| PATENT ASSIGNEE'S COUNTRY | USA |
| UPDATE | 08.00 |
| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | 29.08.00 |
| PATENT TITLE |
Diresorcinyl-alkoxy- and -aryloxy-s-triazines |
| PATENT ABSTRACT |
The invention relates to diresorcinyl-alkoxy- and -aryloxy-triazines of the formula ##STR1## in which R.sub.1 is C.sub.2 -C.sub.30 alkyl; C.sub.2 -C.sub.30 alkenyl; unsubstituted or C.sub.1 -C.sub.5 alkyl-mono- or polysubstituted C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.5 alkoxy-C.sub.1 -C.sub.12 alkyl; amino-C.sub.1 -C.sub.12 alkyl; C.sub.1 -C.sub.5 monoalkylamino-C.sub.1 -C.sub.12 alkyl; C.sub.1 -C.sub.5 dialkylamino-C.sub.1 -C.sub.12 alkyl; a radical of the formula ##STR2## R.sub.2, R.sub.3 and R.sub.4, independently of one another, are hydrogen, hydroxyl, C.sub.1 -C.sub.30 alkyl, C.sub.1 -C.sub.30 alkenyl, R.sub.5 is hydrogen; or C.sub.1 -C.sub.5 alkyl; m.sub.1 is 0 or 1; and n.sub.1 is 1 to 5. The novel compounds are suitable as cosmetic UV-A absorbers. |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | 06.04.99 |
| PATENT FOREIGN APPLICATION PRIORITY DATA | This data is not available for free |
| PATENT REFERENCES CITED |
Chemical Abstracts, 118(24)240480e (for JP 05-25029 filed Jul. 22, 1991). Koopman et al., Recueil, vol. 78, pp. 967-980, (1959). Koopman, Recueil, vol. 80, pp. 158-172, (1961). Brunetti et al., Helv. Chim. Acta, vol. 55(5), pp. 1566-95 (1972). |
| PATENT CLAIMS |
What is claimed is: 1. A compound of the formula ##STR47## in which R.sub.1 is C.sub.6 -C.sub.30 alkyl; C.sub.2 -C.sub.30 alkenyl; unsubstituted or C.sub.1 -C.sub.5 alkyl-mono- or polysubstituted C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.5 alkoxy-C.sub.1 -C.sub.12 alkyl; amino-C.sub.1 -C.sub.12 alkyl; C.sub.1 -C.sub.5 monoalkylamino-C.sub.1 -C.sub.12 alkyl; C.sub.1 -C.sub.5 dialkylamino-C.sub.1 -C.sub.12 alkyl; a radical of the formula ##STR48## R.sub.2, R.sub.3 and R.sub.4, independently of one another, are hydrogen, hydroxyl, C.sub.1 -C.sub.30 alkyl, C.sub.1 -C.sub.30 alkenyl, R.sub.5 is hydrogen; m.sub.1 is 0 or 1; and n.sub.1 is1 to 5. 2. A compound according to claim 1, wherein R.sub.1 is a 2-decylhexadecyl radical. 3. A compound according to claim 1, wherein R.sub.1 is an isooctadecyl radical. 4. A compound according to claim 1, wherein R.sub.1 is an n-octadecyl radical. 5. A compound according to claim 1, wherein R.sub.1 is a 2-hexyldecyl radical. 6. A compound according to claim 1, wherein R.sub.1 is a 2-ethylhexyl radical. -------------------------------------------------------------------------------- |
| PATENT DESCRIPTION |
The present invention relates to novel diresorcinyl-alkoxy- and -aryloxy-triazines, to a process for the preparation of these compounds and to their use in cosmetic compositions. The novel diresorcinyl-alkoxy- and -aryloxy-triazines conform to the formula ##STR3## in which R.sub.1 is C.sub.2 -C.sub.30 alkyl; C.sub.2 -C.sub.30 alkenyl; unsubstituted or C.sub.1 -C.sub.5 alkyl-mono- or polysubstituted C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.5 alkoxy-C.sub.1 -C.sub.12 alkyl; amino-C.sub.1 -C.sub.12 alkyl; C.sub.1 -C.sub.5 monoalkylamino-C.sub.1 -C.sub.12 alkyl; C.sub.1 -C.sub.5 dialkylamino-C.sub.1 -C.sub.12 alkyl; a radical of the formula ##STR4## R.sub.2, R.sub.3 and R.sub.4, in dependently of one another, are hydrogen, hydroxyl, C.sub.1 -C.sub.30 alkyl, C.sub.1 -C.sub.30 alkenyl, R.sub.5 is hydrogen; or C.sub.1 -C.sub.5 alkyl; m.sub.1 is 0 or 1; and n.sub.1 is 1 to 5. Alkyl signifies a branched or unbranched hydrocarbon radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methyihexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, iso-octyl; 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl. Alkoxy