WO2003092643A1

WO2003092643A1 - Light-protection formulations using acrylonitrile derivatives

Info

Publication number: WO2003092643A1
Application number: PCT/EP2003/004479
Authority: WO
Inventors: Erich Dilk; Oskar Koch; Roland Langner; William Johncock
Original assignee: Symrise Gmbh & Co. Kg
Priority date: 2002-05-02
Filing date: 2003-04-30
Publication date: 2003-11-13
Also published as: AU2003224139A1; DE10219433A1

Abstract

Cosmetic preparations containing acrylonitrile derivatives which protect human skin and hair from UV radiation.

Description

Sunscreen preparations using acrylonitrile derivatives

The invention relates to cosmetic preparations for protecting human skin and hair from the damaging effects of ultraviolet

Solar radiation, the new acrylonitrile derivatives contained in these preparations and their use as UV absorbers.

UV absorbers are compounds with a pronounced absorption capacity for ultraviolet radiation. They are used in particular as sunscreens in cosmetic and pharmaceutical preparations, but also to improve the light resistance of technical products such as paints, varnishes, plastics, textiles, polymers such as e.g. Polymers and copolymers of mono- and diolefms, polystyrenes, polyurethanes, polyamides, polyesters, polyureas and polycarbonates, packaging materials and rubbers are used.

Depending on the wavelength, UV rays are converted into UV-A rays (320-400 nm, UV-AI: 340-400 nm, UV-A-II: 320-340 nm) or UV-B rays (280-320 nm ) assigned.

UV rays can cause acute and chronic skin damage, the

Type of damage depends on the wavelength of the radiation. The UV-B radiation can cause sunburn (erythema) and serious skin burns. Reductions in enzyme activities, weakening of the immune system, disorders of the DNA structure and changes in the cell membrane as a damaging effect of UV-B rays are also known. The UV-A rays penetrate into the deeper layers of the skin and can accelerate the aging process of the skin there. The shorter-wave UV-A-II radiation additionally increases the formation of sunburn. In addition, UV-A radiation can trigger phototoxic or photoallergic skin reactions. Selir frequent and unprotected exposure of the skin to sunlight leads to a loss of skin elasticity and increased wrinkling. In extreme cases, pathological skin changes up to skin cancer are observed.

Depending on the location of their absorption maxima, UV absorbers are divided into UV-A and ÜV-B absorbers; If both UV-A and UV-B are absorbed by a UV absorber, one speaks in this case of a UV-A / B broadband absorber.

The number of suitable UV-A absorbers is very limited and they have significant shortcomings:

The filter 4-tert-butyl-4'-methoxy-dibenzoylmethane (absorption maximum at 357 nm), which is frequently used in particular for protection against UV-Al radiation, is not photostable. In combination with the UV-B filters p-methoxycinnamic acid 2-ethylhexyl or isoamyl ester, photo reactions are also observed. In addition, it has only a limited solubility in cosmetic oils, which can lead to problems in the formulation of cosmetic preparations. In addition, sunscreen products containing di-benzoyl methane derivative can leave stains that are extremely difficult to wash out on textiles.

There is therefore a further need for light stabilizers for use in cosmetic and pharmaceutical preparations for the UV-A range. We are looking for light-stable UV-A absorbers with strong absorption so that they effectively protect against the damage caused by UV rays. In addition, the aim is that these UV absorbers also meet the following criteria for being blown away in cosmetic sunscreens:

Compatibility with other UV absorbers under the influence of light

- With crystalline UV absorbers, good solubility in cosmetic solvents and liquid, oil-soluble UV absorbers, such as p-methoxy cinnamon. Acid ethyl, isoamyl and isooctyl ester, ethylhexyl salicylate, homomenthyl salicylate, menthyl anthranilate, p-aminobenzoic acid ethyl hexyl ester, 3,3-diphenyl-2-cyanoacrylic acid ethyl and ethyl hexyl ester;

- Liquid, oil-soluble UV absorbers should be readily miscible with other UV absorbers or cosmetic oil components;

water-resistant UV protection;

- easy processing in cosmetic formulations and stability under conditions of use;

Compatibility with cosmetic raw materials;

- pH stability;

Thermal stability;

no or easily washable discoloration of textiles;

Colorless and odorless;

easily biodegradable;

- not hazardous to water;

low skin penetration;

Refractive index> 1.5 in order to achieve improved transparency of emulsions. The invention relates to light protection preparations containing acrylonitrile derivatives of the formula (I) in which the C = C double bond is in the E or Z configuration,

wherein

R ^{1 can} denote hydrogen, C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₆ -C ₁₂ aryl,

R ² COOR ¹³ , COR ¹³ , CONR ¹³ R ¹⁴ , CN, where R ¹³ - R ^{14 is} hydrogen, C.-C ₂₀ -alkyl, C ₂ -C ₂₀ -alkenyl or C ₂ -C ₂₀ -alkynyl, C ₆ -Cι ₂ -aryl, C ₃ -C ₁₅ cycloalkyl, C.-C ₁₂ heteroaryl, which may optionally be substituted by amino, hydroxy, acetoxy, carboxy, carbalkoxy, carbamoyl, a group W or interrupted by ether oxygen .

R ³ -R ^{12 have} the meaning given under R ¹ or also C ₃ -C- ₅ - cycloalkyl, C ₅ -C ₁₂ heteroaryl, C.-C. _g denotes alkoxy, C ₆ -C ₁₂ aryloxy, amino, hydroxy, acetoxy, carboxy, carbalkoxy, carbamoyl, where they can be substituted by a group W or interrupted by ether oxygen, 3 with the proviso that two substituents of R -R on adjacent C atoms together can mean an optionally substituted CrC ₄ alkylene group, it being possible for a methylene group to be replaced by -O-, -S- or -NH-,

0, 1 or 2

W silanes, oligosilanes and polysiloxanes of the general formulas W ^• I i b.:i,s W s _. iπ

W SiR ¹ _a (OSiR ¹⁵ ₃ ) _b

0, 1, 2 or 3

3, 2, 1 or 0

a + b 3

A is a bond to the neighboring atom

1-10 R 15 is an open-chain or branched aliphatic, araliphatic, cycloaliphatic or optionally substituted aromatic radical, each having up to 18 carbon atoms

mean.

Examples of alkyl radicals are methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl , 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl , 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1, 2 , 2-trimethylpropyl, 1-ethyl-1-methylpropyl, l-ethyl-2-methylpropyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl and n-

Called dodecyl.

Examples of alkoxy radicals are methoxy, ethoxy, iso-propoxy, n-propoxy, 1-methylpropoxy, n-butoxy, n-pentoxy, 2-methylpropoxy, 3-methylbutoxy, 1,1-dimethylpropoxy - To name 2,2-dimethylpropoxy, hexoxy, heptoxy, octoxy.

Compounds of the formula (I A) are preferred

R ² wherein

R ¹ is hydrogen, C.-C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₁₂ alkynyl, can mean phenyl ₂ -C,

R ² COOR ¹³ , COR ¹³ , where R ^{13 represents} hydrogen, C.-C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl or C ₆ -C ₂ aryl, which may be by Amino, hydroxy, acetoxy, carboxy, carbalkoxy, carbamoyl, a group W substituted or interrupted by ether oxygen,

R ³ -R ^{12 have} the meaning given under R ¹ or also C ₃ -C ₁₅ -

Cycloalkyl, C.-C ₁₂ heteroaryl, C - C ₁₆ alkoxy, C ₆ -C ₁₂ aryloxy, amino, hydroxy, acetoxy, carboxy, carbalkoxy, carbamoyl, where they are substituted by a group W or by ether

Oxygen may be interrupted

with the. Provided that two substituents of R -R on adjacent C atoms together can mean an optionally substituted Ci- alkylene group, and

z means 0, 1 or 2.

