DE4107439A1 - Cosmetic used for make=up and hair treating compsn. - contains new 2-(1'-cyano-9'-aryl-vinyl)benzimidazole cpd. as UV absorber - Google Patents

Abstract

(i) A cosmetic contains a new 2-(1'-cyano-2'-arylvinyl) benzimidazole deriv. of formula (I). In (I) R1, R7 = H, 1-6C alkyl, halogen, NO2, OH, RxO alkylcarbonyloxy with 1-20C in the alkyl, Rx-oxycarbonyl, COOR3, SO3R3, CONR5R6 or SO2NR5R6; R3 = H, Na, K or N(R4)4; R4 = H, 1-6C alkyl or 2-4C hydroxyalkyl; R5, R6 = H or 1-12C alkyl, or together form -(CH2)4-, -(CH2)5- or -CH2CH2OCH2CH2-; R2 = H or 1-6C alkyl; Ar = (substd) Ph, naphthyl, pyridinyl, furanyl or thienyl gps. of formula (i)-(v); R8 = H, 1-6C alkyl, halogen, RxO, OH or alkylcarbonyloxy with 1-20C in the alkyl; R9 = H, halogen or 1-6C alkyl, or R7 and R8 form a 3,4-methylenedioxy gp. if R9 = H; R10 = H, 1-6C alkyl, halogen, OH, RxO or alkylcarbonyloxy with 1-20C in the alkyl; R11 = H or 1-6C alkyl; Rx = 1-12C alkyl, 3-12C cycloalkyl (opt. substd with 1,2 or 3 1-6C alkyl gps) 5-12C bicycloalkyl (opt. substd. with 1,2 or 3 1-6C alkyl gps.) or the corresp. unsatd. gps. with 1 or 2 C=C bonds. Also claimed are (A) 2-(1'-cyano-2'-(4"-isopropylphenyl) -vinyl)benzimidazole, 2-(1'-cyano-2'-(4"-tert. butylphenyl) vinylbenzimidazole, 2-(2'-cyano-2'- (benzimidazole -2"-yl) vinyl)benzene sulphonic acid and its Na and K salts, 4-(2'-cyano-2'-(benzimidazole -2"-yl)vinyl)benzene sulphonic acid and its Na and K salts, and (B) as intermediates for (I), 2-cyanomethyl-5-methoxy carbonylbenzimidazole, 2-cyanomethyl-5-(2'-ethylhexyloxy) carbonyl-benzimidazole, 2-cyanomethyl-5-cyclohexyl oxybenzimidazole, and 2-cyanomethyl-benzimidazole 5-sulphonic acid., USE/ADVANTAGE - (I) are UV absorbers. The cosmetic is a coloured or colourless make-up or hair treating compsn., stabilised against light, and protecting the skin or hair against UV radiation. It may be a shampoo, lotion, gel or emulsion for rinsing, waving or treatment lotion or gel for hand-drying or shaping hair, hair lacquer, permanent waving compsn., or bleaching or dyeing compsn. (I) are stable against light, and in vitro have better cell toxicity than dibenzoylmethane derivs. used and UVA filters.

Description

Cosmetic agents containing 2- (1'-cyano-2'-arylvinyl) benzimidazole derivatives containing novel 2- (1'-cyano-2'-arylvinyl) benzimidazole derivatives, method for their manufacture and their use.

The present invention relates to cosmetic compositions which at least one compound of general formula I,

in the
R₁ is hydrogen, C _1-6 alkyl, halogen, nitro, hydroxy, R _X O-, alkylcarbonyloxy having 1 to 20 carbon atoms in the alkyl moiety, R _X -oxycarbonyl, -COOR₃ or SO₃R₃, in which R₃ are each hydrogen, sodium, potassium or N is (R₄) ₄ and R₄ is hydrogen, C _1-6 alkyl or C _2-4 hydroxyalkyl, and R₁ is further CONR₅R₆ or SO₂NR₅R₆, where R₅ and R₆ may be the same or different and are hydrogen or C _{1 12} -alkyl or both together for - (CH₂) ₄-, - (CH₂) ₅- or -CH₂CH₂OCH₂CH₂- stand,
R₂ is hydrogen or C _1-6 -alkyl,
Ar is an optionally mono-, di- or trisubstituted phenyl radical of the formula A,

an optionally substituted naphthyl radical of the formula B,

an optionally substituted pyridinyl radical of the formula C,

an optionally substituted furanyl radical of the formula D,

an optionally substituted thienyl radical of the formula E

means, in which
R₇ has the meanings given for R₁, where radicals R₇ and R₁ can be identical or different,
R₈ is hydrogen, C _1-6 -alkyl, halogen, R _{X is} O-, hydroxy or alkylcarbonyloxy having 1 to 20 carbon atoms in the alkyl part,
R⁹ is hydrogen, halogen or C _1-6 -alkyl or R₇ and R₈ may together form a 3,4-methylenedioxy group when R₉ is hydrogen,
R₁₀ is hydrogen, C _1-6 -alkyl, halogen, hydroxy, R _X O- or alkylcarbonyloxy having 1 to 20 carbon atoms in the alkyl moiety,
R₁₁ is hydrogen or C _1-6 alkyl and
R _{X is} C _1-12 alkyl, C _3-12 cycloalkyl which may be optionally substituted with one, two or three C _1-6 alkyl groups, C _5-12 bicycloalkyl optionally substituted with one, two or three C _1-6 alkyl groups may be substituted, or the said unsaturated groups having one or two double bonds corresponding to these optionally substituted saturated C _1-12 alkyl, cycloalkyl and bicycloalkyl groups,
and their tautomers and cis-trans isomers.

The cosmetic agents and the compounds of the formula I which are known as UV absorbers, in particular UVA absorbers act, are preferably used for Protecting the skin and hair against UV rays, in particular UVA rays. The invention also includes novel compounds of general formula I and process for their preparation and their Use as UV absorber, in particular UVA absorber preferably for the purposes mentioned above.

For the sake of simplicity, the compounds of the invention are in only a tautomeric form represented by Formula I. The However, invention extends to all tautomeric forms of the compounds.  

The compounds of general formula I can also be cis- and trans isomers are present. The present invention extends to both forms as well as on mixtures of the two, even if in the formula I only the trans isomer, in which therefore the benzimidazole and the aryl radical trans each other, is indicated.

The invention also provides the following novel compounds general formula II:

2-Cyanomethylbenzimidazol-5-carboxylic acid
2-cyanomethyl-5-methoxycarbonylbenzimidazole
2-cyanomethyl-5- (2'-ethylhexyloxy) carbonylbenzimidazol
2-cyanomethyl-5-cyclohexyloxybenzimidazol
2-Cyanomethylbenzimidazol-5-sulfonic acid.

They serve as intermediates for the preparation of corresponding Compounds of the formula I.

The damaging effect of the ultraviolet part of solar radiation the skin is well known. While rays of one wavelength, which is smaller than 290 nm, from the ozone layer in the earth's atmosphere be absorbed, causing rays in the range between 290 nm and 320 nm, the so-called UVB range, an erythema, a simple Sunburn or even more or less severe burns. For protection against UVB rays are known numerous compounds in which it to derivatives of 3-Benzylidencamphers, the 4-aminobenzoic acid, the Cinnamic acid, salicylic acid, benzophenone and also the 2-phenylbenzimidazole is.

Also for the range between 320 nm and 400 nm, the so-called UVA range, it is important to have filter substances available since even its rays can cause damage. So it has been proven that UVA radiation damage the elastic and collagen fibers connective tissue, which prematurely ages the skin, and that it as the cause of numerous phototoxic and photoallergic reactions you can see. The damaging influence of UVB radiation can be caused by UVA be strengthened.  

To protect against the rays of the UVA range therefore certain Derivatives of dibenzoylmethane whose photostability (Int. Cosm. Science 10, 53 (1988)) is not sufficiently given and even as the cause of photoallergic reaction of the skin Some people (Der Hautarzt 39, 435 (1988); Photodermatology 3, 140 (1986)).

