MXPA99003313A - Diresorcinil-alcoxi-y-ariloxi-s-triazi - Google Patents

Abstract

The present invention relates to: diresorcinyl-alkoxy-and-aryloxy-s-triazines of the formula (See Formula) in which R1 is C2-C30 alkyl, C2-C30 alkenyl, C5-C12 cycloalkyl-unsubstituted or C5- C12 C 1 -C 5 alkyl-mono- or poly-substituted cycloalkyl, C 1 -C 5 alkoxy-C 1 -C 12 alkyl, C 1 -C 12 amino C 1 -C 5 alkyl monoalkylamino-C 1 -C 12 alkyl C 1 -C 5 -dialkylamino-C 1 -C 12 -alkyl a radical of the formula (See Formula) R2, R3 and R4, independent of each other, are hydrogen, hydroxyl, C1-C30 alkyl, C1-C30 alkenyl, R8 is hydrogen, or C1-C5 alkyl, m1 is 0-1 and n1 is 1 to 5. The novel compounds are usable as cosmetical ultraviolet "A" absorption agents

Description

NB 2- 21 A Diresorcinyl-alkoxy- and -aryloxy-s-triazines The present invention relates to novel diresorcinyl-alkoxy- and -aryloxy-s-triazines, to a process for the preparation of said compounds and to their use in cosmetic compositions. . The novel diresorcinyl-alkoxy- and -aryloxy-s-triazines are composed according to the formula wherein Ri is C2-C3o alkyl; C2-C30 alkenyl; C5-C12 cycloalkyl-unsubstituted or C5-C12 cycloalkyl-C1-C5 alkyl mono or poly substituted, C? -C5alkoxy-C? -C? 2 alkyl; amino-C? -C? 2 alkyl; C1-C5 monoalkylamino-C? -C? 2 alkyl; C1-C5-dialkylamino-C1-C12-alkyl; a radical of the formula R2, R3 and R, independent of each other, are hydrogen, hydroxyl, C1-C30 alkyl, C1-C30 alkenyl, Rs is hydrogen; or C1-C5 alkyl; mi is 0 or 1; and is not 1 to 5. Alkyl means a branched or unbranched hydrocarbon radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, t-butyl, 2-ethylbutyl, n-pentyl, isopentyl, -methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1, 1,3, 3-tetramethylbutyl, 1-methylheptyl, 3-methohyl, n-octyl, isooctyl, 2-ethylhexyl , 1,1,3-trimethylhexyl, 1, 1,3,3-tetramethylpentyl, nonyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl. Alkoxy radicals are straight or branched chains, for example methoxy, ethoxy, propoxy, butoxy or pentyloxy. C5-C12 cycloalkyl means, for example, cyclopentyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl and particularly cyclohexyl. in which, alkenyl includes inter alia allyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecyl, n-dodec-2-enyl, n-octadec-4-enyl, or 3, 7, 11, 11-tetramethyl-2,6,6-undecatrienyl. Preference is given to the compounds of the formula (1) in which R5 is hydrogen. Preference is also given to the compounds of the formula (1) in which Ri is C2-C30 alkyl, particularly C-C3o alkyl, and very particularly C6-C30 alkyl. Of these compounds, particular preference is given to compounds in which Ri is a 2-decihexadecyl radical. Other interesting compounds of formula (1) are those in which Ri are C-C3o alkyl radicals. Of these compounds, particular preference is given to those in which Ri is an isooctadecyl radical, an n-octadecyl or a 2-hexadecyl. Particularly interesting compounds of the formula (1) are those in which i is a 3- to 2-chain, and a couple of a -ethylhexyl radical. Other illustrative representatives of the novel diresorcinyl-alkoxy- and -aryloxy-s-triazines are given in the tables below: The novel resorc n -a cox- and -ar ox -str az nas are prepared, for example, by reaction of cyanuric chloride with the alcohol Ri-OH to give the respective aryloxy- or alkaloxy-dichloro-s-triazines of the formula (2). The novel compounds of the formula (1) are obtained in a second reaction step of a Friedel-Crafts reaction. The reaction can be represented diagrammatically as follows: (twenty-one) The first step of the reaction is generally carried out in the presence of a solvent, for example acetone, methyl ethyl ketone, dimethylacetamide, toluene or xylene. Here the temperatures are between 0 and 130 ° C, particularly from 20 to 70 ° C; the reaction times are from 1 to 48 hours, preferably from 2 to 10 hours. The solvent normally employed in the second reaction step is toluene, nitrotoluene, nitrobenzene, anisole, xylene, benzene, sulfolane, chlorobenzene, dichlorobenzene, hydrocarbons (for example isooctane), chlorinated hydrocarbons, nitroalkanes, carbon disulfide, sulfur dioxide and mixtures of the solvents mentioned.

