Indanylidene compounds, a process for their preparation and their use as UV absorbers

Abstract

Compounds of the formula I according to claim 1 are excellently suitable as UV absorbers for use in cosmetic products, in particular sunscreen compositions, daytime care products and hair care products. They are furthermore suitable for protection of products.

Description

The invention relates to new indanylidene compounds, a process for their preparation and their use as UV absorbers, for example in cosmetic compositions, in particular in sunscreen compositions, daytime care products and hair care products, and also for improving the stability of industrial products, such as paints, varnishes, plastics, textiles, packaging materials and rubbers, to light.

Depending on their wavelength, UV rays are called UV-A rays (320-400 nm, UV-A-I: 340-400 nm, UV-A-II: 320-340 nm) or UV-B rays (280-320 ni). Quite generally, the damaging effect of UV rays on the human skin increases as the wavelength decreases and the duration of exposure increases.

UV rays can thus cause skin damage, it being possible for the UV-B radiation to cause sunburn (erythema) up to extremely severe skin burns. Very frequent and unprotected irradiation of the skin with sunlight also leads to a loss in elasticity of the skin and to increased formation of wrinkles, and overall to premature ageing of the skin. In extreme cases, pathological skin changes up to skin cancer may occur.

UV-A radiation has the effect of rapid, weak direct pigmentation of the skin. UV-A rays penetrate into the lower layers of the skin and can accelerate the ageing process of the skin there. The shorter wavelength UV-A-II radiation assists the development of sunburn. UV-A radiation can furthermore trigger phototoxic or photoallergic skin reactions. Confirmed relationships between UV-A exposure and an increased risk of skin cancer exist.

Depending on the position of their absorption maxima, UV absorbers for cosmetic and pharmacological preparations are classified into UV-A and UV-B absorbers; if both UV-A and UV-B are absorbed by one UV absorber, a UV-A/B broadband absorber is referred to in this case.

The most diverse compounds have already been proposed as UV absorbers, such as octyltriazone (DE-A 3 206 398), 2-hydroxy-4-methoxybenzophenone (U.S. Pat. No. 3,751,563) and 4-tert-butyl-4'-methoxy-dibenzoylmethane (DE-A 2 945 925). These compounds either do not have the desired broad UV-A and UV-B absorption, or have only a low absorption in this range or are not sufficiently photostable.

The invention is therefore based on the object of providing improved UV-A and UV-B broadband absorbers.

The invention relates to the use of compounds of the formula ##STR1## wherein R' to R.sup.4, R.sup.3', R.sup.3", R.sup.4' and R.sup.4" independently of one another denote hydrogen, C.sub.1 -C.sub.8 -alkyl or C.sub.5 -C.sub.10 -cycloalkyl, with the proviso that two substituents on adjacent C atoms together can also denote an optionally substituted C.sub.1 -C.sub.4 -alkylene group, in particular C.sub.3 -C.sub.4 -alkylene, wherein a methylene group can be replaced by --O--, --S-- or --NH--, and furthermore

independently of one another denote C.sub.1 -C.sub.4 -alkoxy, hydroxyl, carboxyl, carbalkoxy or carbamoyl, R.sup.5 to R.sup.8 independently of one another have the meaning of R.sup.1, R.sup.2 or sulpho or aminosulphonyl, X and Y independently of one another denote CN, CO.sub.2 R.sup.9, CO.sub.2 NR.sup.9 R.sup.10 or COR.sup.9, wherein R.sup.9 and R.sup.10 independently of one another represent hydrogen, C.sub.1 to C.sub.8 -alkyl or C.sub.5 -C.sub.10 -cycloalkyl, and furthermore one of the radicals X or Y can additionally denote a C.sub.1 -C.sub.8 -alkyl radical, a C.sub.5 -C.sub.10 -aryl radical, in particular phenyl, or a 5- to 6-membered heteroaryl radical which contains 1 or 2 heteroatoms from the series consisting of N, O and S, or X and Y, together with the .beta. atom to which they are bonded, denote a 5- to 7-membered ring which contains up to 3 heteroatoms, in particular oxygen and/or nitrogen, it being possible for the ring atoms to be substituted, in particular by exocyclically double-bonded oxygen (keto group), preferably in the adjacent position to the .beta. atom, and n and m independently of one another denote zero or 1, as UV absorbers, preferably in sunscreen compositions.