Some compounds of general formula I are from the literature already known. Thus, some were tested for tuberculostatic effect (Pol J. Pharmacol Pharm 27, 187 (1975); ibid 30, 585 (1978); 33, 217 (1981)). Specific derivatives in which Ar is 3-nitrophenyl or 4-nitrophenyl are disclosed in U.S. Patent 2,953,561 Application described in photography. Compounds of the general Formula I are disclosed in German Offenlegungsschrift 2,640,549 Intermediates in the synthesis of optical brighteners called, without that they are characterized in detail. Further examples are described in the Z. f. Nature Research. 32B, 304 (1977); in the Egypt. J. Chem. 20, 157 (1977) [CA 92, 215 342 y (1980)]; in Rev. Roum. Chim. 26, 985 (1981); as well as in Rev. Chim. (Bucharest) 37, 963 (1986) [CA 107, 115 532 BC (1987)].

The property of some compounds of general formula I, To absorb radiation in the UVA range is also known (Rev. Roum. Chim. 26, 985 (1981); Z. f. Nature Research. 32B, 304 (1977); Pole. J. Pharmacol. Pharm. 30, 585 (1978)). Your use in cosmetics will but neither specifically revealed nor suggested.

Unless stated otherwise, the alkyl groups of the invention and alkyl moieties are straight or branched and they each have 1 up to 20 carbon atoms, for example 1 to 12 carbon atoms or 1 up to 6 carbon atoms. The branched alkyl groups have at least 3 carbon atoms. Suitable alkyls are, for. 2-ethyl-hexyl, methyl, Ethyl, n-propyl, isopropyl and butyls, especially tert-butyl.  

Preferred C _1-6 alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, more preferably methyl, isopropyl, tert-butyl, if these stand for R₁, R₂, R₇, R₈, R₉, R₁₀ or R₁₁.

If R₁, R₇, R₈ or R₁₀ is R _X O- or R₁, R₇ is alkoxycarbonyl, then the alkyl radical is preferably methyl, ethyl, propyl, i-propyl, 2-ethylhexyl, particularly preferably methyl or 2-ethylhexyl. If R₁, R₇ or R₁₀ is alkylcarbonyloxy, then the alkyl radical is preferably methyl, ethyl, propyl, n-pentyl, particularly preferably methyl.

The group -SO₃R₃ is sulfonic acid or its salts, -SO₂NR₅R₆ is a sulfonamide group.

R₃ is preferably hydrogen, sodium, potassium, ammonium, tetramethylammonium, ie
R₄ is preferably hydrogen or methyl.

R₅ and R₆ are preferably the same and are preferably methyl or Ethyl, or are preferably both together tetramethylene or Pentamethylene.

Halogen is fluorine, chlorine, bromine or iodine and is preferably chlorine.

Preferred substituents R₁ are hydrogen, methyl, methoxy or chlorine, particularly preferably hydrogen or methyl.

Preferred substituents R₂ are hydrogen or methyl, especially preferably hydrogen.

The aromatic radical Ar in compounds of general formula I is preferably a phenyl radical of the formula A, a naphthyl radical of the formula B or a Furanylrest of the formula D, optionally with the there in each case mentioned substituents.  

The phenyl radical is preferably unsubstituted or monosubstituted, ie R₈ and R₉ are preferably hydrogen. Particularly preferred in this case is R₇ is hydrogen, halogen, C _1-6 alkyl, hydroxy, R _X O-, for the sulfonic acid radical SO₃H or a salt SO₃Na, SO₃K thereof. R₇ is very particularly preferably hydrogen, 4-methyl, 4-isopropyl, 4-tert-butyl, 2-chloro, 4-chloro, 2-hydroxy, 4-hydroxy, 2-methoxy, 4-methoxy, 2-SO₃H, 2-SO₃Na, 2-SO₃K, 4-SO₃H, 4-SO₃Na, 4-SO₃K.

A naphthyl radical of the formula B is preferably a 1-naphthyl radical and particularly preferably carries as substituents R₁₀ hydrogen, 2-hydroxy or 2-methoxy.

A furanyl radical of the formula D is preferably a 2-furanyl radical which particularly preferred as substituents R₁₁ hydrogen or 5-methyl wearing.

Very particularly preferred aryl radicals Ar are phenyl, 4-methylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, Phenyl-2-sulfonic acid, phenyl-4-sulfonic acid, potassium phenyl-2-sulfonate, Potassium phenyl 4-sulfonate, sodium phenyl 2-sulfonate, sodium phenyl 4 sulfonate, 1-naphthyl, 2-furanyl.

Preferred cyclic alkyl radicals R _X are cyclohexyl, 2-methylcyclohexyl, 2-isopropyl-5-methylcyclohexyl. Preferred bicyclic alkyl radicals R _X are, for example, 1,7,7-trimethyl-bicyclo [2.2.1] heptan-2-yl or 1,3,3-trimethyl-bicyclo [2.2.1] heptan-2-yl. Preferred unsaturated alkyl radicals R _X are 2-propen-1-yl, 3,7-dimethyl-2,6-octadien-1-yl, 3,7-dimethyl-6-octen-1-yl.

Compounds of general formula I in which R₁ and / or R₇ independently each other for COOR₃ or SO₃R₃, preferably serve as water-soluble UV filters in cosmetic products, while the rest Compounds of the invention preferably as fat or oil-soluble Find filter use.  

The following compounds of the invention are preferred in used cosmetic products:

