buchinole 4'-tert-Putinore 1 6'-Methylinolacetophenone, 2'-iso—Buchinole 1 4'-tert-octinore—6 '
  • Mouth Pinolie 6 ' Methynoreacet Tophenon 2' — sec — Butinole 1 4 '— iso — Pro Pinoley 6' — Methynolease Tophenone, 2 '— sec — Butinole 1 4' — n — Butinole 6 '— Methinorea , 2 '— sec — pu, chinole 4' — iso — butino 1 6 '— methylacetophenone, 2', 4 '— di sec — butyl 6' — methinolacetophenone, 2 '-sec-butino 1 4 '-tert-butynole 6'-methinoleacetophenone, 2'-sec-butynole 4'-tert-octyl-6'-methylacetophenone,
  • R 5 or R 2 is a hydrogen atom
  • specific examples of the compound represented by the general formula (3) or (3 ′) include the following compound groups (
  • R 4 or R 1 is a hydrogen atom
  • the following compounds can be exemplified.
  • R 4 or R 1 and R 5 or R 2 are not a hydrogen atom, the following compounds can be exemplified.
  • 2 — ethynole 4 _ iso — pentynole benzoic acid
  • 2 — ethynole 4 1 iso — pentyl benzoic acid
  • 2 — ethyl 4 -1 (2 — ethylhexyl) benzoic acid
  • 2 _ iso-butyl-4-methylbenzoic acid, 2,4-iso-butyl-benzoic acid, 2-iso-butyl-4-ethyl-benzoic acid, 2-iso-butynole 4-n-propinolebenzoic acid , 2-iso-butyl-4-n-butylbenzoic acid, 2-iso-butyl-4 sec-butyl-benzoic acid,
  • 2-Ethyl 1 4 1 iso-Propyl 1-6 —methylbenzoic acid, 2-Ethyl — 4 1n — Butynole 1 6 —Methinolebenzoic acid, 2 —Echinolate 4 — iso —Butyl 1 6 —Methylbenzoic acid, 2-Ethyl 4 — Sec 1-butyl-1-6-methylbenzoic acid, 2-ethyl-4-1-tert-butyl-6-methylbenzoic acid, 2-ethyl-1-4-tert-octyl-1-6-methylbenzoic acid,
  • 2-tert-butyl-4,6-dimethylbenzoic acid 2-tert-butyl-4-ethyl-6-methylbenzoic acid, 2-tert-butyl-4-n-propinole 6-methylbenzoic acid, 2-tert-butynolee 4 Iso-propyl-6-methylbenzoic acid, 2-tert-butyl-4—n-butynole-6-methylbenzoic acid, 2-tert-butynoleic 4-iso-butyl-6-6-methylbenzoic acid, 2,4-di 1-tert-butyl-6-methyl benzoic acid, 2-tert-butynole-4—sec—butyl_6—methylbenzoic acid, 2—tert—butyl-4 1 tert—octyl-6-methyl Tyl benzoic acid,
  • the methyl esters, ethyl esters or n-propyl estenoles of the respective benzoic acids are methyl esters, ethyl esters or n-propyl estenoles of the respective benzoic acids.
  • the cosmetic containing the dibenzoylmethane derivative (1) of the present invention is blended with a known cosmetic base described below by a conventional method, and is used as a cream, a solution, an oil, a spray, a stick, an emulsion, a foundation, or the like. And ointments.
  • the ultraviolet absorbent of the present invention contains the dibenzoylmethane derivative according to claim 1 as an active ingredient, but does not prevent the combination with any other ultraviolet absorbent.
  • organic UV absorbers examples include, for example, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-1 2 '-Hydroxypheninole benzotriazo mono, 2-(5'-tert-Butynole 2 '-Hydroxypheninole) benzotriazole, 2-[2'-Hydroxy 1 5 '-(1,1,3,3-tetramethylbutyl) phenyl] benzotriazole, 2- (3', 5'-di-tert-butynole-1'-hydroxyphenone) 1 5 —Black mouth Benzo triazo, 2 — (3 '— tert —Bucinole 1' —Hydro Xy-5'-methinolephenyl-1-5-chlorobenzotriazole, 2— (2'-hydroxy-1 4'octoxyphenyl) benzotriazole,
  • Examples of usable inorganic ultraviolet absorbers include zinc oxide, titanium oxide, kaolin, calcium carbonate, and talc.
  • the cosmetic having the dibenzoylmethane derivative represented by the general formula (1) of the present invention is blended with a known cosmetic base by an ordinary method to give a cream, a solution, an oil, a spray, a stick, an emulsion. , Foundation and ointment.
  • the blending amount of the dibenzoylmethane derivative represented by the general formula (1) in the cosmetic of the present invention can vary depending on the use form, and is not particularly limited, and may be present in an effective amount. Generally, it is advisable to add 0.1 to 20% by weight, preferably 0.5 to 5% by weight in the composition. Further, the dibenzoylmethane derivative represented by the general formula (1) of the present invention may be a mixture of only the dibenzoylmethane derivative itself.
  • dibenzoylmethane derivative represented by the general formula (1) of the present invention can be used together with various additives described later.
  • the base of the external preparation for skin which is a cosmetic according to the present invention, may be any as long as it is inert to the dibenzoylmethane derivative represented by the general formula (1), and may be a solid, a liquid, an emulsion, a foamy liquid, Any of gel and the like may be used.