Compounds of the formula (IB) are particularly preferred

wherein

R ^{1 can be} hydrogen, C ₆ -C ₆ -alkyl or phenyl,

R ³ -R ^{12 are} hydrogen, C.-C ₁₂ -alkyl, C ₂ -C ₁₂ -alkenyl, C ₂ -C ₁₂ -alkynyl, phenyl, C.-C ₁₂ -alkoxy, hydroxy, acetoxy, carboxy, carbalkoxy, carbamoyl can mean, where they can be substituted by a group W or interrupted by ether oxygen,

with the proviso that too. two substituents of R ³ -R ⁸ on adjacent C atoms together can represent an optionally substituted Ci-G _t alkylene group,

_R 16, _R 18 are independently hydrogen, C.-C ₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ -alkynyl, may mean these with C - C ₁₂ alkoxy, hydroxy, Acetoxy, carboxy, carbalkoxy, carbamoyl, a group W substituted or interrupted by ether oxygen,

0.1 or 2

means. 3-Oxo-4,4-dimethyl-pentanenitrile (compounds of the formula (IB) with R ¹⁶ -R ¹⁸ = CH ₃ ) are very particularly preferred.

The following are particularly preferred 3-oxo-4,4-dimethyl-pentanenitriles:

2 - [(2,3-dihydro-1 H -indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2- [(2,3-dihydro-2-methyl-1 H -indole-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2 - [(2,3-dihydro-5-methyl-1 H-indole-1-yl) methylene] -4, 4-dimethyl-3-oxopentanenitrile,

2- [(2,3-dihydro-2,3-dimethyl-1 H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2 - [(2,3-dihydro- 2,5-dimethyl-lH-indol-l-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2 - [(2,3-dihydro-2,3,3-trimethyl-lH-indole -l-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile,

2 - [(2,3-Dihydro-5-methoxy-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2 - [(2,3-dihydro-2-methyl -5-methoxy-lH-indol-l-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2 - [(2,3-dihydro-2,3,3-trimethyl-5-methoxy- 1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2- [1 - (2,3-dihydro-2-methyl-1 H -indol-1-yl) ethylidene] -4,4-dimethyl-3-oxopentanenitrile,

2- [1 - (3, 4-dihydro-1 (2H) -quinolinyl) ethylidene] -4,4-dimethyl-3-oxopentanenitrile and 2 - [(l, 2,3,4,10, ll- Hexahydro-9H-carbazol-9-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile.

The compounds of formula (I) can be prepared by processes known per se, for example by heating NH heterocycles together with orthocarboxylic acid esters and CH-acidic compounds. As NH heterocycles, for example indoline, 2-methyl-indoline, 2,3,3-trimethylindolm, 2,3,3-trimethyl-5-methoxy-indoline, 5-methoxy-indoline, 1,2,3,4, 5,10,11-hexahydrocarbazole and 1,2,3,4-tetrahydroquinoline can be used. Possible Orthocar Examples of bonic acid esters are trimethyl orthoformate, triethyl orthoformate, triethyl orthoacetate, triethyl orthopropionate and trimethyl orthobenzoate. Examples of CH-acidic compounds which can be used are ethyl cyanoacetate, 3-methylbutyl cyanoacetate, 2-ethylhexyl cyanoacetate, dinitrile malonate or pivaloylacetonitrile.

The higher alkyl esters of the formula (I) can also be obtained from the methyl or ethyl esters by transesterification with higher alcohols.

The use of acrylonitrile derivatives of the general formula (I) as UV filters to protect technical products such. B. of plastics is known from DE-A 1 568 541. In contrast, cosmetic and pharmaceutical light protection preparations using acrylonitrile derivatives of the formula (I) as UV-A filters have not been described to date.

The sulfonated acrylonitriles claimed in WO 97/14680 are not suitable for all applications. Due to the extreme water solubility of these compounds, it is difficult, for example, to achieve waterproof cosmetic preparations with these compounds.

The oil-soluble acrylonitrile derivatives of the formula (I) are notable for strong absorption in the UV-A range and also have excellent lightfastness.

They are photostable and have good solubility in cosmetics

Solvents and in liquid oil-soluble UV absorbers. These compounds can be used to produce stable cosmetic preparations in all respects without any problems. Particularly with the very particularly preferred 3-oxo-4,4-dimethyl-pentar nitriles, good protection against the longer-wave UV-A radiation can be achieved due to their strong absorption in the UV-AI range.

The acrylonitrile derivatives of the formula (I) can therefore be used as UV absorbers in cosmetic products, in particular for protection against acute (sunburn) and chronic (premature skin aging) skin damage, particularly in sunscreens, day care products and hair care products.

In cosmetic preparations, the acrylonitrile derivatives of the formula (I) also lead to the photostabilization of UV absorbers with less UV light stability (cf. Table 2).

In particular, they stabilize the very light-unstable UV-A absorber 4-tert-butyl-4'-methoxydibenzoylmethane.

Although the absorption maximum of the acrylonitrile derivatives of the formula (I) is in the UV-A-I range, these acrylonitrile derivatives surprisingly also improve the photostability e.g. the UV-B filter reaches p-methoxy cinnamic acid 2-ethylhexyl or isoamyl ester.

Likewise, a combination of the UV filter p-methoxy-cinnamic acid 2-ethylhexyl or isoamyl ester with 4-tert-butyl-4'-methoxy-dibenzoylmethane in cosmetic preparations is stabilized by the acrylonitrile derivatives of the formula (I) ,

Sunscreen preparations with improved photostability are achieved by using 0.1-10% by weight, preferably 1-10% by weight, of 2-ethylhexyl p-methoxycinnamate, isoamyl p-methoxycinnamate or 4-tert-butyl-4 '-methoxy-diben-zoylmethane with 0.1-10 wt .-% of a compound Her formula (I). Cosmetic formulations with increased light stability can also be prepared by a three-way combination of dibenzoylmethane derivatives and p-methoxycinnamic acid esters with acrylonitrile derivatives of the formula (I) by using, for example, 0.1-5% by weight of 4-tert-butyl-4 ' -methoxy-dibenzoylmethane, preferably 1-3% by weight, 0.1-10% by weight p-methoxycinnamic acid 2-ethylhexyl ester, preferably 1.0-7.5% by weight, and at least 0.2% by weight .-% of a compound of formula (I), preferably 1.0-6.0 wt .-%, preferably in a ratio of 1 part of dibenzoylmethane derivative, 2 parts of p-methoxycinnamate and 2 parts of the compound of formula (I).

It is also advantageous to add one or more very photostable UV absorbers to this combination of three, such as methylbenzylidene camphor, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, octyltriazon, Uvasorb ^® HEB, Tinosorb ^® S, Tinosorb ^® M, Ethylhexyl salicylate, homomenthyl salicylate and phenylene benzimidazole sulfonic acid or phenylene bis-benzimidazole tetrasulfonic acid disodium salt, Mexoryl ^® SX, Mexoryl ^® XL or Parsol ^® SLX.

Furthermore, in cosmetic preparations, surprisingly, by

Use of acrylonitrile derivatives of the formula (I) in combination with others

• UV filters achieved a synergistic increase in the sun protection factor. Examples of a synergistic increase in the sun protection factor are cosmetic

Emulsions containing both a compound of formula (I) and ethylhexyl methoxy cinnamate or octocrylene, or a combination of compound of formula (I) with ethyl hexyl methoxy cirmamate and 2-phenyl benzimidazole sulfonic acid, or ethyl hexyl methoxy cinnamate and methyl benzylidene camphor, or ethyl hexamate and ethyl cylamate and ethyl hexyl methoxy 4-t-butyl-4'-methoxydibenzoylmethane, or Neo Heliopan ^®

AP and ethyl hexyl methoxycinnamate, or a combination of compound of formula (I) with octocrylene, methylbenzylidene camphor and zinc oxide. Combinations of compound of the formula (I) with dibenzoylmethanes, methylbenzylidene camphor, 2-phenylbenzimidazole sulfonic acid, Neo Heliopan ^® AP, Mexoryl ^® SX, Mexoryl ^® XL, Parsol ^® SLX, Tinosorb ^® S, Tinosorb ^® M, Uvinul ^® T150,

Uvasorb ^® HEB and microfine pigments, zinc oxide and titanium dioxide, synergistic increases in the sun protection factor. The UN filter combinations mentioned are given as examples and are not to be understood as being limited to the combinations mentioned above. Thus, all of the above-mentioned particularly suitable UN absorbers as well as all UN filters with compounds of formula (I) or the above combinations, individually or in combination, approved in the monographs or positive lists (USA, Europe, Japan, Australia, South Africa and other countries) any mixtures can be used in combination. These combinations usually achieve a synergistic increase in the UV sun protection factor.