1. 2- (1'-Cyano-2'-phenylvinyl) benzimidazole
2. 2- (1'-cyano-2 '- (2 "-methylphenyl) vinyl) benzimidazole
3. 2- (1'-Cyano-2 '- (3 "-methylphenyl) vinyl) benzimidazole
4. 2- (1'-Cyano-2 '- (4 "-methylphenyl) vinyl) benzimidazole
5. 2- (1'-Cyano-2 '- (4 "-isopropylphenyl) vinyl) benzimidazole
6. 2- (1'-Cyano-2 '- (4''- tert -butylphenyl) vinyl) benzimidazole
7. 2- (1'-Cyano-2 '- (2 "-chlorophenyl) vinyl) benzimidazole
8. 2- (1'-cyano-2 '- (4 "-chlorophenyl) vinyl) benzimidazole
9. 2- (1'-Cyano-2 '- (2'',4''- dichlorophenyl) vinyl) benzimidazole
10. 2- (1'-Cyano-2 '- (2'',6''- dichlorophenyl) vinyl) benzimidazole
11. 2- (1'-Cyano-2 '- (3'',4''- dichlorophenyl) vinyl) benzimidazole
12. 2- (1'-Cyano-2 '- (4''- fluorophenyl) vinyl) benzimidazole
13. 2- (1'-Cyano-2 '- (4 "nitrophenyl) vinyl) benzimidazole
14. 2- (1'-cyano-2 '- (3''- nitrophenyl) vinyl) benzimidazole
15. 3- (2'-Cyano-2 '- (benzimidazol-2-yl) vinyl) benzoic acid
16. 4- (2'-Cyano-2 '- (benzimidazol-2-yl) vinyl) benzoic acid
17. 2- (1'-Cyano-2 '- (4''- methoxycarbonylphenyl) vinyl) benzimidazole
18. 2- (1'-Cyano-2 '- (4 "-ethoxycarbonylphenyl) vinyl) benzimidazole
19. 2- (1'-Cyano-2 '- (4''-(2''' - ethylhexyloxy) carbonylphenyl) vinyl) benzimidazole
20. 2- (1'-Cyano-2 '- (2 "-hydroxyphenyl) vinyl) benzimidazole
21. 2- (1'-Cyano-2 '- (3''- hydroxyphenyl) vinyl) benzimidazole
22. 2- (1'-Cyano-2 '- (4 "-hydroxyphenyl) vinyl) benzimidazole
23. 2- (1'-Cyano-2 '- (2''- ethoxyphenyl) vinyl) benzimidazole
24. 2- (1'-Cyano-2 '- (4''- ethoxyphenyl) vinyl) benzimidazole
25. 2- (1'-Cyano-2 '- (2 "-methoxyphenyl) vinyl) benzimidazole
26. 2- (1'-Cyano-2 '- (3''- methoxyphenyl) vinyl) benzimidazole
27. 2- (1'-Cyano-2 '- (4 "-methoxyphenyl) vinyl) benzimidazole
28. 2- (1'-Cyano-2 '- (4''- tert -butoxyphenyl) vinyl) benzimidazole
29. 2- (1'-Cyano-2 '- (4''- acetoxyphenyl) vinyl) benzimidazole
30. 2- (1'-Cyano-2 '- (2'',4''- dimethoxyphenyl) vinyl) benzimidazole
31. 2- (1'-Cyano-2 '- (3'',4''- dimethoxyphenyl) vinyl) benzimidazole
32. 2- (1'-Cyano-2 '- (4''hydroxy-3''- methoxyphenyl) vinyl) benzimidazole
33. 2- (1'-Cyano-2 '- (2''-hydroxy-3''- methoxyphenyl) vinyl) benzimidazole
34. 2- (1'-Cyano-2 '- (2 "-hydroxy-3" -ethoxyphenyl) -vinyl) -benzimidazole
35. 2- (1'-Cyano-2 '- (3'',4''- methylenedioxyphenyl) vinyl) benzimidazole
36. 2- (2'-cyano-2 '- (benzimidazol-2''- yl) vinyl) benzenesulfonic acid
37. Sodium 2- (2'-cyano-2 '- (benzimidazol-2''- yl) vinyl) benzenesulfonate
38. Potassium 2- (2'-cyano-2 '- (benzimidazol-2''- yl) vinyl) benzenesulfonate
39. 4- (2'-Cyano-2 '- (benzimidazol-2''- yl) vinyl) benzenesulfonic acid
40. Sodium 4- (2'-cyano-2 '- (benzimidazol-2''- yl) vinyl) benzenesulfonate
41. Potassium 4- (2'-cyano-2 '- (benzimidazol-2''- yl) vinyl) benzenesulfonate
42. 1-Methyl-2- (1'-cyano-2'-phenylvinyl) benzimidazole
43. 1-Methyl-2- (1'-cyano-2 '- (4 "-methylphenyl) vinyl) benzimidazole
44. 5-Methyl-2- (1'-cyano-2'-phenylvinyl) benzimidazole
45. 5-Methyl-2- (1'-cyano-2 '- (4 "-methylphenyl) vinyl) benzimidazole
46. 5-Methyl-2- (1'-cyano-2 '- (4''- isopropylphenyl) vinyl) benzimidazole
47. 5-Methyl-2- (1'-cyano-2 '- (4''- tert -butylphenyl) vinyl) benzimidazole
48. 5-Methoxy-2- (1'-cyano-2'-phenylvinyl) benzimidazole
49. 5-Methoxy-2- (1'-cyano-2 '- (4 "-methylphenyl) vinyl) benzimidazole
50. 5-Methoxy-2- (1'-cyano-2 '- (4 "-isopropylphenyl) vinyl) benzimidazole
51. 5-Methoxy-2- (1'-cyano-2 '- (4''- tert -butylphenyl) vinyl) benzimidazole
52. 5-Chloro-2- (1'-cyano-2'-phenylvinyl) benzimidazole
53. 5-Chloro-2- (1'-cyano-2 '- (4''- methylphenyl) vinyl) benzimidazole
54. 5-Chloro-2- (1'-cyano-2 '- (4''- isopropylphenyl) vinyl) benzimidazole
55. 5-Chloro-2- (1'-cyano-2 '- (4''- tert -butylphenyl) vinyl) benzimidazole
56. 2- (1'-Cyano-2'-phenylvinyl) benzimidazole-5-sulfonic acid
57. Sodium 2- (1'-cyano-2'-phenylvinyl) benzimidazole-5-sulfonate
58. Potassium 2- (1'-cyano-2'-phenylvinyl) benzimidazole-5-sulfonate
59. 2- (1'-Cyano-2 '- (2 "-furanyl) vinyl) benzimidazole
60. 5-Methyl-2- (1'-cyano-2 '- (2 "-furanyl) vinyl) benzimidazole
61. 5-Chloro-2- (1'-cyano-2 '- (2''- furanyl) vinyl) benzimidazole
62. 2- (1'-Cyano-2 '- (1''- naphthyl) vinyl) benzimidazole
63. 5-Methyl-2- (1'-cyano-2 '- (1''- naphthyl) vinyl) benzimidazole
64. 5-Methoxy-2- (1'-cyano-2 '- (1''- naphthyl) vinyl) benzimidazole
65. 5-Cyclohexyloxy-2- (1'-cyano-2'-phenylvinyl) benzimidazole
66. 2- (1'-Cyano-2'-phenylvinyl) benzimidazole-5-carboxylic acid
67. 5-Methoxycarbonyl-2- (1'-cyano-2'-phenylvinyl) benzimidazole
68. 2- (1'-Cyano-2'-phenylvinyl) benzimidazole-5-carboxylic acid allyl ester
69. 2- (1'-Cyano-2'-phenyl) benzimidazole-5-carboxylic acid methyl ester
70. 2- (1'-Cyano-2'-phenylvinyl) benzimidazole-5-carboxylic acid isobornyl ester
71. 2- (1'-Cyano-2'-phenylvinyl) benzimidazole-5-carboxylic acid 2 '' - ethylhexyl ester

The compounds 1, 4, 5, 6, 36-41 and 59 listed above and Cosmetic compositions containing them are especially preferred.

With the exception of the connections 1, 4, 7, 8, 13, 14, 20, 21, 22, 25, 26, 27, 30, 32, 42, 44, 59, 60 and 62 are the aforementioned compounds New.

Absorb the compounds of general formula I according to the invention ultraviolet radiation, in particular in the range between 320 nm and 400 nm, where the wavelength of the maximum absorption of the type of Substituents R₁, R₂ or Ar, in particular of the substituents R₇ to R₁₁ to the aromatic radicals Ar, depends and particularly preferred between 340 nm and 360 nm. The molar extinction coefficients E the compounds of the formula I are in the range between 20,000 and 35,000.

The compounds of the invention are characterized by good Photostability. Thus, when irradiated by ethanolic Solutions with a solar simulator even after very large amounts of energy only a cis / trans isomerization at the olefinic Double bond.

The compounds of general formula I are in vitro with respect to their Cytotoxicity commonly used as a UVA filter Superior to dibenzoylmethane derivatives.  

Because of these properties, the compounds of formula I can advantageous as a UV absorber, preferably UVA absorber, in particular in cosmetic means are used.

Benzimidazoles of general formula I are made 2-cyanomethylbenzimidazoles of the general formula II and aldehydes of general formula III according to the following reaction scheme:

wherein R₁, R₂ and Ar have the meaning given above.

Such reactions are known from the literature: Z. f. Nature Research. 32B, 304 (1977); Rev. Roum. Chim. 26, 985 (1981); Pole. J. Pharmacol. Pharm. 27, 187 (1975); US Pat. No. 2,953,561 [CA 55, 1250 d (1961)].

They can be in the neutral, basic or acidic reaction medium be performed. The solvents used in this case are ethers, for. B. Diethyl ether, tetrahydrofuran or 1,2-dimethoxyethane, chlorinated Hydrocarbons, eg. For example, dichloromethane or chloroform, aromatic Hydrocarbons, eg. As benzene or toluene, but preferably alcohols with an alkyl chain of up to four carbon atoms, more preferably Methanol, ethanol or isopropanol, or lower carboxylic acids Number of C atoms, more preferably acetic acid. In cases where Alcohols or carboxylic acids are used, these can also be mixed be used with water.

The reaction temperatures are between the room temperature and the Boiling temperature of the reaction mixture.

If the reaction is carried out under basic conditions, find as Bases use:

Alkali metal hydrides, preferably sodium hydride, preferably in ethers, such as Diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane;

Amines, preferably pyrrolidone, piperidine, morpholine or pyridine, preferably in alcohols such as methanol, ethanol or isopropanol or even in aromatic hydrocarbons such as benzene or toluene preferably using catalytic amounts of the amines;

Alkali metal alcoholates, preferably in alcohols of the same alkyl radical, preferably sodium or potassium alcoholates are used;  Alkali metal hydroxides, preferably in alcohols of up to four C atoms to which water may also be added, preferably sodium or potassium hydroxide;

Alkali metal carboxylates, preferably sodium acetate, in alcoholates with bis to four carbon atoms, preferably in ethanol.

When carrying out the reaction under acidic reaction conditions catalytic amounts of mineral acids, e.g. As sulfuric acid or hydrochloric acid, or sulfonic acids, e.g. As p-toluenesulfonic acid, preferably used in aromatic hydrocarbons such as benzene or toluene below Reaction conditions, which is the azeotropic removal of the water of reaction enable. By nature, acidic reaction conditions are also present when carboxylic acids with low number of carbon atoms as solvent can be used, and it may be advantageous if, in addition catalytic amounts of the above acids are added. at In neutral reaction conditions, the reaction is preferably in alcohols low C-number, especially in methanol, ethanol or Isopropanol.