Here the temperatures range from -10 to 200 ° C, in particular from 0 to 100 ° C. Reaction times range from 1 to 100 hours, preferably from 2 to 50 hours. The second reaction step is generally carried out in the presence of a catalyst. Examples of such catalysts are: aluminum chloride, aluminum bromide, tin chloride, titanium tetrachloride, boron trifluoride and other Lewis acids. Here the catalyst is used in an amount of 0.1 to 3 mol per mole of reactive chlorine. Frequently a dealkylation of the alkoxy radical is observed in the Friedel-Crafts reactions with dichloroalkoxy-s-triazines. Under the conditions according to the invention, i.e. control of the temperature, amount of catalyst and measured addition of the catalyst, the reaction generally proceeds particularly smoothly and without appreciable dealkylation. Another synthetic method for the novel diresorcinyl-alkoxy-and-aryloxy-s-triazines involves the reaction of cyanuric chloride with resorcinol to obtain the 2-chloro-4,6-resorcinyl triazine (compound of the formula (20)) in the first reaction step and reacting it with Ri-OH to obtain the compound of the formula (1) in a second reaction step, according to the following equation: (20) d) The p-hydroxyl groups of the resorcinyl radicals of the novel diresorcinyl-alkoxy-and-aryloxy-s-triazines with the formula (1) can be further alkylated using alkylating agents X-R5 (X = C1, Br, I, F ) to give the alkoxy derivatives corresponding to the formula where R and R are defined as for formula (1). Other usable alkylating agents are the epoxides, tosylates, dialkyl sulfates and ethyl glycidyl ethers. The compounds of the formula in which R 'i is a C 8 -C 2 radical or branched alkyl; a radical of the formula m 'i is 0 or 1 and n' i is 1 to 5, obtained in the first reaction step are novel compounds. These are also provided by the invention. The novel diresorcinyl-alkoxy-and-aryloxy-s-triazine of the formula (1) have an absorption maximum around the nm, that is, the compounds are ultraviolet-sensitive. The compounds are therefore particularly applicable as ultraviolet radiation filters, that is, to protect organic materials that are sensitive to ultraviolet light, in particular human and animal skin and hair, from the harmful effects of ultraviolet radiation. Therefore, these compounds are applicable as light-protecting agents in cosmetic, pharmaceutical and veterinary medicine preparations. They can be used both in dissolved form and in the micronized state. Therefore, the present invention also relates to compounds of a formula (1) in micronized form, wherein Ri is C? -C alkyl; -C30 alkenyl; C5-C12 cycloalkyl-unsubstituted or C5-C12 cycloalkyl-C1-C5 alkyl mono- or poly-substituted, C-C5alkoxy-C? -C? 2 alkyl; amino-C? -C? 2 alkyl; C1-C5 monoalkylamino-C? -C? 2 alkyl; C1-C5-dialkylamino-C1-C12-alkyl; a radical of the formula (1a) - (CH2) - (O) - / \; 0b) m.