radicals are straight-chain or branched radicals, for example methoxy, ethoxy, propoxy, butoxy or pentyloxy. C.sub.5 -C.sub.12 cycloalkyl signifies, for example, cyclopentyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclodocecyl and, in particular, cyclohexyl. Within the scope of the given meanings, alkenyl includes inter alia allyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl, n-octadec-4-enyl or 3,7,11,11-tetramethyl-2,6,10-undecatrienyl. Preference is given to compounds of the formula (1) in which R.sub.5 is hydrogen. Further preference is given to compounds of the formula (1) in which R.sub.1 is C.sub.2 -C.sub.30 alkyl, in particular C.sub.4 -C.sub.30 alkyl and very particularly C.sub.6 -C.sub.30 alkyl. Of these compounds, very particular preference is given to those in which R.sub.1 is a 2-decylhexadecyl radical. Other interesting compounds of the formula (1) are those in which R.sub.1 is C.sub.4 -C.sub.18 alkyl radicals. Of these compounds, very particular preference is given to those in which R.sub.1 is an isooctadecyl radical, an n-octadecyl radical or a 2-hexyldecyl radical. Particularly interesting compounds of the formula (1) are those in which R.sub.1 is a C.sub.3 -C.sub.12 radical, and in particular a 2-ethylhexyl radical. Other illustrative representatives of the novel diresorcinyl-alkoxy- and-aryloxy-triazines are given in the table below: TABLE 1 __________________________________________________________________________ #STR5## - Compound of the formula R .sub.1 __________________________________________________________________________ (3) #STR6## - (4) --O-isoC.sub.18 H.sub.38 - (5) #STR7## - (6) --O-n-C.sub.18 H.sub.37 (7) --O-2-ethylhexyl - (8) #STR8## - (9) #STR9## - (10) #STR10## - (11) #STR11## - (12) #STR12## - (13) #STR13## - (14) #STR14## - (15) #STR15## - (16) #STR16## - (17) #STR17## - (18) #STR18## - (19) ##STR19## __________________________________________________________________________ The novel diresorcinyl-alkoxy- and -aryloxy-triazines are prepared, for example, by reaction of cyanuric chloride with the alcohol R.sub.1 --OH to give the aryloxy- or alkoxy-dichloro-s-triazines respectively of the formula (2). In a Friedel-Crafts reaction, the novel compounds of the formula (1) are obtained in the second reaction stage. The reaction can be represented diagrammatically as follows: ##STR20## The first reaction stage is usually carried out in the presence of a solvent, for example acetone, methyl ethyl ketone, dimethylacetamide, toluene or xylene. The temperatures here range from 0 to 130.degree. C., in particular from 20 to 70.degree. C.; the reaction times from 1 to 48 hours, preferably from 2 to 10 hours. In the second reaction stage, the solvent normally used is toluene, nitrotoluene, nitrobenzene, anisole, xylene, benzene, sulfolane, chlorobenzene, dichlorobenzene, hydrocarbons (e.g. isooctane), chlorinated hydrocarbons, nitroalkanes, carbon disulfide, sulfur dioxide and mixtures of said solvents. The temperatures here are from -10 to 200.degree. C., in particular from 0 to 100.degree. C. The reaction times range from 1 to 100 hours, preferably from 2 to 50 hours. The second reaction stage is normally carried out in the presence of a catalyst. Examples of suitable catalysts are: aluminium chloride, aluminium bromide, tin chloride, titanium tetrachloride, boron trifluoride and other Lewis acids. The catalyst here is used in an amount of from 0.1 to 3 mol per mole of reactive chlorine. In Friedel-Crafts reactions with dichloroalkoxy-s-triazines, dealkylations in the alkoxy radical are frequently observed. Under conditions according to the invention, i.e. control of the temperature; amount