Compounds of the formula ##STR2## wherein R.sub.1, R.sub.2 and R.sub.3 in each case independently of one another can be identical or different and denote a hydrogen atom, halogen atom, hydroxyl group, nitro group, cyano group or monovalent, optionally substituted organic radical and

R.sub.4 denotes a hydrogen atom, halogen atom, nitro group, cyano group or monovalent, optionally substituted organic radical and R.sub.5 can be identical or different and denotes a halogen atom, hydroxyl group, nitro group, cyano group or monovalent, optionally substituted organic radical, are known from EP-A 670 298.

The invention therefore also relates to compounds of the formula (I) with the exception of the compounds mentioned in EP-A 670 298.

The invention preferably relates to compounds of the formula (1) wherein

X and Y are not an unsubstituted or substituted phenyl ring if m=n=zero.

The properties of the compounds I can be varied within wide limits by suitable choice of the substituents. This particularly applies both to the position of the absorption maximum (thus, for example, in the case where R.sup.6 =alkoxy, the maximum lies in the UV-A range, and if R.sup.5 -R.sup.8 =H and n, m=0 and R.sup.1 -R.sup.4 =H, the maximum lies in the UV-B range, and in the case where R.sup.7 =alkyl, the UV-A and the UV-B range are even covered) and to the water- and oil-solubility (sulphonic acid groups in the aromatic ring promote water-solubility, and in the absence of sulphonic acid groups the compounds I are chiefly oil-soluble).

Preferred compounds are those in which X denotes cyano and Y denotes carbo-C.sub.1 -C.sub.4 -alkoxy. Compounds which are furthermore preferred are those in which R.sup.6 denotes alkyl or, in particular, alkoxy; they have a high extinction. The preferred compounds I correspond to the formulae ##STR3##

The compounds according to the invention are particularly suitable for use in sunscreen compositions, preferably in cosmetic and pharmaceutical preparations, but also as anti-ageing agents for industrial products. They are distinguished by an excellent stability to light.

The compounds (I) can be prepared by (Knoevenagel) condensation of compounds of the formula ##STR4## wherein R.sup.1 to R.sup.8 have the abovementioned meanings, with compounds of the formula ##STR5## with the abovementioned meanings for X and Y (cf. Organikum, VEB Deutscher Verlag, Berlin 1986, page 459) and are to be obtained with good to very good yields.

The indanones used for this can be prepared by F.C. reaction of (substituted) acrylic acid esters with (substituted) aromatics or, in the case of hydroxy substituents (R.sup.5 -R.sup.8), by Fies rearrangement of corresponding phenol esters.

The UV absorbers of the formula (I) according to the invention have a fortunate combination of desirable properties, in particular

high UV protection at only low use concentrations, excellent stability to light, excellent heat stability, good solubility in solvents for cosmetics and excellent solubility of the crystalline, oil-soluble UV absorbers in liquid, oil-soluble absorbers such as ethyl, isoamyl and isooctyl p-methoxycinnamate, ethylhexyl salicylate, homomenthyl salicylate, menthyl anthranilate, ethylhexyl p-aminobenzoate and ethyl and ethylhexyl 3,3-diphenyl-2-cyanoacrylate, or combinations of liquid, oil-soluble UV absorbers, compatibility with cosmetic bases, pH stability, problem-free processability in cosmetic formulations and stability under use conditions, compatibility with packaging materials, no discoloration of textiles, or stains can be washed out without problems, colourlessness and odour neutrality, waterproof UV protection.

The compounds according to the invention can be used in cosmetic or pharmaceutical formulations as UV broadband absorbers which prevent passage of UV rays through the film of formulation applied. This is in general the case if the cosmetic or pharmaceutical formulations comprise 0.5 to 15, preferably 1 to 10, in particular 2 to 7% by weight (based on the total weight of the formulation) of the compounds according to the invention.

The formulations comprising the compounds according to the invention can be used for protecting the skin and hair--especially hair already predamaged by permanent waving, colouring and bleaching--against UV irradiation. These cosmetic and pharmaceutical formulations used to protect the skin from UV radiation can be present in the use forms usually used, i.e. as an oil-in-water or water-in-oil emulsion, as a milk or as a lotion or cream, aqueous or aqueous-alcoholic gel or lotion, aerosol, hydrodispersion gel (emulsifier-free) or any other customary cosmetic or pharmaceutical formulation. For protection of the hair against UV rays, formulations as a shampoo, rinse, treatment course, gel, lotion, spray or cream are preferably used.

