CA1064049A - Salts of alkanolamine esters of para dialkylaminobenzoic acid and their use as sun-screening agents - Google Patents
Salts of alkanolamine esters of para dialkylaminobenzoic acid and their use as sun-screening agentsInfo
- Publication number
- CA1064049A CA1064049A CA217,454A CA217454A CA1064049A CA 1064049 A CA1064049 A CA 1064049A CA 217454 A CA217454 A CA 217454A CA 1064049 A CA1064049 A CA 1064049A
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- Prior art keywords
- compound according
- carbon atoms
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- alkyl
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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
Abstract
Abstract of the Disclosure Sun-screening compounds, useful to protect the skin and hair against deleterious effects upon exposure to ultra-violet radiation, of the formula:
where R1 and R2 are independently straight or branched chain lower alkyl; Y is C2 - C6 alkylene; R3 is alkyl of 8 to 18 carbon atoms; X is a cosmetically acceptable mono- or divalent anion; and n is 1 or 2 to provide an electrically neutral compound.
Sun-screening compositions containing such compounds and a cosmetically acceptable diluent or carrier, and methods of using such compositions, are also disclosed.
where R1 and R2 are independently straight or branched chain lower alkyl; Y is C2 - C6 alkylene; R3 is alkyl of 8 to 18 carbon atoms; X is a cosmetically acceptable mono- or divalent anion; and n is 1 or 2 to provide an electrically neutral compound.
Sun-screening compositions containing such compounds and a cosmetically acceptable diluent or carrier, and methods of using such compositions, are also disclosed.
Description
The present invention relates to sun-screen:ing compositions, me~.hods of using the same and novel sun-screening compounds.
Ultraviolet radiation 011 -the skin, such as from the SU117 of a wavelength of 290 - 313 mu is known to produce erythema, particularly in :Eair skinned subjects. On the other hand, ultraviolet radiation of from 315 -320 mus to 350 - 400 mu promotes a tanning of the skin. To be effective, a sun-screening composition must at least remove substantially all of the burning rays, and in many instances a good portion of the tanning rays.
It is,therefore, an object of this invention to provide novel sun-screening compounds that are effective to prevent erythema.
It is a further object of the invention to provide new sun-screening compositions containing the sun-screening compounds of the invention.
These objects are provided by the provision of a sun-screening compound of formula (I):
~I) \ ~ COOY - N - R X
n vhere Rl and R2 are independently straight or branched chain lower alkyl;
~ 20 Y is C2 - C6 alkylene; R3 is alkyl of 8 to 18 carbon atoms; X is a cosmeti-: cally acceptable mono- or divalent anion; and n is l or 2 to provide an elec--~ trically neutral compound.
. The present invention also provides a method of protecting skin or hair from ultraviolet radiation, which comprises applying to the skin or hair a composition containing an effective amount of a compound of -formula I as set forth in above.
Preferably~ X is halide, sulfa~e, phosphate~ p-(lower ~' ,~
.
alkyl) benzene sulfonate, benzoate~ R~-C00 ~ , llOOC-R5-C00 ~ or 9 OOC-R5-C00 ~ , where R~ is alkyl of 1 to 18 carbon atoms and R5 is alkylene of 1 to 18 carbon atoms. Such compounds show absorption of ultraviolet light in the range o-f 290 -315 mu and have good substantivity on the skin. The compounds of formula (I) are water soluble, but the degree of water solubility decreases as the number of carbon atoms in R3 - and/or R~ and/or R5 increase.
The term 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, neopentyl, tert.pentyl, hexyl, and the like. The term 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.
The terms alkyl of 1 to 18 carbon atoms and alkyl of 8 to 18 carbon atoms denote a univalent saturated branched or straight hydrocarbon chain containing from 1 to 18 carbon atoms or 8 to 18 carbon atoms, respectively. Representative of such alkyl groups are thus methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.butyl, tert.butyl, pentyl, isopentyl, neopentyl, tert.pentyl, hexyl, isohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and the like. The terms alkylene of 1 to 18 carbon atoms and alkylene of ~ to 1~ carbon at~ms denote a '' ~, - 2 -, . . . .
f~
divalent saturated branched or straight hydrocarboll chain obtained by removing a hydrogen atom from the alkyl defined above The term halide denotes chloride, bromide, iodide and fluoride, preferably chloride or bromide.
In a preferred embodiment of the inventionJ Rl and R2 are Cl-C3 straight or branched chain alkyl.
It is further preferred to employ compounds in which R3 is alkyl of 11 to 18 carbon atoms, because the more carbon 10 atoms in R3, the greater the substantivity of the compound of formula (I).
It is further preferred to employ compounds in which the anion, R4-COO Q, is alkyl of 7 to 17 carbon atoms, e.g.
as derived from a higher saturated aliphatic carboxylic acid, such as a C8-C18 saturated aliphatic monocarboxylic acid, since such compounds will have reduced water-solubility and thus resist removal from the skin by water washing.
In another preferred embodiment of the invention, the anion, X, is derived from a saturated aliphatic dicarboxylic 20 acid (HOOC-R5-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 ~Ia):
_ (la) / ~ COOY-N - ~ Z-R5-CO0 ~
.' ~d , . ... : ~ : : ,, . , . , . - . -where Rl, R2, R3~ and R and n are as defined abovel Z
i~ -COOH or -CO ~, and n ls 1 when Z i~ COOH and n is 2 when Z is -COO . Preferably~ the no carb~xylic acid is one wherein R5 is lower alkylene, and most pre~erably alkylene Or 1 to 4 carbon atoms.
Compounds which are actlve as sun-screenlng agents are known and include such widely diverse compound~ as dibenzyl-acetone, quinine sulfate and ethyl umbelliferone. Alkyl esters of p-dlalkylaminobenzolc acid have also heen propo~ed for use as sun-screening agents ln U.S. Patents 2,853,423;
3,403,207; and 3,479~428. In view of thls highly empirical nature of the ability o~ a compound selectiYely to absorb ultraviolet radiation in the narrow range of 290 to 315 mu, it was not expected that the compound~ of formula (I) would be useful as sun-screening agents Mono-quaternary ammonium compounds use~ul as intermediates in the preparation o~ therapeutlc agents have been proposed ln U.S. Patent 2,717,905. So far as we are aware9 the sun-screenin~ compound~ of formula (I~ are novel.