The combination of compounds of formula (I) with UV-A absorbers, especially UV-A-II absorbers, provides comprehensive protection against UV-A radiation (320-400 nm). In particular, a combination of compounds of the formula (I) with Νeo Heliopan ^® AP (UV-AII absorber) should be mentioned for a broad UV-A protection performance. Further UV-A filters, which are preferred in combination with compounds of formula (I) alone or in combination of compounds of formula (I) and Νeo Heliopan ^® AP, are Mexoryl SX, Mexoryl ^® XL, Tinosorb ^® M, Tinosorb ^® S, benzophenone-3, benzophenone-4, Νeo Heliopan ^® 357 and Νeo Heliopan ^® MA.

For optimal broadband protection performance against UV-A and UV-B radiation, the aforementioned combinations must be combined with all UV-B filters and mixtures of these filters (cf. above-mentioned particularly suitable UV absorbers). Geeigneteo Heliopan ^® AV, Νeo Heliopan ^® E1000, Νeo Heliopan ^® Hydro, Νeo Heliopan ^® MBC, Νeo Heliopan ^® 303, Νeo Heliopan ^® OS, Νeo Heliopan ^® HMS, Uvinul ^® T150, Uvasorb ^® HEB and dimethylaminobenzoic acid ethylhexyl ester are particularly suitable.

By combining compounds of the formula (I) with Νeo Heliopan ^® AP and a UV-B filter, for example ethylhexyl methoxycinnamate or UV-B filter mixtures and coated or uncoated finely dispersed metal oxides such as zinc oxide, titanium dioxide becomes a UV broadband protective power with a critical wavelength λ _cr it. «380 nm achieved (see also Diffey in Int. J. Cosm. Science 16, 47 (1994)).

Synergies of the acrylonitrile derivatives of the formula (I) with other components which do not absorb UV light with regard to improved protection against UV light are to be expected.

Sun protection products should be waterproof so that adequate UN protection for the user, especially children, is guaranteed after swimming or bathing. The UV absorbers of the formula (I) meet these requirements to a particular extent on account of their hydrophobic character and are therefore particularly suitable for the formulation of water-resistant sun protection products. Furthermore, the water resistance of sun protection products can be improved with water-soluble, single or multiple sulfonated UV filters such as Νeo Heliopan ^® AP,

Mexoryl ^® SX, benzophenone-4, Νeo Heliopan ^® Hydro and the above-mentioned particularly suitable oil-soluble UN absorbers can be significantly increased by combination with compounds of the formula (I).

Liquid acrylonitrile derivatives of the formula (I) are also suitable as solvents for solid UV filters, for which the following compounds are mentioned by way of example but not by way of limitation: camphor derivatives (for example benzylidene camphor and methylbenzylidene camphor), triazine derivatives (for example octyltriazine, dioctylbutamide triazine, Bis (ethyl-hexyloxy, hydroxy) phenyl, methoxyphenyltriazine), benzophenone derivatives (eg oxybenzone), dibenzoylmethane derivatives (eg butylmethoxydibenzoylmethane). The

Solvent properties of the acrylonitrile derivatives according to formula (I) can be increased if they are combined with other liquid constituents of cosmetic preparations, including other liquid UV filters. Examples include, but are not limited to: ethylhexyl p-methoxycinnamate, isoamyl p-methoxycinnamate, ethylhexyl salicylate, octocrylene, menthyl anthanilate, fatty alcohol esters, fatty acid esters, alkyl benzoates, etc. Crystalline acrylonitriles of the formula (I) must be sufficiently dissolved in cosmetic preparations in order to avoid the problem of recrystallization after a long storage period. A sufficient amount of the oil components usually used in cosmetic preparations, liquid oil-soluble UV absorbers or alcohols, e.g. As ethanol, isopropanol or 1-butanol, is necessary to avoid recrystallization. The use of the following oil components and / or UV absorbers is particularly preferred in order to achieve sufficient solubility of the acrylonitrile derivatives:

Ethylhexyl methoxycinnamate, isoamyl methoxycinnamate, octocrylene, ethylhexyl salicylate, homosalate, menthyl anthranilate, Padimate O, diisopropyl adipate, Cι _-15 - alkyl benzoate (Witconol TN), butylene glycol dicaprylate glycol dicaprylate / dicaprate (Miglyol 8810) Cocoglycerides (Myritol 331) Capryl / capr.-triglyceride (Miglyol 812), cetearyl-isononate (Cetiol SN), PVP / hexadecene copolymer (Unimer U151), adipic acid

/ Diethylene glycol / isononanoic acid copolymer (Lexorez 100) Propylenglykoldicapry- lat / dicaprate (Myritol PC), hexyl laurate (Cetiol A), dicapryl ether (Cetiol OE), diethylhexyl naphthalate (Hall Brite ^® TQ), butyloctyl salicylate (Hall Brite ^® BHB), dibutyl adipate (Cetiol B), triethyl citrate (Hydagen CAT), propylene glycol dibenzoate (Finsolv PG 22), tributyl citrate, dioctyl malate (Ceraphyl 45), dipropylene glycol dibenzoate (Benzoflex 245), acetyl tributyl citrate (Citroflex A-4), acetyl nitrate Citroflex A-2). The list of the oils mentioned, which can be used in the sense of the present invention, should of course not be limiting.

It is very disadvantageous if UV absorbers leave stains that cannot be washed out on clothing. In particular, it is known from the UV-A absorber tert-butyl methoxydibenzoyl methane that it produces stains on textiles that can no longer be washed out. The acrylonitriles according to the invention do not have this disadvantage since staining on textiles can be very easily washed out. The present invention also relates to new acrylonitrile derivatives corresponding to formula (IB) and their use as UV absorbers, in particular in cosmetic preparations.

The following new acrylonitrile derivatives of the formula (IB) are particularly preferred:

2 - [(2,3-dihydro-lH-indol-l-yl) methylene] -4,4-dimethyl-3-oxo-pentanenitrile

2- [(2,3-dihydro-2-methyl-1 H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile

2- [(2,3-dihydro-5-methyl-1 H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile 2 - [(2,3-dihydro-2,3 -dimethyl-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile

2 - [(2,3-dihydro-2,5-dimethyl-lH-indol-l-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile 2 - [(2,3-dihydro-2, 3,3-trimethyl-lH-indol-l-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile

2 - [(2,3-Dihydro-5-methoxy-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile

2 - [(2,3-Dihydro-2-methyl-5-methoxy-1 H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile 2 - [(2,3-dihydro -2,3,3-trimethyl-5-methoxy-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile

2- [1 - (2,3-Dihydro - 1 H -indol-1-yl) ethylidene] -4,4-dimethyl-3-oxopentanenitrile 2- [1 - (2,3-dihydro-2-methyl - 1 H-indol-1-yl) ethylidene] -4,4-dimethyl-3-oxopentanenitrile 2- [1- (3,4-dihydro-l (2H) -quinolinyl) ethylidene] -4,4- dimethyl-3-oxo-pentanenitrile

2- [(1, 2,3, 4, 10, 11-hexahydro-9H-carbazol-9-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile

When used in cosmetic or pharmaceutical preparations, the UV absorbers of the formula (I) prevent the UN rays from passing through the applied film of the preparation. Cosmetic and dermatological formulations in the sense of this invention contain one or more conventional UN-A, UN-B and / or broadband filters as individual substances or in any mixtures with one another, in the lipid phase and / or in the aqueous phase. They are satisfactory products in every respect, which are surprisingly characterized by a high UV-A protection performance or a high sun protection factor.

This is generally the case if the preparations contain 0.5 to 15, preferably 1 to 10, in particular 2 to 7,% by weight (based on the total weight of the preparation) of a compound of the formula (I).

