US3448190A - Uv absorbent compositions containing benzoyl-benzofurans - Google Patents

Uv absorbent compositions containing benzoyl-benzofurans Download PDF

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Publication number
US3448190A
US3448190A US538565A US3448190DA US3448190A US 3448190 A US3448190 A US 3448190A US 538565 A US538565 A US 538565A US 3448190D A US3448190D A US 3448190DA US 3448190 A US3448190 A US 3448190A
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United States
Prior art keywords
benzofuran
methyl
compounds
benzoyl
carbon atoms
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Expired - Lifetime
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US538565A
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English (en)
Inventor
Karl Heinrich Baron
Rainer Klink
Fritz Reiff
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Merck KGaA
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E Merck AG
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    • 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
    • C07D307/80—Radicals substituted by oxygen atoms
    • 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

Definitions

  • R represents H, CH or C H R and R each represents H, alkyl of l-l2 carbon atoms, or together an alkylene chain of 3-4 carbon atoms,
  • R, and R each represents H, alkyl of l-12 carbon atoms, or together an alkylene chain of 3-4 carbon atoms,
  • R to R are the same or different and each represents H, SO H, alkyl of 1-12 carbon atoms; and the salts thereof, said salts being selected from the group consisting of sodium, potassium, mono-, di-, and triethanolammonium salts.
  • Particularly efiective compounds are 2-benzoyl- 3 methyl-benzofuran, and 2 (2,4-dimethyl-benzoyl)- benzofuran.
  • This invention relates generally to a group of chemical compounds which are particularly useful as UV absorbents, and more particularly, to the use of these compounds in cosmetics to substantially eliminate the harmful effects of UV radiation.
  • Oxerexposure of the skin to ultraviolet rays within the ultraviolet range of about 290320 m produces radiation burns or erythema.
  • the resulting burning of the skin is known as sunburn.
  • an agent which is a strong absorber of UV radiation is desirably applied to the exposed skin.
  • Another object is to provide processes for the production of these novel and unobvious compounds.
  • a still further object is to provide cosmetic compositions which are resistant to UV radiation.
  • Still another object is to provide a process of administering the cosmetic compositions of this invention to mammals to prevent sunburn.
  • R1 is H, CH3, or C H
  • R to R are the same or different and each represent H, alkyl having 1 to 12, preferably 1 to 4 carbon atoms, more preferably methyl, or the radical combinations selected from the group consisting of R and R and R and R form a single alkylene chain having 3 to 4 carbon atoms, and
  • R to R are the same or different and each represent H, SO H, or alkyl having 1 to 12, preferably 1 to 4 carbon atoms, and the salts thereof, preferably their sodium, potassium, mono-, dior triethanolammonium salts.
  • the excellent UV absorption of the compounds of this invention are shown in the following table wherein the percent transmission of the compounds (A) Z-benzoyl- 3-methyl-benzofuran, and (B) 2-(2,4-dimethylbenzoyl)- benzofuran are tabulated as a function of wavelength 7 ⁇ .
  • the transmission is based on a 2% concentration of these compounds in a methanol solution, measured at a layer thickness of 0.005 mm.
  • the compounds of this invention are particularly suitable for cosmetic applications wherein it is desired to reduce the transmittance of UV radiation in the range of 290-320 mg.
  • the compounds of this invention are particularly suitable for use in cosmetics which are designed to protect the skin from the sun, e.g. to avoid formation of freckles. Moreover, by using a weak concentration on skin exposed to the sun, tanning of the skin is promoted without sacrifice of the protection afforded against sunburn and erythema.