The quaternary salts of formula (I) where ~ is hallde can be prepared by reacting at room temperature~ with or without a ~olventg ap~roxlmately stoichiometric quantitles o~ a dialkylaminoalkyl p-dialklaminobenzoate (II) and an alkyl halide (III) to form the quaternary ammonium hallde (IV), Z5 acoordlng to process (A) be.ow:
-- 4 ~
, . .
N ~ ~ ~ OOY- < + R3-hal~de (II) (III) COOY ~ ~ ~ hallde~
where Rl, R2 and R3 are de~ne~ above, and ~'halide" is chloride, bromlde, lodide or ~luroide, pre~erably chloride or bromide.
Compounds o~ formula (I) where X is other than halide can be formed treating the quaternary ammonium halide (IV) with silver oxide to produce the mono-quaternary ammonlum h,ydroxide. The excess silver oxide and precipitated silver halide ls removed by flltration and the aqueous solution o~ mono-quaternary ammonium hydroxide then is reacted with an Qpproprlate acid to introduce the desired anion, such as sul~onic acld, phosphorlc acid9 p-(lower - alkyl) benzenesulfonic acld~ benzoic acld or a mono-or dicarboxyllc acid of the formula R4-COOH or R5 -(GOOH) Alternatively, the quaternay ammonium halide (IV) can be reacksd wlth the desired acid ln approximately ,. .
stoichiometric quantlkiesg in accordance wlth processes . ~ (B~ or (C).
(B) R4-COOH + (IV) (I) where ~4 is a~ deflned above (C) n(HOOC~R5-COOE~ IV) (Ia~
where n is 1 or 2 and R5 ls a~ de~ined above.
~s . .
- ~ 5 ~
!
The dialkylaminoalkyl _-dialkylaminobenzoate (II) used in process (~) is known, e.~O ~ee IJ ~ Patent 820,830, and can conveniently be made by alkylatln~ and all~yl ~-aminobenzoate with an alkyl halide in an or~anic solvent, and reactin~ the re~ulting al~yl p-dialkylaminobenzoate with a dialkylaminoalkanol.
For use in process tA), the dialkylaminoal~yl p-dlalkylaminobenzoate may be:
dimethylaminoethyl p-dimethylaminobenzoate diethylaminoethyl p-diprop~lam~nobenzoate dimethylaminoethyl ~-dipentylaminobenzoate di-i-propylaminoethyl p-dihexylaminobenzoate dihexylaminoethyl p-di-~-propylamlnobenzoate dimethylaminobutyl p-diethylaminobenzoate dimethylaminohexyl p-diethylaminobenzoate
Ultraviolet radiation 011 -the skin, such as from the SU117 of a wavelength of 290 - 313 mu is known to produce erythema, particularly in :Eair skinned subjects. On the other hand, ultraviolet radiation of from 315 -320 mus to 350 - 400 mu promotes a tanning of the skin. To be effective, a sun-screening composition must at least remove substantially all of the burning rays, and in many instances a good portion of the tanning rays.
It is,therefore, an object of this invention to provide novel sun-screening compounds that are effective to prevent erythema.
It is a further object of the invention to provide new sun-screening compositions containing the sun-screening compounds of the invention.
These objects are provided by the provision of a sun-screening compound of formula (I):
~I) \ ~ COOY - N - R X
n vhere Rl and R2 are independently straight or branched chain lower alkyl;
~ 20 Y is C2 - C6 alkylene; R3 is alkyl of 8 to 18 carbon atoms; X is a cosmeti-: cally acceptable mono- or divalent anion; and n is l or 2 to provide an elec--~ trically neutral compound.
. The present invention also provides a method of protecting skin or hair from ultraviolet radiation, which comprises applying to the skin or hair a composition containing an effective amount of a compound of -formula I as set forth in above.
Preferably~ X is halide, sulfa~e, phosphate~ p-(lower ~' ,~
.
alkyl) benzene sulfonate, benzoate~ R~-C00 ~ , llOOC-R5-C00 ~ or 9 OOC-R5-C00 ~ , where R~ is alkyl of 1 to 18 carbon atoms and R5 is alkylene of 1 to 18 carbon atoms. Such compounds show absorption of ultraviolet light in the range o-f 290 -315 mu and have good substantivity on the skin. The compounds of formula (I) are water soluble, but the degree of water solubility decreases as the number of carbon atoms in R3 - and/or R~ and/or R5 increase.
The term 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, neopentyl, tert.pentyl, hexyl, and the like. The term 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.
The terms alkyl of 1 to 18 carbon atoms and alkyl of 8 to 18 carbon atoms denote a univalent saturated branched or straight hydrocarbon chain containing from 1 to 18 carbon atoms or 8 to 18 carbon atoms, respectively. Representative of such alkyl groups are thus methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.butyl, tert.butyl, pentyl, isopentyl, neopentyl, tert.pentyl, hexyl, isohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and the like. The terms alkylene of 1 to 18 carbon atoms and alkylene of ~ to 1~ carbon at~ms denote a '' ~, - 2 -, . . . .
f~
divalent saturated branched or straight hydrocarboll chain obtained by removing a hydrogen atom from the alkyl defined above The term halide denotes chloride, bromide, iodide and fluoride, preferably chloride or bromide.
In a preferred embodiment of the inventionJ Rl and R2 are Cl-C3 straight or branched chain alkyl.
It is further preferred to employ compounds in which R3 is alkyl of 11 to 18 carbon atoms, because the more carbon 10 atoms in R3, the greater the substantivity of the compound of formula (I).
It is further preferred to employ compounds in which the anion, R4-COO Q, is alkyl of 7 to 17 carbon atoms, e.g.
as derived from a higher saturated aliphatic carboxylic acid, such as a C8-C18 saturated aliphatic monocarboxylic acid, since such compounds will have reduced water-solubility and thus resist removal from the skin by water washing.