R2. R3 and independent of each other, are hydrogen, hydroxyl, C1-C30 alkyl, C1-C30 alkenyl, R5 is hydrogen; or C1-C5 alkyl; nor is it 1 to 5. If the novel ultraviolet absorbers are in micronized form they usually have a particle size from 0.02 to 2 μm, preferably between 0.05 and 1.5 μm, very particularly between 0.1 and 1.0 μm. Micronized methods are described, for example, in GB-A-2303549. The grinding apparatus that can be used to prepare the novel micronized organic ultraviolet absorbers is, for example, a jet, ball or hammer mill, preferably a stirred mill. The milling is preferably carried out using a grinding aid, for example an alkylated vinyl pyrrolidone polymer, a copolymer of vinyl acetate-vinyl pyrrolidone, an acylglutamate or, in particular, a phospholipid. Due to their lipophilic nature the compounds (1) can be easily incorporated into cosmetic formulations containing oils or fats, particularly when Ri is a branched alkyl radical of more than 8 carbon atoms. The invention also provides a cosmetic preparation comprising at least one compound of the formula (1) and cosmetically compatible carrier and auxiliary agents. The novel light protection agents have, for cosmetic use, an average particle size in the range between 0.02 and 2 μm, preferably between 0.05 and 1.5 μm, very particularly between 0.1 and 1.5 μm. As mentioned above, the novel ultraviolet radiation absorption agents can be brought to the desired particle size by means of the usual grinding methods. The grinding is preferably carried out in the presence of grinding aids of 0.1 to 30% by weight, preferably 0.5 to 15% by weight, based on the weight of the ultraviolet absorption agent. The cosmetic preparation, in addition to the ultraviolet absorption agent, may also contain one or more protective substances with a carrier of the following classes of substances: 1. Derivatives of p-aminobenzoic acid, for example 2- ethylhexyl-4- dimethylaminobenzoate; 2. Derivatives of acetylsalicylic acid, for example 2-ethylhexyl salicylate. 3. Derivatives of the benzophenone, for example 2-hydroxy-4-ethoxybenzophenone and its 5-sulfonic acid derivative; 4. Derivatives of dibenzoylmethane, for example l- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione; 5. Diphenyl acrylates, for example 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate and 3- (benofuranyl) -2-cyanoacrylate; 6. 3-imidazol-4-yl-acrylic acid and 3-imidazol-4-yl acrylates; 7. Derivatives of benzofuran, particularly 2- (p-aminophenyl) -enofofuran derivatives, described in EP-A-582,189, US-A-5,338,539, US-A-5, 518, 713 and EP-A-613, 893; 8. Polymeric ultraviolet absorption agents, for example the benzylidine malonate derivatives described in EP-A-709, 080; 9. Derivatives of cinnamic acid, for example 2-ethylhexyl or isoamyl 4-methoxycinnamate or cinnamic acid derivatives published in US-A-5, 601, 811 and WO 97/00851; 10. Derivatives of camphor, for example the polymer of 3- (4 '-methyl) benzylidenebornane-2-one, 3-benzylideneboronone, N- and - -ox orn- - en-me ac acrylamide, 3- (4 'trimethyl ammonium) -benzylidenebornan-2-one, 3, 3' - (1,4-phenylenedimethine) bis (7,7-dimethyl-2-oxo-bicyclo [2.2.1] heptane) methyl sulfate -1- methanesulfonic acid and its salts, 3- (4'-sulfo) enzilidenebornan-2-one and its salts 11. Derivatives of trianilino-s-triazine, for example 2,4, 6-trianilin- (p-carbo ~ 2 'ethyl-1' oxy) 1,3,5-triazine and the ultraviolet absorption agents published in US-A-5,332,568, EP-A-517, 104, EP-A-507, 691, WO 93 / 17002 and EP-A-570, 838. 12. Derivatives of 2-hydroxyphenyl benzotriazole, 13. 2-phenylbenzimidazole-5-sulfonic acid and salts thereof, 14. Menthyl o-aminobenzoate, 15. Ti02 (with various coatings). , ZnO and mica It is also possible to use the ultraviolet absorption agents described in "Sunscreen", Eds. NJ Lowe, NA Shaath, Sea cel Dekker, Inc, New York and Basel or in "Cosmetics & Toiletries "(107), 50ff (1992) in the novel formulation as additional ultraviolet protection substances Moreover, the novel cosmetic preparation can also be used together with known antioxidants, for example vitamin E, carotenoids or HALS-like compounds (= "Hindered Amine Light Stabilizers") The novel cosmetic preparation comprises between 0.1 to 15% by weight, preferably 0.5 to 10% by weight based on the total weight of the composition, of an absorbing agent of ultraviolet or a mixture of ultraviolet absorbing agents and a cosmetically compatible auxiliary The cosmetic preparation can be prepared by physically mixing the ultraviolet absorbent agents with the auxiliary agent by means of usual methods, for example by simply stirring the individual components together. The novel cosmetic preparation can be formulated as a water-in-oil or oil-based emulsion. e in water, as an oil-in-alcohol lotion, as a vesicular dispersion of an ionic or nonionic amphiphilic lipid, as a gel, as a solid stick or as an aerosol formulation. As a water-in-oil or oil-in-water emulsion, the cosmetically compatible auxiliary preferably comprises from 5 to 50% of an oily phase, from 5 to 20% of an emulsifier and from 30 to 90% of water. The oily phase may comprise any oil applicable for cosmetic formulations, for example one or more carbohydrate oils, a wax, a natural oil, a silicone oil, a fatty acid ester or a fatty alcohol. The above mono- and polyols are eio, sopropane, prop in g, hexylene glycol glycerol and sorbitol. Any conventional emulsifier can be used for the novel cosmetic preparation, for example one or more ethoxylated esters of natural derivatives, for example polyethoxylated esters of hydrogenated castor oil; or a silicone oil emulsifier, for example silicone polyol; an optionally ethoxylated fatty acid soap; an ethoxylated fatty alcohol; an optionally ethoxylated sorbitol ester; or an ethoxylated glyceride. The cosmetic preparation can also contain other components, for example emollients, emulsion stabilizers, skin moisturizers, skin tanning accelerators, thickeners, for example xanthan, humectants, for example glycerol, preservatives, fragrances and dyes. The novel cosmetic preparation is notable for its excellent protection of human skin from the harmful effects of sunlight. The novel diresorcinyl-alkoxy-and-aryloxy-s-triazines are notable for their high thermal stability and are therefore used as stabilizers of organic polymers, in particular in surface coatings, against damage caused by light, oxygen and oxygen. hot. The material stabilized by the use of the novel compounds is notable for its excellent resistance to weathering and to the effects e a uz and for the excellent photostability of the built-in stabilizer. The materials to be stabilized can be, for example, oils, fats, waxes or biocides. Its use in polymeric materials, such as those present in plastics, rubbers, paints, surface coatings, photographic material or adhesives is of particular interest. Therefore the invention also provides a composition containing (A) an organic material sensitive to damage by light, oxygen and / or heat, and (B) a compound of the formula (1) as a stabilizer. The invention also relates to a method of stabilizing organic material from damage by light, oxygen and / or heat, wherein a compound of the formula (1) is added as a stabilizer to such a material, and also to the use of the compound of the formula (1) to stabilize organic material. The amount of stabilizer to be used depends on the organic material to stabilize and the intended use of the stabilized material. In general, the novel composition comprises, for every 100 parts by weight of the component (A), between 0.01 and 15 parts by weight, in particular 0.05 to 10 parts by weight and especially 0.1 to 5 parts by weight of the stabilizing component (B ). it is at least or can not be a mixture of two or more compounds of the formula (1). The novel composition may comprise, in addition to the novel compounds, other stabilizers or other additives, for example antioxidants, other light-protecting agents, metal deactivators, phosphites and phosphonites. The type and quantity of the additional stabilizers is determined by the type of substrate to be stabilized and by its intended use; frequently between 0.1 and 8% by weight is used, based on the polymer to be stabilized. The incorporation into organic polymers, for example in organic synthetics, particularly in thermoplastics, polymers, can take place by the addition of the novel triazine compounds and other optional additives by methods customary in the art. The incorporation can take place expediently before or during forming, for example by mixing powdered components or by adding the stabilizer to the melt or solution of the polymer, or by applying the dissolved or dispersed compound on the polymer, with subsequent evaporation of the solvent if necessary. In the case of elastomers, these can also be stabilized as grids. Another possible way to incorporate the novel mixtures into polymers involves their addition before or during the polymerization of the corresponding monomers or their cross-linked state. Stabilized polymer compositions obtained in this way can be converted into formed articles, for example fibers, films, tapes, shapes, sheets, multiple wool sheets, tubes and other profiles by conventional methods, for example by hot pressing, spinning , extrusion or injection molding. The polymers stabilized in this way are notable for their high resistance to weathering, especially for their high resistance to ultraviolet light. Therefore they retain their mechanical properties and their color and brightness even when used outdoors for long periods of time. In the following examples the percentages are by weight. The amounts used in the case of the diresorcinyl triazines refer to the pure substance. Examples of preparations. Example: Preparation of the compound of the formula Cyanuric chloride (9.22g, 0.05mol) is introduced to toluene (80ml). Over the course of 40 minutes a mixture of 2-decyl-1-tetradecanol (20. lg, 0.057 mol), dimethylacetamide (6.53 g, 0.075 mol) and toluene (20 ml) at 30-55 ° C is added dropwise. . The mixture is then stirred at 50 ° C for 4 hours and filtered through kieselguhr. The filtrate is extracted by shaking with tert-butyl methyl ketone (50 ml) and ice-cold 10% NaCl solution (150 ml), separated and dried over Na2SO4. Once the solvent has been removed, the oil obtained is worked with a chromatographic column (silica gel, toluene / hexane 7: 3). This gives a colorless oil of the compound of the formula (101a). Yield: 18.4g (73%) 13C NMR (90MHz, CDC13, TMS) d = 14.50; 23.09; 27.08; 29.74; 29.76; 29.97; 30.04; 30.26; 30.32; 31.31; 32.32; 37.75; 73.68; 171.63; 172.84. Analysis by elements:% C% H% N Calculated: 64.52 9.83 8.36 Found: 65.0 9.9 8.2 Example lb: Preparation of the compound of the formula (101) Resorcinol (4.9g, 0.044mol) is introduced in nitrobenzene (40 ml). At 10 - 15 ° C, powdered aluminum chloride (5.9 g, 0.044 mol) is introduced in portions. The mixture is then stirred for 30 minutes, the compound of the formula (101a) (10.05g, 0.020 mol) is dissolved in nitrobenzene (10 ml) and added dropwise in the course of 30 minutes at 10-15 ° C, and then the mixture is stirred during 5 hours. The mixture is then stirred for another 3 hours at room temperature. The reaction can be monitored using thin layer chromatography (silica gel, toluene / acetone 9: 1). The reaction mixture is poured under stirring into a mixture of ice water (100 ml) and 2N HCl (25 ml). A precipitate is separated. The nitrobenzene residues are removed by steam distillation. The solid residue is dissolved in acetone, dried using Na 2 SO 4, concentrated by evaporation and separated by a chromatographic column (silica gel, toluene / ethyl acetate 8: 2). This gives 5.7 g of a yellow powder which, after a recrystallization of hexane / dioxane 6: 4, is produced in an analytical grade grade. This gives pale yellow crystals of the compound (101). Yield: 4. Ig (31%) Melting point: 165 - 166 ° C UV / Vis (EtOH):? Max (e) = 350 (34482) nm 13C NMR (90MHz, D6-DMSO, TMS) d = 14.6 (CH2); 23.0; 27.0 (CH2); 29.8 (CH2); 30.0 (CH2); 30.06 (CH2); 30.11 (CH2); 30.3 (CH2); 31.3 (CH2); 32.3 (CH2); 37.6 (CH); 71.2 (CH20); 103.8 (CH); 109.0 (CH); 109.4 (CH); 131.6 (CH); 164.6 (Cq); 65.1 (Cq); 67.8 (Cq); 171.5 (Cq).

