DE2728241A1 - COSMETIC LIGHT PROTECTION AGENTS FOR THE UV-A AREA - Google Patents

Description

Henkel KGaA PcientG and Literati ?! ' • 3 - r> 5553

Cosmetic light heaters for the UV "A" range

The subject of the invention are kosn: etischo light stabilizers for the UV-A range with a content of cyclopentanone or Cyclohexanone derivative found at topiscbor Aiiwondunj on the Take a shelter from the damaging influences of the läruierwellen UV-A proportion of sunlight with prolonged exposure to sunlight grant.

The preparations generally used as cosmetic sunscreens or light stabilizers contain, in order to prevent sunburn, components which absorb or reflect the short-wave UV-B component of sunlight. They reduce the dose of short-wave radiation that penetrates the outer layers of the skin and thus prevent the formation of swollen erythema without the tanning caused by the longer-wave portion being suppressed. This longer-wave portion of sunlight, which roughly covers the range from 320 - 400 nm, not only enables the skin to be tanned comfortably, but is also held responsible for the chronically photodamaged skin. These damages were previously considered to be age-related; one generally spoke of aging skin. Today we know, however, that they essentially depend on the total duration and strength of the exposure to light. Such skin damage can be seen through increased wrinkling of the skin as a result of loss of elasticity, thinning of the epidermis, yellow-brown discoloration of the facial skin, pigment shifts and finally through keratoses, which can lead to cancer precursors and skin cancers such as spinaliomas and basal cell carcinomas.

There is therefore not only from a purely aesthetic point of view a need for cosmetic agents that

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borrowed side effects of a long and intensive exposure to the long wave UV ~ A antuils of sunlight. The agents must also be toxicologically and dermatologically safe, have good light and heat stability and adhere well to the skin.

It has now been found that cosmetic light stabilizers containing cyclopentanone or cyclohexanone derivatives general formula

0 (1) 0 (II)

ti ti

respectively.

in which η denotes the numbers 2 or 3 and R denotes the radicals Ar or -CH = CII-Ar, where Ar is an aryl radical, in particular a phenyl radical, optionally substituted by one or more C .. -Cj, -alkyl radicals , one or several hydroxyl groups, one or more C ₁ -C. -alkoxy groups, one or more amino or di- (C.-C.) -alkylamino groups, one or more halide atoms or a methylenedioxy group can be substituted, represents the requirements set largely meet.

The cyclopentanone or cyclohexanone derivatives used in the cosmetic light stabilizers according to the invention can be prepared by processes known from the literature Condensation of the corresponding cyclic ketone with a suitable aromatic aldehyde under alkaline conditions take place. One can proceed in such a way that the cyclic ketone and the aromatic aldehyde together in one dissolves suitable solvent and the solution is mixed with a base. But you can also first use the cyclic ketone and

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27282A1

Put the base in a suitable solvent and then add the aromatic aldehyde to the mixture Condensation of the reactants can already be at low temperatures Avie room temperature and below take place or can also be carried out only at higher temperatures. The required reaction temperatures and general reaction conditions depend on the chemical constitution of the reactants and can easily be determine.

In order to obtain the cyclopentanone or cyclohexanone derivatives of the general formula (II), a ratio of the reactants of aromatic aldehyde to cyclic ketone of 2: 1 is chosen, the cyclic ketone having to be unsubstituted on the carbon atoms adjacent to the carboxyl group. If , on the other hand, one wishes to produce a cyclopentanone or cyclohexanone derivative of the general formula (i), a ratio of the reactants of aromatic aldehyde to cyclic ketone of 1: 1 or a small excess of aromatic aldehyde is used. It is also necessary to modify the cyclic ketone in such a way that a condensation reaction can only take place at one of the carbon atoms adjacent to the carbonyl group, in order to avoid the formation of by-products of the general formula (II). This modification can be carried out in such a way that the cyclic ketone is reacted with morpholine to give an N- (1-cycloalkenyl) morpholine. This substituted morpholine is then condensed with the aromatic aldehyde , and then the condensation product obtained is • cleaved under acidic conditions to give the desired cyclopentanone or cyclohexanone derivative of the general formula (i) «

For economic reasons, the base used in the condensation reaction is generally an alkali hydroxide, • in particular sodium hydroxide »