The cosmetic and / or dermatological formulations according to the invention can be composed as usual and the cosmetic and / or dermatological light protection, furthermore for the treatment, care and cleaning of the

Skin and / or hair and as a make-up product in decorative cosmetics.

These cosmetic and pharmaceutical preparations, which serve to protect skin and hair from UV radiation, can be in the commonly used application forms, i.e. as an oil-in-water, water-in-oil or mixed emulsion, as milk, as a lotion or cream, aerosol, hydrodispersion or oil gel (emulsifier-free), spray, foam, solution, powder, stick preparation or as any other usual cosmetic or pharmaceutical preparation. To protect the hair from UV rays, preparations are preferred as shampoo,

Conditioner, cure, gel, lotion, spray or cream used.

Accordingly, the preparations according to the invention, depending on their structure, can be used, for example, as skin protection cream, cleansing milk, sun protection lotion, nutrient cream, day or night cream, etc. It is possibly possible and advantageous to use the preparations according to the invention as the basis for pharmaceutical products. to use pharmaceutical formulations. Those cosmetic and dermatological preparations which are in the form of a skin care or make-up product are particularly preferred.

For use, the cosmetic and dermatological preparations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics. Those cosmetic and dermatological preparations which are in the form of a sunscreen are particularly preferred.

The cosmetic and dermatological preparations according to the invention can contain cosmetic auxiliaries, as are usually used in such preparations. e.g .:

Emulsifiers, surface-active compounds, lanolin, petroleum jelly, water, fats,

(e.g. triglycerides of fatty acids), polyethylene glycols, fatty alcohols, ethoxylated fatty alcohols, fatty acid esters (e.g. isopropyl palmitate, isooctyl stearate, adipic acid diisopropyl ester etc.), natural or synthetic oils or waxes, pigments, (e.g. titanium dioxide, zinc oxide, pearlescent pigments), color pigments e.g. hydroxyethyl cellulose, carboxymethyl cellulose, bentonite, etc.), foam stabilizers, film formers, dyes, electrolytes, pH regulators, preservatives, bactericides, moisturizers, vitamins and biogenic agents (e.g. plant extracts and protein hydrolyzates), silicone derivatives, alcohols and polyols (e.g. ethyl alcohol, isopropanol , Glycerin), perfume oils, polymers such as Polyacrylates, polyurethanes, polyglycerols, polyvinyls, alkene and alkyne polymers,

Polysaccharides, polyvinylpyrrolidone, substances to prevent foaming, antioxidants, electrolytes, organic solvents, complexing agents, repellents, glycerides and radical scavengers such as HALS (= "hindered amine light stabilizers") or phenol derivatives. Non-ionic emulsifiers or dispersants in question the group that is formed come from Polyglyceryl-2-dipolyhydroxystearate (Dehymuls ^® PGPH), polyglyceryl-3-diiso-stearate (Lameform ^® TGI), Polyglyceryl-4 isostearate (Isolan ^® GI 34), polyglyceryl-3-oleates, diisostearyl-polyglyceryl-3-diisostearate (Isolan ^® PDI), polyglyceryl-3-methylglucose distearate (Tego Carey ^® 450), polyglyceryl-3-beeswax (Gera Bellina ^® ), polyglyceryl-4- caprate (Polyglycerol caprate T2010 / 90), Polyglyceryl-3-cetylether (Chimexane ^® NL), Polyglyceryl-3-distearate

(Cremophor ^® GS 32), polyglyceryl-2-stearate (Hostacerin ^® DGMS) and polyglyceryl polyricineoleate (Admul WOL 1403) as well as their mixtures.

The lipid phase of the preparations can advantageously be selected from the following group of substances:

Mineral oils, mineral waxes; Oils, such as triglycerides of capric or caprylic acid, as well as natural oils such as e.g. Castor oil;

Fats, waxes and other natural and synthetic fat bodies, preferably esters of fatty acids with alcohols of low C number, e.g. with isopropanol, propylene glycol or glycerin, or esters of fatty alcohols with low C number alkanoic acids or with fatty acids;

benzoates;

Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.

The oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions for the purposes of the present invention is advantageously selected from the group of esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 carbon atoms, from the group of aromatic esters

Carboxylic acids and saturated and / or unsaturated, branched and / or unsaturated branched alcohols with a chain length of 3 to 30 carbon atoms. Such ester oils can then advantageously be selected from the group of isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononylisononanoate, 2-ethylhexyl-ethyl-2-ethylhexyl-ethyl-palylate Hexyldecyl stearate, 2-octyldodecyl palmitate, oleyl oleate, olerlerucate, erucyl oleate, erucylerucate and synthetic, semi-synthetic and natural mixtures of such esters, for example jojoba oil.

Furthermore, the oil phase can advantageously be selected from the group of branched and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and also the fatty acid triglycerides, especially the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12 to 18, carbon atoms. The fatty acid triglycerides can, for example, advantageously be selected from the group of synthetic, semisynthetic and natural oils, e.g. Olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.

Any mixtures of such oil and wax components can also be used advantageously for the purposes of the present invention. It may also be advantageous to use waxes, for example beeswax and its derivatives, as the sole lipid component of the oil phase.

The oil phase is advantageously selected from the group consisting of 2-ethylhexyl isostearate, octyl dodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C ₁₂ . ₁₅ alkyl benzoate, caprylic capric acid triglyceride and dicaprylyl ether.

Mixtures of C _12-15 alkyl benzoate and 2-ethylhexyl isostearate, mixtures of C _2-15 alkyl benzoate and isotridecyl isononanoate and are particularly advantageous Mixtures of C ₁₂ -is alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.

Of the hydrocarbons, paraffin oil, squalane and squalene can be used advantageously for the purposes of the present invention.

The oil phase can advantageously also contain cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or the silicone oils.

Cyclomethicone (octamethylcyclotetrasiloxane) is advantageously used as the silicone oil to be used according to the invention. However, other silicone oils can also be used advantageously for the purposes of the present invention, for example hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).

Mixtures of cyclomethicone and isotridecyl isononanoate and of cyclomethicone and 2-ethylhexyl isostearate are particularly advantageous.

The aqueous phase of the preparations according to the invention advantageously advantageously contains:

Alcohols, diols or polyols of low C number and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerin. Ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl,

monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analog products, furthermore low C number alcohols, e.g. Ethanol, isopropanol, 1,2-propanediol, glycerol and in particular one or more thickeners, which one or more can advantageously be selected from the group silicon dioxide, aluminum silicates,

Polysaccharides or their derivatives, for example hyaluronic acid, xanthan gum, Hydroxypropylmethyl cellulose, particularly advantageously from the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopoles, for example carbopoles of types 980, 981, 1382. 2984, 5984, each individually or in combination.

The cosmetic and dermatological preparations according to the invention advantageously contain, in addition to the UV-A, UV-B and / or broadband filters used, although not necessarily, inorganic pigments based on metal oxides and / or other metal compounds which are sparingly soluble or insoluble in water, in particular those Oxides of titanium (TiO ₂ ), zinc (ZnO), iron

(e.g. Fe ₂ O ₃ ), zirconium (ZrO ₂ ), silicon (Si0 ₂ ), manganese (e.g. MnO), aluminum (A1 ₂ 0 ₃ ), cerium (e.g. Ce ₂ O ₃ ), mixed oxides of the corresponding metals and mixtures such oxides. These pigments are X-ray amorphous or non-X-ray amorphous. Pigments based on TiO _{2 are} particularly preferred.

X-ray amorphous oxide pigments are metal oxides or semimetal oxides which show no or no discernible crystal structure in X-ray diffraction experiments. Such pigments are often obtainable by flame reaction, for example by reacting a metal or semimetal halide with hydrogen and air (or pure oxygen) in a flame.

In cosmetic, dermatological or pharmaceutical formulations, X-ray amorphous oxide pigments are used as thickening and thixotropic agents, flow aids for stabilizing emulsions and dispersions and as carriers

(for example to increase the volume of finely divided powders or powders).

