DE1642090A1 - UV light protection agents for cosmetic purposes - Google Patents

Description

mo.9

ϊη ti 6fr 570 IVa / 30i)

B. M e r c k May 2, 1966

Corporation

Darmstadt

UV-Loves protectants for cosmetic purposes

The invention relates to UV-absorbing agents for cosmetic purposes, to be informed by a salary on one or more compounds of the formula I.

in which the remnants

S, E and ir hydrogen or one of him®η a methyl group

mean,

I. in addition to the usual additives and / or carriers.

It has been found that compounds of the formula I have good UV absorption (low permeability) in the UV range from about 290-320 na. Overdosing of UV rays in this area is responsible for the burns in the human skin known under the name "Sonrenbrand".

For example, in the following table the permeability ·! of the following substances depending on the Wavelength specified:

Ia * 2- (2,4-Dlmeth ^ lphen, yl) ~ benzo furan Ib * 2- (2,4-diroettylphenyl) -5-methylbeneofuran Ic = «2- (2,4 * ~ dimethylphenyl) -6-methyl-benzo-furan Id «2- (2,4-dimethylphenyl) -7-methylbenzofuran

109821/2261 bad OB.G.N «.

Di · data relate to solutions of 1 mg in loo ml Ieopropanol cm and a layer thickness of the first

Wavelength in nm

Yes

Ib

3 * permeability Id

280 14.6 15.3 17.3 26.1 285 ll _r 7 13, b 15.4 21.7 290 9.6 12.0 12.8 17.0 295 8.4 11.0 10.5 14.5 300 7.0 9.8 8.2 12.7 305 9.5 7.2 5.6 10.4 310 14.4 12, a 10 ,? 15.4 315 17.3 17.2 13.7 20, ö 320 46.5 15.7 13 ", 7 23.5 325 83.9 65.0 52.9 51.9 330 93.1 ö6 _f ö 83, ö 91.9

As one sifts, the area that is "harmless to the skin" becomes extensively absorbed between 290 and 320 nm, while the tanning rays in the range above 330 are not used again Effect can come,

The compounds of the formula I are particularly notable due to an unusually good solubility in oils and paraffin oil which unexpectedly is much better than the of the unsubstituted 2-rhenylbenr.o furane and others Liethyl groups-substituted 2-1 henylbenzofurans, such as from the following table gives t

Compound solubility>: / 100 .. FaraffinöJ DAB 6

Yes Ib

Ic Id

17.0 7.0 3 * 3

25.0

2-i ^J about «yiben2o furan

1.5

2PToLa mexhyl-benzoi " ran 0.5

Ί 0 9 8ii / 2261

BATH ORIGINAL

Ια DRP 676103 is ready to use τοη connections the general formula

wherein

B an aromatic learn * " g * Also a methine group and

. Y can also mean an oxygen atom and the oarbocyolieohe Six-membered rings represent a benzene ring eollfjale radiation -

Protective agents for human skin described · Neither Compounds of the above general formula I or one of the four individual compounds Ia, Ib, Ic or included in it Id are mentioned by name in this patent specification, and the surprising, advantageous solubility properties of these substances are not disclosed there.

The UV rays absorbing agents according to the invention, as well as the ones on which they are based, are accordingly Compounds of the formula I in the sense of patent law new

The subject of the invention are UV rays absorbing. Agents for cosmetic purposes, characterized in that they contain one or more compounds of the formula I. in addition to the usual additional and / or carrier set of fan ",

The advantages of the new means over the already known ones Anti-fire agents are in addition to their selective absorption especially in their good chemical stability and their low toxicity, high light and weather resistance and odorless.

Compared to the currently all radiation filters commercially available compounds, all of which are top-quality products p-Methoxyzimteäu e-ethoxyäthylsster and p-Diaethylaminobenzoic acid methylet * r or -glyeerinester may be mentioned, The substances contained in the new remedies are particularly beneficial because they have no bewitching groups included and therefore also under aruob values

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not subject to decomposition (saponification). The stability the new means guarantees a constant effectiveness.

You compounds of the formula I can in the usual feiee too Radiation protection agents processed for cosmetic purposes will.