In another preferred embodiment of the invention, the anion, X, is derived from a saturated aliphatic dicarboxylic 20 acid (HOOC-R5-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 ~Ia):
_ (la) / ~ COOY-N - ~ Z-R5-CO0 ~
.' ~d , . ... : ~ : : ,, . , . , . - . -where Rl, R2, R3~ and R and n are as defined abovel Z
i~ -COOH or -CO ~, and n ls 1 when Z i~ COOH and n is 2 when Z is -COO . Preferably~ the no carb~xylic acid is one wherein R5 is lower alkylene, and most pre~erably alkylene Or 1 to 4 carbon atoms.
Compounds which are actlve as sun-screenlng agents are known and include such widely diverse compound~ as dibenzyl-acetone, quinine sulfate and ethyl umbelliferone. Alkyl esters of p-dlalkylaminobenzolc acid have also heen propo~ed for use as sun-screening agents ln U.S. Patents 2,853,423;
3,403,207; and 3,479~428. In view of thls highly empirical nature of the ability o~ a compound selectiYely to absorb ultraviolet radiation in the narrow range of 290 to 315 mu, it was not expected that the compound~ of formula (I) would be useful as sun-screening agents Mono-quaternary ammonium compounds use~ul as intermediates in the preparation o~ therapeutlc agents have been proposed ln U.S. Patent 2,717,905. So far as we are aware9 the sun-screenin~ compound~ of formula (I~ are novel.
The quaternary salts of formula (I) where ~ is hallde can be prepared by reacting at room temperature~ with or without a ~olventg ap~roxlmately stoichiometric quantitles o~ a dialkylaminoalkyl p-dialklaminobenzoate (II) and an alkyl halide (III) to form the quaternary ammonium hallde (IV), Z5 acoordlng to process (A) be.ow:
-- 4 ~
, . .
N ~ ~ ~ OOY- < + R3-hal~de (II) (III) COOY ~ ~ ~ hallde~
where Rl, R2 and R3 are de~ne~ above, and ~'halide" is chloride, bromlde, lodide or ~luroide, pre~erably chloride or bromide.
Compounds o~ formula (I) where X is other than halide can be formed treating the quaternary ammonium halide (IV) with silver oxide to produce the mono-quaternary ammonlum h,ydroxide. The excess silver oxide and precipitated silver halide ls removed by flltration and the aqueous solution o~ mono-quaternary ammonium hydroxide then is reacted with an Qpproprlate acid to introduce the desired anion, such as sul~onic acld, phosphorlc acid9 p-(lower - alkyl) benzenesulfonic acld~ benzoic acld or a mono-or dicarboxyllc acid of the formula R4-COOH or R5 -(GOOH) Alternatively, the quaternay ammonium halide (IV) can be reacksd wlth the desired acid ln approximately ,. .
stoichiometric quantlkiesg in accordance wlth processes . ~ (B~ or (C).
(B) R4-COOH + (IV) (I) where ~4 is a~ deflned above (C) n(HOOC~R5-COOE~ IV) (Ia~
where n is 1 or 2 and R5 ls a~ de~ined above.
~s . .
- ~ 5 ~
!
The dialkylaminoalkyl _-dialkylaminobenzoate (II) used in process (~) is known, e.~O ~ee IJ ~ Patent 820,830, and can conveniently be made by alkylatln~ and all~yl ~-aminobenzoate with an alkyl halide in an or~anic solvent, and reactin~ the re~ulting al~yl p-dialkylaminobenzoate with a dialkylaminoalkanol.
For use in process tA), the dialkylaminoal~yl p-dlalkylaminobenzoate may be:
dimethylaminoethyl p-dimethylaminobenzoate diethylaminoethyl p-diprop~lam~nobenzoate dimethylaminoethyl ~-dipentylaminobenzoate di-i-propylaminoethyl p-dihexylaminobenzoate dihexylaminoethyl p-di-~-propylamlnobenzoate dimethylaminobutyl p-diethylaminobenzoate dimethylaminohexyl p-diethylaminobenzoate
2-dimethylamlno-2-methyl~ethyl ~dimethylaminobenzoate The alkyl halide (III~ used in process (A) is also known, and may be bromooctane, chlorooctane, iodooctane, rluro-octaneD bromonoane~ chlorodecane, bromoundecane, bromododecane, chlorotetradecane, chlorohexadecane, bromooctadecane, chloro-octadecane and iodooctadecane.
The aliphatic monocarboxylic acld R4 -CQOH used in reaction (B) may be acetic acid, n or i-propanoic acid, n or i-valeric acid3 caprylic acid, octanolc acid, capric acid, lauric acid, myristic acid, palmltic acid, stearic acid and nonadecanoic acid.
The aliphatic dicarboxyllc acid R5-(COOH)2 used in reaction (C) may be malonic acldg succinic acid~ adipic acid, _ 6 -, ;, 2~2'-dimethylglutaric acid, suberic acld5 sebaclc acid, dodecanedioic acid, tetradecanedioic acid, hexadecanediolc aicd5 and nonadecanedloic acid The .following are represenkative sun screenin~
compounds of formula (I):
(1) dimethyloctyl-(p-dlethylaminobenzoyloxethyl)-a~monlum bromide (2) dlmethyloctyl-(p-diethylaminobenzoyloxyethyl)-ammonium acetate
The aliphatic monocarboxylic acld R4 -CQOH used in reaction (B) may be acetic acid, n or i-propanoic acid, n or i-valeric acid3 caprylic acid, octanolc acid, capric acid, lauric acid, myristic acid, palmltic acid, stearic acid and nonadecanoic acid.