The cosmetic and pharmaceutical formulations can comprise the constituents usually used in these compositions, such as, for example, emulsifiers, surface-active compounds, lanolin, vaseline, water, triglycerides of fatty acids, polyethylene glycols, fatty alcohols, ethoxylated fatty alcohols, fatty acid esters (for example isopropyl palmitate, isooctyl stearate, diisopropyl adipate and the like), naturally occurring or synthetic oils or waxes, pigments (for example titanium dioxide, zinc oxide, pearlescent pigments, coloured pigments), thickeners (for example hydroxyethylcellulose, bentonite and the like), preservatives, moisturizing agents, vitamins, silicone oils, glycerol, ethyl alcohol and perfume oils.

The compounds according to the invention can be employed in the corresponding formulations individually or as a mixture; they can also be employed in combination with UV absorbers of other classes of substance. Examples of such compounds include

p-aminobenzoic acid ethyl p-aminobenzoate, ethoxylated (25 mol) 2-ethylhexyl p-dimethylaminobenzoate ethyl p-aminobenzoate, N-propoxylated (2 mol) glycerol p-aminobenzoate homomenthyl salicylate 2-ethylhexyl salicylate triethanolamine salicylate 4-isopropylbenzyl salicylate menthyl anthranilate ethyl diisopropylcinnamate 2-ethylhexyl p-methoxycinnamate methyl diisopropylcinnamate isoamyl p-methoxycinnamate p-methoxycinnamic acid diethanolamine salt isopropyl p-methoxycinnamate 2-ethylhexyl 2-cyano-3,3-diphenylacrylate ethyl 2-cyano-3,3'-diphenylacrylate 2-phenylbenzimidazolesulphonic acid and salts 3-(4'-trimethylanmmonium)benzylidene-bornan-2-one methylsulphate terephthalylidene-dibornanesulphonic acid and salts 4-t-butyl-4'-methoxy-dibenzoylmethane .beta.-imidazole-4(5)-acrylic acid (urocaninic acid) 2-hydroxy-4-methoxybenzophenone 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid dihydroxy-4-methoxybenzophenone 2,4-dihydroxybenzophenone tetrahydroxybenzophenone 2,2'-dihydroxy-4,4'-dimethoxybenzophenone 2-hydroxy-4-n-octoxybenzophenone 2-hydroxy-4-methoxy-4'-methylbenzophenone 3-(4'-sulpho)benzylidene-bornan-2-one and salts 3-(4'-methylbenzylidene)-d,l-camphor 3-benzylidene-d,l-camphor 4-isopropyldibenzoylmethane 2,4,6-trianilino-(p-carbo-2'-ethylhexyl-1'-oxy)-1,3,5-triazine phenylene-bis-benzimidazyl-tetrasulphonic acid disodium salt N-[(2 and 4)-[2-(oxoborn-3-ylidene)methyl]benzyl]acrylamide polymer.

Particularly suitable UV absorbers are:

2-ethylhexyl p-methoxycinnamate, isoamyl p-methoxycinnamate, 2-phenylbenzimidazolesulphonic acid, 3-(4'-methylbenzylidene)-d,l-camphor, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl salicylate, 4-tert-butyl-4'-methoxydibenzoylmethane and phenylene-bis-benzimidazyl-tetrasulphonic acid disodium salt.

Combination of the compounds I with finely divided pigments, such as, for example, titanium dioxide, zinc oxide and iron oxide, in sunscreen and daytime care products with UV protection is also possible.

The compounds according to the invention are also particulary suitable for photostabilization of UV absorbers of low stability to UV light. Photostabilization of the dibenzoylmethane compounds, which are very unstable to light, is particularly successful.

A light-stable UV filter combination for protecting human skin against UV rays in the range of 280-380 nm in cosmetic products is achieved by employing 1 to 5% by weight of, for example, 4-tert-butyl-4'-methoxydibenzoylmethane and at least 1% by weight of the compound according to formula 1, preferably in a ratio of 2-4 parts of the compound according to formula I to 1 part of tert-butylmethoxydibenzoylmethane. The molar ratio should be 1 or higher.