Preferred reaction conditions for the preparation of compounds of general formula I according to the reaction scheme given above are:

• 1) heating the reactants of the general formulas II and III in acetic acid.
• 2) heating the reactants of the general formulas II and III in Methanol, ethanol or isopropanol in the presence of catalytic amounts Pyrrolidine, piperidine or morpholine, preferably with piperidine in Ethanol.
• 3) Reaction of compounds of general formulas II and III in Methanol, ethanol or isopropanol containing up to 20% of sodium or  Contains potassium hydroxide, at a temperature between 20 ° C and the Boiling temperature of the reaction mixture.

It may be advantageous to prepare compounds of the general formula I from other derivatives I according to the invention. This is especially true when one of the substituents R₁, R₇, R₈ or R₁₀ is an ether, a carboxylic acid or a sulfonic acid substituent or when R₂ is C _1-6 alkyl.

Thus, in the event that R₁, R₇, R₈ or R₁₀ is R _X O, such a compound of a compound of formula I in which the same substituent is hydroxy can be obtained by alkylation with an R _X halide, wherein the halogen is preferably iodine or bromine and the reaction is carried out in an inert organic solvent such as toluene or dimethylformamide in the presence of a base such as potassium hydroxide.

Compounds of general formula I in which one of the substituents R₁, R₇, R₈ or R₁₀ is hydroxy, can be converted by standard methods of organic synthesis into derivatives I, in which this substituent is alkylcarbonyloxy. Such esterification may be accomplished by using a C _1-21 acyl chloride or acyl anhydride or other activated derivative of the subject alkanoic acid, optionally in the presence of an organic base such as pyridine or triethylamine, or an inorganic base such as potassium carbonate, optionally with the aid of catalysts such as potassium chloride. (N, N-dimethylamino) pyridine in an inert solvent.

Compounds of the general formula I in which one of the radicals R₁ or R₇ is R _X -oxycarbonyl can be obtained by standard methods of esterification with C _1-12 -alcohols from derivatives I in which this radical represents a carboxylic acid group. In this case, preference is given in an inert organic solvent with the participation of condensation reagents, for. As dicyclohexylcarbodiimide, or by other methods for the removal of the water of reaction, for. B. by azeotropic removal in boiling benzene or toluene in the presence of an acidic catalyst, eg. For example, p-toluenesulfonic acid, worked. By the same methods are from such carboxylic acid derivatives I, the carboxylic acid amides of the formula I in which R₁ or R₇ is CONR₅R₆, with amines of the formula HNR₅R₆ available.

Compounds of the formula I in which R₁ or R₇ is SO₂NR₅R₆ can be prepared from compounds of general formula I, in which this substituent is the sulfonic acid radical or an alkali metal sulfonate SO₃R₃ according to formula I, wherein R₃ is sodium or potassium. there First, the corresponding sulfonic acid chloride is obtained, preferably with chlorosulphonic acid or chlorides of phosphorus, e.g. B. with Phosphorus (V) chloride or phosphorus oxychloride in inert organic Solvents at elevated temperature, eg. In dimethylformamide, and this subsequently reacted with amines of the general formula HNR₅R₆. For amines HNR₅R₆, which have not more than five carbon atoms, or if the amine is morpholine, the reaction may also be in the same as Solvent, optionally at elevated temperature, are performed. Otherwise, an inert organic solvent is used, such as toluene, Dichloromethane or dimethylformamide and in the presence of an additional Base, such. As pyridine, sodium or potassium hydroxide, sodium or Worked potassium carbonate or sodium acetate.

Compounds of general formula I in which R₁ or R₇ for SO₃R₃ or is COOR₃ and R₃ is defined according to the general claim, can from corresponding sulfonic acids or carboxylic acids of the general Formula I, in which R₁ or R₇ SO₃H or COOH, are obtained. In the event that R₃ is sodium or potassium, this can be done by Neutralization with NaOH or Na₂CO₃ or KOH or K₂CO₃ carried out for the Case that R₃ is (NR₄) ₄ and R₄ according to the general claim is defined by neutralization with a corresponding amine N (R₄) ₃ or by reaction with a corresponding ammonium salt N (R₄) ₄X ', in X 'preferably represents chlorine, bromine or acetate.  

Conversely, from the abovementioned sulfonates or Carboxylates also the free acids, so compounds of the general Formula I, in which R₁ or R₇ SO₃H or COOH means are obtained, by reacting the salts with strong acids, preferably with Mineral acids such as hydrochloric acid or sulfuric acid or acidic Ion exchangers.

Compounds of general formula I in which R₂ is C _1-6 alkyl may be obtained from compounds of formula I in which R₂ is hydrogen by reacting such compounds with a C _1-6 alkyl halide, preferably with an iodide or a bromide, or with a dialkyl sulfate, preferably in the presence of a base. Preferred reaction conditions are the use of alkali metal hydrides such as sodium hydride in ethers such as tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, alkali metal hydroxides such as sodium or potassium hydroxide in alcohols, e.g. As ethanol, or alkali metal carbonates such as sodium or potassium carbonate in tetrahydrofuran, ethanol, dimethylformamide or toluene. Especially in the case where R₂ is methyl, the alkylation can also be carried out with dimethylformamide dimethyl acetal, preferably at elevated reaction temperature. In the case of compounds of the general formula I in which R₁, R₇, R₈ or R₁₀ is hydroxyl, it is of course possible for mixtures of compounds of the general formula I to be obtained in that alkylation is also carried out on the hydroxyl group as described above.

The required for the preparation of compounds of general formula I. Precursors of the general formula II are known or customary Methods of Synthesis of Benzimidazole Derivatives Available (Chemical Reviews 74, 279 (1974); The Chemistry of Heterocyclic Compounds, Vol. 40, Part I, p. 1 et seq., Wiley-Interscience, New York (1981)).

Preferred starting compounds for this are ortho-phenylenediamines of general formula IV, in which R₁ and R₂ are as defined above.  

Particular preference is given to compounds of the general formula IV Derivatives of cyanoacetic acid V, which are preferably the Acid itself, its ethyl ester, methyl ester or its amide, so X preferably OH, OC₂H₅, OCH₃ or NH₂ means, by methods such as Example in the Journal of the American Chemical Society 65, 1072 (1943) or in the Archives of Pharmacy 293, 758 (1960) are described, as in the following reaction scheme:

wherein R₁ and R₂ have the meaning given above and preferably X = OH, OCH₃, OCH₂CH₃ or NH₂.

In some cases, it may be beneficial to use compounds of the general Formula II into other compounds of formula II by the above for Compounds of general formula I described transformations of  Substituents R₁ or R₂ to convert to corresponding compounds of formula I to arrive.

The compounds of the formula III are known or by known methods available.

The cosmetic compositions according to the invention can be composed as usual and for the treatment of the skin and / or the hair and as Make up product in decorative cosmetics. They contain preferred 0.01% by weight to 30% by weight, but in particular 0.1% by weight to 10% by weight, at least one compound of the formula I, based on the Total weight of the agent. Preferably, one, two or three of these Contain compounds or their tautomers or cis-trans isomers.

For use, the cosmetic compositions of the invention in the for Cosmetics usual way to the skin and / or hair in sufficient Quantity applied.

Particularly preferred are those cosmetic agents which are in the form of a Sunscreen available. Preferably, these additionally contain at least one UVB filter and / or at least one further UVA filter and / or at least one inorganic pigment.

Cosmetic compositions according to the invention for the protection of the skin UV rays can be in various forms, such as. B. usually be used for this type of agent. That's the way they can be z. As a solution, a water-in-oil (W / O) or type emulsion Oil-in-water (O / W), a gel, a solid stick or even an aerosol represent.

The cosmetic compositions according to the invention can cosmetic adjuvants contain, as they are commonly used in such funds, z. Preservatives, bactericides, perfumes, preventing agents foaming, dyes, pigments which have a coloring effect, Thickeners, surfactants, emulsifiers, softening  Remedies, moisturizers, moisturizers, fats, oils, waxes or other common ingredients of a cosmetic formulation such as Alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.