of catalyst, metered addition of the catalyst, the reaction proceeds particularly smoothly and without notable dialkylation. Another method of synthesizing the novel diresorcinyl-alkoxy- and -aryloxy-triazines involves reacting cyanuric chloride with resorcinol to give the 2-chloro-4,6-resorcinyltriazine (compound of the formula (20) in the first reaction stage and reacting it with HO--R.sub.1 to give the compound of the formula (1) in a second reaction stage, in accordance with the following equation: ##STR21## The p-hydroxyl groups of the resorcinyl radicals of the novel diresorcinyl-alkoxy- and -aryloxy-triazines of the formula (1) can, if desired, be further alkylated using suitable alkylating agents X--R.sub.5 (X.dbd.Cl, Br, I, F) to give the corresponding alkoxy derivatives of the formula ##STR22## in which R.sub.1 and R.sub.5 are defined as for formula (1). Other suitable alkylating agents are epoxides, tosylates, dialkyl sulfates and alkyl glycidyl ethers. The compounds of the formula ##STR23## in which R.sub.1 is a branched C.sub.8 -C.sub.20 alkyl radical; a radical of the formula ##STR24## m.sub.1 is 0 or 1; and n'.sub.1 is 1 to 5, obtained in the first reaction stage are novel compounds. They are also provided by the invention. The novel diresorcinyl-alkoxy- and -aryloxy-triazines of the formula (1) have an absorption maximum of ca. 350 nm, i.e. these compounds are UV-A absorbers. The compounds are therefore suitable in particular as UV filters, i.e. for protecting organic materials which are sensitive to ultraviolet light, in particular the skin and hair of humans and animals, from the harmful effects of UV radiation. These compounds are therefore suitable as light protection agents in cosmetic, pharmaceutical and veterinary medicine preparations. They can be used either in dissolved form or in the micronized state. The present invention thus also relates to compounds of the formula (1) in micronized form, in which R.sub.1 is C.sub.1 -C.sub.7 alkyl; C.sub.2 -C.sub.30 alkenyl; unsubstituted or C.sub.1 -C.sub.5 alkyl-mono- or polysubstituted C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.5 alkoxy-C.sub.1 -C.sub.12 alkyl; amino-C.sub.1 -C.sub.12 alkyl; C.sub.1 -C.sub.5 monoalkylamino-C.sub.1 -C.sub.12 alkyl; C.sub.1 -C.sub.5 dialkylamino-C.sub.1 -C.sub.12 alkyl; a radical of the formula ##STR25## R.sub.2, R.sub.3 and R.sub.4, independently of one another, are hydrogen, hydroxyl, C.sub.1 -C.sub.30 alkyl, C.sub.1 -C.sub.30 alkenyl, R.sub.5 is hydrogen; or C.sub.1 -C.sub.5 alkyl; m.sub.1 is 0 or 1; and n.sub.1 is 1 to 5. If the novel UV absorbers are in micronized form, they usually have an average particle size of from 0.02 to 2 .mu.m, preferably from 0.05 to 1.5 .mu.m, very particularly from 0.1 to 1.0 .mu.m. The methods for micronization are described, for example, in GB-A-2303549. The grinding apparatus which can be used to prepare the novel micronized organic UV absorbers are, for example, a jet, ball, vibration or hammer mill, preferably a high-speed stirred mill. The grinding is preferably carried out using a grinding aid, for example an alkylated vinyl pyrrolidone polymer, a vinyl pyrrolidone-vinyl acetate copolymer, an acylglutamate or, in particular, a phospholipid. Because of their lipophilicity, the compounds (1) can be easily incorporated into oil- and fat-containing cosmetic formulations particularly when R.sub.1 is a branched alkyl radical having more than 8 carbon atoms. The invention also provides a cosmetic preparation comprising at least one compound of the formula (1), and cosmetically compatible carriers or auxiliaries. For cosmetic use, the novel light protection agents normally have an average particle size in