Another light-stable UV filter combination is achieved by employing 1-10% by weight of ethylhexyl or isoamyl p-methoxycinnamate with at least 1% by weight of the compound of the formula 1, preferably in a ratio of 1:1. The molar ratio should be 0.8 or higher.

Combinations of p-methoxycinnamic acid esters and dibenzoylmethane derivatives and compounds of the formula I can be formulated in a light-stable form by employing, for example, 1-5% by weight of 4-tert-butyl-4'-methoxydibenzoylmethane, 1-10% by weight of ethylhexyl or isoamyl p-methoxycinnamate and at least 2% by weight of the compounds of the formula I, preferably in a ratio of 1 part of dibenzoylmethane derivative, 2 parts of p-methoxycinnamic acid ester and 2 parts of the compound of the formula I.

A further, very photostable UV absorber, such as, for example, methylbenzylidene-camphor, 2-ethylhexyl 2-cyano-3,3'-diphenylacrylate or octyltriazone, is further advantageously to be added to this three-component combination.

The compounds according to the invention can furthermore also be combined with UV absorbers which are employed for protection of industrial products. Examples of such UV absorbers are compounds from the series consisting of benzotriazoles, benzophenones, triazines, cinnamic acid esters and oxalanilides.

EXAMPLES

Example 1 ##STR6## 32 g (0.2 mol) of 5-methoxy-1-indanone, 20 g (0.2 mol) of methyl cyanoacetate, 17 g of proplonic acid and 2 g of ammonium acetate are mixed and the mixture is heated at 120.degree. C. for 5 hours. After cooling to room temperature, the crude product is recrystallized from methanol. Yield: 60% of theory; E.sup.1/1 1268 (.lambda..sub.max 345 nm).

Example 2 ##STR7## 3,3,6-Trimethyl-1-indanone and isoamyl cyanoacetate are reacted analogously to Example 1. Yield: 70% of theory; E.sup.1/1 566 (.lambda..sub.max 332 nm)/E.sup.1/1 551 (.lambda..sub.max 309 nm).

Example 3 ##STR8## 3,3,4,6-Tetramethyl-5-methoxy-1-indanone and methyl cyanoacetate are reacted analogously to Example 1. Yield: 70% of theory; E.sup.1/1 800 (.lambda..sub. 338 nm).

Example 4 ##STR9## 0.1 mol of the compound from Example 1 is heated at 70 to 80.degree. C. in a mixture of 0.2 mol of acetic anhydride and 0.2 mol of concentrated sulphuric acid for 30 minutes. After cooling to room temperature, isopropanol is added to the reaction mixture and the product which has then precipitated out is filtered off with suction and dried. Yield: 70% of theory; E.sup.1/1 800 (.lambda..sub.max 345 nm).