Analysis by elements:% C% H% N Calculated: 72.08 9.15 6.47 Found: 72.04 9.16 6.48 Example 2a: preparation of the compound of the formula (102a) The compound of the formula (102a) is prepared analogously to the compound of the formula (101a) of example 1. The crude product obtained as a liquid is purified by distillation at high vacuum (boiling point 118-119 ° C / 0.2). The crude product can also be purified by column chromatography on silica gel (toluene / hexane 9: 1). The compound has already been described in US-A-3, 542, 752 (American Cyanamid). Example 2b: Preparation of the compound of the formula (102): Initially, the compound of the formula (102a) (11. lg, 0.040 mol), resorcinol (9.7 g, 0.088 mol), xylene (80 ml) and sulfolane (30 ml) are introduced. At 35-40 ° C, powdered aluminum chloride (11.7 g, 0.088 mol) is introduced over the course of 20 minutes and the mixture is stirred for 5 hours. The two-phase reaction mixture is separated. The lower orange-reddish phase is allowed to flow to a mixture of ice water (250 ml) and 32% hydrochloric acid (20 ml). The solid that separates is filtered off, washed with acetone and dried. It is recrystallized several times from dioxane. This results in pale yellow crystals of the compound of the formula (102). Solubility in ethanol (25 ° C): 1.50% Melting point: 235 356 ° C Yield 5 g (29%; UV / Vis (EtOH):? Max (e) = 350 (39177) nm 13C NMR (90MHz, Ds -DMSO, TMS) d = 11.6 (CH3), 14.7 (CH3), 23.3 (CH2), 24.0 (CH2), 29.3 (CH2), 30.6 (CH2), 38.9 (CH), 71.0 (CH20), 103.9 (CH2); ); 109.5 (CH); 131.9 (CH); 164.4 (Cq); 165.1 (Cq); 167.9 (Cq); 171.5 (Cq) Analysis by elements:% C% H% N Calculated: 64.93 6.40 9.8 Found: 64.6 6.4 9.9 emp oa: preparac ne compues oea rmu aa The compound of the formula (102a) is prepared analogously to the compound of the formula (101a) of example 1. The alcohol component used is a mixture of isoctadecanol isomers (CA. Reg. No. 27458-93-1) Example 3b: preparation of the compound of the formula (103): Initially, resorcinol (6.6 g, O.OdO ol), nitrobenzene (40 ml) and a mixture of xylene isomers (20 ml) are introduced. At 45-50 ° C powdered aluminum chloride (7.0 g / 7.7 g, 0.052 mol) is added and the mixture is stirred for 30 minutes. Then a mixture at 0-5 ° C of the compound of the formula (103a) (10.5g, 0.025 mol) and xylene (10 ml) is added dropwise over the course of 1.5 hours and the mixture is then stirred for 5 hours at 2 - 3 ° C. To complete the work, the reaction mixture is allowed to flow to a mixture of ice water (100 ml) and 2N HCl (25 ml). The nitrobenzene is removed by steam distillation. Use u met ter (200 m to extract the crude product from the residue) The organic phase is washed with a 5% solution of NaCl, dried and freed from the solvent, then column chromatography (silica gel, toluene) is used. / acetone 9: 1) to separate the mixture.This gives beige crystals of the compound of the formula (103) Yield: 4.6 g (32%) Melting point: 166 - 167 ° C UV / Vis (EtOH ):? max (e) = 351 nm 13C NMR (90MHz, D6-DMSO, TMS) 5 = 13.9 (CH2); 22.1 (CH2); 26. 1 (CH2); 28.77 (CH2); 28.82 (CH2); 29.0 (CH2); 29.1 (CH2); 29. 4 (CH2); 30.6 (CH2); 31.3 (CH2); 31.4 (CH2); 36.7 (CH); 70. 5 (CH20); 103.1 (CH); 108.4 (CH); 108.7 (CH); 131.0 (CH); 163.4 (Cq); 164.4 (Cq); 167.2 (Cq); 170.8 (Cq). Analysis by elements:% C% H% N Calculated: 70.06 8.37 7.43 Found: 70.2.5 7.3 Example 4a: preparation of the compound of the formula (104a): (104a) The composition is prepared analogously to the compound of the formula (101a) of Example 1. The alcohol component used is 2-hexyldecanol. Example 4b: preparation of the compound of the formula (104): Resorcinol (6.6 g, 0.060 mol) are introduced into a solution of the compound of the formula (104a) (9.76 g, 0.025 mol) in toluene (80 ml) at 0-5 ° C within 30 minutes. Then powdered aluminum chloride is introduced (7.0 g, 0.025 mol) to the reaction mixture in small portions at 2 ° C within 30 minutes and the mixture is stirred for 4 hours. The cold bath is removed and the mixture is stirred overnight at room temperature. The reaction can be monomer-based or chroma-to-layer (silica gel, toluene / acetone 9: 1). Emptying the reaction mixture in dilute hydrochloric acid (150 ml of H20 + 25 ml of concentrated HCl) results in phase separation at 50 ° C. The toluene is removed from the upper organic phase by steam distillation. The solid that separated is extracted with tert-butyl methyl ether. The dried extract over Na 2 SO 4 is concentrated by evaporation and separated by a chromatographic column (silica gel, toluene / acetone 8: 2). This results in pale yellow crystals of the compound of the formula (104) (dioxane / hexane). Yield: 10.1 g (74.8%) Melting point: 175 - 176 ° C UV / Vis (EtOH):? Max (e) = 351 (36148) nm 13C NMR (90MHz, D5-DMSO, TMS) d = 14.7 ( CH3); 23.0 (CH3); (CH2); 26.9 (CH3); 27.0 (CH3); 29.6 (CH3); 29.8 (CH3); 29.9 (CH3); 30.2 (CH3); 31.4 (CH3); 31.5 (CH3); 32.1 (CH3); 32.2 (CH3); 37.6 (CH); 71.3 (CH20); 103.9 (CH); 109.2 (CH); 109.5 (CH); 164.5 (Cq); 165.1 (Cq); 168.0 (Cq); 171.6 (Cq).

