US3499914A - Benzofuran derivatives suitable as uv-absorbents - Google Patents

Benzofuran derivatives suitable as uv-absorbents Download PDF

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Publication number
US3499914A
US3499914A US638762A US3499914DA US3499914A US 3499914 A US3499914 A US 3499914A US 638762 A US638762 A US 638762A US 3499914D A US3499914D A US 3499914DA US 3499914 A US3499914 A US 3499914A
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US
United States
Prior art keywords
dimethylphenyl
benzofuran
acid
oil
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US638762A
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English (en)
Inventor
Rainer Klink
Karl-Heinz Baron
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Merck KGaA
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E Merck AG
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Publication date
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero 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
    • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C07D307/84—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C07D307/85—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 2

Definitions

  • This invention relates to novel derivatives of hemefuran, and more particularly to suntan preparations based n such derivatives.
  • An object of this invention is to provide effective and novel compounds suitable as improved UV- absorbents.
  • Another object is to provide processes and intermediates for the production of the novel compounds.
  • Still another object is to provide cosmetic preparations for the prevention of sunburn.
  • a still further object is to provide a process for absorbing and/or screening out UV-radiation by directing a source of UV-radiation on an object or mammal treated with a compound of this invention.
  • R R and R represent hydrogen or methyl, with the provision that at least two of R R and R representhydrogen.
  • Patented ru to, rare is tabulated below as a function of wavelength for the following compounds:
  • compositions For the production of suntan compositions, about 0.5 to 10, preferably 1 to 5 parts by weight of the novel active agents of this invention are incorporated with parts by weight of a cosmetically acceptable carrier.
  • Suitable cosmetically acceptable carriers are, for example, hydrocarbons, such as solid or liquid paraffin, ceresin, montan wax; vegetable or animal oils and fats,
  • t such as olive oil, peanut oil, sesame oil, or almond oil; cocoa butter, beesu mineral Wax or carnauba wax, wool fat, spermaccti; fatty acids and fatty acid esters, such as stearic, palmitic, and oleic acids, glycerin monoor distearate, glycerin monooleate, isopropyl myristate, isopropyl stearate, butyl stearate; and ethyl, isopropyl, cetyl, stearyl, and palmityl alcohols.
  • Moisturizing agents such as polyvalent alcohols, e.g.
  • glycol, glycerine and sorbitol are useful additives.
  • liquids either oil-inwater or water-in-oil systems can be used, using commercially available emulsifiers of the non-ionic, cationic, anionic, or ampholytic types.
  • thickeners such as methyl, ethyl, or carboxymethyl cellulose, polyacrylic acid, tragacanth, agaragar, or gelatin.
  • additives such as insect repellents, aerosol propellants, perfumes, preservatives, or physiologically compatible dyestuffs.
  • Typical insect repellents are, for instance, the N,N-diethyl amides of caprylic and m-toluic acids, dimethyl phthalate, 2- ethyl-l,3-hexanediol, and butoxy polypropylene glycol.
  • Suitable aerosol propellants comprise trichlorofiuoromethane and dichlorodifiuoromethane, furthermore nitrogen, carbon dioxide, propane, and butane.
  • an effective amount of the active agent must be applied to the skin, this amount varying with the intensity and duration of the UV source, as Well as with the complexion of the persons skin. In general, however, it is estimated that an application of about 10 to 100 mg. of active agent per 100 squart centimeters of skin surface should prevent sunburn for approximately 24 hours under direct midday summer light radiating in the northern temperate zone.