Components used ______________________________________Trade name Chemical name Supplier______________________________________Abil 100 Polydimethylsiloxane 7Antaron V-216 Vinylpyrrolidone/ 18 hexadecene copolymerArlacel 1689 Sorbitan monooleate/ 4 propylglyceryl 3-ricinoleateArlacel 165 Glycerol stearate/polyethylene glycol 4 (MW 100) stearate mixtureArlatone 983 S Polyethylene glycol (MW 5) 4 glyceryl stearateArlatone G hardened with 25 mol of 4 ethylene oxideBaysilone Fluid PK 20 Silicone oil 5Betone Gel MIO Mineral oil, quatemium-18 17 hectorite, propylene carbonateBrij 76 Polyethylene glycol (MW 10) 4 stearyl etherCarbopol 2984 Polyacrylic acid 2Carbopol 954 Polyacrylic acid 2Cetiol HE Polyol-fatty acid ester 3Cetiol OE Dicaprylyl ether 3Cetiol SN Cetyl/stearyl isononanoate 3Copherol F 1250 D-.alpha.-tocopheryl acetate 3Cutina CBS Glycerol stearate, cetyl/stearyl 3 alcohol, cetyl palmitate, coconut glyceridesDehymuls PG PH Polyglycerol poly-12-hydroxystearate 3Diisopropyl adipate Adipic acid diisopropyl ester 3D-Panthenol Panthothenyl alcohol 15EDTA B. liq. Tetrasodiumethylenediamine- 6 tetraacetateEusolex TA Titanium dioxide 13Eutanol G 2-Octyldodecanol 3Eumulgin B2 Cetyl/stearyl alcohol, etherified with 3 20 mol of ethylene oxideFinsolv TN Alkylbenzoate 23Genapol LRO liq. Polyethylene glycol (MW 5) 9 glyceryl stearateGlycerol 1,2,3-Propane triol 3Isopropyl myristate Myristic acid isopropyl ester 3Jojoba oil Jojoba oil 19Lameform TGI Triglycerol diisostearate 3Lamepon S Protein/coconut fatty acid 3 condensate, potassium saltLanette O Cetyl/stearyl alcohol mixture 3Macadamia nut oil Macadamia nut oil 20Myritol 318 Caprylic/capric triglyceride 3Natrosol 250 HHR Hydroxyethylcellulose 11NEO HELIOPAN .RTM. AV Isooctyl p-methoxycinnamate 1NEO HELIOPAN .RTM. BB 2-Hydroxy-4-methoxybenzophenone 1NEO HELIOPAN .RTM. Isoamyl p-methoxycinnamate 1E1000NEO HELIOPAN .RTM. Phenylbenzimidazolesulphonic acid 1HYDRONEO HELIOPAN .RTM. 3-(4-Methylbenzylidene)-d, 1MBC 1-camphorNEO HELIOPAN .RTM. OS 1-Ethylhexyl salicytate 1NEO HELIOPAN .RTM. 303 Isooctyl .alpha.-phenyl-.beta.-cyano-cinnamate 1Olive oil Olive oil 21Parsol 1789 Butylmethoxydibenzoylmethane 12Permulgin 2550 Wax 14Permulgin 3220 Wax 14Permulen TR 1 Polyacrylate 2Phenonip Mixture of p-hydroxybenzoic acid 8 esters and phenoxyethanolPolymer JR 400 Polyquaternium-10 211,2-Propylene glycol 1,2-Propanediol 6Texapon MG 3 Magnesium lauryl sulphate/disodium 3 lauryl sulphosuccinateTocopherol oil Soya oil with D-.alpha.-tocopherol 22Uvinul T 150 Isooctyl triazinyl-p-aminobenzoate 6Veegum Ultra Magnesium aluminium silicate 10ZINC OXIDE Zinc oxide 1NEUTRAL H&RZinc stearate Zinc stearate 16______________________________________ Suppliers ______________________________________1. Haarmann & Reimer GmbH., Holzminden2. B. F. Goodrich Company, Neuss3. Henkel KGaA, Dusseldorf4. ICI Speciality Chemicals, Frankfurt5. Bayer AG, Leverkusen6. BASF, Ludwigshafen7. Godschmidt AG, Essen8. Nipa Lab. Ltd., Pontypridd, Mid Glam., Wales/GB9. Hoechst AG, Frankfurt10. R. T. Vanderbilt Company Inc., Norwalk/USA11. Hercules Inc., Wilmington, Delaware/USA12. Hoffmann-LaRoche, Basle/CH13. E. Merck, Darmstadt14. Koster Keunen Holland BV, Bladl/NL15. Akzo Chemie GmbH, Duren16. Chemische Werke Barlocher, Munich17. Rheox Inc., Hightstown, New Jersey/USA18. ISP Global Technologies Deutschland GmbH, Frechen19. Henry Lamotte, Bremen20. Erhard Wagner GmbH, Bremen21. Nordmann & Rassmann GmbH & Co., Hamburg22. Richter GmbH, Berlin23. Witco Surfactants GmbH, Steinau a.d. Stra.beta.e______________________________________

Example 5

Sunscreen lotion (O/W) ______________________________________CONSTITUENTS %______________________________________A) Arlatone 983 S 1.75 Brij 76 1.25 Lanette O 1.15 Myritol 318 5.00 Eutanol G 6.00 Cetiol SN 6.00 Phenonip 0.20 UV absorber according to formula (I) 3.00B) Distilled water 46.65 1,2-Propylene glycol 2.00 Phenonip 0.30C) Distilled water 25.00 Carbopol 2984 0.30 Sodium hydroxide, 10% strength in water 1.00D) Perfume oil 0.40PREPARATION INSTRUCTIONS:Part A: Melt at about 80.degree. C.Part B: Heat to about 90.degree. C.,add Part B to Part A with stirring.Part C: Disperse the Carbopol in water without lumps,neutralize with sodium hydroxide solutionto give a gel, add to Part A/B at about 60.degree. C.Stir until room temperature is reached.Part D: Perfume the emulsion at about 30.degree. C.,check the pH (6.5 to 7.0).______________________________________