  • cosmetic compositions there are generally employed about 0.5 to 10%, preferably 1 to 5% of active UV absorbent by weight of the total composition.
  • UV absorbents such as ethoxyethly p-methoxycinnamate and methyl or (A) compounds wherein R is hydrogen, R to R have the previously indicated meaning, R to R represent H, or only one group is SO H.
  • R and R are the same or different and each represent H, or CH and R to R represent H, or only one of these groups is SO3H.
  • R to R have the previously indicated meaning, and R to R represent H, SO H, or alkyl of 1-12 carbon atoms, preferably methyl.
  • R is CH R is H, or CH R and R are H, R, is H, or alkyl of l-l2 carbon atoms, R R and R are H, or one of them SO H, and R is H, or alkyl of l-12 carbon atoms.
  • R to R represent H, alkyl of l-12 carbon atoms, preferably methyl, with the provision that one of R to R is SO H.
  • R to R represent H, or alkyl of l-12 carbon atoms, and the salts of the compounds of (A) to (E), preferably their sodium, potassium, mono-, di-, or triethanolammonium salts.
  • alkyl substituents of the benzene ring of the benzofuran system or at the phenyl ring: ethyl, propyl, isopropyl, nbutyl, isobutyl, sec.-butyl, tert.-butyl, n-amyl, isoamyl, nhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl.
  • 2-benzoyl-benzofuran 2-(2,4-dimethylbenzoyl)-benzofuran, boiling point 190 C./1 mm.
  • 2-(3,4-dimethylbenzoyl)-benzofuran M.P. 10l-l03 C.
  • 2-benzoyl-S-methyl-benzofuran as well as the sulfonic acid derivatives thereof, especially 2-benzoyl-benzofuran sulfonic acid, and 2-benzoyl-3-methyl-benzofuran sulfonic acid (the sulfonic acid group being presumably located at position 5 of the benzofuran system) and their salts, preferably the sodium salts.
  • the compounds of this invention are provided for all types of applications and in all types of cosmetic compositions in which UV absorbents are conventionally employed.
  • compositions for topical administration can be described as having a form ranging from a liquid to thixotropic non- Newtonian liquids, to semi-solids such as pastes, to oily solids having, for example, a consistency like butter.
  • the compounds of this invention lacking sulfonic acid groups are soluble in mineral oils, vegetable oils, and fats, e.g. in liquid paraffin or saturated fatty acid triglycerides.
  • the compounds of Formula I which do contain a sulfonic acid group, particularly 2-benzoyl-3-methyl-benzofuran sulfonic acid and its salts, preferably its sodium, potassium, monoethanolammonium-, diethanolammonium and triethanolammonium salts, are easily soluble in water.
  • carrier for these compounds depends therefore, on whether a sulfonic acid group is present.
  • carriers usually associated with UV- resistant cosmetic preparations can be employed, such as solid or liquid parafiin, ceresin, mineral wax; vegetable or animals oils and fats such as olive oil, peanut oil, sesame oil or almond oil; cocoa butter, beeswax, mineral wax or carnauba wax, wool fat, spermaceti; fatty acids and fatty acid esters such as stearic, palmitic and oleic acids, glycerin monoor distearates, glycerin monooleate, isopropy myristate, isopropyl stearate, butylstearate; ethyl, isopropyl, cetyl, stearyl and palmityl alcohols; wetting agents of multivalent alcohols such as glycol, glycerin, sorbitol; emulsions of oil in water or water in oil systems,
  • the UV absorbents of this invention can, if desired, be used in combination with one or more of the conventional UV absorbents, such as 2-phenylbenzimidaz0l-5- sulfonic acid-sodium salt, 3,4-dimethylphenylglyoxylic acid sodium salt, 4-phenylbenzophenone, isooctyl-4- phenylbenzophenone-2'-carboxylate.
  • the conventional UV absorbents such as 2-phenylbenzimidaz0l-5- sulfonic acid-sodium salt, 3,4-dimethylphenylglyoxylic acid sodium salt, 4-phenylbenzophenone, isooctyl-4- phenylbenzophenone-2'-carboxylate.
