US3875198A - Sun-screening compounds I - Google Patents

Sun-screening compounds I Download PDF

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Publication number
US3875198A
US3875198A US465247A US46524774A US3875198A US 3875198 A US3875198 A US 3875198A US 465247 A US465247 A US 465247A US 46524774 A US46524774 A US 46524774A US 3875198 A US3875198 A US 3875198A
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US
United States
Prior art keywords
coo
sun
acid
skin
compound according
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Expired - Lifetime
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US465247A
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English (en)
Inventor
Albert Frederick Strobel
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ISP Investments LLC
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GAF Corp
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
Priority to US465247A priority Critical patent/US3875198A/en
Application filed by GAF Corp filed Critical GAF Corp
Priority to CA217,455A priority patent/CA1051917A/en
Priority to GB83075A priority patent/GB1434901A/en
Priority to JP50013931A priority patent/JPS50140641A/ja
Priority to DE19752509646 priority patent/DE2509646A1/de
Priority to CH288175A priority patent/CH616841A5/de
Publication of US3875198A publication Critical patent/US3875198A/en
Application granted granted Critical
Priority to FR7513031A priority patent/FR2268788B1/fr
Assigned to CHASE MANHATTAN BANK, THE NATIONAL ASSOCIATION reassignment CHASE MANHATTAN BANK, THE NATIONAL ASSOCIATION SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DORSET INC. A CORP OF DELAWARE
Assigned to GAF CHEMICALS CORPORATION reassignment GAF CHEMICALS CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE ON 04/11/1989 Assignors: DORSET INC.
Assigned to DORSET INC., A DE CORP. reassignment DORSET INC., A DE CORP. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE APRIL 10, 1989 Assignors: GAF CORPORATION, A DE CORP.
Assigned to CHASE MANHATTAN BANK (NATIONAL ASSOCIATION), THE reassignment CHASE MANHATTAN BANK (NATIONAL ASSOCIATION), THE SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GAF CHEMICALS CORPORATION, A CORP. OF DE
Assigned to ISP INVESTMENTS INC. reassignment ISP INVESTMENTS INC. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE ON 06/06/1991 Assignors: ISP 3 CORP.
Assigned to ISP 3 CORP reassignment ISP 3 CORP ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: GAF CHEMICALS CORPORATION
Anticipated expiration legal-status Critical
Assigned to SUTTON LABORATORIES, INC., GAF CHEMICALS CORPORATION, GAF BUILDING MATERIALS CORPORATION reassignment SUTTON LABORATORIES, INC. RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: CHASE MANHATTAN BANK, THE (NATIONAL ASSOCIATION)
Expired - Lifetime legal-status Critical Current

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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
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A61K8/445—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof aromatic, i.e. the carboxylic acid directly linked to the aromatic ring

Definitions

  • R and R are independently straight or branched chain lower alkyl; Y is C -C alkylene; X is R COO, HOOCR COO' or OOC--R- COO', where R is alkyl of l to 18 carbon atoms and R is alkylene of l to 18 carbon atoms; and n is 1 when X is R COO or I-IOOCR COO or n is 2 when X is OOCR COO.
  • Sucn compounds show absorption of ultraviolet light in the range of 290-315 mu and have good substantivity on the skin.
  • lower alkyl denotes a univalent saturated branched or straight hydrocarbon chain containing from 1 to 6 carbon atoms.
  • Representative of such lower alkyl groups are thus methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. butyl, tert. butyl, pentyl, isopentyl,
  • alkylene of 2 to 6 carbon atoms denotes a divalent saturated straight or branched hydrocarbon obtained by removing a hydrogen atom from the lower alkyl defined above, excluding methyl.
  • alkyl of l to 18 carbon atoms denotes a univalent saturated branched or straight hydrocarbon chain containing from 1 to 18 carbon atoms.
  • Representative of such alkyl groups are thus methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. butyl, tert. butyl, pentyl, isopentyl, neopentyl, tert.
  • alkylene of 1 to 18 carbon atoms denotes a divalent saturated branched or straight hydrocarbon chain obtained by removing a hydrogen atom from the alkyl defined above.
  • R and R are C,-C straight or branched chain alkyl.
  • anion, X is derived from a higher saturated aliphatic carboxylic acid, such as a C -C saturated ali-.
  • R R and Y are as defined above, and R is straight or branched chain alkyl of 7 to 17 carbon atoms.
  • the anion, X is derived from a saturated aliphatic dicarboxylic acid (I-IOOCR -COOH), and n is 1 or 2, preferably 2.
  • the double salt of the dicarboxylic acid is preferred over the mono-salt, since the double salt shows improved affinity for the skin.
  • Such compounds have the formula (III):
  • the dicarboxylic acid is one where R, is lower alkylene, and most preferably alkylene of 1 to 4 carbon atoms.
  • Dialkylaminoalkyl esters of diakylamino benzoic acid are proposed in U.S. Pat. No. 820,830, but such compounds are strong bases (pH 11-12 in aqueous solution) and hence would be too irritating and harmful to the eyes and skin for application to the skin or hair.
  • the compounds of formula (I) can be prepared by reacting dialkylaminoalkyl p-dialkylaminobenzoate with the desired aliphatic monoor dicarboxylic acid according to processes A or B.
  • n is one and R, R R and Y are as defined above.
  • dialkylaminoalkyl p-dialkylaminobenzoate is known, e.g. see US. Pat. No. 820,830, and can conveniently be made by alkylating an alkyl paminobenzoate with an alkyl halide in an organic solvent, and reacting the resulting alkyl pdialkylaminobenzoate with a dialkylaminoalkanol.
  • dialkylaminoalkyl p-dialkylaminobenzoate may be:
  • the aliphatic monocarboxylic acid R COOI-I used in reaction (A) may be acetic acid, nor i-propanoic acid, nor i-valeric acid, caprylic acid, octanoic acid, capric acid, lauric acid, my
  • the aliphatic dicarboxylic acid R (COOI-I) used in reaction (B) may be malonic acid, succinic acid, adipic acid, 2, 2'-dimethylglutaric acid, suberic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid and nonadecanedioic acid.
  • N,N-dimethyl-N-(p-dimethylaminobenzoyloxyethyl)-ammonium acetate N,N-dimethyl-N-(p-dimethylaminobenzoyloxybutyl)-ammonium propionate N,N-dimethyl-N-(p-diethylaminobenzoyloxyethyl )-ammonium stearate N,N-dihexyl-N-(p-dipropylaminobenzoyloxyethyl)-ammonium acetate 9.
  • the sun-screening agents of formula (I) are applied to the skin in the form of a sunscreen composition
  • a sunscreen composition comprising the compound of formula (I) and a cosmetically acceptable diluent or carrier.
  • cosmetically acceptable diluent or carrier denotes a nontoxic, non-irritating substance which when mixed with the compound of formula (I) makes the compound more suitable to be applied to the skin.
  • the compositions can thus be solutions, oils, lotions, ointments, liquid or solid creams, aerosols and the like.
  • the sun-screening composition of the invention is formed by admixing, dissolving or dispersing the sunscreening compound of formula (I) into the desired cosmetically acceptable diluent or carrier.
  • Solutions are formed by dissolving the sun-screening compound in water or other solvent.
  • Oils are prepared by using vegetable and/or mineral oils, such as sesame oil and/or white mineral oil as the cosmetically acceptable diluent or carrier.
  • Creams may be prepared by adding lanolin and a suitable absorbent base to the vegetable and/or mineral oils. Oil-in-water emulsions may be employed as the vehicle to form lotions, but are not preferred,
  • An alcoholic lotion containing an alcohol, such as ethanol or isopropanol, and a film-forming substance as the cosmetically acceptable diluent or carrier is preferred, since this tends to provide more permanent protection even after exposure of the skin to water.
  • Preferred film-forming agents for alcoholic lotions are castor oil, lauryl and oleyl alcohols, glycol and glyceryl ricinoleates, glycol and glyceryl laurates, glycol and glyceryl oleates, mannitol and sorbitol oleate, laurate, or ricinoleate, butyl stearate, ethyl oleate, laurate, orricinoleate and methyl oleate, laurate or ricinoleate.
  • Perfumes, anti-oxidants, colorants, insect-repellants and the like may be included in the sun-screening composition, if desired.
  • the sun-screening composition of the invention contains an effective amount of the sun-screening compound of formula (I) to prevent erythema.
  • an amount of 0.2 to 10 percent, preferably 1-3 percent, by weight of the total composition, of the sun-screening compound of formula (I) may be used.
  • the composition is applied topically every few hours, as needed, in the same manner as conventional sun-screening compositions.
  • the compounds of the invention may also be used to protect blond and light-colored hair from the deleterious effects of ultraviolet radiation.
  • the compounds of formula (I) are admixed with the cosmetically acceptable diluent or carrier to provide a composition containing from 0.05 to 10 percent by weight, preferably 2 to 5 percent by weight, of the compound of formula(I).
  • the hair-protection compositions are applied to the hair in the same manner as a conventional hair lotion, hair cream or hair tonic, before exposure to ultraviolet radiation, and thereafter as desired.
  • Cosmetically' acceptable diluents or carriers used in such conventional hair preparations may be used in the hair-protection composition of the invention.
  • a 2 percent by weight solution of the candidate compound in 50 percent ethanol-5O percent water is then rubbed into the skin, dried in air, and part of the airdried surface is rinsed with water for two minutes. Examination of the rinsed and unrinsed sections of skin was then made in UV (black) light. The retention of the UV absorber on the skin is determined by observing TEST PROCEDURE FOR HAIR
  • the substantivity of the candidate compound to hair is tested in the following manner.
  • the candidate compound is dissolved in 100 mls. of water to provide an 0.1 percent by weight aqueous solution. gms. of hair is immersed in the resulting aqueous solution, stirred for one-half hour, removed, rinsed and dried.
  • the UV absorption of the aqueous solution into which the hair was immersed is measured both before and after the immersion of the hair in the solution using the same technique described above.
  • the percent of the compound left after rinsing determines the amount of substantivity.
  • aqueous solution containing the acetate was diluted with water to a 5 percent by weight aqueous solution. This was applied to skin by rubbing. Skin so treated, on exposure to sun, was protected against burning in contrast to untreated skin. The product also showed resistance to removal by water treatment in contrast to a commercially available UV agent having the formula:
  • the maximum absorption of the acetate is at 3 13 m .1..
  • Example 2 This was then treated as in Example 1 with dimethylaminoethanol and then with glacial acetic acid to yield an aqueous solution of N,N-dimethyl-N-(pdimethylaminobenzoyloxyethyl)-ammonium acetate.
  • n cooy-u-a x' R where R and R are independently straight or branched chain lower alkyl; Y is C C alkylene; X is R --COO HOOCR COO* or OOCR- COO where R is alkyl of l to 18 carbon atoms and R is alkylene of 1 to 18 carbon atoms; and n is 1 when X is R -COO or HOOCR.,COO' or n is 2 when X is OOCR -COO (H C N 2.
  • R and R are straight or branched chain alkyl of 1 to 3 carbon atoms.
  • R is straight or branched chain alkyl of 7 to 17 carbon 40 atoms.
  • the compound according to claim 1 which is 10.
  • the compound according to claim 1 which is i 6 C0QC H N(CH 2 l l C0O 11.
  • the compound according to claim 1 which is 9 9 (H C) N COOC H E(CH 2 CH COO 12.
  • the compound according to claim 1 which is 0 (11 C) N COOC H liI (CH 2 C H COO 13.
  • the compound according to claim 1 which is G 6 COOC H Ii1(CH 2 C H COO 14.
  • the compound according to claim 1 which is 16.
  • the compound according to claim 1 which is a ca cu coocu cn coo- 2 2 (u c n ooc u u (ca 2 665 (u c 2N cooc n r ucn 2 cn coo