The aliphatic dicarboxyllc acid R5-(COOH)2 used in reaction (C) may be malonic acldg succinic acid~ adipic acid, _ 6 -, ;, 2~2'-dimethylglutaric acid, suberic acld5 sebaclc acid, dodecanedioic acid, tetradecanedioic acid, hexadecanediolc aicd5 and nonadecanedloic acid The .following are represenkative sun screenin~
compounds of formula (I):
(1) dimethyloctyl-(p-dlethylaminobenzoyloxethyl)-a~monlum bromide (2) dlmethyloctyl-(p-diethylaminobenzoyloxyethyl)-ammonium acetate
(3) dihexloctyl-(p-diethylaminobenzoyloxyethyl)-ammonlum : laurate
(4) dimethyloctyl-(p-diethylaminobenzoyloxyethyl) ammonium stearate : (5) dlmethyldecyl~ dihexylaminobenzoyloxyethyl)-ammonium chloride . (6) dimethyldodecyl~(p-dimethylaminobenzoyloxyethyl)-ammonium ; 2-ethylhexanoate (7) dlmethyloctadecyl~ dlmethylamlnobenzoyloxyekhyl)-; ammonium bromlde 20 (8) dimethyloctadecyl~ dlmethylaminoben~oyloxyethyl)-ammonium 2-ethylhexanoate -. (9) dimethyldodecyl (p-dimethylamlnobenzoyloxybutyl~-ammonium caprylake . (10) bls-~dimethyloctyl~ dlethylaminobenzoyloxyethyl)~
; 25 ammonlum] malonake ', (11) bi~-cdimethyldodecyl-(~~dimekhylaminobenæoyloxybutyl) ammonium] succ~nate (12) dlmethyldodecyl~ diethylaminobenzoyloxyethyl)-ammonlum succinate .
: ~ - 7 The sun screenin~ a~ent.s of formula (I) are applled to the skin in the ~orm o~ a ~un-~creen compositlon comprising the compound of formula (I~ and a cosmetically acceptable diluent or carrier. The term "co~metically acceptable diluent or carrier" denotes a non-toxic, non-irritating substance whlch when mixed with the compound o~ ~ormula (I) makes the compound more ~uitable to be applied ko the skin. he composLtions can thus be solutions, oils, lotlons, ointments, liquid or solld creams, aerosols and the llke.
The sun~screening composltion o~ the invention is formed by admlxing, dissolvin~ or dispersing the sun-screening compound o~ formula (I) into the deslred cosmetica:Lly accept-able diluent or carrier. Solutions are ~ormed by dlssolvin~
the sun-screening compound in water or other solvent. Oils are prepared by using vegetable and/or oil mineral oils) such as sesame oil and/or white mineral oil as the cosmetically acceptable diluent or carrler. Creams may be pre~ared by addin~ lanolin and a suitable absorbent base to the vegtable and/or mineral oils. Oll-in~water emulsions may be employed as the vehicle to form loklons, but are not preferred since such compositions tend to wash o~f more easily than others.
An alcoholic lotion containg an alcohol, such as ethanol or l~opropanol, and a ~ilm-~orming substance as the cosmetically acceptable diluent or carrier is pre~erred, since thi~ tends to pro~ide ~ore permanent protection even a~ter expo~ure of the skin to water. Pre~erred ~ilm-rorming a~ents ~or alcoholic lotions are castor oil, lauryl and oleyl alcohols~ glycol and glyceryl oleates, mannitol and sorbitol oleate9 laurate or ricinoleate, butyl skearake, ethyl oleate~
laurate, or ricinoleate and methyl oleate~ lauxate or rlcinoleate~
, ~ ., ~' ' .
L~
Perfumes, anti-oxidants, colorants~ insect-repellants and the like may be inclucled in the sun-screening - composition~ if desired.
The sun-screenlng compositLon o~ the invention contains an effectlve amount of the sun-screening compound o~
~ormula (I) to prevent erythema. In general3 an amount o~
0.01 to 10%, preferably 0.05 to 3%, by weight, of the total compositlon, of the sun-screening compound formula (I) may be used. The composition is applied topically every rew 10 hours, as neededg ln the same manner as convetnional sun-screening compositions.
The compounds of the invention may also be used to protect blond and liht colored hair from the cleleterious e~fects o~ ultraviolet radiation. In this case, khe compounds 15 f formula (I) are admixed with the cosmetically acceptable diluent or carrier to provide a composition containing ~rom 0 05 to 10~, by weight, preferably 2 to 5%, by wei~ht, of the compound o~ ~ormula (I). ~he hair protection compositions are applied to the hair in the same manner as a convenkional 20 hair lotion, hair cream or hair tonic, berore exposure to ultraviolet radlation~ and thereafte~ as desired. Cosmetically acceptable diluents or carriers used in ~uch con~entlonal hair preparatlons may be used ln the hair-protection composition of the lnventlon.
In the Examples, the following procedures were , used:
o~c~lr~ r.
Reference solutions o~ the candidate com~ound ln 50/50 ethanol-water solvent are prepared ln concentraions o~
2%, by wei~ht, and below. Such solution are ap~lied to the .
_ g ...
skin and dried in air. ~xamination o~ thc treated section of skin under W light reveals a bluish-white color for untreated skin and brownish-black to balck color for treated skin.
A 2~, by welght, solution of the candidate compound in 50~ ethanol-50% water is then rubbed lnto the skin, dried ln air, and part of the air-dried surface is rinsed with water for 2 minutes, Examinatlon Or the rinsed and unrinsed sections of skin was then made in W (black) light. The retention Or the W absorber on the skin is determined by observing the color o~ the treated and untreated section under UV light and comparing the color to the reference solutions.
Tests for sunburn protection are carried out b~
applying a 2%, by weight~ solution of the candidate compound in 50% ethanol-50% water to a small patch o~ skin, followed by exposure to sun for 2 hours. ~o be successful, a compound must prevent erythema after exposure for two hours to the sun at a latitude o~ New York City.
` Test Procedure ~or Hair ; The substantlvity of the candidate com~ound to hair ls tested in the following manner. The candidate compound is dissolved in 100 mls. o~ water to provide a 0.1~, b~ weight, aqueous solutlon. 10 gms. of halr is imm~rsed in the resultin~
aqueou~ solution, stirred for 1/2 hour, removed, rinsed and dried. The W absorption of the aqueous solution into whlch the hair was lmmersed is measured both be~ore and after the ~ immersion o~ the hair in the solution, uslng the same technique :
'~
.