  • the compounds of Formula I lacking a sulfonic acid group are obtained by the conventional reaction, in the presence of aluminum chloride, of the respective benzofuran-Z-carboxylic acid chloride (such as benzofuran-Z- carboxylic acid chloride, 3-methyl-, 3,5-dimethyl-, 3- methyl-5-nonyl-, 3-phenylor 5-methyl-benzofuran-2- carboxylic acid chloride), or the corresponding bromides with benzene or alkylbenzenes such as toluene, 0-, i or p-xylene, cumene, p-cymene, tert.-butylbenzene, indane or Tetraline.
  • benzofuran-Z-carboxylic acid chloride such as benzofuran-Z- carboxylic acid chloride, 3-methyl-, 3,5-dimethyl-, 3- methyl-5-nonyl-, 3-phenylor 5-methyl-benzofuran-2- carboxylic acid chloride
  • these compounds can be obtained by the reaction of the sodium salts of salicylic aldehydes or ohydroxyphenylketones (such as salicylaldehyde, S-methylsalicylaldehyde, o-hydroxyacetophenone, Z-hydroxy-S- EXAMPLE 1 Suntan oil:
  • the lipsticks thus produced provide effective protection against ultra-violet rays within the range of 290 to 340 :m
  • the use of this type of preparation is particularly advisable at high altitudes where the suns rays are intense.
  • EXAMPLE 12 (a) 38.9 g. 3-methyl-benzofuran-2-carboxylic acid chloride are dissolved in 50 ml. benzene and mixed with 28 g. aluminum chloride. The resultant mixture is refluxed for 1 hour and then decomposed with ice water. The benzene phase is separated, the aqueous phase extracted with benzene, and the solvent distilled oil from the combined benzene solutions. After the residue is distilled at 2l4-216 C./12 mm. there is obtained 43.8 g. 2-benzoy-l- 3-methyl-benzofuran, M.P. 51-52 C.
  • benzofuran 12.2 salicylaldehyde and 18.2 g. w-chloro-2,4-dimethylacetophenone are dissolved in 250 m1. ethanol and mixed with 14 g. potassium carbonate. The mixture is refluxed for 4 hours, concentrated, and poured into water. Extraction with chloroform and subsequent distillation yields 2-(2,4-dimethylbenzoyl)-benzofuran having a boiling point of C./1 mm.
  • a cosmetic composition for protection against UV- radiation comprising an intimate mixture of a cosmetically acceptable carrier and based on the weight of the total composition, about 0.5-10% by weight of a compound selected from the group consisting of a member of the formula v 4T Rs ⁇ 0/-CO wherein R represents H, CH or G l-I R and R each represents H, alkyl of 1-12 carbon atoms, or together an alkylene chain of 3-4 carbon atoms,
  • R, and R each represents H, Alkyl of 1-12 carbon atoms, or together an alkylene chain of 3-4 carbon atoms,
  • R and R are the same or different and each represents 2- 4-dode cylbenzoyl) -3 -methyl- 7 H, SO H, or alkyl of 1-12 carbon atoms; and the salts thereof, said salts being selected from the group consisting of sodium, potassium, mono-, di-, and triethanolammoniu-m salts.
  • composition as defined by claim 1 wherein said compound is selected from the group consisting of 2- benzoyl-benzofuran; 2-benzoyl-3-methyl-benzofuran; 2- (2,4 dimethylbenzoyl) benzofuran; 2 (2,4-di-methy1 benzoyl)-3-methy1-benzofuran and mixtures thereof.
  • R to R have the previously indicated meaning
  • R to R represent H or alkyl of 1-12 carbon atoms.
  • R is H, or CH R3 and R5 are H,
  • R is H, or alkyl of 1-12 carbon atoms
  • R R and R represent H or SO H
  • R is H, or alkyl or 1-12 carbon atoms.
  • R to R represent H, alkyl of 1-12 carbon atoms, with the provision that one of R to R is SO H.
  • a composition as defined by claim 1 wherein said compound is selected from the group consisting of 2- benzoyl 3 methyl-benzofuran, 2-(2,4-dimethylbenzoyl)- benzofuran, 2 (2,4 dimethylbenzoyl)-3-methyl-benzofuran, 2-benzoyl-3,S-dimethylbenzofuran, 2-benzoyl-3- methyl 5 nonyl-benzofuran, and 2-benzoyl-3-phenylbenzofuran.
  • a process for decreasing the effect of UV radiation on mammalian skin which process comprises topically adminstering a composition as defined by claim 1.
  • a process for decreasing the effect of UV radiation on mammalian skin which process comprises topically administering a composition as defined by claim 2.