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)
US465247A 1974-04-29 1974-04-29 Sun-screening compounds I Expired - Lifetime US3875198A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US465247A US3875198A (en) 1974-04-29 1974-04-29 Sun-screening compounds I
CA217,455A CA1051917A (en) 1974-04-29 1975-01-07 Carboxylate salts of alkanolamine esters of para dialkylaminobenzoic acid and their use as sun-screening agents
GB83075A GB1434901A (en) 1974-04-29 1975-01-08 Quaternary compounds of dialkyl benzoic acid derivatives and their use as sun-screening agents
JP50013931A JPS50140641A (enrdf_load_stackoverflow) 1974-04-29 1975-01-31
DE19752509646 DE2509646A1 (de) 1974-04-29 1975-03-05 Neue derivate der dialkylaminoalkyl-p-dialkyl-aminobenzoesaeureester
CH288175A CH616841A5 (enrdf_load_stackoverflow) 1974-04-29 1975-03-06
FR7513031A FR2268788B1 (enrdf_load_stackoverflow) 1974-04-29 1975-04-25

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US465247A US3875198A (en) 1974-04-29 1974-04-29 Sun-screening compounds I

Publications (1)

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US3875198A true US3875198A (en) 1975-04-01

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ID=23847019

Family Applications (1)

Application Number Title Priority Date Filing Date
US465247A Expired - Lifetime US3875198A (en) 1974-04-29 1974-04-29 Sun-screening compounds I

Country Status (7)

Country Link
US (1) US3875198A (enrdf_load_stackoverflow)
JP (1) JPS50140641A (enrdf_load_stackoverflow)
CA (1) CA1051917A (enrdf_load_stackoverflow)
CH (1) CH616841A5 (enrdf_load_stackoverflow)
DE (1) DE2509646A1 (enrdf_load_stackoverflow)
FR (1) FR2268788B1 (enrdf_load_stackoverflow)
GB (1) GB1434901A (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4840788A (en) * 1986-07-15 1989-06-20 Ici Americas Inc. Nonalcoholic sunscreen gel
US6607735B2 (en) 2000-12-21 2003-08-19 Johnson & Johnson Consumer Companies, Inc. Method for reducing the appearance of dark circles under the eyes
US20040191206A1 (en) * 2000-10-02 2004-09-30 Curtis Cole Methods for reduction of inflammation and erythema
US20040213754A1 (en) * 2000-10-02 2004-10-28 Cole Curtis A. Method for cleansing sensitive skin using an alkanolamine
US20050238730A1 (en) * 2001-11-21 2005-10-27 Agnes Le Fur Compositions comprising an ethanolamine derivative and organic metal salts
US7396526B1 (en) 1998-11-12 2008-07-08 Johnson & Johnson Consumer Companies, Inc. Skin care composition
CN109232285A (zh) * 2018-10-16 2019-01-18 新乡学院 一种具有抗菌活性的苯佐卡因双取代衍生物的合成方法和应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3536723A (en) * 1966-09-27 1970-10-27 Menarini Soc In Accomandita Se P - (2 - alkyloxy - benzoyl) - aminobenzoates of n - dialkylamine - alkyl and their quaternary salts

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3536723A (en) * 1966-09-27 1970-10-27 Menarini Soc In Accomandita Se P - (2 - alkyloxy - benzoyl) - aminobenzoates of n - dialkylamine - alkyl and their quaternary salts

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4840788A (en) * 1986-07-15 1989-06-20 Ici Americas Inc. Nonalcoholic sunscreen gel
US7396526B1 (en) 1998-11-12 2008-07-08 Johnson & Johnson Consumer Companies, Inc. Skin care composition
US20040191206A1 (en) * 2000-10-02 2004-09-30 Curtis Cole Methods for reduction of inflammation and erythema
US20040213754A1 (en) * 2000-10-02 2004-10-28 Cole Curtis A. Method for cleansing sensitive skin using an alkanolamine
US6607735B2 (en) 2000-12-21 2003-08-19 Johnson & Johnson Consumer Companies, Inc. Method for reducing the appearance of dark circles under the eyes
US20030202951A1 (en) * 2000-12-21 2003-10-30 Curtis Cole Method for reducing the appearance of dark circles under the eyes
US20050238730A1 (en) * 2001-11-21 2005-10-27 Agnes Le Fur Compositions comprising an ethanolamine derivative and organic metal salts
CN109232285A (zh) * 2018-10-16 2019-01-18 新乡学院 一种具有抗菌活性的苯佐卡因双取代衍生物的合成方法和应用

Also Published As

Publication number Publication date
FR2268788B1 (enrdf_load_stackoverflow) 1977-04-15
JPS50140641A (enrdf_load_stackoverflow) 1975-11-11
FR2268788A1 (enrdf_load_stackoverflow) 1975-11-21
CA1051917A (en) 1979-04-03
DE2509646A1 (de) 1975-11-13
CH616841A5 (enrdf_load_stackoverflow) 1980-04-30
GB1434901A (en) 1976-05-12

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