  • the agents of this invention can also be incorporated with one or more other UV-absorbents, such as Z-phenylbenzimidazole-5-sulfonic acid sodium salt, 3,4-dimethylphenylglyoxylic acid sodium salt, 4-phenylbenzophenone, and isooctyl-4-phenylbenzophenone-2carboxylate.
  • UV-absorbents such as Z-phenylbenzimidazole-5-sulfonic acid sodium salt, 3,4-dimethylphenylglyoxylic acid sodium salt, 4-phenylbenzophenone, and isooctyl-4-phenylbenzophenone-2carboxylate.
  • the compounds of Formula I can be produced by standard reactions. For example, they can be obtained by reacting phenol (or 0-, m-, or p-cresol) with chloroacetic acid to form phenoxyacetic acid (or o-, m-, or ptolyloxyacetic acid); conversion of the thus-obtained product (for example, with thionyl chloride) into the corresponding acid halogenides "(for example, phenoxyacetyl chloride);, Priedel-Crafts reaction with m-Xylene (for example, in the presence of aluminum chloride) to obtain 2,4-dimethyl-w-phenoxyacetophenone (or 2,4-dimethyl-o, -m-, or -p-tolyloxyacetophenone); and several hours of heating the same with polyphosphoric acid to temperatures between l00 and 170 C,, preferably about 130 C., rearrangement taking place to 2-(2,4-dimethylphenyl)--benzofurans.
  • reaction products can likewise be obtained by re- I acting salicylaldehyde (or 3-, 4-, or S-rnethyl-salicylalde hyde) with lower alkyl esters of wbrOmQ-(ZAdimethyI- phenyl)-acetic acid (preferably the methyl or ethyl ester thereof), subsequent saponification of the thus-obtained 2-(2,4-dimethylphenyl)-3-hydroxy 2,3 dihydrobenzofuran-Z-carboxylic acid esters, as well as decarboxylation and dehydration.
  • lower alkyl esters of wbrOmQ-(ZAdimethyI- phenyl)-acetic acid preferably the methyl or ethyl ester thereof
  • the compounds are also useful for technical and industrial uses. Chemical compositions and articles of manufacture can be provided which are resistant to UV radiation.
  • the compounds of the invention are particularly advantageous for the inhibition of UV-initiated deterioration of organic polymers, both natural and synthetic, including polyvinyl chloride, poly methacrylates, cellulose acetate, polystyrene, polyvinyl acetate, and polyolefins such as polyethylene and polypropylene, and of common lacquers based on nitrocellu- 1 lose, airor oven-dried polyesters, epoxide resins, or polyol-diisocyanates
  • Important novel intermediates in the process of manufacture of the novel benzofurans include:
  • EXAMPLE A (a) 280 g. phenoxyacetyl chloride are dissolved in 830 ml. m-xylene; 155 g. aluminum chloride are added, and the mixture is heated for one hour under reflux conditions. After ice Water is added to the reaction mixture, the resultant xylene phase is separated, and the resultant aqueous phase is extracted with benzene. The solvents are distilled from the combined solutions, and the residue is distilled at 205-210" C./ 12 mm. There is thus obtained 273 g. of a-phenoxy-2,4-dirnethylacetophenone.
  • EXAMPLE B (a) 25 g. salicylaldehyde and 50 g. u-bromo-(2,4-dimethylphenyl)-acetic acid ethyl ester are boiled for 4 hours in 100 ml. methylethyl ketone with the addition of 32 g. anhydrous potassium carbonate. The reaction mixture is cooled, diluted with ether, and filtered from the undissolved salt. The solvent is distilled from the filtrate, and the residue is degasified on a steam bath by a water jet aspirator.
  • R1 (EH3 wherein: R R and R represent hydrogen or methyl
  • a compound as defined by claim 1 wherein said compound is 2-(2,4-dimethylphenyl)-benzofuran.
  • a compound as defined by claim 1 wherein said compound is 2 (2,4 dimethylphenyl) S-methyl-benzofuran.
  • a compound as defined by claim 1 wherein said compound is 2 (2,4 dimethylphenyl) 6-methyl-beuzofuran.
  • a compound as defined by claim 1 wherein said compound is 2 (2,4 dimethylphenyl) 7-methy1-benzofuran.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Dermatology (AREA)
  • Cosmetics (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
US638762A 1966-05-20 1967-05-16 Benzofuran derivatives suitable as uv-absorbents Expired - Lifetime US3499914A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEM0069570 1966-05-20