One can duroh addition of ointment or cream bases greasy Liehtsohutzsalben or by mixing with Lösungemitteln optionally with Zueatz of emulsifiers liquid Liohtsehutzpräparate here tellen ₀ Suitable additives and solvents are beispielsweiset hydrocarbons such as solid or liquid paraffin, ceresin, montan wax; pflaoz-

P lehe or animal oils and fats such as olive, peanut,

Sesame or almond oil, cocoa butter, bees, earthen or carnauba owls, wool fat, whale rat; Fatty acids and fatty acid esters such as stearic acid, palmitic acid, oleic acid, glycerine mono- or distearate, glycerine mono-oleate, isopropyl myristate, isopropyl stearate, butyl stearate, alcohols such as ethyl, isopropyl, cetyl, stearyl ipalmityl alcohol; polyhydric alcohols such as glycol, glycerin, sorbitol, which serve as humectants; Emulsifiers of the systems oil in water and water in UI _9, where the commercially available ionic or non-ionic, cationic or anionic or ampholytic emulsifiers are possible; Thickeners such as methyl, ethyl or carboxymethyl cellulose, polyacrylic acid, tragacanth, agar-agar,

"Gelatine. Furthermore, if required or at will, further additives such as perfumes, preservatives or phyeiologically harmless dyes can be added." will·

The compounds of the formula I are accessible in a manner known per se. For example, they can be obtained by reacting Ihenol (or o-, m- or p-cresol) with chlorine acid to form phenoxyeaetic acid (or o-, m- or p-tolyloxyeacetic acid), Umwasdlung (eg with thionyl chloride) in the corresponding acid relialo ^ enides (e.g. Phsnoxyacetylchlorid), Priedel-Crafts Seaktion with m-xylene (e.g. in the presence of

109821/2261 ~ ⁵ "

BATH ORIGINAL

Aluuiiniumohlorld) see 2,4-Dimethyl - <& - pheno: Ky-aeetophenon (or 2,4-Dinsethyl- o », -a» or -p-tolyloxy-acetophenon) and heating them for several hours with poly phosphoric acid to temperatures between 100 and 170 ° _f, preferably about 130 °, with rearrangement to 2- (2 _f 4-dimethylphenyl) benzofurans taking place. They can also be obtained by reacting salicylaldehyde (dew. 3-, V- or 5-lfethyleallcylaldehyde) with lower α-bromo (2,4-dlmethylphesiyl) acylic acid alkylates. (preferably the methyl or ethyl ester), followed by saponification of the obtained 2- (2,4-dimethylphenyl) -3-hydroxy-2,3 ·· dihydroxo-oxofuran-2 <"oarbonic acid as well as deoerboxylation and dehydration.

The founding liquid funds can be useful one or the other contain several other UV-A isorbers, such as 2-Phtmylbenasi-idazol-3-Bulfon'-Acid-Hatriumsals, 3 '4-Diaethylphenylglyoxyläure-Xatri ^ salt, 4-Phenylbenzophenon-2 * -ocarbonaure-Iooctyiestyey.

Die Zab} Jö In the related formulation games, Gfilchtsteile are. On Ste.Me of the specified active ingredient 2- (2, / - dimethylphenyl) -b * nzofuran (Ia) it is also possible to use the abovementioned compounds Ib ₉ Ic or Id. Furthermore ne.oh iunsoh .or &. Usual additives (»3 · Perfumes, dyes, Konevierungefflittel) may be added

«Ia> iel II sun hat> oil

i »(2,4-dimethylphen ₎ yl) -benEofuran 2

Pi raffin oil 30 E. 'nut oil, refined 68 Example 2 ι Βυηηβηβο uta oil with repellent effect

2- (2,4-> dimethylphen, yl) -benaofuran 3

Paraffin, liquid 20 Isopropyl myristate 57

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Oaprylic acid diethylamide 5

m-Ioluyleäuredläthylamid 5

Dime thyphthalate 10 Example 3t Sonneniehutzorerae

2- (2,4-dimethylphenyl) benzofuran x 3

Getyl «stearyl sulphate, sodium« l »2 Cetyl alcohol IO

Tbsellne 20

Ootedec / l alcohol 5

Whale Council 1

oleoerine monoetearate 1

Wool grease 1

Siirbit solution 70> o 5

Waeser 47

Example 4z Soxmenschuteailch

3.0

Paraffin liquid 10.0 Stearic acid polyoxyethylene 10, 0 Ieopropylmyriet 10.0

Sorbitol solution $ 70 5, ü

Sodium Lauryl Ether Sulphate 0.5

61.5

Example 5> Light »chi tzoreme

2- ( 2 _t 4-DiJBethylphenyl-b * n23furan 3

Wool grease 67

Olive oil 10

Water 20

Case 6: Aerofol

Mixture according to Example 1 80 Mixture! Prichlorfluorne-'ran and Diohlor-

difluoromethane (70:30) (7 eir. ^ ae) 20

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BATH ORIGINAL

Example 7s light protection cream

2- (2,4-diraethylphenyl) benzene ofuran 2

2-phenyl-benzimidaeol-5-sulfonic acid

triethanolsmineals: 5096 3

Customary Crenie base

(System Gl / water or water / oil) 95

Example ti: lipsticks

100 g of commercially available lipstick compound is melted and 2 g of 2- (2,4-i) imethylphenyl) benzene is soldered into it. Di · Hasse is poured into cooled lipstick mold and removed the molded body after the cooling.