Example 6

Sunscreen lotion (O/W) ______________________________________CONSTITUENTS %______________________________________A) Arlatone 983 S 1.75 Brij 76 1.25 Lanette O 1.15 Myritol 318 15.00 Cetiol SN 15.00 Phenonip 0.20 UV absorber according to formula (I) 5.00B) Distilled water 31.65 1,2-Propylene glycol 2.00 Phenonip 0.30C) Distilled water 25.00 Carbopol 2984 0.30 Sodium hydroxide, 10% strength in water 1.00D) Perfume oil 0.40______________________________________PREPARATION INSTRUCTIONS:Part A: Melt at about 80.degree. C.Part B: Heat to about 90.degree. C.,add Part B to Part A with stirring.Part C: Disperse the Carbopol in water without lumps,neutralize with sodium hydroxide solutionto give a gel, add to Part A/B at about 60.degree. C.Stir until room temperature is reached.Part D: Perfume the emulsion at about 30.degree. C.,check the pH (6.5 to 7.0).______________________________________

Determination of the in-vitro light protection factor in accordance with the method of Diffey and Robson ("A new substrate to measure sunscreen protection factors throughout the ultra violet spectrum", J. Soc. Cosm. Chem. 40 (3), 123-133 (1989)) gave a value of 11.0.

Example 7

Sunscreen milk (W/O) ______________________________________CONSTITUENTS %______________________________________A) Dehymuls PG PH 5.00 Permulgin 3220 0.50 Zinc stearate 0.50 Myritol 318 15.00 Cetiol SN 15.00 UV absorber according to formula (I) 5.00B) Distilled water 52.50 Glycerol 86% 5.00 Magnesium sulphate 7 H.sub.2 O 0.50 Phenonip 0.50C) Perfume oil 0.50PREPARATION INSTRUCTIONS:Part A: Melt carefully at about 90.degree. C.Part B: Heat to about 95.degree. C.,then add Part B to Part A with stirring.Stir until room temperature is reached.Part C: Add Part C at 30.degree. C. and then homogenize______________________________________ Determination of the invitro light protection factor in accordance with the method of Diffey and Robson ("A new substrate to measure sunscreen protection factors throughout the ultra violet spectrum", J. Soc. Cosm. Chem. 40 (3), 123-133 (1989)) gave a value of 11.9.

Example 8

Sunscreen lotion (O/W) ______________________________________CONSTITUENTS %______________________________________A) Ariatone 983 S 1.75 Brij 76 1.25 Lanette O 1.15 Myritol 318 15.00 Cetiol SN 15.00 Finsolv TN 5.00 Phenonip 0.20 UV absorber according to formula (I) 4.00 Parsol 1789 1.50B) Distilled water 26.15 1,2-Propylene glycol 2.00 Phenonip 0.30C) Distilled water 25.00 Carbopol 2984 0.30 Sodium hydroxide, 1.00 10% strength in waterD) Perfume oil 0.40PREPARATION INSTRUCTIONS:Part A: Melt at about 80.degree. C.Part B: Heat to about 90.degree. C.,add Part B to Part A with stirring.Part C: Disperse the Carbopol in water without lumps,neutralize with sodium hydroxide solutionto give a gel, add to Part A/B at about 60.degree. C.Stir until room temperature is reached.Part D: Perfume the emulsion at about 30.degree. C.,check the pH (6.5 to 7.0).______________________________________

Example 9

Sunscreen lotion (O/W) ______________________________________CONSTITUENTS %______________________________________A) Ariatone 983 S 1.75 Brij 76 1.25 Lanette O 1.15 Myritol 318 12.00 Cetiol SN 12.00 UV absorber according to formula (I) 7.00 NEO HELIOPAN .RTM. E 1000 7.00 Phenonip 0.20B) Distilled water 28.65 1,2-Propylene glycol 2.00 Phenonip 0.30C) Distilled water 25.00 Carbopol 2984 0.30 Sodium hydroxide. 10% strength in water 1.00D) Perfume oil 0.40PREPARATION INSTRUCTIONS:Part A: Melt at about 80.degree. C.Part B: Heat to about 90.degree. C.,add Part B to Part A with stirring.Part C: Disperse the Carbopol in water without lumps,neutralize with sodium hydroxide solution togive a gel, add to Part A/B at about 60.degree. C.Stir until room, temperature is reached.Part D: Perfume the emulsion at about 30.degree. C.,check the pH (6.5 to 7.0).______________________________________