the range from 0.02 to 2.mu., preferably from 0.05 to 1.5.mu., very particularly from 0.1 to 1.0.mu.. As mentioned above, the insoluble novel UV absorbers can be brought into the desired particle size by customary grinding methods. The grinding is preferably carried out in the presence of from 0.1 to 30% by weight, preferably from 0.5 to 15% by weight, based on the UV absorber, of a grinding aid. In addition to the novel UV absorber, the cosmetic preparation can also comprise one or more further UV protective substances from the following classes of substance: 1. p-Aminobenzoic acid derivatives, for example 2-ethylhexyl 4-dimethylaminobenzoate; 2. Salicylic acid derivatives, for example 2-ethylhexyl salicylate; 3. Benzophenone derivatives, for example 2-hydroxy-4-methoxybenzophenone and its 5-sulfonic acid derivative; 4. Dibenzoylmethane derivatives, for example 1-(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-(benzo-furanyl) 2-cyanoacrylate; 6. 3-Imidazol-4-yl-acrylic acid and 3-imidazol-4-yl acrylates; 7. Benzofuran derivatives, in particular 2-(p-aminophenyl)benzofuran derivatives, described in EP-A-582,189, U.S. Pat. No. 5,338,539, U.S. Pat. No. 5,518,713 and EP-A-613,893; 8. Polymeric UV absorbers, for example the benzylidene malonate derivatives described in EP-A-709,080; 9. Cinnamic acid derivatives, for example the 2-ethylhexyl or isoamyl 4-methoxycinnamate or cinnamic acid derivatives disclosed in U.S. Pat. No. 5,601,811 and WO 97/00851; 10. Camphor derivatives, for example 3-(4'-methyl)benzylidenebornan-2-one, 3-benzylidenebornan-2-one, N-[2(and 4)-2-oxyborn-3-ylidene-methyl)benzyl]acrylamide-polymer, 3-(4'-trimethylammonium)-benzylidenebornan-2-one methyl sulfate, 3,3'-(1,4-phenylenedimethine)bis(7,7-dimethyl-2-oxo-bicyclo-[2.2.1]heptane -1-methanesulfonic acid) and salts, 3-(4'-sulfo)benzylidenebornan-2-one and salts; 11. Trianilino-s-triazine derivatives, for example 2,4,6-trianiline-(p-carbo-2'-ethyl-1'-oxy)-1,3,5-triazine and the UV absorbers disclosed in U.S. Pat. No. 5,332,568, EP-A-517,104, EP-A-507,691, WO 93/17002 and EP-A-570,838; 12. 2-Hydroxyphenylbenzotriazole derivatives; 13. 2-Phenylbenzimidazole-5-sulfonic acid and salts thereof; 14. Menthyl o-aminobenzoate; 15. TiO.sub.2 (with various coatings), ZnO and mica. It is also possible to use the UV absorbers described in "Sunscreens", Eds. N. J. Lowe, N. A. Shaath, Marcel Dekker, Inc., New York and Basel or in Cosmetics & Toiletries (107), 50ff (1992) as additional UV protective substances in the novel formulation. Furthermore, the novel cosmetic preparation can also be used together with known antioxidants, for example vitamin E, carotinoids or HALS (="Hindered Amine Light Stabilizers") compounds. The novel cosmetic preparation comprises from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight, based on the total weight of the composition, of a UV absorber or a mixture of UV absorbers and a cosmetically compatible auxiliary. The cosmetic preparation can be prepared by physically mixing the UV absorber(s) with the auxiliary by customary methods, for example by simply stirring the individual components together. The novel cosmetic preparation can be formulated as a water-in-oil or oil-in-water emulsion, 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 oil phase, from 5 to 20% of an emulsifier and from 30 to 90% of water. The oil phase can comprise any oil suitable for cosmetic formulations, for example one or more hydrocarbon oils, a wax, a natural oil, a silicone oil, a fatty acid ester or a fatty alcohol. Preferred mono- or polyols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol. For the novel cosmetic preparation, it is possible to use any conventional