Known and often used in cosmetic or dermatological galenics are the X-ray amorphous oxide pigments, the silicon oxides of the type Aerosil (CAS-

No. 7631 -85-9). Aerosile ^® available from DEGUSSA company stand out small particle size (for example between 5 and 40 nm), the particles being spherical particles of very uniform dimensions. Aerosile ^® are macroscopically recognizable as loose, white powders. For the purposes of the present invention, X-ray amorphous silicon dioxide pigments are particularly advantageous, and among these, those of the Aerosil type are preferred.

Examples of advantageous Aerosil ^® types are Aerosil ^® 0X50, Aerosil ^® 130, Aerosil ^® 150, Aerosil ^® 200, Aerosil ^® 300, Aerosil ^® 380, Aerosil ^® MQX 80, Aerosil ^® MOX 170, Aerosil ^® COK 84, Aerosil ^® R 202 , Aerosil ^® R 805, Aerosil ^® R 812, Aerosil ^® R 972, Aerosil ^® R 974 and Aerosil ^® R976.

According to the invention, the cosmetic or dermatological light protection preparations contain 0.1 to 20% by weight, advantageously 0.5 to 10% by weight, very particularly preferably 1 to 5% by weight of X-ray amorphous oxide pigments.

According to the invention, the non-X-ray amorphous inorganic pigments are advantageously in hydrophobic form, i.e. they are treated on the surface to be water-repellent. This surface treatment can consist in that the pigments are provided with a thin hydrophobic layer by methods known per se. For example, hydrophobicized pigments shown in analogy to DE-A 33 14 742 are advantageous.

Advantageous TiO ₂ pigments are available, for example, under the trade name T 805, advantageous TiO ₂ / Fe ₂ O ₃ mixed oxides under the trade name T 817 from Degussa.

The total amount of inorganic pigments, in particular hydrophilic and hydrophobic inorganic micropigments in the finished cosmetic or dermatological preparations, is advantageously in the range from 0.1-30% by weight, preferably 0.1-10.0, in particular 0.5-6 , 0% by weight, based on the total weight of the preparations. An additional content of antioxidants in the cosmetic and dermatological preparations according to the invention is generally preferred. According to the invention, all the antioxidants suitable or customary for cosmetic and / or dermatological applications can be used as favorable antioxidants.

The antioxidants are advantageously selected from the group consisting of amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-

Carnosine, L-carnosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. a-carotene, b-carotene, lycopene) and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other ethiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, y-linoleyl -, Cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts), phenolic acid amides of phenolic benzylamines (eg homo vanillic acid, 3,4-dihydroxy acid- phenylphenylphenyl , Ferulic acid, sinapic acid, caffeic acid, dihydroferulic acid, dihydrocaffeic acid, vanillomandelic acid or 3,4-dihydroxymandelic acid amides of 3,4-dihydroxybenzyl-, 2,3,4-trihydroxy-benzyl- or 3, 4,5-trihydroxybenzyl amines) and sulfoximine compounds (e.g. Buthionine sulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, heptathionine sulfoximine) in very low tolerable doses, further (metal) chelators (e.g. -

Hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-linolenic acid, linoleic acid, linoleic acid, linoleic acid, linoleic acid, linoleic acid, linoleic acid , Oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives

(e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and Derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) as well as coniferyl benzoate of benzoin, rutinic acid and its derivatives, α-glycosyl rutin, ferulic acid, furfurylidene glucitol, Ca nosin, butylated hydroxytoluene, butyl hydroxy anoxy resin, nordihydrog , Nordihydroguaj aretic acid,

Trihydroxybutyrophenone, uric acid and its derivatives, marmose and its derivatives, zinc and its derivatives (e.g. ZnO, ZnSO), selenium and its derivatives (e.g. selenium methionine), stilbenes and their derivatives (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention ( Salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active ingredients.

The amount of the aforementioned antioxidants (one or more compounds) in the preparations according to the invention is preferably 0.001 to 30% by weight, particularly preferably 0.05-20% by weight, in particular 1-10% by weight, based on the total weight the preparation.

If vitamin E and / or its derivatives represent the antioxidant (s), it is advantageous to choose their respective concentrations from the range of 0.001-10% by weight, based on the total weight of the formulation.

If vitamin A or vitamin A derivatives or caroline or their derivatives represent the antioxidant or antioxidants, it is advantageous to have their respective concentrations in the range from 0.001-10% by weight, based on the total weight of the formulation, to choose.

Skin lightening agents can also be used in the cosmetic preparations. Benzaldoximes with at least one aromatic hydroxyl or alkoxy group, benzo-condensed or heterocyclically condensed 2-hydrazino-1,3-thiazoles, 2-thio-1,3,4-heterodiazoles, their anionic or cationic salts and mixtures may preferably be used as skin lightening agents the same, kojic acid, kojic acid derivatives, ascorbic acid, ascorbic acid derivatives, hydroquinone,

Hydroquinone derivatives, sulfur-containing molecules (e.g. glutathione or cysteine) or other synthetic or natural active ingredients for skin lightening, the latter also in the form of an extract from plants (for example tocopherols and derivatives, arbutin [for example from Bearberry extract], aloesine [for example from aloe extract], grapefruit extract and rice Extract) can be used.

The cosmetic and dermatological preparations according to the invention advantageously also contain complexing agents (e.g. from the class of amino-polycarboxylic acids, aromatic hydroxy and amino derivatives, enolates).

In addition, the cosmetic and dermatological preparations can also have anti-inflammatory agents which come from the compound classes of the salicylic, acetic and propionic acid derivatives, the pyrazoles, fenams and oxicams.

The cosmetic and dermatological preparations can also contain auxiliary substances

Cooling and refreshing effect, e.g. Menthol and derivatives derived from it.

A comprehensive description of the raw materials and active ingredients used in cosmetic products is presented in DE-A 199 19 630.

The amounts of cosmetic or dermatological auxiliary substances and carriers and perfume to be used in each case can easily be determined by a person skilled in the art by simply trying them out, depending on the type of the respective product.

The acrylonitrile derivatives of the formula (I) can be used individually or in a mixture in the corresponding preparations; they can also be used in combination with UN absorbers of other substance classes or with these in any mixtures with one another. The list of UV absorbers mentioned below, which can be used for the purposes of the present invention, is of course not intended to be limiting. p-aminobenzoic acid p-aminobenzoic acid ethyl ester p-dimethylaminobenzoic acid 2-ethylhexyl ester p-aminobenzoic acid ethyl ester p-aminobenzoic acid glycerol ester

Salicylic acid homomethyl ester (homosalates) (Neo Heliopan ^® HMS)

2-ethylhexyl salicylic acid (Neo Heliopan ^® OS)

triethanolamine

4-isopropylbenzyl

Anthranile acid ethyl ester (Neo Heliopan ^® MA)

Ethyl diisopropyl cinnamate 2-ethylhexyl p-methoxy cinnamate (Neo Heliopan ^® AV)

Diisopropyl cinnamic acid methyl ester p-methoxy cinnamic acid isamyl ester (Neo Heliopan ^® E 1000) p-methoxy cinnamic acid diethanolamine salt p-methoxy cinnamic acid isopropyl ester

2-ethylhexyl-2-cyano-3,3-diphenyl acrylate (Neo Heliopan ^® 303)

Ethyl 2-cyano-3, 3'-diphenyl acrylate

2-phenylbenzimidazole sulfonic acid and salts (Neo Heliopan ^® Hydro)

3- (4'-trimethylammonium) -benzylidene-boman-2-one methyl sulfate

Terephthalylidene-dibomansulfonic acid and salts (Mexoryl ^® SX)

4-t-butyl-4'-methoxy-dibenzoylmethane (avobenzone) / (Neo Heliopan ^® 357) ß-imidazole-4 (5) -acrylic acid (urocanic acid)

2-hydroxy-4-methoxybenzophenone (Neo Heliopan ^® BB)