The following examples are those for the manufacture some of the substances that can be used in the invention.

Example A.

a) 2bO g of phenoxyethyl chloride are dissolved in 30 ml of xylene, 1 ^ 5 i: alumuminum chloride is added and the mixture is heated to reflux for 1 hour Solutions, the solvents are distilled off and the residue is distilled off at 205-210 ° / 12. 273 l of a-phenoxy-2,4-diweth / j acetophsnon are obtained

Similarly, j

with o-tolyloxyiicetyloislorid: a- (2-meth; ylphenos: y) «> 2, ^ dime th;, ·! acetophenone, b.p. 220-222 ° / 12 mt &; with m-Toliloxvacetylchloridi a-C3-Mstliylphenoxy) »2,4 ^ diBethylfecetofhenon, bp 219-221 ° / 12 amj
with p-Tolyloxyacetylchloridi a- (4-llethylphenoxy) -2 _e 4-dl-

^109821/2261 "Iadowginal

b) 16.5 g of a-Pherioxy-P ^ -dimethyl-acetophenone and 165 g of polyphoephoreic acid are stirred for 2 hours at 132 ° warmed up «You pour on Elswasaer, extracted with ether, washes the ethereal solution with sodium bicarbonate solution and dries over magnesium sulfate. After distilling off, dee Solvent, the residue is distilled at 195-197 ° / 12 mi. 10 g of 2- (2,4-dimethylphenyl) -bsneofuran are obtained, which can then be recrystallized from isopropanol bfi Melts 50-51 °.

Analog are available »

2- (2,4 ~ dimethylphenyl) -5-methyl-bensofuran _t P. 67-69 ° J Xp. 210-215% 2mm;

2- (2,4-Dimethylphenyl) -6-methyl-benzofuran, P, 80-82 ° (from isopropanol);

2- (2,4-Diaethylphenyl) -7- «ethyl-benzofuran, boiling point 200-205 ° / 12hb.

Example B.

a) 25 g of salioylaldehyde and 50 g of a-bromo (2,4-dimethylphenyl) -esslgsäureäthylester are boiled with the addition of 32 g of anhydrous potassium carbonate in 100 ml of methyl ethyl ketone for 4 hours. It is cooled, diluted with ether and filtered ron undissolved salt, Tom Ti.Ltrat, the solvent is distilled off and the residue in a water jet vacuum to dta Steam bath degassed. 3-Hydroiy-2- (2,4-dimethylphenyl) -2,3-dihydrobeneofuran-2-carboxylic acid ethyl ester remains as the residue, which is 60 al 32% sodium hydroxide solution Tereetst and as long as it is heated on the steam bath, bit the contents of the flask have solidified. Ss is sucked off, the Residue dissolved in water i; ad with concentrated hydrochloric acid , .ngeuert. The oil which separates out is taken up in chloroform, washed with water, dried and the solvent is distilled off. 30 g of 3-hydroxy-2- (2,4-dimethylphenyl) ~ 2,5-dihydro-oensofuran-2-carboxylic acid are obtained.

. 9 109821/2261 BAD ORIGINAL

b) 10 g of the crude 3-hydroxy ~ 2 ~ (2,4-dimethylphenyl) -2,3-

dihydro-benzofuron-2-earbonsäure be aufgeeolilSmmt in 25 ml water, then 10 ml of concentrated sulfuric acid added and the mixture heated until the end of C0 ₂ evolution on the steam bath, Daa crude product obtained is deotillierto obtained 8 g of 2- (2, 4-dimethylphenyl) benzofuran with a bp 195-197 ° / 12 mm. P. 50-51 °.

109821/2261 -10-

BATH ORIGINAL

Claims (1)

üche Ι »UV-absorbing agents for cosmetic purposes, characterized by a content of one or more compounds of formula 1 in which the remnants R ₉ R and R ^{y are} hydrogen or one of them is a methyl group mean, in addition to the usual additives and / or carriers. 2 ο means according to claim 1, characterized by a salary of 2- (2,4-dimethylphenyl) benzofuran. 3 «smock according to claim 1 or 2 ₉ characterized by a Kuaätzllchen content of one or more other UY- Abaorbem · 4 ο Connections of Pormel Io 5 ο 2- (2,4-Dimethylphenyl) -benzofuran, 6 ο 2- (2,4-dimethylpheny1) -5-methy1-benzofuranο 7. 2- (2,4-Dimethylphenyl) -6-methylbenaofuran » β, 2- (2,4-Dime thy 1 i'heny 1) -7 ~ iae thy! -benzo furan «, 109821/2261