Example 10

Sunscreen lotion (O/W) ______________________________________CONSTITUENTS %______________________________________A) Arlacel 165 3.00 Eumulgin B 2 1.00 Lanette 1.00 Myritol 318 4.00 Cetiol OE 2.00 Abil 100 1.00 Bentone Gel MIO 3.00 Cutina CBS 1.00 Phenonip 0.20 NEO HELIOPAN .RTM. OS 3.00 (octyl salicylate) NEO HELIOPAN .RTM. AV 5.00 (octyl methoxycinnamate) NEO HELIOPAN .RTM. E 1000 5.00 (isoamyl p-methoxy-cinnamate) NEO HELIOPAN .RTM. MBC 1.00 (4-methylbenzylidenecamphor) Eusolex TA 3.00 UV absorber according to formula (I) 3.00B) Distilled water 45.60 Glycerol. 86% strength 3.00 Phenonip 0.30 Veegum Ultra 1.00 Natrosol 250 HHR 0.30 NEO HELIOPAN .RTM. HYDRO, 13.30 employed as a 15% strength solution after neutralization with sodium hydroxide (phenylbenzimidazolesulphonic acid), corresponds to active substance: 2.0%C) Perfume oil 0.30PREPARATION INSTRUCTIONS:Part A: Melt at about 80.degree. C.,then disperse the Eusolex TA carefully.Part B: Heat to about 90.degree. C. without the Veegumand Natrosol, then disperse the Veegumand Natrosol, add Part B to Part A withstirring. Stir until room temperature is reached.Part C: Add Part C at 30.degree. C. and then homogenize.Check the pH (7.0-7.5).______________________________________

Example 11

Sunscreen lotion (W/O) ______________________________________CONSTITUENTS %______________________________________A) Arlacel 1689 3.50 Finsolv TN 6.00 NEO HELIOPAN .RTM. E 1000 7.00 (isoamyl p-methoxy-cinnamate) Uvinul T 150 (octyltriazone) 1.00 UV absorber according to formula (I) 3.00 Copherol F 1250 2.00 Permulgin 2550 1.00 Myritol 318 6.00 Cetiol SN 6.00 ZINC OXIDE NEUTRAL H&R (zinc oxide) 7.00B) Distilled water 51.70 Glycerol 86% 5.00 Phenonip 0.50C) Perfume oil 0.30PREPARATION INSTRUCTIONS:Part A: Melt carefully at about 90.degree. C.(without ZINC OXIDE NEUTRAL H&R).Then disperse ZINC OXIDE NEUTRALH&R carefully.Part B: Heat to about 95.degree. C.,then add Part B to Part A with stirring.Stir until room temperature is reached.Part C: Add Part C at 30.degree. C. and then homogenize.______________________________________

Example 12

Sunscreen oil ______________________________________CONSTITUENTS %______________________________________A) NEO HELIOPAN .RTM. E 1000 7.50 (isoamyl p-methoxy-cinnamate NEO HELIOPAN .RTM. OS 5.00 (octyl salicylate) UV absorber according to formula (I) 3.00 Myritol 318 34.70 Diisopropyl adipate 5.00 Olive oil 1.00 Jojoba oil 1.00 Macadamia nut oil 1.00 Tocopherol oil 1.00 Isopropyl myristate 35.00 Antaron V-216 5.00 Phenonip 0.50 Perfume oil 0.30PREPARATION INSTRUCTIONS:Mix all the constituents carefully.______________________________________