2-hydroxy-4-methoxybenzophenone-5-sulfonic acid

Dihydroxy-4-methoxybenzophenone

2,4-dihydroxybenzophenone

tetrahydroxy

2,2'-dihydroxy-4,4'-d_methoxybenzophenon 2-hydroxy-4-n-octoxybenzophenone 2-hydroxy-4-methoxy-4'-methylbenzophenone 3- (4'-sulfo) benzylidene-boman-2-one and salts 3- (4'-methylbenzylidene) -d, l camphor (Neo Heliopan ^® MBC) 3-benzylidene-d, l-camphor 4-isopropyldibenzoylmethane

2,4,6-Trianilino- (p-carbo-2'-ethylhexyl-1 '-oxy) -1,3,5-triazine phenylene-bis-benzimidazyl-tetrasulfonic acid disodium salt (Neo Heliopan ^® AP) 2,2' - (1,4-phenylene) -bis- (1 H -benzimidazole-4,6-disulfonic acid), monosodium salt N - [(2 and 4) - [2- (oxobom-3-ylidene) methyl] benzyl] acrylamide -Polymer phenol, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-methyl-3 (l, 3,3,3-tetramethyl-l- (trimethylsilyl) -oxy) -disiloxyanyl) propyl), (Mexoryl XL ^®) 4,4 '- [(6- [4- (l, l-dimethyl) aminocarbonyl) phenylamino] -l, 3,5-triazine-2,4-diyl) diimino ] -bis- (2-ethylhexyl benzoate) (Uvasorb ^® HEB) 2,2 '-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- 1,1,3,3-tetramethylbutyl) -phenol), (Tinosorb ^® M)

2,4-bis- [4- (2-ethylhexyloxy) -2-hydroxyphenyl] -1,3,5-triazine benzylidene malonate polysiloxane (Parsol ^® SLX) glyceryl ethylhexanoate dimethoxycinnamate-

Disodium 2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulfo-benzophenone dipropylene glycol salicylate, sodium hydroxymethoxybenzophenone sulfonate

4,4 ', 4- (l, 3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester) (Uvinul ^® T150)

2,4-bis - [{(4- (2-ethylhexyloxy) -2-hydroxy} phenyl] -6- (4-methoxyphenyl) -l, 3,5-triazine, (Tinosorb ^® S)

2,4-bis - [{(4- (3-sulfonato) -2-hydroxypropyloxy) -2-hydroxy} phenyl] -6- (4-methoxyphenyl) -1, 3,5-triazine sodium salt

2,4-bis - [{(3- (2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy} phenyl] -6- (4-methoxyphenyl) -1, 3,5-triazine 2,4-bis - [{4- (2-ethylhexyloxy) -2-hydroxy} phenyl] -6- [4- (2-methoxyethylcarbonyl) phenylamino] -l, 3,5-triazine 2 , 4-bis - [{4- (3- (2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy} phenyl] -6- [4- (2-ethylcarboxyl) phenylamino] -l, 3rd , triazine-5

2,4-bis - [{4- (2-ethylhexyloxy) -2-hydroxy} phenyl] -6- (l-methyl-pyrrol-2-yl -) - 1,3,5-triazine

2,4-bis - [{4-tris (trimethylsiloxysilylpropyloxy) -2-hydroxy} phenyl] -6- (4-methoxyphenyl) -1, 3,5-triazine

2,4-bis - [{4- (2 "-methylpropenyloxy) -2-hydroxy} phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine

2,4-bis- [{4- (1 ', 1', 1 ', 3' 5 ', 5', 5 '-heptamethylsiloxy-2 "-methyl-propyloxy) -2-hydroxy} phenyl] -6- (4-methoxyphenyl) -l, 3,5-triazine

Particularly suitable UV absorbers are:

p-aminobenzoic acid

3- (4'-trimethylammonium) -benzylidene-bornan-2-one-methylsulfate salicylic acid homomethyl ester (Neo Heliopan ^® HMS) 2-hydroxy-4-methoxy-benzophenone (Neo Heliopan BB) 2-phenylbenzimidazole sulfonic acid (Neo Heliopan ^® Hydro) Terephthalylidene-dibomane sulfonic acid and salts (Mexoryl ^® SX) 4-tert-butyl-4'-methoxydibenzoylmethane (Neo Heliopan ^® 357) 3- (4'-sulfo) benzylidene-bornan-2-one and salts 2-ethylhexyl-2- cyano-3,3-diphenyl acrylate (Neo Heliopan ^® 303) N - [(2 and 4) - [2- (oxoborn-3-ylidene) methyl] benzyl] acrylamide polymer p-methoxycinnamic acid 2-ethylhexyl ester (Neo Heliopan ^® AV) p-aminobenzoic acid ethyl ester p-methoxycinnamic acid isoamyl ester (Neo Heliopan "El 000) 2,4,6-trianilino- (p-carbo-2'-ethylhexyl-r-oxy) -l, 3,5-triazine (Uvinul ^® T150) phenol, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-methyl-3 (1, 3, 3, 3-tetramethyl-1 - (trimethylsi_yl) -oxy) -disiloxyanyl) -propyl), (Mexoryl ^® XL)

4,4 '- [(6- [4- (l, l-dimethyl) aminocarbonyl) phenylamino] -1, 3,5-triazine-2,4-diyl) diimino] bis (benzoic acid-2 -ethylhexyl ester), (UvasorbHEB)

3- (4'-methylbenzylidene) -d, l-camphor (Neo Helipan ^® MBC)

3-benzylidene camphor

2-ethylhexyl salicylic acid (Neo Helipan ^® OS)

2-ethylhexyl 4-dimethylaminobenzoate (Padimate O)

Hydroxy-4-methoxy-benzophenone-5-sulfonic acid and Na salt

2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4-l, 1,3,3-tetramethylbutyl) phenol),

(Tinosorb ^® M)

Phenylene-bis-benzimidazyl-tetrasulfonic acid disodium salt (Neo Heliopan ^® AP)

Benzylidene malonate polysiloxane (Parsol ^® SLX)

Menthyl anthranilate (Neo Heliopan ^® MA)

It can also be advantageous to use polymer-bound or polymeric UV absorbers in preparations according to the present invention, in particular those as described in WO 92/20690.

The list of the UV filters mentioned, which can be used in the sense of the present invention, should of course not be limiting.

The total amount of all (single and multiple sulfonated) water-soluble UV filter substances in the finished cosmetic or dermatological preparations, for example phenylene-bis-benzimidazyl-tetrasulfonic acid disodium salt or its salts and / or the corresponding disulfonic acid or its salts and / or 2 Phenylbenzimidazole-5-sulfonic acid or its salts and / or 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid or its salts and / or 4- (2-oxo-3-bornylidenemethyl) benzene sulfonic acid or their salts and / or 2-methyl-5- (2-oxo-3- bomylidene-methyl) -benzenesulfonic acid or its salts and / or benzene-1, 4-di- (2-oxo-3-bornylidenemethyl) -10-sulfonic acid or its salts, is advantageously in the range from 0.1 to 10 , 0 wt .-%, preferably 0.5 to 6.0 wt .-%, based on the total weight of the preparations, if the presence of these substances is desired.

The total amount of oil-soluble UV filter substances in the finished cosmetic or dermatological preparations, for example 4,4 ', 4 "- (1,3,5-triazine, 2,4,6-triyltriimino) -tris-benzoic acid-tris- ( 2-ethylhexyl ester) and / or 4-tert-butyl-4'-methoxy-dibenzoylmethane and / or 4-methylbenzylidene camphor and / or

Octyldimethyl-p-aminobenzoic acid and / or Mexoryl ^® XL and / or Uvasorb ^® HEB and / or Tinosorb ^® S and / or Benzophenon-3 and / or Parsol ^® SLX and / or Neo Heliopan ^® MA is advantageous from the range of 0. 1 to 10.0% by weight, preferably 0.5 to 6.0% by weight, based on the total weight of the preparations, if the presence of these substances is desired.

The total amount of 2-ethylhexyl p-methoxy cinnamate and / or p-methoxy cinnamic acid isoamyl ester in the finished cosmetic or dermatological preparations is advantageously in the range from 0.1 to 15.0% by weight, preferably 0.5 to 7.5% by weight, based on the total weight of the preparations, if the presence of these substances is desired.

The total amount of ethylhexyl-2-cyano-3,3-diphenyl acrylate in the finished cosmetic or dermatological preparations, if the presence of this substance is desired, is advantageously in the range from 0.1 to 15.0% by weight, preferably 0 , 5 to 10.0 wt .-%, selected, based on the total weight of the preparations.

The total amount of one or more salicylic acid derivatives in the finished cosmetic or dermatological preparations is advantageously selected from the range from 0.1 to 15.0% by weight, preferably 0.5 to 10.0% by weight, based on the Total weight of the preparations. If ethylhexyl salicylate is chosen, it is advantageous to choose its total amount from the range of 0.1 to 5.0% by weight. When choosing homomethyl salad, it is advantageous to choose its total amount from the range of 0.1 to 10.0% by weight.

Furthermore, the acrylonitrile derivatives of the formula (I) according to the invention can also be combined with UV absorbers which are used for technical product protection. Examples of such UV absorbers correspond primarily to compounds from the series of benzotriazoles, benzophenones and malonic esters.

The following examples are intended to illustrate the present invention without restricting it. Unless otherwise stated, all quantities, parts and percentages are based on the weight and the total amount or on the total weight of the preparations.

Unless otherwise stated, the acrylonitrile derivatives were separated or purified by crystallization, distillation or column chromatography on silica gel 60 (elution with n-hexane / ethyl acetate = (5-10): l).

Examples

Examples 1-6

General instructions for the preparation of 2-cyano-2-propenoic acid esters

A mixture of 0.5 mol of orthocarboxylic acid ester, 0.5 mol of alkyl cyanoacetate and 0.5 mol of the corresponding NH-heterocyclic compound is heated to 120 ° C. for 2-3 hours and the alcohol which is split off is distilled off. The residue obtained is purified by crystallization, distillation or column chromatography.

Examples 7-12

General instructions for the preparation of 3-oxo-4,4-dimethyl-pentanenitriles

A mixture of 0.5 mol of orthocarboxylic acid ester, 0.5 mol of pivaloylacetonitrile and 0.5 mol of the corresponding NH-heterocyclic compound is heated to 120 ° C. for 2-3 hours and the alcohol which is split off is distilled off. The residue obtained is purified by crystallization, distillation or column chromatography.

Table 1

Example 13

Sun protection soft cream (O / W), waterproof

Manufacturing process:

Part A: Heat to approx. 85 ° C.

Part B: Weigh raw materials without Carbopol. Disperse Carbopol with Ultra Turrax. Heat to approx. 85 ° C. Add B to A. Part C: Add immediately to A / B and then homogenize hot (Ultra

Turrax).

Let cool while stirring. Part D: Add and stir. Example 14

Sun protection lotion (O / W)

Production method :

Part A: Heat to approx. 85 ° C.

Turrax). Let cool while stirring. Part D: Add and stir. Example 15

Sun protection milk (O / W)

Production method ;

Part A Heat to 80-85 ° C. Part B Heat to 80-85 ° C, add Part B to Part A while stirring. Disperse Part C Carbopol in the water and neutralize with NaOH while stirring.

Add part C at approx. 60 ° C while stirring. Let cool to RT.

Part D: Add and stir. Example 16

Sun protection lotion (O / W)

Production method :

Part A: Heat to 80-85 ° C.

Part B: Heat to 80-85 ° C, add Part B to Part A while stirring.

Part C: Disperse Carbopol in the water and neutralize with NaOH while stirring.

Add part C at approx. 60 ° C while stirring. Let cool to RT. Part D: Add and stir. Example 17

Sun protection lotion (O / W)

Production method :

Part A: Dissolve UV absorber according to formula 1 in the oils or liquid UV filters (heating up to approx. 70 ° C). Allow to cool to approx. 30 ° C, add the remaining ingredients except Carbopol and Pemulen and mix at room temperature (stir for approx. 5 minutes). Stir in the Carbopol and Pemulen.

Part B: Dissolve Solbrole in phenoxyethanol while heating. With water and

Mix glycerin, add to part A while stirring. Approximately Stir for 60 minutes.

Part C: Add to A / B, homogenize with the Ultra Turrax. Example 18

Sun protection cream (W / O), waterproof

Production method:

Part A: Heat to approx. 85 ° C.

Part B: Heat to approx. 85 ° C (without zinc oxide; disperse zinc oxide with the Ultra Turrax). Add B to A.

Allow to cool with stirring, then homogenize.

Example 19

Sun protection soft cream (W / O),

Production method :

Part A: Heat to approx. 85 ° C.

Part B: Heat to approx. 85 ° C (without zinc oxide; disperse zinc oxide with the Ultra Turrax). Add B to A. Let cool while stirring. Part C: Add and then homogenize Example 20

Sun protection milk (W / O)

Production method:

Part A Heat to approx. 85 ° C. Part B Heat to approx. 85 ° C. Add B to A. Allow to cool while stirring. Add part C and then homogenize. Example 21

Day care cream with UV protection

Production method :

Part A: Heat to 80 ° C.

Part B: Heat to 80 ° C. Add to Part A while stirring.

Part C: Disperse Carbopol in water and neutralize with sodium hydroxide solution.

Add to part A / B at approx. 55 ° C. Part D: Add at RT and homogenize. Example 22

Sunscreen Spray

Production method:

Part A: Lara Care A-200 with stirring in the other ingredients of Part

Release A. Part B: Weigh in all raw materials (without Pemulen) and dissolve the crystalline sub with heating. Disperse the pemules. Add part B to part A and homogenize for 1 minute. Add part C + D and homogenize again with the Ultra Turrax for 1-2 minutes. Example 23

Sun protection hydrodispersion gel (web)

Production method:

Disperse Part A Carbopol in water and neutralize with sodium hydroxide solution. Add part B to part A while stirring. Part C Detach crystalline constituents from part C while heating (max.40 ° C) in the other raw materials and add to part A / B. Mix well and then homogenize. (Homozenta). Example 24

Hαzr conditioner with UV filters

Production method:

Part A: Heat to 80 ° C.

Part B: Heat to 80 ° C. Add to part A while stirring.

Part C: Add at 40 ° C and cool to RT.

Determination of photostability

From a 5% solution of the UV filter to be tested or a combination with other commercially available UV absorbers such as OMC (octyl methoxy cinnamate) and / or BMDM (tert-butyl methoxy dibenzoyl methane), 20 μl are uniformly distributed over 10 cm Glass plate with a roughened surface. After a storage period of 30 minutes in the dark, the sample is irradiated in a Suntest device with a solar standard filter and global sensor for 140 minutes with an irradiance of 765 W / m. During the irradiation, the glass plates are on the cooled bottom of the sun tester. A total of 4 glass plates are irradiated at the same time. After the end of irradiation, the samples are rinsed with ethanol from the glass plates into a 25 ml volumetric flask. The content of light stabilizer in the samples thus obtained is determined by means of a photometer or HPLC. In parallel, blank samples are applied to the glass platelets as described above and then rinsed and measured like the irradiated samples.

Table 2

Claims

claims

1. light protection preparations containing acrylonitrile derivatives of the formula (I) in which the C = C double bond is in the E or Z configuration,

wherein

R ^{1 can} denote hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C _2Q alkenyl, C ₂ -C ₂₀ alkynyl, C ₆ -C ₁₂ aryl

R "COOR ¹³ , COR ¹³ , CONR ¹³ R ¹⁴ , CN, where R ¹³ - R ^{14 is} hydrogen, C.-C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl or C ₂ -C ₂₀ alkynyl, C ₆ -Cι ₂ -aryl, C ₃ -C ₁₅ cycloalkyl, C.-C ₁₂ heteroaryl, which may optionally be substituted by amino, hydroxy, acetoxy, carboxy, carbalkoxy, carbamoyl, a group W or interrupted by ether oxygen .

R ³ -R ^{12 have} the meaning given under R ¹ or else C ₃ -C ₁₅ cycloalkyl, C - C ₁₂ heteroaryl, C - C ₁₆ alkoxy, C ₆ -C ₁₂ aryloxy, amino, hydroxy, Mean acetoxy, carboxy, carbalkoxy, carbamoyl, where they can be substituted by a group W or interrupted by ether oxygen, with the proviso that two substituents of R ³ -R ¹² on adjacent C atoms together can mean an optionally substituted C 1 -C 4 alkylene group, it being possible for a methylene group to be replaced by -O-, -S- or -NH-,

0, 1 or 2

W silanes, oligosilanes and polysiloxanes. of the general formulas W ¹ to

W • ^] m

W ^J SiR ¹⁵ _a (OSiR ¹⁵ ₃ ) _b

a 0, 1, 2 or 3

3, 2, 1 or 0

a + b 3

A is a bond to the neighboring atom 1-10

R. 15 is an open-chain or branched ahphatic, araliphatic, cycloaliphatic or optionally substituted aromatic radical, each having up to 18 carbon atoms

mean.

Sunscreen preparations according to claim 1 containing compounds of

Formula (I A)

wherein

R ^{1 can be} hydrogen, C _f C ₁₂ -alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl, phenyl,

R ² COOR ¹³ , COR ¹³ , where R ^{13 is} hydrogen, C.-C ₁₂ -alkyl, C ₂ -C ₁₂ -alkenyl, C ₂ -C ₁₂ -alkynyl or C ₆ -C ₁₂ -alkyl, which may be by Amino, hydroxy, acetoxy, carboxy, carbalkoxy, carbamoyl, a group W substituted or interrupted by ether oxygen, M 19 1

R -R have the meaning given under R or also C ₃ -C ₁₅ cycloalkyl, C ₅ -C ₁₂ heteroaryl, C.-C ₁₆ alkoxy, C ₈ -C ₁₂ aryloxy, amino, hydroxy, acetoxy, carboxy , Carbalkoxy, carbamoyl, where they can be substituted by a group W or interrupted by ether oxygen,

with the proviso that two substituents of R ³ -R ¹² on adjacent C atoms together can mean an optionally substituted C ₁ -C ₄ alkylene group, and

z means 0, 1 or 2.

3. Light protection preparations according to claim 1 or 2 containing compounds of the formula (I B)

wherein

R ^{1 can be} hydrogen, C ₆ -C ₆ -alkyl or phenyl,

R> 3 ^J - τR. 1 ^X 2 hydrogen, C _f C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ -A_jdnyl, phenyl, C.-C ₁₂ alkoxy, hydroxy, acetoxy, carboxy, carbalkoxy, carbamoyl can mean, where they can be substituted by a group W or interrupted by ether oxygen,

with the proviso that two substituents of R ³ -R ^{8 together} on adjacent C atoms together form an optionally substituted one

C ₁ -C ₄ alkylene group can mean

R ¹⁶ -R ¹⁸ independently of one another are hydrogen, C - C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl,

C ₂ -C ₁₂ alkynyl, which may be substituted by C.-C ₁₂ alkoxy, hydroxy, acetoxy, carboxy, carbalkoxy, carbamoyl, a group W or interrupted by ether oxygen,

z means 0.1 or 2.

Sunscreen preparations according to Claim 3, characterized in that the radicals R ¹⁶ , R ¹⁷ and R ¹⁸ in the formula (IB) each represent CH ₃ .

5. Sunscreen preparations according to claims 1 to 4 under additional

Use of UV-B and UV-A absorbers.

6. Sunscreen preparations according to claim 5, wherein as UV-B and UN-A absorber compounds from the groups of cinnamates, salicylates, p-aminobenzoates, benzophenones, diphenyl acrylates, camphor derivatives,

Triazines, benzylidene malonates, benzotriazoles, benzimidazoles, dibenzoyl methanes, polymeric filters or silicone filters can be used.

7. Sunscreen preparations according to claim 5, wherein as UV-B and UV-A absorber p-methoxycinnamic acid 2-ethylhexyl ester, p-methoxycinnamic acid isoamyl ester, 4-methylbenzylidene camphor, 2-phenylbenzimidazole sulfone acid, salicylic acid-2-ethylhexyl ester, 2-ethylhexyl-2-cyano-3, 3 -diphenyl-acrylate, 2,2 '- (1, 4-phenylene) -bis- 1 H -benzimidazole-4,6-disulfonic acid- monosodium salt or 4-tert-butyl-4'-methoxydibenzoylmethane can be used.

8. Light protection preparations according to claims 1 to 7 in which additionally coated or non-coated inorganic pigments based on metal oxides, in particular the oxides of titanium, zinc and iron, are contained.

9. Use of compounds of formula (I) according to spoke 1 for

Photo stabilization of other UV filters.

10. Use of compounds of formula (I) according to spoke 1 for the photostabilization of UV absorbers of the type dibenzoylmethane derivatives and methoxycinnamates.

11. Use of compounds of formula (I) according to claim 1 for the photostabilization of combinations of UV absorbers of the type of methoxycinnamate derivatives with dibenzoylmethane derivatives.

12. Use of compounds of formula (I) according to spoke 1 in combination with one or more further UV absorbers for the synergistic enhancement of the photo protection effect in cosmetic and pharmaceutical light protection preparations.

13. Use of compounds of formula (I) according to spoke 1 in combination with one or more further UV absorbers and coated or non-coated pigments or nanopigments of metal oxides for the synergistic enhancement of the photo protection effect in cosmetic and pharmaceutical light protection preparations.

14. Use of compounds of formula (I) according to spoke 1 in combination with one or more further UN absorbers and coated or non-coated pigments or opanopigments of metal oxides so that a UN broadband protection performance with a critical

5 wavelength λ _cr jt. «380 nm results.

15. light protection preparations according to claims 1 to 8 which further cosmetic auxiliaries such as fats, emulsifiers, nerdickers, emollients, organic solvents, polymers, silicones, antioxidants, perfumes,

10 preservatives, vitamins, complexing agents, skin lightening agents,

Contain plant extracts, dyes and coolants or refreshments.

16. light protection preparations according to claims 1 to 8 as an emulsion, milk, lotion or cream, aerosol, hydrodispersion or oil gel, spray,

15 Foam, solution, powder, grease stick or other common cosmetic or pharmaceutical preparation.

17. Light protection preparations according to claims 1 to 8 which are present as a waterproof formulation.

20

18. Compounds of formula (I B) according to claims 3 and 4.

19. Compounds from the group of 3-oxo-4,4-dimethyl-pentanenitrile from the series

25

2 - [(2,3-dihydro-1 H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2- [(2,3-dihydro-2-methyl-1 H -indole-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2 - [(2,3-dihydro-5-methyl-1H-indol-1-yl) methylene] -4.4 -dimethyl-3-oxopentanenitrile,

, 30 2- [(2,3-dihydro-2,3-dimethyl-1 H-indole-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2- [(2,3 - Dihydro-2,5-dimethyl-1H-indol-1-yl) methylene] -4,4- dimethyl 1-3 -oxopentanenitrile, 2- [(2,3-dihydro-2,3,3-trimethyl-1H-indol-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile , 2 - [(2,3-dihydro-5-methoxy-1H-indol-l-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2 - [(2,3-dihydro-2 - methyl-5-methoxy-lH-indol-l-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2 - [(2,3-dihydro-2,3,3-trimethyl-5- methoxy-1 H-indole-1-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile, 2- [1 - (2,3-dihydro-2-methyl-1 H-indole-1 -yl) ethylidene] -4,4-dimethyl-3-oxopentanenitrile, 2- [1 - (3, 4-dihydro-1 (2H) -quino-linyl) methylene] -4,4-dimethyl- 3-oxopentanenitrile, 2- [1 - (3,4-dihydro-1 (2H) - quinolinyl) ethylidene] -4,4-dimethyl-3-oxopentanenitrile, 2 - [(l, 2,3, 4.10, 1 l-hexahydro-9H-carbazol-9-yl) methylene] -4,4-dimethyl-3-oxopentanenitrile.

20. Use of compounds of formula (I B) according to claims 3 and 4 for the protection of technical products such as paints, varnishes, plastics, textiles, polymers, packaging materials and rubbers against the damaging effects of UV radiation.