  • the cosmetic base of the present invention for example, olive oil, camellia oil, cottonseed oil, castor oil, soybean oil, coconut oil, cocoa butter, lanolin, beeswax, carnauba wax, hardened oil, or steary oil Acid, palmitic acid, myristic acid, ascorbic acid, behenic acid, their esters, their metal salts, or higher alcohols such as decyl ethynole, oleinole, lauryl, cetinole or stearinole alcohol, synthetic oils , Mineral oil and the like.
  • Examples of the synthetic oil include squalane, glyceride monostearate, synthetic polyester oils, sorbitan monoolate, lanolin and hydrogenated products thereof, and squalane.
  • Examples of the mineral oil include paraffin, decellin, liquid paraffin, and microcrystalline wax.
  • Suitable additives include, for example, W / O or OZW type emulsifiers.
  • emulsifier a commercially available emulsifier may be used, and examples thereof include polyglycerin fatty acid ester, polyoxyethylene lanolin derivative, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene polyoxypropylene alkyl ether, and polyoxyethylene.
  • Tylene sorbitol fatty acid esters sucrose fatty acid esters, propylene glycol fatty acid esters, and the like.
  • ethyl cellulose, polyacrylic acid, gelatin, and agar thickeners can be added as needed.
  • a fragrance, a humectant, an adhesive, a preservative, an emulsion stabilizer, a medicinal ingredient and the like may be added as necessary.
  • humectant examples include glycerin, propylene glycol, sorbitol, polyethylene glycol, and sodium pyrrolidonecarboxylate.
  • Examples of the pressure-sensitive adhesive include polyvinyl alcohol, sodium carboxymethylcellulose, sodium alginate, propylene glycol ester and the like.
  • preservative examples include benzoic acid, sorbic acid, dehydroacetic acid, and p-hydroxybenzoic acid esters.
  • Examples of the solvent include ethanol, acetate, acetate, isopanol, and the like.
  • the temperature was raised to 10 ° C, and further raised to 120 ° C over 2 hours, and the methanol distilled during this time was collected. Thereafter, water was added, neutralized with dilute sulfuric acid, and further washed with water. The organic layer was concentrated to give a brown oil (80 g). Vacuum distillation is carried out, and the target compound is a yellow oil having a boiling point of 240 to 24 ° C / 130 to 16 OPa, 4_tert—butyl-4'-methoxy
  • a suspension of 60% sodium hydride (4.58 g, 1.5 equivalents) and dry tetrahydrofuran (50 ml) is stirred at 50 ° C in a stream of nitrogen gas.
  • 2—methinole 4 tert-butylacetophenone (14.45 g, 76.4 mmo 1) was added to dry tetrahydrofuran (50 ml).
  • the solution is added dropwise over 1 hour.
  • the mixture was kept at 50 ° C. for 30 minutes and then methyl 2,4-dimethoxybenzoate (15.0 g, 76.4 mmol) was added to dry tetrahydrofuran (50 ml). Is added dropwise over 1.5 hours.
  • composition of the sunscreen cream (oZw type) according to the present invention will be described.
  • the cream containing the compound of Example 1 "4'-Methoxy-2,4-dimethyldibenzoylmethane” was given to Kuchishushi under the brand name PAR SOL 17889.
  • Lithium hydroxide 100 The components A and B having the above mixing ratios were each dissolved by heating in a water bath at 80 to 82 ° C. Subsequently, the component B was gradually added to the component A while stirring, and the mixture was stirred with a homogenizer, cooled, added with the component C at 60 ° C, cooled to 30 ° C, and filled in a container.
  • a sunscreen cream (oZw type) according to the present invention was produced in the same manner as in Formulation Example 1 except that the compounds of Examples 2 to 5 were used instead of the compound of Example 1 in Formulation Example 1. .
  • component A was heated and dissolved at 80 to 85 ° C and component B at 75 ° C on a water bath.
  • the solution A was gradually added to the solution B while stirring to perform emulsification, further stirred with a homogenizer, cooled, and the component C was added at 50 ° C, cooled to 30 ° C, and filled in a container.
  • Novel dibenzoylmethane derivatives and a method for producing the same.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Emergency Medicine (AREA)
  • Materials Engineering (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Engineering & Computer Science (AREA)
  • Dermatology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Abstract