Analysis by elements:% C% H% N Calculated: 69. 25 8. 06 7. 81 Found: 69. 1 7. 9 7. 8 Example 5a: preparation of the compound of the formula (105a) The compound of the formula (105a) is prepared analogously to the compound of the formula (101a) of example 1. The alcohol component used is 1-octadecanol. Example 5b: Preparation of the compound of the formula (105): Initially, nitrobenzene (40 ml), resorcinol (6.6 g, 0.06 mol) and a mixture of xylene isomers (20 ml) are introduced at room temperature. Then powdered aluminum chloride (7.0 g, 0.05 mol) is added n and the mixture is stirred for 30 minutes at 45-50 ° C. Then, at 0-5 ° C, a 35-minute course is added dropwise over the course of 35 minutes. Solution of the compound of the formula (108a) in a mixture of xylene isomers (15 ml). The mixture is stirred for 3 hours at 0-5 ° C and then at 5-10 ° C for 1.5 hours. The reaction suspension is passed under stirring to a mixture of ice water (200 ml) and 4N hydrochloric acid (25 ml) and heated to 50 ° C. Extraction is carried out with tert-butyl methyl ether (200 ml) and the organic phase is concentrated in a rotary evaporator. Water is added to the residue and the nitrobenzene residues / mixture of xylene isomers are removed by steam distillation. The crude product is recrystallized from dioxane / acetone 6: 4. The reaction can be monitored by thin layer chromatography (silica gel, toluene / acetone 9: 1). This gives pale yellow crystals. Yield: 6.9 g (48.8%) Melting point: 213-214 ° C. UV / Vis (EtOH):? Max (e) = 350 (31662) nm Analysis by elements:% C% H% N Calculated: 70.06 8.37 7.43 Found: 70.4 8.6 7.5 Example 6a: Preparation of the compound of the formula (106a) The compound of the formula (106a) is prepared analogously to the compound of the formula (101a) of example 1. The alcohol component used is 2-butyl-1-octanol. Example 6b: preparation of the somatic compound of the formula (106): Initially, the compound of the formula (106a) (16.7 g, 0.05 mol), toluene (150 ml) and resorcinol (13.2 g, 0.12 mol) is introduced at room temperature. At 0-5 ° C powdered aluminum chloride (14.7g, 0.11 mol) is introduced in small portions and over the course of 1 hour with 15 minutes and the mixture is stirred at 0-5 ° C for 6.5 hours. 2N HCl (60 ml) is added to the reaction mixture under cooling. The yellow emulsion is extracted with butyl methyl ether. The organic phase is washed with a 10% solution of NaCl, dried over Na 2 SO 4 and freed from the solvent. The solid residue is purified by column chromatography (silica gel, toluene / butyl methyl ether 75:25). The reaction can be monitored by thin layer chromatography (silica gel, toluene / acetone 9: 1). From this, beige crystals are obtained. Yield: 7. Og (29.1%) Melting point: 170-172 ° C 13C NMR (90MHz, D6-DMSO, TMS) d = 14.7; 23.0; 23.3; 27.0; 29.3; 31.2; 31.5; 32.1; 37.5; 67.2; 103.9; 109.2; 109.5; 131.6; 164.5 (Cq); 165.1 (Cq); 168.0 (Cq); 171.6 (Cq). Analysis by elements:% C% H% N Calculated: 67.34 7.33 8.73 Found: 67.3 7.4 8.5 Example 7a: Preparation of the compound of the formula (107a): The compound of the formula (107a) is prepared analogously to the compound of the formula (101a) of example 1. The alcohol component used is methanol. Example 7b: Preparation of the compound of the formula (107): The compound of the formula (107a) is prepared according to the method described for the compound of the formula (105). The solid that has been separated is stirred with warm methanol, treated with methanol, dried and recrystallized from acetonitrile / N-methyl-2-pyrrolidone. The resulting crystalline powder is extracted with boiling methanol in order to remove the included N-methyl-2-pyrrolidone, filter and dry. The reaction can be monitored by thin layer chromatography (silica gel, toluene / acetone 8: 2). From this, pale yellow crystals are obtained. The product was published in EP-A-0, 165, 608. Solubility in ethanol (25 ° C): 0.08% Yield: 10.8g (66.0%) Melting point: > 300 ° C UV / Vis (EtOH):? Max (e) = 350 (36949) nm 13 C NMR (90 MHz, D 6 -DMSO, TMS) d = 53.9 (OCH 3); 102.0 (CH); 107.6 (CH); 130.0 (CH); 107.3 (Cq); 162.5 (Cq); 163.2 (Cq); 166.2 (Cq); 169.5 (Cq). Analysis by elements:% C% H% N Calculated: 58.72 4.00 12.84 Found: 58.64 4.18 12.76 Example 8a: preparation of the formula (108a) The compound of the formula (108a) is prepared analogously to the compound of the formula (101a) of example 1. The alcohol component used is ethanol. Example 8b: preparation of the somatic compound of the formula (108): The compound of the formula (108) is prepared according to the compound of the formula (105). The reaction can be monitored by thin layer chromatography (silica gel, toluene / acetone 8: 2). From this, pale beige crystals are obtained. Solubility in ethanol (25 ° C): 0.17% Yield: 3.6 g (42.2%) Melting point: > 300 ° C UV / Vis (EtOH):? Max (e) = 350 (36761) nm 13C NMR (90MHz, D6-DMSO, TMS) d = 14.8 (CH3); 64.9 (CH2); 103.8 (CH); 109.1 (Cq); 164.4 (Cq); 165.0 (Cq); 167.5 (Cq); 171.4 (Cq). Example 9a: preparation of the somatic compound of the formula (109a): The compound of the formula (109a) is prepared analogously to the compound of the formula (101a) of example 1. The alcohol component used is 2-octyl-l-dodecanol . Example 9b: preparation of the compound of the formula (109): Resorcinol (13.2g, 0.12 mol) is introduced to nitrobenzene (30 ml). At 50-60 ° C a solution of the compound of the formula (109a) (22.3g, 0.05mol) in toluene (70ml) is added. TO 0 -. 0 - 5 ° C powdered aluminum chloride is introduced (14. Ig, 0.11 mol) over the course of 40 minutes and then the mixture is stirred for 6 hours at 0-5 ° C. The mixture is then poured under stirring into 2N HCl and the nitrobenzene is removed by steam distillation. The solid residue is separated and extracted with butyl methyl ether. The organic phase is washed with 10% NaCl solution and Na2C03 at 2%, dried over Na2SO and evaporated. The crude product is purified by column chromatography (silica gel, toluene / acetone 85:15). An analytical grade product is obtained by recrystallization of subsequent acetone.