, - ., . : :
described above. The % of the compound left after rlnsing determin0s the amount of substantivity.
The following Examples illustrate the invention.
In the Examples~ all percentages and parts are by weight unless stated otherwise.
Preparation and application to the skin of:
(/5C2)2n ~ COOC2H4N - CH3 ~ X , where X = Br \ (Compound A) C H or CH3C00-8 17 ~Compound B).
148g. ethyl p-aminobenæoate, 4~5g. ethyl iodide and 600 ml. ethanol were heated in an autoclave for 6 hours at 185C.
Then the solvent and excess ethyl iodide were evaporated at 120C
under atmospheric pressure, producing about 150g. ethyl ~-diethylaminobenzoate.
70g. of this product~ 2g. of sodium methoxide and 86g. dimethylaminoethanol were heated to 140C for 24 hours while distilling off the ethanol tha~t was liberated. The product was extracted with 200 ml. water and 100 ml. benzene9 the water layer removed and the benzene evaporated to give abou~ 80g. crude dimethylaminoethyl ester of p-dimethylaminobenzoic acid.
'~6.4g. of this compound was m.ixed with 21g. bromooctane ', 20 and 100 ml. isopropanol. The mix~ure was refluxed for 24 hours5 and the product evaporated to dryness on a steam bath. Compound ' ' .
~A) was recovered. An aqueous 0.1% solution of compound ~A) was applied to skin and afforded protection against sunburn, but allowed tanning.
To a 1% aqueous solution of compound ~A) was added 10% sodium acetate ~based on the weight of the solution). The compo~md ~B) precipitated, was filtered off and dried.
When lOg. hair was treated with 100 ml. aqueous solution containing 0.1% of compound (B), the hair was protected against undue deterioration on exposure to UV light. Sub-stantivity was 75%, obtained by determining the K value of -the solution before and after immersion of the hair. It also has similar substantivity and protective properties when applied to skin.
When the pH of the aqueous solution is adjusted to 8~5, compound tB) has higher substantivity on the skin and gives good protection against s~mburn.
Maximum absorption of compounds ~A) and (B) is at 313 mu.
Example 2 Praparation and application to the skin of the com-pound having ~he formula:
( s 2)2N
- l? -`:
A 0.1% aqueous solution o~ the Compowld (A) ofExample 1 was adjusted to pH 7.0 with sodium laurate salt.
Skin treated with this preparation was protected against sun-burn. Skin substantivity was excellent. Maximum absorption is at 313 mu.
~- Example 3 - Preparation and application to the skin of the compound having the formula:
` ':
t 5 2)2 ~ 2 4 ~3 X , where X is Br 12 25 CH3~CH2)3CHC00 ; L _ Compound (D) :
` 10 26.4g. of dimethylaminoethyl ester o p-dimethyl-amino benzoate was mixed with 28 gO bromododecane and 100 ml.
isopropanol. The mixture was refluxed for 24 hours, and the product evaporated to dryness on a steam bath to give Compound `' (C).
An aqueous 0.1% solution of Compound ~C) was adjust-ed to pH 7.0 with sodium 2-ethylhexoate to produce Compound tD).
~;~ Maximum absorption of Compound (D) was at 313 mu.
Skin substantivity of Gompound CD) ~as excellent and thPre was a high degree of protection against sun-burn.
Example 4 Preparation and application to the skin of the ~,~ product having the formula:
;~, 13 ,,.~
~(H Czll ~ / 2 5 l 3 ~ 2 5 Compound ~E) or 18 3 C~13~CH2)3C11C
_ (Compound F) 82.5 g. ethyl ~-aminobenzoate, lOQ ml. methanol and 65 g. dimethyl sulfate were mixed and gradually heated to 75 C. After 3 hours the charge was treated with 50 g. sodium carbonate to delta paper neutrality. It was then treated with lO0 ml. benzene and 200 ml. water and the layers separated.
The upper layer was evaporated free from benzene to give 80 g.
ethyl ~ imethylaminobenzoate.
22.1 g. of this productJ 0.50 g. sodium methoxide and 50 g. diethylaminoethanol were heated to 140C. for 24 hours while distilling off the ethanol ~hat was liberated. The product was extracted with 200 ml. water and lQ0 ml. benzene, the water layer removed and the benzene evaporated from the water layer to give about 8Q g. crude diethylaminoethyl ester o~
~-dimethylaminobenzoic acid.
This product was then mix~d with 23 g. bromooctadecane and lO0 ml. isopropanol. The mixture was refluxed for 24 hours, and the produc~ evaporated to dryness on a steam bath to gi~e Compound (E).
An a~ueous Q.1% solution of ~ompound (E) was adjusted -.
- i.. . . -: . :: :-. ~ . .
to p~l 7.0 with sodium 2~ethylhe~oate to produce Compound ~F~, ~ich was highly skin substantive and afforded excellent pro-tection against sun-burning.
ple 5 In the manner of Examp:le 2, to a 1% aqu~ous solution of Compound (A) was added 10% sodium stearate to form:
C2~2N - ~ C 17 This compound had absorption at 313 mu, affording excellent sun-burn protection on the skin against W radiation, and a high degree of substantivity.
Example 6 An aqueous 0.1% solution of ~ ¦ ll;5 2~2 ~ COOC2H4N - C~ B~
: C12H~5 is trea~ed with half the equimolar amoun~ of ~he di-sodium salt of succinic acid to give 2)2N - ~ CC2H N - Cll 1 2 Cl 2H25 CH2C
. ~ _ 2 The preclpitated product is filtered rrom the mixture and dried.
An aqueous 0.1~ solution of`
L 5C2)2 N ~ CO C2}l4~l \ 3 was treated with an equimolar amount of the mono-sodium salt Or succinic acid CIH2COONa \~H2COOEJJ
to give (}I~C2)2 N ~ O ~ cooc2}l4N - CH3 c}l2cC
, -- __ :~ The precipltated product i5 filtered from the mixture and .. .
drle d ' .`; :
.~ .
~ 16 -. : - ~
,
; 25 ammonlum] malonake ', (11) bi~-cdimethyldodecyl-(~~dimekhylaminobenæoyloxybutyl) ammonium] succ~nate (12) dlmethyldodecyl~ diethylaminobenzoyloxyethyl)-ammonlum succinate .
: ~ - 7 The sun screenin~ a~ent.s of formula (I) are applled to the skin in the ~orm o~ a ~un-~creen compositlon comprising the compound of formula (I~ and a cosmetically acceptable diluent or carrier. The term "co~metically acceptable diluent or carrier" denotes a non-toxic, non-irritating substance whlch when mixed with the compound o~ ~ormula (I) makes the compound more ~uitable to be applied ko the skin. he composLtions can thus be solutions, oils, lotlons, ointments, liquid or solld creams, aerosols and the llke.
The sun~screening composltion o~ the invention is formed by admlxing, dissolvin~ or dispersing the sun-screening compound o~ formula (I) into the deslred cosmetica:Lly accept-able diluent or carrier. Solutions are ~ormed by dlssolvin~
the sun-screening compound in water or other solvent. Oils are prepared by using vegetable and/or oil mineral oils) such as sesame oil and/or white mineral oil as the cosmetically acceptable diluent or carrler. Creams may be pre~ared by addin~ lanolin and a suitable absorbent base to the vegtable and/or mineral oils. Oll-in~water emulsions may be employed as the vehicle to form loklons, but are not preferred since such compositions tend to wash o~f more easily than others.
An alcoholic lotion containg an alcohol, such as ethanol or l~opropanol, and a ~ilm-~orming substance as the cosmetically acceptable diluent or carrier is pre~erred, since thi~ tends to pro~ide ~ore permanent protection even a~ter expo~ure of the skin to water. Pre~erred ~ilm-rorming a~ents ~or alcoholic lotions are castor oil, lauryl and oleyl alcohols~ glycol and glyceryl oleates, mannitol and sorbitol oleate9 laurate or ricinoleate, butyl skearake, ethyl oleate~
laurate, or ricinoleate and methyl oleate~ lauxate or rlcinoleate~
, ~ ., ~' ' .
L~
Perfumes, anti-oxidants, colorants~ insect-repellants and the like may be inclucled in the sun-screening - composition~ if desired.
The sun-screenlng compositLon o~ the invention contains an effectlve amount of the sun-screening compound o~
~ormula (I) to prevent erythema. In general3 an amount o~
0.01 to 10%, preferably 0.05 to 3%, by weight, of the total compositlon, of the sun-screening compound formula (I) may be used. The composition is applied topically every rew 10 hours, as neededg ln the same manner as convetnional sun-screening compositions.
The compounds of the invention may also be used to protect blond and liht colored hair from the cleleterious e~fects o~ ultraviolet radiation. In this case, khe compounds 15 f formula (I) are admixed with the cosmetically acceptable diluent or carrier to provide a composition containing ~rom 0 05 to 10~, by weight, preferably 2 to 5%, by wei~ht, of the compound o~ ~ormula (I). ~he hair protection compositions are applied to the hair in the same manner as a convenkional 20 hair lotion, hair cream or hair tonic, berore exposure to ultraviolet radlation~ and thereafte~ as desired. Cosmetically acceptable diluents or carriers used in ~uch con~entlonal hair preparatlons may be used ln the hair-protection composition of the lnventlon.
In the Examples, the following procedures were , used:
o~c~lr~ r.
Reference solutions o~ the candidate com~ound ln 50/50 ethanol-water solvent are prepared ln concentraions o~
2%, by wei~ht, and below. Such solution are ap~lied to the .
_ g ...
skin and dried in air. ~xamination o~ thc treated section of skin under W light reveals a bluish-white color for untreated skin and brownish-black to balck color for treated skin.
A 2~, by welght, solution of the candidate compound in 50~ ethanol-50% water is then rubbed lnto the skin, dried ln air, and part of the air-dried surface is rinsed with water for 2 minutes, Examinatlon Or the rinsed and unrinsed sections of skin was then made in W (black) light. The retention Or the W absorber on the skin is determined by observing the color o~ the treated and untreated section under UV light and comparing the color to the reference solutions.
Tests for sunburn protection are carried out b~
applying a 2%, by weight~ solution of the candidate compound in 50% ethanol-50% water to a small patch o~ skin, followed by exposure to sun for 2 hours. ~o be successful, a compound must prevent erythema after exposure for two hours to the sun at a latitude o~ New York City.
` Test Procedure ~or Hair ; The substantlvity of the candidate com~ound to hair ls tested in the following manner. The candidate compound is dissolved in 100 mls. o~ water to provide a 0.1~, b~ weight, aqueous solutlon. 10 gms. of halr is imm~rsed in the resultin~
aqueou~ solution, stirred for 1/2 hour, removed, rinsed and dried. The W absorption of the aqueous solution into whlch the hair was lmmersed is measured both be~ore and after the ~ immersion o~ the hair in the solution, uslng the same technique :
'~
.
, - ., . : :
described above. The % of the compound left after rlnsing determin0s the amount of substantivity.
The following Examples illustrate the invention.
In the Examples~ all percentages and parts are by weight unless stated otherwise.
Preparation and application to the skin of:
(/5C2)2n ~ COOC2H4N - CH3 ~ X , where X = Br \ (Compound A) C H or CH3C00-8 17 ~Compound B).
148g. ethyl p-aminobenæoate, 4~5g. ethyl iodide and 600 ml. ethanol were heated in an autoclave for 6 hours at 185C.
Then the solvent and excess ethyl iodide were evaporated at 120C
under atmospheric pressure, producing about 150g. ethyl ~-diethylaminobenzoate.
70g. of this product~ 2g. of sodium methoxide and 86g. dimethylaminoethanol were heated to 140C for 24 hours while distilling off the ethanol tha~t was liberated. The product was extracted with 200 ml. water and 100 ml. benzene9 the water layer removed and the benzene evaporated to give abou~ 80g. crude dimethylaminoethyl ester of p-dimethylaminobenzoic acid.
'~6.4g. of this compound was m.ixed with 21g. bromooctane ', 20 and 100 ml. isopropanol. The mix~ure was refluxed for 24 hours5 and the product evaporated to dryness on a steam bath. Compound ' ' .
~A) was recovered. An aqueous 0.1% solution of compound ~A) was applied to skin and afforded protection against sunburn, but allowed tanning.
To a 1% aqueous solution of compound ~A) was added 10% sodium acetate ~based on the weight of the solution). The compo~md ~B) precipitated, was filtered off and dried.
When lOg. hair was treated with 100 ml. aqueous solution containing 0.1% of compound (B), the hair was protected against undue deterioration on exposure to UV light. Sub-stantivity was 75%, obtained by determining the K value of -the solution before and after immersion of the hair. It also has similar substantivity and protective properties when applied to skin.
When the pH of the aqueous solution is adjusted to 8~5, compound tB) has higher substantivity on the skin and gives good protection against s~mburn.
Maximum absorption of compounds ~A) and (B) is at 313 mu.
Example 2 Praparation and application to the skin of the com-pound having ~he formula:
( s 2)2N
- l? -`:
A 0.1% aqueous solution o~ the Compowld (A) ofExample 1 was adjusted to pH 7.0 with sodium laurate salt.
Skin treated with this preparation was protected against sun-burn. Skin substantivity was excellent. Maximum absorption is at 313 mu.
~- Example 3 - Preparation and application to the skin of the compound having the formula:
` ':
t 5 2)2 ~ 2 4 ~3 X , where X is Br 12 25 CH3~CH2)3CHC00 ; L _ Compound (D) :
` 10 26.4g. of dimethylaminoethyl ester o p-dimethyl-amino benzoate was mixed with 28 gO bromododecane and 100 ml.
isopropanol. The mixture was refluxed for 24 hours, and the product evaporated to dryness on a steam bath to give Compound `' (C).
An aqueous 0.1% solution of Compound ~C) was adjust-ed to pH 7.0 with sodium 2-ethylhexoate to produce Compound tD).
~;~ Maximum absorption of Compound (D) was at 313 mu.
Skin substantivity of Gompound CD) ~as excellent and thPre was a high degree of protection against sun-burn.
Example 4 Preparation and application to the skin of the ~,~ product having the formula:
;~, 13 ,,.~
~(H Czll ~ / 2 5 l 3 ~ 2 5 Compound ~E) or 18 3 C~13~CH2)3C11C
_ (Compound F) 82.5 g. ethyl ~-aminobenzoate, lOQ ml. methanol and 65 g. dimethyl sulfate were mixed and gradually heated to 75 C. After 3 hours the charge was treated with 50 g. sodium carbonate to delta paper neutrality. It was then treated with lO0 ml. benzene and 200 ml. water and the layers separated.
The upper layer was evaporated free from benzene to give 80 g.
ethyl ~ imethylaminobenzoate.
22.1 g. of this productJ 0.50 g. sodium methoxide and 50 g. diethylaminoethanol were heated to 140C. for 24 hours while distilling off the ethanol ~hat was liberated. The product was extracted with 200 ml. water and lQ0 ml. benzene, the water layer removed and the benzene evaporated from the water layer to give about 8Q g. crude diethylaminoethyl ester o~
~-dimethylaminobenzoic acid.
This product was then mix~d with 23 g. bromooctadecane and lO0 ml. isopropanol. The mixture was refluxed for 24 hours, and the produc~ evaporated to dryness on a steam bath to gi~e Compound (E).
An a~ueous Q.1% solution of ~ompound (E) was adjusted -.
- i.. . . -: . :: :-. ~ . .
to p~l 7.0 with sodium 2~ethylhe~oate to produce Compound ~F~, ~ich was highly skin substantive and afforded excellent pro-tection against sun-burning.
ple 5 In the manner of Examp:le 2, to a 1% aqu~ous solution of Compound (A) was added 10% sodium stearate to form:
C2~2N - ~ C 17 This compound had absorption at 313 mu, affording excellent sun-burn protection on the skin against W radiation, and a high degree of substantivity.
Example 6 An aqueous 0.1% solution of ~ ¦ ll;5 2~2 ~ COOC2H4N - C~ B~
: C12H~5 is trea~ed with half the equimolar amoun~ of ~he di-sodium salt of succinic acid to give 2)2N - ~ CC2H N - Cll 1 2 Cl 2H25 CH2C
. ~ _ 2 The preclpitated product is filtered rrom the mixture and dried.
An aqueous 0.1~ solution of`
L 5C2)2 N ~ CO C2}l4~l \ 3 was treated with an equimolar amount of the mono-sodium salt Or succinic acid CIH2COONa \~H2COOEJJ
to give (}I~C2)2 N ~ O ~ cooc2}l4N - CH3 c}l2cC
, -- __ :~ The precipltated product i5 filtered from the mixture and .. .
drle d ' .`; :
.~ .
~ 16 -. : - ~
,
Claims (23)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Sun-screening compounds of the formula:
where R1 and R2 are independently straight or branched chain lower alkyl;
Y is C2 - C6 alkylene, R3 is alkyl of 8 to 18 carbon atoms; X is a cos-metically acceptable mono- or divalent anion; and n is 1 or 2 to provide an electrically neutral compound.
where R1 and R2 are independently straight or branched chain lower alkyl;
Y is C2 - C6 alkylene, R3 is alkyl of 8 to 18 carbon atoms; X is a cos-metically acceptable mono- or divalent anion; and n is 1 or 2 to provide an electrically neutral compound.
2. A compound according to claim 19 wherein X is halide, sulfate, phosphate, p-(lower alkyl) benzene sulfonate, benzoate, R4-COOO?; HOOC-R5-COO? or ?OCC-R5-COO?, where R4 is alkyl of 1 to 18 carbon atoms and R5 is alkylene of 1 to 18 carbon atoms.