L'invention porte sur de nouveaux dérivés de dibenzoylméthane de la formule générale (1) qui présentent un grand pouvoir d'absorption des ultraviolets et une grande stabilité à la lumière, ainsi qu'une capacité à inhiber la décoloration même en présence d'un ion métallique. L'invention porte sur un procédé de préparation de ces dérivés, et sur des absorbeurs d'ultraviolets et sur des cosmétiques caractérisés en ce qu'ils contiennent ces absorbeurs. Dans cette formule, R1 à R6 représentent chacun un élément sélectionné parmi hydrogène, alkyle et alcoxy à condition que, lorsque R1 représente alkyle, R4 représente alcoxy, tandis que, lorsque R1 représente alcoxy, R4 représente alkyle, et à condition que l'un ou l'autre de R1 et R4, et l'un ou l'autre de R2 et R5 soient sélectionnés parmi les éléments précités, excepté hydrogène.
PCT/JP2000/002820 1999-04-28 2000-04-28 Derives de dibenzoylmethane, leurs procedes de preparation et d'utilisation Ceased WO2000066527A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU41450/00A AU4145000A (en) 1999-04-28 2000-04-28 Dibenzoylmethane derivatives, process for the preparation of the same and uses thereof

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP12196099 1999-04-28
JP11/121960 1999-04-28
JP2000050004 2000-02-25
JP2000/50004 2000-02-25

Publications (1)

Publication Number Publication Date
WO2000066527A1 true WO2000066527A1 (fr) 2000-11-09

Family

ID=26459197

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2000/002820 Ceased WO2000066527A1 (fr) 1999-04-28 2000-04-28 Derives de dibenzoylmethane, leurs procedes de preparation et d'utilisation

Country Status (2)

Country Link
AU (1) AU4145000A (fr)
WO (1) WO2000066527A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003081910A (ja) * 2001-09-11 2003-03-19 Chemiprokasei Kaisha Ltd ジベンゾイルメタン系誘導体、その製造方法および用途

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4387089A (en) * 1978-11-13 1983-06-07 Givaudan Corporation 4-(1,1-Dimethylethyl)-4'-methoxydibenzoylmethane
US4489057A (en) * 1975-10-03 1984-12-18 Merck Patent Gesellschaft Mit Beschraenkter Haftung U.V. Absorbing cosmetic compositions
US4562067A (en) * 1983-01-22 1985-12-31 Haarmann & Reimer Gmbh Preparation of novel dibenzoylmethane derivative sunscreen agents
US5015777A (en) * 1989-11-02 1991-05-14 Witco Corporation Process for the preparation of aromatic beta-diketones
JPH08217617A (ja) * 1995-02-15 1996-08-27 Shiseido Co Ltd 化粧料
US5672337A (en) * 1994-12-12 1997-09-30 L'oreal Amido photostabilization of dibenzoylmethane sunscreens