The reaction can be monitored by thin layer chromatography (silica gel, toluene / acetone 9: 1). Pale yellow crystals are obtained. Yield: 7.1 g (23.9%) Melting point: 166-167 ° C 13 C NMR (90MHz, D6-DMSO, TMS) d = 14.6; 23.0; 27.0; 29.6; 29. 7; 29.9; 28.0; 30.2; 30.3; 31.4; 32.2; 37.6; 71.2; 103. 9; 109.1; 109.5; 131.8; 164.5 (Cq); 165.1 (Cq); 168. 0 (Cq); 171.6 (Cq). Example 10: preparation of the somatic compound of the formula (110): The compound of the formula (101) (9.8 g, 0.015 mol), acetone, (85 ml), water (40 ml) and 2N NaOH (15.8 ml) are initially introduced at room temperature. At 40 ° C dimethyl sulfate (4.16 g, 0.04 mol) is added dropwise and the mixture is then stirred for 2 hours at 0 ° C. IN HCl is used to adjust the pH to 6 and the solid is filtered. The filter residue is dissolved in toluene, extracted by stirring with H20, dried and freed from the solvent. The separation is then carried out by column chromatography (silica gel, toluene) and recrystallization from diethyl ether. The reaction can be monitored by thin layer chromatography (silica gel, toluene / acetone 95: 5). From this, pale biege crystals are obtained. Yield: 3.1 g (30.5%) Melting point: 79-80 ° C UV / Vis (EtOH):? Max (e) = 347 (36219) nm 13C NMR (90MHz, D5-DMSO, TMS) d = 15.5; 24.1; 28.2; 30.8; 31. 1; 31.4; 32.5; 33.3; 38.9; 56.9 (OCH3); 72.7; 109.4; 111. 2 (COCH3); 132.4; 165.9 (Cq); 167.1 (Cq); 168.8 (Cq); 172. 8 (Cq); Analysis by elements:% C% H% N Calculated: 72.64 9.37 6.2 Found: 72.77 9.39 6.20 Example 11: preparation of the formula of the formula (111): The compound of the formula (104) (10.8 g, 0.02 mol) is introduced into dioxane (100 ml). At 40 ° C 2N NaOH (21 ml) is added and the mixture is stirred for 15 minutes. Dimethyl sulfate (4.2 ml) is added at 40 ° C and the mixture is stirred for 5 hours. The solvent is separated by the use of a rotary evaporator and the residue is dissolved in toluene. The organic phase is extracted by stirring with 10% NaCl solution and dried. The pure product is obtained by column chromatography (silica gel, toluene / acetone 98.5: 1.5) and the subsequent recrystallization of hexane. The reaction can be monitored by thin layer chromatography (silica gel, toluene / acetone 9: 1). Pale beige crystals are obtained. Yield: 7.5 g (66.3%) Melting point: 99-100 ° C UV / Vis (EtOH):? Raax (e) = 348 (34123) nm 1C NMR (90MHz, CDC13, TMS) d = 14.5; 23.1; 27.20; 27.21; 29.8; 30.0; 30.1; 30.4; 31.5; 32.27; 32.31; 38.9; 55.8 (OCH3); 71.7; 101.6; 108.4; 110.2; 131.2; 164.9 (Cq); 166.0 (Cq); 167.8 (Cq); 172.0 (Cq). Analysis by elements:% C% H% N Calculated: 70.06 8.37 7.43 Found: 70.0 8.4 7.1 Example 12: preparation of the formula tax (112) The compound of the formula (112) is prepared analogously to the compound of the formula (110). The solvent used is dioxane. The product of the filtration is washed with dioxane / H20 and methanol and dried. It is then recrystallized from methyl cellosolve. Pale yellow crystals are obtained. Yield: 5.7 g (64.2%) Melting point: 193-194 ° C UV / Vis (Dioxan):? Max (e) = 347 (37680) nm Application examples: Example 13: Micronization 50 g of the compound of the formula (108) are ground together with 7% alkyl polyglucoside, 43% H20 and 80 g zirconium sand to achieve a particle size of dso = 150 nm. The grinding sand is separated from the suspension, which contains the compound of the formula (108) micronized.