3. A compound according to claims 1 or 2 wherein Rl and R2 are straight or branched chain alkyl of 1 to 3 carbon atoms.
4. A compound according to claim 1, wherein R3 is straight or branched chain alkyl of 11 to 18 carbon atoms.
5. A compound according to claim 1, wherein X is halide.
6. A compound according to claim 1, wherein X is R4-COO? and n is 1, where R4 is alkyl of 1 to 18 carbon atoms.
7. A compound according to claim 6, wherein R4 is alkyl of 7 to 17 carbon atoms.
8. A compound according to claim 1, wherein X is HOOC-R5-COO? and n is 1 and R5 is alkylene of 1 to 18 carbon atoms.
9. A compound according to claim 8, wherein R5 is lower alkylene.
10. A compound according to claim 1 wherein X is ?OOC-R5-COO? and n is 2 and R5 is alkylene of 1 to 18 carbon atoms.
11. A compound according to claim 10, wherein R5 is lower alkylene.
12. A compound according to claim 1, which is
13. A compound according to claim 19 which is
14. A compound according to claim 1, which is
15. A compound according to Claim 1, which is
16. A compound according, to Claim 1, which is
17. A compound according to Claim 1, which is
18. A compound according to Claim 1, which is
19. A compound according to Claim 1, which is
20. A compound according to Claim 1, which is
21. A compound according to Claim 1, which is
22. A method of protecting skin or hair from ultraviolet radiation, which comprises applying to the skin or hair a composition containing an effective amount of a compound of formula I as set forth in claim 1.
23. The method according to claim 24, wherein the composition is applied to the skin in an amount effective to prevent erythema.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US465259A US3878229A (en) | 1974-04-29 | 1974-04-29 | Sun-screening compounds III |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1064049A true CA1064049A (en) | 1979-10-09 |
Family
ID=23847063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA217,454A Expired CA1064049A (en) | 1974-04-29 | 1975-01-07 | Salts of alkanolamine esters of para dialkylaminobenzoic acid and their use as sun-screening agents |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3878229A (en) |
| JP (1) | JPS50140642A (en) |
| CA (1) | CA1064049A (en) |
| CH (1) | CH616842A5 (en) |
| DE (1) | DE2509647A1 (en) |
| FR (1) | FR2268789B1 (en) |
| GB (1) | GB1428648A (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59140694A (en) * | 1983-01-31 | 1984-08-13 | Sharp Corp | Refresh method of dynamic ram |
| CA1242740A (en) * | 1984-06-21 | 1988-10-04 | Donald E. Conner | Benzene sulfonate quaternary ammonium salts of organic sunscreen carboxylic acids |
| US5451394A (en) * | 1993-08-25 | 1995-09-19 | Isp Van Dyk Inc. | Quaternary salts of para-dialkylamino benzamide derivatives |
| US5543083A (en) * | 1994-07-26 | 1996-08-06 | The Procter & Gamble Company | Fatty amine derivatives of butylated hydroxy toluene for the protection of surfaces from physical and chemical degradation |
| WO1996003486A1 (en) * | 1994-07-26 | 1996-02-08 | The Procter & Gamble Company | Rinse added fabric softener compositions containing sunscreens for sun-fade protection for fabrics |
| ES2152413T3 (en) * | 1994-07-26 | 2001-02-01 | Procter & Gamble | SOFTENING COMPOSITIONS OF RINSED FABRICS THAT CONTAIN ANTIOXIDANTS FOR PROTECTION OF FABRICS AGAINST DECOLORATION. |
| US5474691A (en) * | 1994-07-26 | 1995-12-12 | The Procter & Gamble Company | Dryer-added fabric treatment article of manufacture containing antioxidant and sunscreen compounds for sun fade protection of fabrics |
| US7396526B1 (en) | 1998-11-12 | 2008-07-08 | Johnson & Johnson Consumer Companies, Inc. | Skin care composition |
| US20040213754A1 (en) * | 2000-10-02 | 2004-10-28 | Cole Curtis A. | Method for cleansing sensitive skin using an alkanolamine |
| KR20020027198A (en) * | 2000-10-02 | 2002-04-13 | 차알스 제이. 메츠 | Method for reduction of inflammation and erythema |
| US6607735B2 (en) * | 2000-12-21 | 2003-08-19 | Johnson & Johnson Consumer Companies, Inc. | Method for reducing the appearance of dark circles under the eyes |
| US20080063844A1 (en) * | 2001-06-29 | 2008-03-13 | Mannington Mills, Inc. | Surface coverings containing aluminum oxide |
| US20050238730A1 (en) * | 2001-11-21 | 2005-10-27 | Agnes Le Fur | Compositions comprising an ethanolamine derivative and organic metal salts |
| CN109232285B (en) * | 2018-10-16 | 2021-02-26 | 新乡学院 | Synthetic method and application of benzocaine disubstituted derivative with antibacterial activity |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1181406A (en) * | 1966-09-27 | 1970-02-18 | Menarini Sas | N-Dialkylaminoalkyl p-(2-Alkoxy-Benzoyl)-Aminobenzoates and their Quaternary Ammonium Salts and Processes for their Preparation |
-
1974
- 1974-04-29 US US465259A patent/US3878229A/en not_active Expired - Lifetime
-
1975
- 1975-01-07 CA CA217,454A patent/CA1064049A/en not_active Expired
- 1975-01-08 GB GB82975A patent/GB1428648A/en not_active Expired
- 1975-01-31 JP JP50013932A patent/JPS50140642A/ja active Pending
- 1975-03-05 DE DE19752509647 patent/DE2509647A1/en not_active Withdrawn
- 1975-03-06 CH CH288275A patent/CH616842A5/de not_active IP Right Cessation
- 1975-04-25 FR FR7513032A patent/FR2268789B1/fr not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB1428648A (en) | 1976-03-17 |
| FR2268789B1 (en) | 1979-08-17 |
| FR2268789A1 (en) | 1975-11-21 |
| DE2509647A1 (en) | 1975-11-13 |
| US3878229A (en) | 1975-04-15 |
| JPS50140642A (en) | 1975-11-11 |
| CH616842A5 (en) | 1980-04-30 |
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