Example 13

Sunscreen cream gel ______________________________________CONSTITUENTS %______________________________________A) Distilled water 75.35 Phenonip 0.50 EDTA B liquid 0.10B) NEO HELIOPAN .RTM. AV 7.00 (octyl methoxycinnamate) NEO HELIOPAN .RTM. 303 (octocrylene) 3.00 NEO HELIOPAN .RTM. MBC 1.00 (4-methylbenzylidene-camphor) UV absorber according to formula (I) 3.00 Cetiol SN 5.00 Eutanol G 3.00 Lameform TG I 1.00 Perfume oil 0.30 Permulen TR-l 0.25 Carbopol 954 0.05C) Triethanolamine 0.45PREPARATION INSTRUCTIONS:Part A: Dissolve the contents in water.Part B: Mix all the constituents(without the Permulen and Carbopol).Dissolve the NEO HELIOPAN .RTM. MBCand the UV absorber according toformula (I) with gentle heating.Disperse the Carbopol and Permulen.Then add Part B to Part A and stirintensively for 45 minutes.Part C: Add the triethanolamine to Part A/B,with stirring. Continue to stiruntil the product is homogeneous.Check the pH (about 7.0).______________________________________

Example 14

Hair shampoo ______________________________________CONSTITUENTS %______________________________________A) Genapol LRO liquid 18.00 Texapon MG3 36.00 Lamepon S 6.00 Perfume oil 0.60 Phenonip 0.50 Arlatone G 2.00 UV absorber according to formula (I) 0.50 NEO HELIOPAN .RTM. E 1000 1.00 (isoamyl p-methoxycinnamate)B) Distilled water. 33.00 Polymer JR 400 0.20 D-Panthenol 1.00 Sodium chloride 1.00 Sodium hydroxide 10% strength in water 0.20PREPARATION INSTRUCTIONS:Part A: Dissolve the UV absorber in theNEO HELIOPAN .RTM. E 1000 andPhenonip with gentle heating,then add the Arlatone G andperfume oil and mix thoroughly.Weigh in the remaining constituents.Part B: Dissolve the polymer in the water,with stirring, add the remainingconstituents and dissolve.Add Part B to Part A and stir(check the pH, about 5.5).______________________________________

Claims

1. Compounds of the formula ##STR10## wherein R.sup.1 to R.sup.4, R.sup.3', R.sup.3", R.sup.4' and R.sup.4" independently of one another denote hydrogen, C.sub.1 -C.sub.8 -alkyl or C.sub.5 -C.sub.10 -cycloalkyl, with the proviso that two substituents on adjacent C atoms together can also denote an optionally substituted C.sub.1 -C.sub.4 -alkylene group, in which a methylene group may be replaced by --O--, --S-- or --NH--, and furthermore independently of one another denote C.sub.1 -C.sub.4 -alkoxy, hydroxyl, carboxyl, carbalkoxy or carbamoyl,

R.sup.5 to R.sup.8 independently of one another have the meaning of R.sup.1, R.sup.2 or sulpho or aminosulphonyl,

X and Y independently of one another denote CN, CO.sub.2 R.sup.9, CO.sub.2 NR.sup.9 R.sup.10 or COR.sup.9, wherein R.sup.9 and R.sup.10 independently of one another represent hydrogen, C.sub.1 to C.sub.8 -alkyl or C.sub.5 -C.sub.10 -cycloalkyl, and furthermore one of the radicals

X or Y can additionally denote a C.sub.1 -C.sub.8 -alkyl radical, a C.sub.5 -C.sub.10 -aryl radical, or a 5- to 6-membered heteroaryl radical which contains 1 or 2 heteroatoms selected from the group consisting of N, O and S, or

X and Y, together with the .beta. atom to which they are bonded, denote a 5- to 7-membered ring which contains up to 3 heteroatoms selected from the group consisting of oxygen and nitrogen, substituted by exocyclically double-bonded oxygen (keto group) and

n and m independently of one another denote zero or 1, with the exception of compounds of the formula ##STR11## wherein R.sub.1, R.sub.2 and R.sub.3 in each case independently of one another can be identical or different and denote a hydrogen atom, halogen atom, hydroxyl group, nitro group, cyano group or monovalent, optionally substituted organic radical and

R.sub.4 denotes hydrogen, a halogen atom, nitro group, cyano group or monovalent, optionally substituted organic radical and

R.sub.5 can be identical or different and denotes a halogen atom, hydroxyl group, nitro group, cyano group or monovalent, optionally substituted organic radical and with the exception of ##STR12##

2. Process for the preparation of the compounds according to claim 1, which comprises condensing compounds of the formula with compounds of the formula ##STR13##