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  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Dermatology (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Cosmetics (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US538565A 1965-03-30 1966-03-30 Uv absorbent compositions containing benzoyl-benzofurans Expired - Lifetime US3448190A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEM0064705 1965-03-30
DEM0067379 1965-11-24

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US (1) US3448190A (enrdf_load_stackoverflow)
BE (1) BE678535A (enrdf_load_stackoverflow)
CH (1) CH467077A (enrdf_load_stackoverflow)
DE (1) DE1492403A1 (enrdf_load_stackoverflow)
FR (1) FR1482903A (enrdf_load_stackoverflow)
GB (1) GB1063158A (enrdf_load_stackoverflow)
NL (1) NL6602929A (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3892844A (en) * 1968-12-16 1975-07-01 Hoffmann La Roche Method of protecting the skin from ultraviolet radiation
FR2493845A1 (fr) * 1980-11-12 1982-05-14 Menarini Sas Derives de benzofuranne-2 substitues utiles comme medicaments et procedes de preparation
US4606913A (en) * 1978-09-25 1986-08-19 Lever Brothers Company High internal phase emulsions
US4994263A (en) * 1984-06-27 1991-02-19 L'oreal Medicinal combination used in photochemotherapy
US5152983A (en) * 1989-11-10 1992-10-06 Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. Sunscreen compositions comprising pongomol
US5596106A (en) * 1994-07-15 1997-01-21 Eli Lilly And Company Cannabinoid receptor antagonists
US20040044059A1 (en) * 2000-03-10 2004-03-04 Pinney Kevin G. Tubulin binding ligands and corresponding prodrug constructs

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU71012A1 (enrdf_load_stackoverflow) * 1974-09-26 1976-08-19
DE19635655A1 (de) * 1996-09-03 1998-03-05 Haarmann & Reimer Gmbh Verwendung substituierter 2-Acetylbenzofurane als Riechstoffe

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3012042A (en) * 1956-12-21 1961-12-05 Belge Produits Chimiques Sa Benzofurans
US3165537A (en) * 1963-07-08 1965-01-12 Jurd Leonard Preparation of benzofuran derivatives

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3012042A (en) * 1956-12-21 1961-12-05 Belge Produits Chimiques Sa Benzofurans
US3165537A (en) * 1963-07-08 1965-01-12 Jurd Leonard Preparation of benzofuran derivatives

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3892844A (en) * 1968-12-16 1975-07-01 Hoffmann La Roche Method of protecting the skin from ultraviolet radiation
US4606913A (en) * 1978-09-25 1986-08-19 Lever Brothers Company High internal phase emulsions
FR2493845A1 (fr) * 1980-11-12 1982-05-14 Menarini Sas Derives de benzofuranne-2 substitues utiles comme medicaments et procedes de preparation
US4994263A (en) * 1984-06-27 1991-02-19 L'oreal Medicinal combination used in photochemotherapy
US5152983A (en) * 1989-11-10 1992-10-06 Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. Sunscreen compositions comprising pongomol
US5596106A (en) * 1994-07-15 1997-01-21 Eli Lilly And Company Cannabinoid receptor antagonists
US5747524A (en) * 1994-07-15 1998-05-05 Eli Lilly And Company Cannabinoid receptor antagonists
US20040044059A1 (en) * 2000-03-10 2004-03-04 Pinney Kevin G. Tubulin binding ligands and corresponding prodrug constructs
US7091240B2 (en) * 2000-03-10 2006-08-15 Oxigene, Inc. Tubulin binding ligands and corresponding prodrug constructs

Also Published As

Publication number Publication date
BE678535A (enrdf_load_stackoverflow) 1966-09-28
DE1492403A1 (de) 1969-12-04
GB1063158A (en) 1967-03-30
CH467077A (de) 1969-01-15
FR1482903A (fr) 1967-06-02
NL6602929A (enrdf_load_stackoverflow) 1966-10-03

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