If the cosmetic product is a solution or lotion, can used as solvent:

• - Oils, such as triglycerides of capric or caprylic, preferably but castor oil;
• - fats, waxes and other natural and synthetic fats, preferably esters of fatty acids with alcohols of low C number, z. B. with isopropanol, propylene glycol or glycerol, or esters of Fatty alcohols with alkanoic acids of low C number or with fatty acids;
• Alcohols, diols or polyols of low C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, Ethylene glycol, ethylene glycol monoethyl or monobutyl ether, Propylene glycol monomethyl, monoethyl or monobutyl ether, Diethylene glycol monomethyl or monoethyl ether and analogues Products.

A preferred cosmetic agent is an oily or oily-alcoholic Solution or lotion, especially a sun oil.

In particular, mixtures of the abovementioned solvents used. For alcoholic solvents, water can be another Be part of it.

Emulsions according to the invention z. B. in the form of a sunscreen or a sunscreen milk are preferred and contain z. As the mentioned Fats, oils, waxes and other fatty substances, as well as water and a  Emulsifier, as is customary for such a type of formulation is used.

Gels according to the invention usually contain lower alcohols C number, z. As ethanol, isopropanol, 1,2-propanediol, glycerol and water or an above-mentioned oil in the presence of a thickener, in oily-alcoholic gels, preferably silica or a Aluminum silicate, in aqueous-alcoholic or alcoholic gels preferably a polyacrylate.

Solid pins according to the invention contain z. B. natural or synthetic waxes, fatty alcohols or fatty acid esters. To be favoured Lip balm.

Aerosols can be classic propellants such as alkanes, fluorocarbons or chlorofluorocarbons.

The cosmetic agents for the protection of the skin contain compounds of the Formula I z. B. in amounts of 0.1 wt .-% to 30 wt .-%, preferably in Amounts of from 0.5% by weight to 10% by weight, but especially 1% by weight to 6% by weight based on the total weight of the agent.

Preferably, they may also contain substances that UV radiation in Absorb UVB range, the total amount of the filter substances z. B. 0.1 wt .-% to 30 wt .-%, preferably 0.5 to 10 wt .-%, in particular 1 to 6 wt .-%, based on the total weight of the agent to to provide cosmetic products that protect the skin from the protect entire area of ultraviolet radiation. You can also to serve as a sunscreen.

The UVB filters may be oil-soluble or water-soluble. As oil-soluble Substances are z. To name, for example:

• 3-benzylidene camphor derivatives, preferably
  3- (4-methylbenzylidene) camphor, 3-benzylidene camphor;
• 4-aminobenzoic acid derivatives, preferably (2-ethylhexyl) 4- (dimethylamino) benzoate,
  4- (dimethylamino) benzoesäureamylester;
• - esters of cinnamic acid, preferably
  4-methoxycinnamate (2-ethylhexyl) ester,
  4-Methoxyzimtsäureisopropylester;
• - esters of salicylic acid, preferably
  Salicylic acid (2-ethylhexyl) ester,
  Salicylic acid (4-isopropylbenzyl) ester,
  salicylate;
• - Derivatives of benzophenone, preferably
  2-hydroxy-4-methoxybenzophenone,
  2-hydroxy-4-methoxy-4'-methylbenzophenone,
  2,2'-dihydroxy-4-methoxybenzophenone;
• Esters of benzalmalonic acid, preferably
  4-methoxybenzalmalonate (2-ethylhexyl) ester;
• 2,4,6-trianilino (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine.

As water-soluble substances z. To name, for example:

• Salts of 2-phenylbenzimidazole-5-sulphonic acid, such as its sodium, Potassium or its triethanolammonium salt, and the sulfonic acid even;
• Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;
• - Sulfonic acid derivatives of 3-Benzylidencamphers, such as. B. 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) sulfonic acid and its salts.

The list of mentioned UVB filters, in combination with the Compounds of general formula I can be used should Of course, not limiting.

The invention also relates to the combination of an inventive UVA filters with a UVB filter or a cosmetic according to the invention Agent that also contains a UVB filter.

It may also be advantageous to use compounds of the general formula I To combine UVA filters that were previously commonly used in cosmetic Funds are included. These substances are preferably derivatives of dibenzoylmethane, in particular 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione and vice versa 1-Phenyl-3- (4'-isopropylphenyl) propane-1,3-dione. Also these combinations or agents containing these combinations are the subject of Invention. It may be the quantities used for the UVB combination be used.

Cosmetic agents with compounds of general formula I may also contain inorganic pigments, which are commonly used in cosmetics for Protecting the skin from UV rays can be used. That's it oxides of titanium, zinc, iron, zirconium, silicon, manganese, Aluminum, cerium and mixtures thereof, as well as modifications in which the Oxides are the active agents. Particularly preferred are Pigments based on titanium dioxide. Also these combinations of UVA filters and pigment or agents containing this combination are Subject of the invention. It can be for the above Combinations mentioned quantities can be used.

For cosmetic products to protect the hair from UV rays according to the Invention is, for example, shampooing agents, Means, when rinsing the hair before or after shampooing, before or after the permanent wave treatment, before or after the dyeing or Decolouring the hair can be applied to means for blow drying or inserting the hair, means for dyeing or decolorizing to a hairdressing and  Treatment lotion, a hair lacquer or permanent waving agent. The Cosmetic products contain active ingredients, and adjuvants, as they usually do for this type of hair care and hair treatment be used. As auxiliaries are preservatives, surfactants, antifoaming agents, emulsifiers, Thickeners, fats, oils, waxes, organic solvents, Bactericides, perfumes, dyes or pigments, whose function is the Hair or the dye itself, electrolytes, remedies for that Greasing the hair.

Cosmetic agents that constitute a shampooing agent contain preferably at least one anionic, nonionic or amphoteric surfactant, or mixtures thereof, at least one Compound of the general formula I in an aqueous medium and auxiliaries, as they are usually used for this. The surface active Agent may be present in a concentration between 1% and 50% by weight in the Shampooning present.

If the cosmetic product is in the form of a lotion that is rinsed out and Z. Before or after decolorization, before or after shampooing, between two shampooing steps, before or after the permanent wave treatment is applied, so it is z. B. to aqueous or aqueous-alcoholic solutions, optionally surface-active Contains agents, preferably nonionic or cationic surface active Agents whose concentration is between 0.1 and 10% by weight, preferably between 0.2 and 5 wt .-%, may be. This cosmetic Agent may also use an aerosol with those commonly used Represent aids.

A cosmetic in the form of a lotion that is not rinsed out, In particular, a lotion for inserting the hair, a lotion, the Blowing the hair is used, a hairdressing and treatment lotion, is generally an aqueous, alcoholic or aqueous-alcoholic Solution and contains at least one cationic, anionic, nonionic or amphoteric polymer or else mixtures thereof,  and at least one compound of general formula I. The amount of used polymers is z. B. between 0.1 and 10 wt .-%, preferably between 0.1 and 3 wt .-%.

Cosmetic means for the treatment and care of the hair, at least contain a compound of general formula I according to the invention, may be in the form of emulsions other than nonionic or anionic Type are. Non-ionic emulsions contain oils or water in addition to water Fatty alcohols, which, for example, also polyethoxylated or may be polypropoxylated, or mixtures of the two organic Components. These emulsions optionally contain cationic surfactants. Anionic emulsions are preferably of the type a soap and contain at least one compound of the general Formula I with anionic or non-ionic character.

Cosmetic agents for the treatment and care of hair can be used as gels present, in addition to at least one compound of the general formula I. and for solvents commonly used organic Thickener, z. Gum arabic, xanthan gum, sodium alginate, Cellulose derivatives, preferably methylcellulose, hydroxymethylcellulose, Hydroxyethyl cellulose, hydroxypropyl cellulose, Hydroxypropylmethylcellulose or inorganic thickening agents, e.g. B. Aluminum silicates such as bentonites, or a mixture of Polyethylene glycol and polyethylene glycol stearate or distearate, contain. The thickener is in the gel z. B. in a crowd between 0.1 and 30% by weight, preferably between 0.5 and 15% by weight, contain.

The amount of the compounds according to the invention is preferably in a means intended for the hair 0.05 wt .-% to 10 wt .-%, in particular 0.5 wt .-% to 5 wt .-% based on the total weight of Agent.