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4489057A (en) * 1975-10-03 1984-12-18 Merck Patent Gesellschaft Mit Beschraenkter Haftung U.V. Absorbing cosmetic compositions
US4387089A (en) * 1978-11-13 1983-06-07 Givaudan Corporation 4-(1,1-Dimethylethyl)-4'-methoxydibenzoylmethane
US4562067A (en) * 1983-01-22 1985-12-31 Haarmann & Reimer Gmbh Preparation of novel dibenzoylmethane derivative sunscreen agents
US5015777A (en) * 1989-11-02 1991-05-14 Witco Corporation Process for the preparation of aromatic beta-diketones
US5015777B1 (en) * 1989-11-02 1994-12-20 Witco Corp Process for the preparation of aromatic beta-diketones
US5672337A (en) * 1994-12-12 1997-09-30 L'oreal Amido photostabilization of dibenzoylmethane sunscreens
JPH08217617A (ja) * 1995-02-15 1996-08-27 Shiseido Co Ltd 化粧料

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003081910A (ja) * 2001-09-11 2003-03-19 Chemiprokasei Kaisha Ltd ジベンゾイルメタン系誘導体、その製造方法および用途

Also Published As

Publication number Publication date
AU4145000A (en) 2000-11-17

Similar Documents

Publication Publication Date Title
TW449610B (en) Hydroxyphenyltriazines
US5955060A (en) Bis(resorcinyl)triazines useful as sunscreens in cosmetic preparations
KR100577935B1 (ko) 레조르시닐-트리아진,이의제조방법및이를포함하는향장조성물
US5175340A (en) New liposoluble unsaturated benzalmalonate derivatives and their use as absorbers for ultraviolet radiation in cosmetics
EP0833812A1 (fr) Composes chimiques et leurs procedes de production
US5565191A (en) Cosmetic and dermatological compositions for the protection against UV radiation containing stilbene derivatives
US5332568A (en) S-triazine derivatives having light-protecting action
Gabbutt et al. Synthesis and photochromic properties of some fluorine-containing naphthopyrans
US5320833A (en) Arylpolyenecarboxylic acids and their derivatives as sunscreen agents in cosmetic preparations
US10315994B2 (en) Photostable compounds, absorbing compounds and uses thereof
CN105793239B (zh) 紫外吸收化合物、其组合物及其用途
JPS6396120A (ja) 日焼け止め化粧品
WO2000066527A1 (fr) Derives de dibenzoylmethane, leurs procedes de preparation et d'utilisation
JPH04290882A (ja) γ−ピロン誘導体、これを含有する紫外線吸収剤及び化粧料
US5146002A (en) Aroyl ketone derivative, uv ray absorber comprising the same, and cosmetic composition containing the same
Tsuge et al. Studies of Acenaphthene Derivatives. XVI. The Wittig Reaction with Acenaphthenequinone
US5191121A (en) Aroyl ketone derivative, UV ray absorber comprising the same, and cosmetic composition containing the same
US6114546A (en) Aminomethylene derivatives and ultraviolet absorbent comprising thereof
Garcia-Garibay et al. Photochemical generation, intramolecular reactions, and spectroscopic detection of oxonium ylide and carbene intermediates in a crystalline ortho-(1, 3-dioxolan-2-yl)-diaryldiazomethane
US3862951A (en) 2{40 Quinoldinyl glycerol compounds
Li et al. Functional Polymers. XXII. Ultraviolet Absorbers with 2 (2-Hydroxyphenyl) 2H-benzotriazole and 2-Hydroxybenzophenone (or Acetophenone) Chromophors in the Same Molecule
JP2001278870A (ja) アルキル化法及び新規ヒドロキシフェニルベンゾトリアゾール
JP2003081910A (ja) ジベンゾイルメタン系誘導体、その製造方法および用途
US5536453A (en) Light screening agent
JPH0717892A (ja) １，３−ブタジエニルケトン誘導体、紫外線吸収剤及びそれを配合した皮膚外用剤

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref country code: JP

Ref document number: 2000 615360

Kind code of ref document: A

Format of ref document f/p: F

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase