NL8202949A - AGAINST LIGHT PROTECTIVE AGENT. - Google Patents

Description

ί / VO 3 ^ 32

Against light protective agent.

The invention relates to new photo-protective agents which are due to a content of a compound of the formula I, wherein R 1 hydrogen or C 1 -C 2 alkyl, most preferably hydrogen or methyl, R 1 hydrogen or C 1 -C 2 alkyl , preferably methyl, X a group (-CH2-) n or (-CHgOCHg-J ^ .j 5 m - 1 - 5, preferably 1, n * 0 - 1 *, preferably 0, and p = Ί - 3, preferably 1 or 2, in dissolved or dispersed form, are characterized The invention also relates to the use of the compounds of the formula 1 in dissolved or dispersed form as light-protecting agents.

Methyl, ethyl, propyl, and isopropyl can be used as C 1 -C 6 alkyl groups. Methyl is preferred. The C ^ -C ^ groups can also be straight or branched, e.g. butyl, isobutyl, amyl, hexyl, heptyl etc.

Preferred compounds of the formula 1 are: propylene glycol di- (p-methoxy cinnamic acid ester), 1,3-butylene glycol di- (p-methoxy cinnamic acid tester, triethylene glycol di- (p-methoxy cinnamic acid) ester.

Further representatives of the formula 1 are: ethylene glycol di- (p-methoxy cinnamic acid ester, trimethylene glycol di- (p-methoxy cinnamic acid ester), 2,3-butylene glycol di- (p-methoxy cinnamic acid ester, diethylene glycol di- (p-methoxy cinnamic acid ester, glycerol triester) - (p-methoxy-cinnamic acid Jester, dipropylene glycol di- (p-methoxy-cinnamic acid) ester, 25 2-methyl-2, k-pentanediol-di- (p-methoxy-cinnamic acid Jester, 1,1 | -hutane di-di- (p-methoxy-cinnamic acid) Your star, 1.5-pentanediol-di- (p-methoxy-cinnamic acid Jester, 1,6-hexanediol-di- (p-methoxy-cinnamic acid Jester, 2,5-hexanediol-di- (p-methoxy-cinnamic acid Jester), and 30 sorbitol-hexa- (p-methoxy-cinnamic acid J -ester.

8202949 - 2 - »%

The compounds of the formula I absorb the erythema-inducing ultraviolet rays of the sun (between 280 and 320 nm) in a pronounced manner, i.e. they keep these rays away from the living epidermis cells. The compounds of the formula I can thus be used as light-protecting agents. The invention also relates to a process for preparing a photo-protective agent which is characterized in that a compound of the formula 1 is dyed in a base customary for cosmetics.

As a cosmetic base customary for light-protecting agents within the scope of the invention, any conventional formulation that meets cosmetic requirements may be used, e.g. creams, emulsions, ointments, (alcoholic) solutions, sprays, sticks, milk and the like, see also GANovak, Die Kosmetischen Praparate, 1st edition, 1969, 2nd edition 1975. (Augsburg), many publications about the solvents to be used in the preparation of cosmetic preparations (especially polar solvents in the present case), solvent additives, emulsifiers, thickeners, fragrances, condensing agents, dyes and any further auxiliary substances. The light-protecting effect naturally also depends on the base used.

20. The intensity of the photo-protective effect further depends on the same basis of the concentration of active substance. Suitable concentrations are e.g. between .1 and 6%, preferably between 2 and in particular at about 3% of the compound of the formula 1 in an etetic composition.

Due to their lipophilic properties, the compounds of the formula I can be painted in a sufficient concentration in oil and fat-containing cosmetic preparations; they have optimum properties due to their sufficient fat solubility and pronounced absorption of UV-B radiation. In addition, the compounds of formula 1 as neutral substances are well tolerated on the skin.

The cosmetic preparations may also contain still further licbb-absorbing substances, e.g. further UV-A and / or UV-B filters.

Examples of UV-A filters are: U-isopropyl-dihenzoylmethane, 35 ^ - (1,1-dimethylethyl) - ^ - methoxydibenzoylmethane, 8202949 '' IT - * - 3 - dianisoylmethane, and hydroxybenzophenones. dihydroxybenzophenone.

As UV-B filters., D. For example, as a substance with absorption maxima between about 290 and 320 am, conventional UV-B filters, such as those under 5, can be called organic compounds belonging to the most diverse compound classes.

1) Derivatives of p-aminobenzoic acid, such as ethyl p-aminobenzoate and other esters such as propyl, butyl, isobutyl p-amiaobeazoate, 5 ethyl p-dimethylamiaobeazoate, glyceryl p-aminobeazoate, and anyl-p-dimetbyl Λ Amiaobeazoate.

2. Derivatives of cinnamic acid, such as 2-ethoxyethyl-p-methoxy cinnamic acid ester, 2-ethylhexyl-2-methoxy cinnamic acid ester, p-methoxy cinnamic acid ester mixtures, cinnamic acid ester mixtures, ammonium salts of p-methoxy-cinnamic acid. 15 3l Dibenzalazines.

k). Heterocyelic nitrogen compounds such as derivatea of 2-phenyl-benzimidazole, such as 2-pheaylbenzimidazole-5-sulfonic acid.

5) Derivatea of salicylic acid, such as salicylic acid methyl ester, salicylic acid bombomeathyl ester and others, salicylic acid pheayl ester.

20. 6}. Derivatea of beazopheaoa, such as h-phenylbenzophenone, phenyl-beazopheaoa-2-carbonic acid, and ethyl acetate 2-hydroxy-methoxybeazopheaoa-5-sulfonic acid.

7) Coumarin derivative, such as 7-oxycumariae, β-umbelliferone-acetic acid and 6,7-dioxycumariae.

8) Derivatea of gallic acid, such as digalloyl trioleate.

9l Arylidene cycloalkanones, such as beazylide camphor, p-tert-butyl-beazylidene camphor (preferably! Or methyl benzylidene camphor).

10) Derivative of anthraic acid such as anthranilic acid methyl ester and others 111 Hydroxyphenylbenztriazole.

3d The oader 2) stepped-up verbiadiagea, especially the 2-ethylB'exyl-p-metboxyacetic ester, are preferred.

"The verbia diagea of the formula I is side-beaded or kunaea is prepared on a self-contained vordea. Thereby, the p-methoxy cinnamic acid, preferably in the form of a reactive derivative, such as chloride, is esterified with the polyalcobol. Preferably stoichiometri- 8202949. - —τ- "... ....

- k - and use of skimmed amounts of dairy / alcohol. The acid derivative is preferably formed in a solvent, e.g. a chlorinated hydrocarbon, such as chloroform, and the alcohol, preferably dissolved in an amine, such as dimethylaniline, is added as a solvent at 0-20 ° C. Preferably, a complete course of the reaction is heated.

The product is then preferably poured on ice and purified by re-extraction and solidification as well as recrystallization.

The compounds of formula 1 can also be obtained by transesterification reactions. To this end, a lower alkyl ester of p-methoxy cinnamic acid, e.g. the methyl or ethyl ester, with the best polyalcohol, e.g. ethylene glycol or glycerol, reacted in the presence of a catalyst. Suitable catalysts are bases, such as sodium methylate or sodium ethylate. The reaction temperature is preferably selected in this way. . 15 that the formed methyl or ethyl alcohol can form at atmospheric pressure. distilled.

Examples - A) Preparation of the active substances.

Example I

• - ^ -. 3.

20- 100 g of p-methoxy cinnamic acid chloride (prepared according to Farmacia (Bucharest) £ (1961), 3 ^ 5-50; CA) were introduced into a 1 dm 4 four-necked round bottom equipped with a stirrer, thermometer, reflux condenser and dropping funnel. 56, 8312 i) and 200 ml of chloroform. The mixture was cooled to 10 ° C and a mixture of 60.5 g of dimethylaniline and 19.1 g of propylene glycol was added dropwise over 1 hour at this temperature with stirring.

The reaction is completed by heating to the boiling temperature for 2 hours.

After cooling, the reaction mixture is poured on ice. The dimethylaniline hydrochloride was taken up in 25 ml of chloroform and solid with 10% hydrochloric acid and then solidified to neutral reaction with water.

The solvent was distilled off and the residue (90 g of crude product). from acetone: water = h: 1 recrystallized. 50.1 g of propylene glycol di- (p-methoxy-cinnamic acid) ester were obtained; Snip. 97 DEG-99 DEG C; 310 = ® = II63.

Example II

3 35 Ih a round base of 1 dm, that of a stirrer and an attachment vas 8202949 -5-

V

173 g of p-methoxy cinnamic acid methyl ester, 38 g of propylene glycol, 10 g of sodium methylate and 300 cm of anhydrous xylene were added. The mixture was heated with stirring and the formed methanol (32 g) was slowly distilled off. The reflux temperature was maintained for an additional 5 hours. After cooling, 5 was neutralized with 5.5 g of acetic acid, taken up in ether and washed with water. After drying with sodium sulfate, the ether was distilled off.

177 g of new product were obtained. After recrystallization from methanol, the propylene glycol di- (p-methoxy cinnamic acid) ester was obtained, m.p. 96 DEG-98 DEG.

Example III

100 g of p-methoxy cinnamic acid chloride and 200 cm of chloroform were introduced into a 1-necked four-necked round bottom equipped with a stirrer, thermometer, reflux condenser and dropping funnel. The mixture was cooled to 10 ° C and a mixture of 60.5 g of dimethylaniline and 15.5 g of glycerol was added dropwise at this temperature for half an hour. The reaction was completed by refluxing for 1 hour.

After cooling, the reaction mixture was poured onto ice. It was taken up in 200 en chloroform and the dimethylaniline was washed with 10 # hydrochloric acid and then washed with water until neutral reaction. The solvent was distilled off and the solid residue (113 g of crude product) recrystallized from 200 ml of toluene. 51.1 g of glyerol tri- (p-methoxy cinnamic acid) ester were obtained.

Mp. 10k - 105 ° C; Q = 67970. E = 1163. Yield 52.5%.

Example IV

In the manner described in Examples I and III, from 100 g of p-methoxy cinnamic acid chloride and 37.5 g of triethylene glycol in the presence of 60.5 g of dimethylaniline in chloroform: 8 g of triethylene glycol di- (p-methoxy cinnamic acid) ester obtained; Mp. 82-83 ° C; ~ 1 * 6900; E = 995 · Yield 69% of the theoretical.

The following esters were prepared analogously: ethylene glycol di- (p-methoxy cinnamic acid) ester;

Mp. = iVr - 1 9 ° C; e310 = 1 * 1 * 932; E * 1175.

Trimethylene glycol di- (p-methoxy cinnamic acid) ester;

Mp. = 11 * 0 - 11 * 1 ° C; & * 1 * 5150; E = 1139 • 35 1,3-butylene glycol di- (p-methoxy cinnamic acid) ester; 8202949 - 6 -

Mp. 97.5 - 99.5 ° C; ^ 310 = 1 + 1 + 870; E = 1090.

2,3-butylene glycol di- (p-methoxy cinnamic acid) ester;

Mp. 15 DEG-156 DEG C .; £ = 1 + β2β0; E = 1127.

2-methyl-2,1 + pentanediol-di- (p-methoxy-cinnamic acid) ester; 5 Mp. 100-110 ° C; -1 ^ 3368; E = 989.

ls5-pentanediol di (p-methoxy cinnammr) ester;

Mp. 76.5-78 ° C; € = 1 + 7250; E = 1115.

1,6-hexanediol-di- (p-methoxy-cinnamic acid) star;

Mp. 92.5 - 93.5 ° C; £ Q = 1 + 7300; E »1080.

2,5-hexanediol di- (p-methoxy cinnamic acid) ester;

Mp. 126.5-128.5 ° C; £ 1 + 1 + 700; E = 1020.

diethylene glyeol di- (p-methoxy cinnamic acid) ester;

Mp. 77.5-78.5 ° C; = 1 + 5000; E = 1055.

B. Preparations 15 Example V

Protect from sun & cream, half fat (0 / w).

gey, din A). 1 + - (1,1-dimethylethyl) -1 + methoxydiBenzoylmethane 1.5 propylene glycol di-ip-methoxy cinnamic acid ester 3.0 20 stearic acid, pressed three times 10.0 cetyl alcohol 1% glycerol monomyristate 5.0 isopropyl adipate 7.0 oleyl alcohol 1+ , Methyl and propyl p-aminobenzogir (70/30, 0.25 B). diethanolamine acetyl phosphate 3.0 C) distilled water 59.25 propylene glycol 6.0 D) perfume q. s.

The combined components A1 were heated to 85 ° C on a water had, then B) was added at this temperature. C) was heated to 75 ° C and added to A) + B) and the resulting mixture was stirred.

After cooling at 35 ° C, any water losses were compensated and D) added.

8202949 '- ψ - 7 -

Example ΥΣ

Protected against 20η milk (0 / W) parts by weight A) ethyl alcohol 2.0 5 glycerol monomyriatate 0 arachis oil hydrogenated 2.0 isopropyl adipate 5.0 propylene glycol di- (p-methoxy cinnamic acid 2.0 5.0 B) diethanolamine acetyl phosphate 3.0, 10 C) distilled water 7.0-68.5 propylene glyeol 3.0 urea 5.0 D) perfume. fl.s.

preservative q.s.

The mixture A) heated on a water bath at 85 ° C, then added at this temperature B). The unified components of C). then heated to 75 ° C and then added to A) + B). The water losses were concentrated after cooling to 25 DEG-30 DEG C., followed by addition of D). Stirring was continued until a temperature of 25 ° C was reached. .

Example VII

Sun protection cream for sportsmen (W / 0) x parts A) propylene glycol di- (p-methoxy cinnamic acid) 1.5 25 (1,1-dimethylethyl) -1f-methoxydibenzoylmethane 1.0 sorbitylsesquioleate -9.0 lanolin 1.0 paraffin oil 8.0 methyl and propyl p-amnobenzoic acid ester (70/30) 0.25 30 B) isopropyl myristate 10.0 'aluminum stearate 0.1 C) • magnesium sulfate 0.3 propylene glyeol 3.0 distilled water 67.35 perfume. 0.5 8202 949 -— «· - 8 -

The aluminum stearate is carefully mixed with the isopropyl myristate and the mixture B) formed is added to the combined components A) · heated to 80 ° C. Slowly add the solution C) heated to T5 ° C to the hot mixture A) + B). A) + B) + C.) was allowed to cool with stirring. At 0 ° C the water losses were compensated and the perfume added. Hereafter homogenized,

Preface VIII

Sun protection oil.

found in propylene glycol di- (p-methoxy cinnamic acid) ester 1 *, 0 propylene glycol diacrylate and diacrate 26.0 petroleum jelly (s.g. = 0.8 ^ 9 - 0.866) 70.0 oil soluble dye q.s.

perfume (0.5 - 1 $) q.s.

The combined components were heated to 80 ° C, then cooled and perfumed.

Example IX

Sun protection pen.

found. din 20 ^ - (1,1-dimfethylethyl) -¼ '-methoxy dibenzoylmethane 2.0 propylene glycol di- (p-methoxy cinnamic acid) star 5.0 oleyl alcohol (Satol) 17.0 cracked hydrogenated castor oil 19.0 microcrystalline wax 30 .0 25 Vaseline oil 10.0 Methyl and propyl p-aminobenzoic acid ester (70/30) 0.25 Vaseline 16.75 Perfume 0.5

The combined components were melted together and perfumed.

30 Then poured into molds.

8202949

Claims (7)

A light-protecting agent, characterized by a content of a compound of the formula I of the formula sheet, containing hydrogen or C 1 -alkyl, R 2 oi> ci γ-al ^ yl »X a group (-CHg-) n or (-CEpOCHg-) and m = 1 - 5, n = 0-lienp = 1-3, 5 in dissolved or dispersed form and optionally further materials usual in photo-protective agents. A light-protecting agent according to claim 1, characterized in that the content of 1 in the agent is 1-6 parts. 3. A light-protecting agent according to claim 1 or 2, characterized in that the propylene glycol contains di- (p-methoxy-cinnamic acid). K. A light-protecting agent according to claim 1 or 2, characterized in that the 1, 3-Butylene glycol di- (p-methoxy cinnamic acid) ester. Light-protecting agent according to claim 1 or 2, characterized in that it contains triethylene glycol di- (p-methoxy cinnamic acid) ester. 6. Use of compounds of the formula 1, wherein R 1 hydrogen or or C 1 -alkyl, X is a group (-CHg-) n or (-CHgOCHg -) ^ and m = 1-5, n = 0- Suggest Henp = 1-3, in dissolved or dispersed form as a light protectant. 20 7 · Use of propylene glycol di- (p-methoxy cinnamic acid ester in dissolved or dispersed form as a light-protecting agent. 8. Use of 1,3-butylene glycol di- (p-methoxy cinnamic acid ester in dissolved or dispersed form as a light protecting agent. 9. Use of triethylene glycol di- (p-methoxy-cinnamic acid ester 25 in dissolved or dispersed form as a light-protecting agent. 82 02 9 4 9 ~ ........