The present invention also includes a method of protecting the skin and the hair from UVA radiation, which is characterized in that one  a cosmetic agent containing at least one of the compounds of general formula I, in sufficient amount on the skin or Applying hair, as well as the use of these compounds in particular for these purposes.

Likewise, the present invention also includes a method of protection colorless or colored cosmetic agent against UVA rays as well these funds, which are z. B. to the above means for Treatment and care of hair, in particular hair colorants, hair lacquers, Shampoo, color shampoo, around Make-up products such. Nail polishes, lipsticks, complexions, Creams for the treatment of the skin or any other cosmetic Means whose constituents are stability problems due to light can bring in storage, characterized in that the Cosmetic agent at least one compound of general formula I. in for the stabilization against light, in particular UVA rays, sufficient amount.

The amount of the compounds according to the invention is preferably in these preparations 0.01 wt .-% to 10 wt .-%, in particular 0.1 wt .-% to 3 wt .-% based on the total weight of the composition.

All quantities, percentages and percentages are, unless otherwise stated indicated on the weight and the total amount or on the total weight of the agent.

The invention also provides the process for the preparation of cosmetic agent according to the invention characterized that in a conventional manner compounds of the formula I in incorporates cosmetic formulations.

The following examples are intended to illustrate the present invention without limiting it:
lambda _max = wavelength of the UV absorption maximum
ε = molar extinction coefficient

Example 1 Sodium 2- (2'-cyano-2 '- (benzimidazol-2' '- yl) vinyl) benzenesulfonate

1.6 g (10 mmol) of 2-benzimidazolylacetonitrile and 2.4 g (10 mmol) of sodium 2-formylbenzenesulfonate dihydrate are dissolved in 20 ml Dissolved ethanol, mixed with 10 drops of piperidine and 15 min under Reflux cooked. After cooling, it is filtered off with suction and from ethanol recrystallized.

Yield: 2.9 g (83%), pale yellow crystals, mp 342-344 ° C

The following compounds were prepared as described above Method synthesized:

example 2 2- (1'-cyano-2 '- (4' '- tert-butylphenyl) vinyl) benzimidazole

Yield: 1.45 g (48%)

yellow crystals, mp 275-277 ° C  

example 3 5-chloro-2- (1'-cyano-2 '- (4' '- methylphenyl) vinyl) benzimidazole

Yield: 2.6 g (88%)

yellow crystals, mp 257-258 ° C

example 4 (Methylphenyl) vinyl 1'-cyano-2 '- - (4' ') -benzimidazole 5-methoxy-2-

Yield: 2.6 g (90%)

yellow crystals, mp 204-206 ° C

example 5 2- (1'-cyano-2 '- (2' '- pyridinyl) vinyl) benzimidazole

Yield: 790 mg (32%)

yellow crystals, mp. 196-197 ° C

example 6 3- (2'-cyano-2 '- (benzimidazol-2' '- yl) vinyl) benzoic acid

Yield: 2.4 g (83%)

yellow crystals, mp. 318-320 ° C  

example 7 2- (1'-cyano-2 '- (1' '- naphthyl) vinyl) benzimidazole

There are 1.6 g (10 mmol) of 1-naphthaldehyde and 1.6 g (10 mmol) 2-Benzimidazolylacetonitrile dissolved in 20 ml of glacial acetic acid and the Reaction mixture stirred for 10 min at a heating bath temperature of 90 ° C. To After cooling, the yellow precipitate is filtered off with suction, with a little glacial acetic acid and then washed with plenty of water. After recrystallization Methanol will get the substance in yellow crystals.

Yield: 1.95 g (65%)
Mp .: 234-236 ° C
Lit .: Egypt. J. Chem. 20, 157 (1977) [CA 92, 215 342 y (1980)]

The same method was used:

example 8 5-methyl-2- (1'-cyano-2 '- (4' '- isopropylphenyl) vinyl) benzimidazole

Yield: 1.0 g (33%)

yellow crystals, mp 198-199 ° C

example 9 2- (1'-cyano-2 '- (4' '- isopropylphenyl) vinyl) benzimidazole

2.2 g (40 mmol) of KOH are dissolved in 60 ml of methanol, 2.0 g (12.8 mmol) 2-Benzimidazolylacetonitrile added and 5 min. stirred. After adding  of 3.55 g (24 mmol) of 4-isopropylbenzaldehyde is added overnight Room temperature stirred, then the reaction mixture on ice acidified with glacial acetic acid, the precipitate is filtered off with suction, in vacuo dried and recrystallized from ethanol.

Yield: 2.1 g (57%)
beige crystals, mp 253-254 ° C

The same method was used:

example 10 2- (1'-cyano-2 '- (4' '- methoxycarbonylphenyl) vinyl) benzimidazole

Yield: 1.0 g (26%)

yellow crystals, mp 247 ° C

example 11 2- (1'-cyano-2'-phenylvinyl) benzimidazole-5-carboxylic acid

5.0 g (33 mmol) of 3,4-diaminobenzoic acid and 6.4 g (65 mmol) of methyl cyanoacetate are in a small distillation apparatus 2 h heated to 190 ° C. After cooling, use water / charcoal boiled, filtered, the yellowish filtrate was concentrated, several times Ethanol / chloroform added and concentrated in vacuo. After drying in Vacuum is the 2-cyanomethylbenzimidazole-5-carboxylic acid as in the air obtained deliquescent crystals, which continue to be used as the crude product becomes.  

1.3 g of the carboxylic acid and 850 mg (8 mmol) of benzaldehyde are added as under Example 1 described and reacted together after crystallization low ethanol 200 mg (11%) of 2-vinylbenzimidazole in yellow crystals obtained from mp. 303-305 ° C.

example 12 benzimidazole 5-methoxycarbonyl-2- (1'-cyano-2'-phenylvinyl)

There are 250 mg (0.86 mmol) of the compound described above in Dissolve 20 ml of dry methanol, concentrate with five drops Sulfuric acid added and boiled under reflux for 12 h. After concentration is stirred with sodium bicarbonate solution, the precipitate filtered off and recrystallized from ethanol.

Yield: 150 mg (57%)
yellow crystals, mp 117-119 ° C

example 13 2- (1'-cyano-2 '- (4' '- acetoxyphenyl) vinyl) benzimidazole

There are 2.6 g (10 mmol) of the known from the literature 2- (1'-cyano-2 '- (4' '- hydroxyphenyl) vinyl) benzimidazoles, the analogous example 7 in 69% yield, dissolved in 50 ml of dry acetone, mixed with 1.4 g (10 mmol) of calcium carbonate and heated to 50 ° C for 15 min. During 20 minutes, 1.25 g (16 mmol) of acetyl chloride are then slow added dropwise, refluxed for 1 h, after cooling the yellow The precipitate is filtered off with suction, washed with water and from ethanol recrystallized.

Yield: 1.6 g (53%) of yellow crystals, mp 237-238 ° C  

example 14 benzimidazole 1-methyl-2- (1'-cyano-2'-phenylvinyl)

240 mg (6 mmol) of NaOH are dissolved in 20 ml of ethanol, 1.5 g (6 mmol) of the from the literature known 2- (1'-cyano-2'-phenylvinyl) benzimidazole, the obtained analogously to Example 9 in 74% yield, and 950 mg (6.7 mmol) Added iodomethane and the mixture was refluxed for 1 h. After cooling, the reaction mixture is added to ice / 2N acetic acid, the precipitate is filtered off, dried and the reaction product over a Silica gel column (eluent CH₂Cl₂ / EtOH 99: 1) separated. To Crystallization from EtOAc / PE gives 300 mg (19%) of yellow crystals of the mp. 138-139 ° C.

(Ref .: CA 107, 115 532 v (1987))
lambda _max = wavelength of the UV absorption maximum
ε = molar extinction coefficient

example 15

suntan oil - compound of Example 9 | 30.0 g - 3- (4'-methylbenzylidene) camphor, available under the name "Eusolex 6300" from Merck 25.0 g Myristyl alcohol, polyoxypropylated with 3 moles of propylene oxide, available under the name "Witconol APM" from Witco 608.0 g - C₁₂-C₁₅-alcohol benzolate, available under the name "Finsolv TN" Fa. Witco 152.0 g Glycerol monococoate, polyoxyethylated with 7 mol of ethylene oxide, obtainable under the name "Cetiol HE" from Henkel 100.0 g - ethanol 65.0 g 2-octadodecanol 20.0 g - Perfume, corrigents, additives, antioxidants in sufficient quantity upon need.