Example 14: protective formulation against the sun (/ O) Components by weight Oily phase PEG-30 dipolyhydrostearate (Arlacel P 135"3.00 PEG-22 / dodecyl glycol copolymer (Elfacos ST 37®) 1.00 Microcrystalline wax 1.00 Hydrogenated castor oil 0.50 Magnesium stearate 1.00 Octyl stearate 15.00 Coconut glycerides 2.00 Mineral oil 3.00 Phenoxyethanol and parabens 1.00 Octyl methoxycinnamate 5.00 Dimethicone 0.10 Aqueous phase Deionized water 52.40 Magnesium sulphate (MgSO4x7H20) 1.00 propylene glycol 4.00 50% suspension corresponding to example 13 10.00 Preparation instructions: The oil and the aqueous phase are heated separately to 80 ° C, they are mixed and the mixture is vigorously homogenized.

The mixture is then allowed to cool to 40 ° C under gentle agitation. The 50% suspension of the micronized ultraviolet absorption agent of the formula (108) is added in portions with stirring, and the stirring is continued for another 15 minutes. SPF (in vivo) (Sun protection factor) = 16 (COLIPA) [without the micronized compound of the formula (108): SPF = 6] Example 15: sun protection emulsion (O /) Components% by weight A Polyglyceryl-3-methylglucose distearate (Tego® Care 450) 2.0 Decyl oleate 5.7 Isopropyl palmitate 5.0 Caprylic / Capric triglyceride 6.5 Compound of formula (101) 3.5 B Glycerol 3.0 Phenonip 0.5 Deionized water 72.4 Carbomer 141 0.2 Isopropyl palmitate 0.8 D NaOH (10%) 0.4 Preparation procedure: Phases A and B are heated separately at 80 ° C and then mixed with gentle agitation. C is added to the mixture of A and B and vigorously homogenized. The homogenate is allowed to cool to room temperature under gentle agitation. If necessary, adjust the pH by adding D.

SPF (In vitro) = 3.0 / SPF Optometrics SPF 290 Analyzer, 2 μl / cm2 on Transpore® tape) The Australian / New Zealand standard, 15 / NSZ 2604: 1993 is met (less than 10% transmission between 320 and 360 nm ). Example 16: solar radiation emulsion (O / W) Components% by weight A Polyglyceryl-3-methylglucose distearate (Tego® Care 450) 2.0 Decyl oleate 5.7 Isopropyl palmitate 5.0 Caprylic / Capric triglyceride 6.5 Compound of formula (101) 3.0 Methyl methoxycinnamate 5.0 B Glycerol 3.0 Phenonip 0.5 Deionized water 67.9 C Carbomer 141 0.2 Isopropyl palmitate 0.8 D NaOH (10%) 0.4 Preparation procedure: Phases A and B are heated separately at 80 ° C and then mixed with gentle agitation. C is added to the mixture of A and B and homogenized vigorously. The omogena is allowed to run in a mild form. If necessary adjust the pH by adding D. SPF (In vitro) = 11.0 / SPF Opto etrics SPF 290 Analyzer, 2 μl / cm2 on Transpore® tape) The Australian / New Zealand standard, 15 / NSZ 2604: 1993 ( less than 10% transmission between 320 and 360 nm).

Example 17: Sunscreen cream (W / O) Components% in Weight Oily phase Metoxy PEG-22 / Dodecyl glycol copolymer (Elfacos E 200ß 3.00 PEG-22 / Dodecyl glycol copolymer (Elfacos ST 37®) 3.00 Hydroxyoctacosanyl hydroxy stearate (Elfacos C 26®) 3.00 Octyl stearate 15.00 Coconut glycerides 2.00 Oil mineral 3.00 Phenoxyethanol and parabens 0.70 Compound of the formula (104) 3.50 4-methylbenzylidene camphor 4.00 Tcoferil acetate l'.OO Dimethicone 0.20 Aqueous phase Deionized water 56.80 uaoe magnes og 4x 20. Propylene glycol 4.00 Preparation procedure: Phases A and B are heated separately at 80 ° C and mixed with gentle agitation. C is added to the mixture of A and B and vigorously homogenized. The homogenate is allowed to cool to room temperature under gentle agitation. If necessary adjust the pH by adding D. SPF (In vitro) = 12.0 / SPF Optometrics SPF 290 Analyzer, 2 μl / cm2 on Transpore® tape) Australian / New Zealand standard, 15 / NSZ 2604: 1993 (less 10% transmission between 320 and 360 nm). Example 18: solar protection cream Components% in Weight 1 Deionized water up to 100 2 Dioxide of titanium (and) isopropyl mistrato 6.25 3 Phenoxyethanol and parabens 0.50 4 Saleare SC91 2.50 Glycerol 2.00 6 Compound of the formula (104) 0.70 7 Isopropyl palmitate - 5.00 8 Caprylic / capric triglyceride 2.50 Propylene glycol 1.00 Methylene bis (benzotriazolyl) (tetramethylbutyl) phenol (50% suspension) 6.00 Preparation procedure: The substances from (2) to (5) are added to the water (1) in the given sequence under vigorous agitation. The solution of (6) is then added in a mixture of (7) and (8) under moderate agitation. Similarly, (9) and (10) are added under agitation. Continue stirring until the composition is homogeneous. The Australian / New Zealand standard, 15 / NSZ 2604: 1993 (less than 10% transmission between 320 and 360 nm) is met.

Claims (8)

1. e v n sas 1. A compound of the formula wherein Ri is C2-C30 alkyl; C2-C30 alkenyl; C5-C12 cycloalkyl-unsubstituted or C5-C12 cycloalkyl-C1-C5 alkyl mono or poly substituted, C? -C5alkoxy-C? -C? 2 alkyl; amino-C? -C? 2 alkyl; C1-C5 monoalkylamino-C? -C? 2 alkyl; C1-C5-dialkylamino-C1-C12-alkyl; a radical of the formula Ó (1d) 2, 3 and 4, hydroxyl, C 1 -C 30 alkyl, C 1 -C 30 alkenyl, R 5 is hydrogen; or C1-C5 alkyl; i is 0 or 1; and is not 1 to 5.
2. 2. A compound according to claim 1, wherein R6 is hydrogen.
3. 3. A compound according to claim 1 or 2, wherein Ri is C2-C3alkyl.
4. 4. A compound according to any of claims 1 to 3, wherein Ri is C6-C30alkyl.
5. 5. A compound according to any one of claims 1 to 4 wherein Ri is a 2-decylhexadecyl radical.
6. 6. A compound according to any of claims 1 to 4 wherein Ri is an isooctadecyl radical.
7. 7. A compound according to any of claims 1 to 4 wherein Ri is an n-octadecyl radical.
8. 8. A compound according to any one of claims 1 to 4 wherein Ri is a 2-hexyldecyl radical. . n comps or according to what was the claims 1 to 4 in which Ri is a 2-ethylhexyl radical. 10. A compound of the formula (1) in micronized form, in which Ri is C2-C3o alkyl; C2-C3o alkenyl; C5-C12 cycloalkyl-unsubstituted or C5-C12 cycloalkyl-C1-C5 alkyl mono or poly substituted, C? -C5alkoxy-C? -C? 2 alkyl; amino-C? -C? 2 alkyl; C1-C5 monoalkylamino-C? -Ci2 alkyl; C1-C5 dialkylamino-C1-C12-alkyl; a radical of the formula OR R2 / 3 and R .. - independent of each other, are hydrogen, hydroxyl, C1-C30 alkyl, C1-C30 alkenyl, R5 is hydrogen; or C1-C5 alkyl; m is 0 or 1; and neither is a. 11. A process for the preparation of the compounds of the formula (1), in which, in the first reaction step, cyanuric chloride is reacted with the compound R? ~ OH to give the dichloroaryloxytriazines of the formula (2) and, in a second step, in a Friedel-Crafts reaction, these compounds are reacted with resorcinol to give the compound of the formula (1), according to the following reaction equation: (twenty-one)

   12. The use of the compound of the formula (1) to protect human and animal hair and skin from the harmful effects of ultraviolet radiation. 13. A cosmetic preparation containing at least one or more compounds of the formula (1) according to claims 1 to 10 with cosmetically compatible carriers and auxiliaries. 14. A preparation according to claim 13, which contains other ultraviolet protective substances.

   15. A preparation according to claims 13 or 14 containing, as ultraviolet radiation protective substances, triazines, oxanilides, triazoles, amides containing vinyl groups or cinnamides. 16. A compound of the formula Wherein R 'i is a branched C8-C3oalkyl; a radical of the formula m / i is 0 or 1; and n 'i is 1 to 5. 17. A composition containing a co-reactive organic mineral, oxygen and / or heat, and (B) a compound according to any one of claims 1 to 10 as a stabilizer. Summary of the invention The invention relates to diresorcinyl-alkoxy- and aryloxy-s-triazines of the formula wherein Ri is C2-C3o alkyl; C2-C3o alkenyl; Cs-C? 2-cycloalkyl-unsubstituted or C5-C12 cycloalkyl-C1-C5 alkyl mono- or poly-substituted, C? -C5alkoxy-C? -C? 2 alkyl; amino-C? -C? 2 alkyl; C1-C5 monoalkylamino-C? -C? 2 alkyl; C1-C5-dialkylamino-C1-C12-alkyl; a radical of the formula R2 / R3 and R4. independent of one another, are hydrogen, hydroxyl, C 1 -C 30 alkyl, C 3 -C 3 alkenyl, R 5 is hydrogen; or C1-C5 alkyl; nor is it 1 to 5. The novel compounds are usable as "ultraviolet" absorption agents for cosmetics.