emulsifier, 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 sorbitan ester; an ethoxylated fatty acid; or an ethoxylated glyceride. The cosmetic preparation can also comprise 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 the human skin from the harmful effects of sunlight. The novel diresorcinyl-alkoxy- and -aryloxy-s-triazines are notable for high thermal stability and are thus used as stabilizers for organic polymers, in particular surface coatings, against their damage by light, oxygen and heat. The material stabilized using the novel compounds is notable for excellent resistance to weathering and light effects, and excellent photostability of the incorporated stabilizer. The materials to be stabilized can be, for example, oil, fats, waxes or biocides. Of particular interest is the use in polymeric materials, as are present in plastics, rubbers, paints, surface coatings, photographic material or adhesives. The invention thus also provides a composition comprising (A) an organic material which is sensitive to damage by light, oxygen and/or heat, and (B) as stabilizer, a compound of the formula (1). 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 stabilizer to said material, and also to the use of the compound of the formula (1) for stabilizing organic material. The amount of stabilizer to be used depends on the organic material to be stabilized and the intended use of the stabilized material. In general, the novel composition comprises, per 100 parts by weight of component (A), from 0.01 to 15 parts by weight, in particular from 0.05 to 10 parts by weight, and especially from 0.1 to 5 parts by weight of the stabilizer (component (B)). The stabilizer (component (B)) can also be a mixture of two or more compounds of the formula (1). The novel compositions can, in addition to the novel compounds, also comprise other stabilizers or other additives, for example antioxidants, further light protection agents, metal deactivators, phosphites or phosphonites. The type and amount of further stabilizers added is determined by the type of substrate to be stabilized and its intended use; frequently, from 0.1 to 5% by weight, based on the polymer to be stabilized, are used. Incorporation into the organic polymers, for example into the synthetic organic, in particular thermoplastic, polymers, can take place by adding the novel triazine compounds and optionally further additives by methods customary in the art. Incorporation can expediently take place before or during shaping, for example by mixing the pulverulent components or by adding the stabilizer to the melt or solution of the polymer, or by applying the dissolved or dispersed compounds onto the polymer, if necessary with subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized as latices. Another possible way of incorporating the novel mixtures into polymers involves adding them before or during polymerization of the corresponding monomers or before crosslinking. The stabilized polymer compositions obtained in this way can be converted into shaped articles, for example fibres, films, tapes, sheets, multi-wool sheets, containers, tubes and other profiles, by conventional methods, for example by hot pressing, spinning, extrusion or injection moulding. The polymers stabilized in this way are notable for high weathering resistance, especially for high resistance to UV light. They thus retain their mechanical properties and their colour and gloss even when used outdoors for a long period. In the following examples, percentages are by weight. The amounts in the case of the diresorcinyl triazine compounds used refer to the pure substance. |
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