The components of the sun oil are mixed together and optionally heated to 40 to 50 ° C for homogenization.  

example 16

Sonnengel 2- (1'-cyano-2 '- (4 "-methylphenyl) vinyl) benzimidazole according to the invention | 18.0 g 2,4,6-trianilino- (p-carbo-2'-ethylhexyl-1'-oxy) -1,3,5-triazine (Uvinul T-150 from BASF) 25.0 g - isopropyl myristate 189.0 g - C₁₂-C₁₅-alcohol benzoate, available under the name "Finsolv TN" Fa. Witco 76.0 g Myristyl alcohol, polyoxypropylated with 3 moles of propylene oxide, available under the name "Finsolv TN" from Witco 304.0 g - Caprylic / Caprinsäuretriglycerid, available as "Miglyol neutral oil" Fa. Dynamit-Nobel 195.0 g - "Bentone-38" from the company Kronos-Titan 150.0 g - Propylene carbonate 20.0 g - ethanol 23.0 g - Perfume, corrigents, additives, stabilizers in sufficient quantity upon need

With the above ingredients is in a conventional manner Made of sun angel.  

example 17

hydrogel - compound of example 1 | 15.0 g 2-phenylbenzimidazole-5-sulfonic acid, available under the name "Eusolex 232" from Merck 27.0 g - allantoin 2.0 g Sorbitol fl., Available under the name "Karion F" from Merck 22.0 g "Carbopol 394" from B.F. Goodrich 15.0 g - tris (hydroxymethyl) aminomethane 27.0 g - Propylene glycol 10.0 g - ethanol 300.0 g - Water 582.0 g - Perfume, corrigents, additives, stabilizers in sufficient quantity upon need

A hydrogel is prepared in a customary manner with the constituents mentioned.  

example 18

Oil-in-water emulsion (sunscreen) - compound of example 9 | 20.0 g 2-phenylbenzimidazole-5-sulfonic acid, available under the name "Eusolex 232" from Merck 32.0 g Stearyl alcohol, which is oxyethylated with 2 moles of ethylene oxide, available under the name "Brÿ 72" Fa. ICI 30.0 g Stearyl alcohol, which is oxyethylated with 21 moles of ethylene oxide, available under the name "Brÿ 721" Fa. ICI 20.0 - Cetylstearyl alcohol 25.0 g Myristyl alcohol, polyoxypropylated with 3 moles of propylene oxide, available under the name "Witconol APM" from Witco 64.0 g - C₁₂-C₁₅-alcohol benzoate, available under the name "Finsolv TN" Fa. Witco 16.0 g - Propylene glycol 35.0 g - tris (hydroxymethyl) aminomethane 14.0 g - Water 744.0 g - Perfume, corrigents, additives, stabilizers in sufficient quantity upon need

The fats are heated to 80 to 85 ° C, the oil-soluble UV filter dissolved in it. The water-soluble ingredients are dissolved in water at the same temperature, both phases below mixed vigorously with stirring, and with moderate stirring allowed to cool.

example 19

Oil-in-water emulsion (sunscreen) - compound of Example 1 | 33.0 g 2,4,6-trianilino- (p-carbo-2'-ethylhexyl-1'-oxy) -1,3,5-triazine, obtainable under the name Uvinul T-150 from BASF 18.0 g - C₁₂-C₁₅-alcohol benzoate, available under the name "Finsolv TN" from Witco 47.0 g - Cetylstearyl alcohol 30.0 g Mixture of stearic acid mono- and diesters of glycerol, and stearic acid esters of polyethylene oxide, available under the name "Arlacel 165" from. ICI 50.0 g Myristyl alcohol, polyoxypropylated with 3 moles of propylene oxide, available under the name "Witconol APM" from Witco 185.0 g - Water 637.0 g - Perfume, corrigents, additives, stabilizers in sufficient quantity upon need

The emulsion is, as described in the previous example, prepared.

example 20

Water-in-oil emulsion (sunscreen milk) - compound of Example 1 | 20.0 g - 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, available under the name "Parsol 1789" from Givaudan 15.0 g 4'-methoxycinnamic acid 2'-ethylhexyl ester, available under the name "Parsol MCX" from Givaudan 35.0 g - esters of saturated fatty acids with polyethylene oxide, available under the name "Arlacel 989" from. ICI 37.0 g Esters of unsaturated fatty acids with glycerol and sorbitan, available under the name "Arlacel 481" from ICI 13.0 g Myristyl alcohol, polyoxypropylated with 3 moles of propylene oxide, available under the name "Witconol APM" from Witco 160.0 g - C₁₂-C₁₅-alcohol benzoate, available under the name "Finsolv TN" Fa. Witco 40.0 g - Magnesium sulfate heptahydrate 7.0 g - Water 673.0 g - Perfume, corrigents, additives, stabilizers in sufficient quantity upon need

The emulsion is prepared in the same manner as described below Example 18 described.

example 21

Water-in-oil emulsion (sunscreen milk) - compound of example 1 | 15.0 g 4'-methoxycinnamic acid 2'-ethylhexyl ester, available under the name "Parsol MCX" from Givaudan 15.0 g - 3- (4'-methylbenzylidene) camphor, available under the name "Eusolex 6300" from Merck 3.0 g Esters of unsaturated fatty acids with glycerol and sorbitan, available under the name "Arlacel 481" from ICI 60.0 g - Microwax the name "Lunacera 11" Fa. Fuller 10.0 g - Caprylic / Caprinsäuretriglycerid, available as "Miglyol neutral oil" Fa. Dynamit-Nobel 20.0 g Myristyl alcohol, polyoxypropylated with 3 moles of propylene oxide, available under the name "Witconol APM" from Witco 145.0 g - C₁₂-C₁₅-Alkohobenzoat, available under the name "Finsolv TN" Fa. Witco 37.0 g - magnesium stearate 10.0 g - Propylene glycol 37.0 g - Magnesium heptahydrate 7.0 g - Water 641.0 g - Perfume, corrigents, additives, stabilizers in sufficient quantity upon need

The emulsion is prepared in the same manner as described below Example 18 described.

example 22

Water-in-oil emulsion (sunscreen milk) 2- (1'-cyano-2 '- (4 "-methylphenyl) vinyl) benzimidazole according to the invention | 33.0 g 4'-methoxycinnamic acid 2'-ethylhexyl ester, available under the name "Parsol MCX" from Givaudan 15.0 g - 3- (4'-methylbenzylidene) camphor, available under the name "Eusolex 6300" from Merck 3.0 g Esters of unsaturated fatty acids with glycerol and sorbitan, available under the name "Arlacel 481" from ICI 60.0 g - Microwax the name "Lunacera 11" Fa. Fuller 10.0 g - Caprylic / Caprinsäuretriglycerid, available as "Miglyol neutral oil" Fa. Dynamit-Nobel 20.0 g Myristyl alcohol, polyoxypropylated with 3 moles of propylene oxide, available under the name "Witconol APM" from Witco 119.0 g - C₁₂-C₁₅-alcohol benzoate, available under the name "Finsolv TN" Fa. Witco 30.0 g - magnesium stearate 10.0 g - Propylene glycol 37.0 g - Magnesium sulfate heptahydrate 7.0 g - Water 656.0 g - Perfume, corrigents, additives, stabilizers in sufficient quantity upon need

The emulsion is prepared in the same manner as described below Example 18 described.

example 23

Firm sunbathe (lip protection) First, a stick base is prepared from the following ingredients in the usual manner: - Beeswax, bleached | 125,0 g - carnauba wax 75.0 g - lanolin 50.0 g - isopropyl myristate 80.0 g - mineral oil 30.0 g - castor oil 638.5 g - Correctives, additives and stabilizers 1.5 g

800 g of this pin base are heated until a forms liquid phase, in each case 10 g of the compound of Example 9 and 3- (4'-methylbenzylidene) camphor, as well as perfume, flavor and Dyes dissolved therein as needed, with castor oil to 1000 g filled and cooled to room temperature.

example 24

Cationic emulsion for rinsing the hair Compound of example 1 | 2.0 g Dimethyldistearylammonium chloride, available under the name "Arosorf TA 100" from Rewo 50.0 g - Vaseline 50.0 g - isopropyl palmitate 20.0 g - Cetyl alcohol 10.0 g - Water 864.0 g - glycerin 4.0 g - perfume, corrigents, additives and stabilizers upon need

With the specified ingredients in the usual way a Hair conditioner made.