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Cyclopentanone or cyclohexanone derivatives which can be used in the cosmetic light protection agents according to the invention are, for example, 2-benzylidenecyclopentanone, 2-enjiylidene-cyclohexanone, Z- (h ^% -chlorobenzylidone) -cyclopentanone, Z- ( h'-methylbenzylidene ) -cyclopentanone, 2 ~ (p-dimethylaminobenzylidene) -cyclopentanone, 2-anisylidenecyclopentanone, 2- (p-IIydroxybenzylidene) -cyclopentanone, Z- (J ¹ _t k '-dimethoxybenzylidene) -cyclopentanone, 2- (3'-hydroxybenzylidene) -cyclopentanone, 2 ~ (3 ^!, 4 ^! -Diethylbenzylidene) -cyclopentanone, 2- ( k'-aminobenzylidene) -cyclopentanone, 2-anisylidenecyclohexanone, 2- (U-chlorobenzylidene) -cyclohexanone, 2- (p-Dimethylaininobenzyliden) -cyclohexanone, 2- (3 '»^' -dichlorobenzylidene) -cyclohexanone, 2- (p-hydroxybenzylidene) -cyclohexanone, 2- (3 ', 4'-dibutylbenzylidene) -cyclohexanone, 2,5-dibenzylidenecyclopentanone, 2 , 5-bis- (3 '-dichloi'benzylidenj-cyclopentanone, 2, i-dianisylidenecyclopentanone, 2, S-disalicylidenecyclopentanone, 2,5-bis- (3'-methoxy-U-hydroxybenzylidenj-cyclopentanone, 2,5-bis- (p-hydroxybenzylidene) -cyclopentanone, 2,5-dipiperonylidenecyclopentanone, 2,5-bis- (3 '»^' - dimethoxy-benzylidene) -cyclopentanone, 2,5-dicinnainylidenecyclopentanone, 2,6- Bis- (2 ', 3 -dimethoxybenzylidene) -cyclohexanone, 2, ö-dibenzylidenecyclohexanone, 2,6-dianisylidenecyclohexanone, 2,6-bis- (3', U'-dimethoxybenzylidene) -cyclohexanone, 2,6-bis- (p-dimethylaminobenzylidene) -cyclohexanone, 2,6-bis- (4'-isobutylbenzylidene) -cyclohexanone, 2,6-bis- (3'-methoxy-U'-hydroxybenzylidene) -cyclohexanone, 2,6-bis- ( 3'-isopropylbenzylidene) -cyclohexanone, 2,6-bis- (p-aminobenzylidene) -cyclohexanone, 2,6-Bls ~ (k -ethylaminobenzylidene) -cyclohexanone should be mentioned "

When used in cosmetic sunscreens, the cyclopentanone or cyclohexanone derivatives to be used according to the invention can be used be incorporated into liquid, pasty or solid cosmetic preparations, such as aqueous solutions, aqueous suspensions, emulsions, solutions in organic solvents, oils, ointments, creams, pens or powders, case this use as a light protection agent against the longer wave

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The cyclopentanone or cyclohexanone derivatives are used in amounts of 0 _f 5 to 20 percent by weight, preferably 2 to 10 percent by weight, based on the total formulation of the cosmetic agent.

In addition to the sole use in cosmetic sun protection agents, the joint use with conventional UV-B filter substances, which serve to prevent sunburn, will be in the foreground of the use -B-filter substances used, such as p-aminobenzoic acid ethyl ester, -propyl ester, -butyl ester, -isobutyl ester, -monoglycerol ester, p-dimethylaminobenzoic acid ethyl ester, -amyl ester, p-diethylaminobenzoic acid ethyl ester, -amyl ester, salicylic acid ethyl ester, -amylester, salicylic ester, -thomenthyl glycol ester, 2-ethylhexyl ester, -tert, butyl ester, -bornyl ester, -phenyl ester, triethanolammonium salt of salicylic acid, anthranilic acid-menthyl ester, -bornyl ester, p-methoxycinnamic acid 3-ethoxyethyl ester, -2-ethylhexyl ester, p-acotamidocinnamate, 2,2-isopropyl-hydroxy-isopropyl ester 4, k '-dimethoxybenzophenon, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n -octoxy-benzophenone, 4-phenylbenzo- phenone, 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid, ^ -phenyl- benzophenone-2-carboxylic acid isooctyl ester, 7-ethylamino - ^ - methyl coumarin, 7 »8- Dihydroxycoumarin, 6,7-dihydroxycoumarin, 7-hydroxycoumarin, 4-methyl-7-hydroxycoumarin, 2-phenylbenzimidazole-5-sulfonic acid, sodium 3 »Ί-dimethoxyphenylglyoxylate, butylbenzalacetone, benzalacetophenone, 3-campylidene-D, 3- (p-methylbenzylidene) -D, L-camphor and urocanic acid.