Publications (1)

Publication Number Publication Date
US3499914A true US3499914A (en) 1970-03-10

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US638762A Expired - Lifetime US3499914A (en) 1966-05-20 1967-05-16 Benzofuran derivatives suitable as uv-absorbents

Country Status (9)

Country Link
US (1) US3499914A (enExample)
BE (1) BE698629A (enExample)
CH (1) CH480074A (enExample)
DE (1) DE1642090A1 (enExample)
ES (1) ES340745A1 (enExample)
FR (1) FR1548293A (enExample)
GB (1) GB1114030A (enExample)
NL (1) NL6706409A (enExample)
SE (1) SE320387B (enExample)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2238644A1 (de) * 1971-08-13 1973-02-22 Hoechst Ag Benzofuran-derivate, verfahren zu deren herstellung und verwendung als optische aufheller
US4665112A (en) * 1986-01-02 1987-05-12 General Electric Company Ultraviolet radiation stabilized polyphenylene ether resins
US4798427A (en) * 1982-03-24 1989-01-17 Sevendart Limited, A Limited Company Of U.K. Apparatus for use in sunbathing
US5468470A (en) * 1993-08-06 1995-11-21 3V Inc. Benzofuran derivatives and the use thereof as stabilizers against UV radiations
US6764693B1 (en) 1992-12-11 2004-07-20 Amaox, Ltd. Free radical quenching composition and a method to increase intracellular and/or extracellular antioxidants
CN104237150A (zh) * 2014-10-13 2014-12-24 深圳市星源材质科技股份有限公司 有机溶液中石蜡油浓度的检测方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU71012A1 (enExample) * 1974-09-26 1976-08-19
LU85544A1 (fr) * 1984-09-19 1986-04-03 Cird Derives heterocycliques aromatiques,leur procede de preparation et leur application dans les domaines therapeutique et cosmetique
US5362481A (en) * 1993-03-05 1994-11-08 3V Inc. Benzofuran derivatives and the use thereof as stabilizers against UV radiations
IT1278535B1 (it) * 1995-12-14 1997-11-24 3V Sigma Spa Derivati di benzofurano e loro uso come fotostabilizzanti e filtri solari

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE676103C (de) * 1933-03-31 1939-05-25 I G Farbenindustrie Akt Ges Strahlungsschutzmittel

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE676103C (de) * 1933-03-31 1939-05-25 I G Farbenindustrie Akt Ges Strahlungsschutzmittel

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2238644A1 (de) * 1971-08-13 1973-02-22 Hoechst Ag Benzofuran-derivate, verfahren zu deren herstellung und verwendung als optische aufheller
US4798427A (en) * 1982-03-24 1989-01-17 Sevendart Limited, A Limited Company Of U.K. Apparatus for use in sunbathing
US4665112A (en) * 1986-01-02 1987-05-12 General Electric Company Ultraviolet radiation stabilized polyphenylene ether resins
US6764693B1 (en) 1992-12-11 2004-07-20 Amaox, Ltd. Free radical quenching composition and a method to increase intracellular and/or extracellular antioxidants
US5468470A (en) * 1993-08-06 1995-11-21 3V Inc. Benzofuran derivatives and the use thereof as stabilizers against UV radiations
CN104237150A (zh) * 2014-10-13 2014-12-24 深圳市星源材质科技股份有限公司 有机溶液中石蜡油浓度的检测方法

Also Published As

Publication number Publication date
BE698629A (enExample) 1967-11-20
GB1114030A (en) 1968-05-15
CH480074A (de) 1969-10-31
NL6706409A (enExample) 1967-11-21
FR1548293A (enExample) 1968-12-06
DE1642090A1 (de) 1971-05-19
SE320387B (enExample) 1970-02-09
ES340745A1 (es) 1968-09-16

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