For the preparation of cosmetic products is a water-soluble UV filter in the aqueous phase and an oil-soluble UV filter in the fat phase solved. In the above examples, the dissolved oil-soluble UV filter according to the invention in the fat phase.

Claims (17)

1. Cosmetic agents which comprise at least one compound of general formula I, in the
R₁ is hydrogen, C _1-6 -alkyl, halogen, nitro, hydroxy, R _X O-,
Alkylcarbonyloxy having 1 to 20 carbon atoms in the alkyl moiety, R _X -oxycarbonyl, -COOR₃ or SO₃R₃ in which R₃ is in each case hydrogen, sodium, potassium or N (R₄) ₄ and R₄ is hydrogen, C _1-6 -alkyl or C _{2- 4} -Hydroxyalkyl, and R₁ is further CONR₅R₆ or SO₂NR₅R₆, where R₅ and R₆ may be the same or different and represent hydrogen or C _1-12 -alkyl or else both together for - (CH₂) ₄-, - (CH₂) ₅- or -CH₂CH₂OCH₂CH₂- stand,
R₂ is hydrogen or C _1-6 -alkyl,
Ar is an optionally mono-, di- or trisubstituted phenyl radical of the formula A, an optionally substituted naphthyl radical of the formula B, an optionally substituted pyridinyl radical of the formula C. an optionally substituted furanyl radical of the formula D, an optionally substituted thienyl radical of the formula E means, in which
R₇ has the meanings given for R₁, where radicals R₇ and R₁ can be identical or different,
R₈ is hydrogen, C _1-6 -alkyl, halogen, R _{X is} O-, hydroxy or alkylcarbonyloxy having 1 to 20 carbon atoms in the alkyl part,
R₉ is hydrogen, halogen or C _1-6 -alkyl or R₇ and R₈ may together form a 3,4-methylenedioxy group when R₉ is hydrogen,
R₁₀ is hydrogen, C _1-6 -alkyl, halogen, hydroxy, R _X O- or alkylcarbonyloxy having 1 to 20 carbon atoms in the alkyl moiety,
R₁₁ is hydrogen or C _1-6 alkyl and
R _{X is} C _1-12 alkyl, C _3-12 cycloalkyl which may be optionally substituted with one, two or three C _1-6 alkyl groups, C _5-12 bicycloalkyl optionally substituted with one, two or three C _1-6 alkyl groups may be substituted, or the said unsaturated groups having one or two double bonds corresponding to these optionally substituted saturated C _1-12 alkyl, cycloalkyl and bicycloalkyl groups,
and their tautomers and cis-trans isomers. 2. Cosmetic composition according to claim 1, characterized in that it contains as compound of the formula I at least one of the compounds selected from the following group:
benzimidazole 2- (1'-cyano-2'-phenylvinyl)
2- (1'-cyano-2 '- (4''- methylphenyl) vinyl) benzimidazole
2- (1'-cyano-2 '- (4''- isopropylphenyl) vinyl) benzimidazole
2- (1'-cyano-2 '- (4''- tert-butylphenyl) vinyl) benzimidazole
2- (2'-cyano-2 '- (benzimidazol-2''- yl) vinyl) benzenesulfonic acid
Sodium 2- (2'-cyano-2 '- (benzimidazol-2''- yl) vinyl) benzenesulfonate
Potassium 2- (2'-cyano-2 '- (benzimidazol-2''- yl) vinyl) benzenesulfonate
4- (2'-cyano-2 '- (benzimidazol-2''- yl) vinyl) benzenesulfonic acid
Sodium 4- (2'-cyano-2 '- (benzimidazol-2''- yl) vinyl) benzenesulfonate
Potassium-4- (2'-cyano-2 '- (benzimidazol-2''- yl) vinyl) benzenesulfonate
2- (1'-cyano-2 '- (2''- furanyl) vinyl) benzimidazole. 3. Cosmetic composition according to claim 1, characterized that it is 0.01 wt .-% to 30 wt .-% of at least one compound of Formula I, based on the total weight of the agent contains. 4. Cosmetic composition according to claim 1 for use on the Skin, characterized in that it is in the form of a solution or aqueous-alcoholic or alcoholic gel, as a pencil or as Aerosol is present. 5. Cosmetic composition according to claim 1, characterized that it additionally contains, as auxiliaries, preservatives, Bactericides, perfumes, antifoaming agents, Dyes, pigments that have a coloring effect, Thickeners, surfactants, emulsifiers, softening agents, moisturizers, moisturizers, Fats, oils, waxes, alcohols, polyols, polymers, Foam stabilizers, electrolytes, organic solvents or Contains silicone derivatives. 6. Cosmetic composition according to claim 1 in the form of a Sunscreen agent, characterized in that it additionally at least one UVB filter and / or at least one other UVA filter and / or at least one inorganic pigment contains. 7. Cosmetic composition according to claim 6, characterized that the UVB filter is selected from the group consisting of 3-benzylidene camphor derivatives, 4-aminobenzoic acid derivatives, Esters of cinnamic acid, esters of salicylic acid, derivatives of Benzophenone, esters of benzalmalonic acid, 2,4,6-trianilino- (p- carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine, salts of 2-phenylbenzimidazole-5-sulfonic acid, sulfonic acid derivatives of Benzophenones and sulfonic acid derivatives of the 3-benzylidene camphor.   8. Cosmetic composition according to claim 6, characterized that the UVA filter is a derivative of dibenzoylmethane, 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione or 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione. 9. Cosmetic composition according to claim 6, characterized that it contains pigments based on titanium dioxide. 10. Cosmetic composition according to claim 1, for application to the Hair, characterized in that it is in the form of a Shampoo, a lotion, a gel or a Emulsion for rinsing, a hairdressing or treatment lotion or a suitable gel, a lotion or a gel for blow-drying or to insert the hair, as a hair coat, as Perming agent, as a decolorization or staining agent is present. 11. Cosmetic composition according to claim 10, characterized that it also contains at least one cosmetic excipient, selected from surfactants, thickeners, Polymers, preservatives, foam stabilizers, Electrolytes, organic solvents, silicone derivatives, oils, Waxes, dyes and pigments containing. 12. Cosmetic composition according to claim 1 in the form of a colored or colorless cosmetic agent which is resistant to light is stabilized, characterized in that it is a Representing hair treatment or a make-up product. 13. Method of protecting the skin and hair from UV rays, characterized by applying a sufficient amount of cosmetic agent containing at least one compound of Formula I according to claim 1, to the skin or the hair. 14. A compound of the formula I selected from the group
2- (1'-cyano-2 '- (4''- isopropylphenyl) vinyl) benzimidazole
2- (1'-cyano-2 '- (4''- tert-butylphenyl) vinyl) benzimidazole
2- (2'-cyano-2 '- (benzimidazol-2''- yl) vinyl) benzenesulfonic acid
Sodium 2- (2'-cyano-2 '- (benzimidazol-2''- yl) vinyl) benzenesulfonate
Potassium 2- (2'-cyano-2 '- (benzimidazol-2''- yl) vinyl) benzenesulfonate
4- (2'-cyano-2 '- (benzimidazol-2''- yl) vinyl) benzenesulfonic acid
Sodium 4- (2'-cyano-2 '- (benzimidazol-2''- yl) vinyl) benzenesulfonate
Potassium-4- (2'-cyano-2 '- (benzimidazol-2''- yl) vinyl) benzenesulfonate. 15. A process for preparing the compounds of the formula I according to claim 1, characterized in that reacting 2-cyanomethylbenzimidazoles of the formula II with aldehydes of the formula III according to the following reaction scheme: wherein R₁, R₂ and Ar have the abovementioned meaning. 16. Compounds of formula II selected from the group 2-cyanomethylbenzimidazole-5-carboxylic acid
2-cyanomethyl-5-methoxycarbonylbenzimidazole
2-cyanomethyl-5- (2'-ethylhexyloxy) carbonylbenzimidazol
2-cyanomethyl-5-cyclohexyloxybenzimidazol
2-Cyanomethylbenzimidazol-5-sulfonic acid. 17. Use of the compounds of the formula I according to claim 1 as UV absorbers.