The amount of UV-B filter substances in these is on one Combination of products based on UV-A and UV-B protective substances 1 to 10 percent by weight, preferably 2 to 6 percent by weight, based on the total cosmetic light protection agent

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Derartice sunscreens impart when applied topically not only effective protection against the dreaded sunburn, but also against the chronic effects longer permanent influences of the longer-wave UV-A components of sunlight,

The following examples are intended to make the subject matter of the invention elucidate in more detail, without, however, restricting it to this.

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For games

The following examples are intended to demonstrate the protective properties the cyclopentanone to be used according to the invention or cyclohexanone derivatives as well as their suitability for use in cosmetic light protection agents.

The preparation of the cyclopentanone or cyclohexanone derivatives was carried out by methods known from the literature, such as those given in DT-OS 2 2k5 518, for example. Below is the preparation of the new compound 2,6-bis- (2 ^f , 3'-dimethoxybenzylidene). cyclohexanone listed.

Preparation of 2 «6-Bia- (2 *, 3'-dimethoxybenzylidene) -cyclohexanone.

36.6 g of 2,3-dimethoxybenzaldehyde and 9 | 8 g of cyclohexanone were dissolved in 200 ml of methanol. After adding a solution of 10 g of caustic soda in 5 ml of water, the mixture was kept at 35 ° -5 ° C. for 1 hour while stirring. 39 B of a yellow condensation product separated out. After recrystallization from ethanol, the following analytical values were obtained:

calculated: C. 73, 1 H 6, 6th O 20, 3 found : C. 73, 5 H 6, 1 O 20, k

Similar to that of DT-OS 2 2 ^ 5518 the following compounds for testing in sunscreens were produced. In the following table 1, in addition to the designation of the products, their absorption parameters are listed.

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Table 1

No. product 2 max Ig

(nm)

1 2-anisylidene cyclopentaiion 327 4.2

2 2,5-bis (3'-methoxy-4'-hydroxybenaylidene) -

cyclopentanone

3 2- (3 ^f , 4'-dimethoxybenzylidene) cyclopentanone

4 2,5-dibenzylidene-cyclopentanone

5 2,5-uianisylden-cyclopentanone

6 2, S-üisalicylidon-cyclopentanone

7 2- (p-Dimethylaminobenzylidene) cyclopentanone

8 2,5-bis (p-hydroxybenzylidene) cyclopentanone

9 2,5-Dipiporonyliden-cyclopentanone

10 2,5-bis (3 », 4'-dimethoxybenzylidene) -

cyclopentanone

11 2,5-dicinnamylidene-cyclopentanone

12 2-Anisyliden-cyclohexanone

13 2,6-bis (2 ', 3'-dimethox3'-benzylidene) -

cyclohexanone

14 2, δ-dibenzylidene-cyclohexanone

15 2,6-dianisylidone-cyelohexanone

16 2,6-bis- (3 ', 4 -dimethoxybenzylldone) -

cyclohexanone

17 2- (p-Dimethylaminobenzylidene) cyclohexanone

Some examples of cosmetic sunscreens according to the invention with a content of cyclopentanone or cyclohexanone derivatives are listed below:

1. 80 g of 2,5-dibenzylidene-cyclopentanone are used to produce a light protection oil

345 V5 345 3.8 354 *. * 390 4.6 391 fr.5 393 *, 5 397 * .3 400 * .5 403 4.6 407 316 4.0 319 4.4 327 4.4 358 4.4 372 4.4 382 * f3

suspended under heating in 100 g paraffia oil, and

thereafter

share

then at approx. 25 ° C with the following additional bedding

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300 g vegetable oil containing lecithin 400 g olive oil

100 g xaopropylinyristinate 100g purcollin oil

intimately mixed,

2, To be used in the manufacture of a light protection powder

150 g of 2,6-dibenzylidene-cyclohexanone in a powder mixer intensively

35O g rice starch 35O g colloidal clay 100 g Lycopodium 100 g talc

brought into homogeneous distribution,

3. Be used to make a light protection cream

ko g glycerine monostearate 160 g beeswax i * 20 g mineral oil
50 grams of ceresin
50 g of an absorption base based on

Cholesterol, beeswax, stearyl alcohol and petrolatum 90 g of 2-anisylidene-cyclopentanone

melted together at 65 C, Xn this warm mixture becomes a mixture of heated to the same temperature

2 kf g water 13 e borax 2 g p- oxybenzoic acid ethyl ester

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incorporated with vigorous stirring, and the cream obtained The mixture is stirred further until room temperature is reached.

H. To produce a light protection emulsion, a mixture of

20 g glycerine ionostearate

70 grams of stearic acid

30 g oleic acid

20 g ceryl alcohol

80 g of 2, δ-dianisylidene-cyclohexanone

with vigorous stirring a mixture of

800 g of water
10 g glycerin
9 g triethanolamine

given. The lotion obtained is then stirred until cold.

The above emulsion can also be packaged in aerosol form using a propellant gas in a ratio of 80 parts of lotion: 20 parts of propellant gas.

5. Be used to make a sunscreen oil

80 g of 2- (3 *, 4'-dimethoxybenzylidene) cyclopentanone kO g of 2-ethylhexyl p-methoxycinnamate

. finely suspended in 100 g of paraffin oil while warming, and then at approx. 25 ° C with the following additional ingredients

3OO g vegetable oil containing lecithin 360 g of olive oil

100 g of Ieopropyl myristate

100 g purcellin oil

intimately mixed »- 13 -

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6. Be used to making a sunscreen

kO g glycerol monostearate
g beeswax
39O g of mineral oil
50 grams of ceresin
50 g of an absorption base based on cholesterol,

Beeswax, stearyl alcohol and petrolatum 90 g 2, 5-bis- (3'-niethoxy-V-hydroxybenzylidene) -

cyclopentanone
Ίθ g 3- (p-methylbenzylidene) -D, L-camphor

melted together at 65 ^{° C.} Into this warm mixture is a mixture of heated to the same temperature

g of water
13 g borax
2 g of methyl p-oxybenzoate

incorporated with vigorous stirring, and the resulting cream is stirred until it reaches room temperature,

7 · For the production of a sun protection emulsion is in one on approx. 80 C heated mixture of

20 g glycerol monostearate

70 g stearic acid ^r

30 g oleic acid

20 g of cetyl alcohol

80 g of 2,6-bis (3 ', 4'-dimethoxybenzylidene) cyclohexanone kO s p-dimethylaminobenzoic acid 2-ethylhexyl ester

with vigorous stirring a mixture of

s water 10 g glycerine 9 g triethanolarain

given. The lotion obtained is then stirred until cold.

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The above emulsion can also be used with a Propellant gas in a ratio of 80 parts lotion: 20 parts propellant gas Pack in Acrosolforni.

Instead of the cyclopentanone or cyclohexanone derivatives used in the aforementioned formulations, the other cyclopentanone or cyclohexanone derivatives listed above can be used, and the UV-B filter substance mentioned in the recipes can also be replaced by the other listed UV-B filter substances occur.

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Claims (1)

Claims ?; Π \ Cosmetic light protection agents for the UV-E er ο me, characterized by a content of cyclopontanone or cyclohexanone derivatives of the general formula H ₂ C 0 η (ι) CH-R R-HC respectively. in which η denotes the numbers 2 or 3 and R denotes the radicals Ar or -CH = CH-Ar, where Ar is an aryl radical, in particular a Phehylrest, which is optionally replaced by one or more Cj-C ^ -alkyl radicals, one or more hydroxyl groups, a or several C ₁ -C 4 alkoxy groups, one or more amino or di (C ₁ -C 4) - alkylamino groups, one or more halogen atoms or a methylenedioxy group can be substituted. 2. Cosmetic light protection agents according to claim 1, characterized in that they contain the cyclopentanone or cyclohexanone derivatives in an amount of 0.5 to 20 percent by weight, preferably 2 to 10 percent by weight, based on the total cosmetic agent. • 09882/0111 Hang! KGaA patents and literature -? - D 5553 3 »Ko sine ti s cli e sunscreens after. Claims 1 and 2, characterized in that s: i ο nob on don Cyclopentanoiibzv /, Cyclohoxanonderrivatcn usual; UV-E-Filtorsubstaixzion in a Men ^ o of 1 to 10 weight percent, preferably 2 to 6 weight percent, boss ο gene on the total kosnioticcho means, contain, "- 3 - S09882 / 0116