US3749732A - Triazolyl ketones - Google Patents

Triazolyl ketones Download PDF

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US3749732A
US3749732A US00122132A US3749732DA US3749732A US 3749732 A US3749732 A US 3749732A US 00122132 A US00122132 A US 00122132A US 3749732D A US3749732D A US 3749732DA US 3749732 A US3749732 A US 3749732A
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triazole
phenyl
hydroxy
acid
methyl
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J Rody
H Lind
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Novartis Corp
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Ciba Geigy Corp
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/496—Triazoles or their condensed derivatives, e.g. benzotriazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
    • C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
    • G03C1/8155—Organic compounds therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S524/925—Natural rubber compositions having nonreactive materials, i.e. NRM, other than: carbon, silicon dioxide, glass titanium dioxide, water, hydrocarbon or halohydrocarbon
    • Y10S524/929—Natural rubber broadly disclosed, nonclaimed

Definitions

  • the present invention relates to new 2-phenyl-4-(2'- hydroxybenzoyl)-v-triazoles (1,2,3-triazoles), to processes for their production, and to their use as protective agents against light rays for light-sensitive organic materials, the protective agents protecting these materials against the harmful eifect of the UV-rays of light, e.g. where the protective agents form a constituent of protective filters against light rays, in that protection is provided by the material to be protected being covered by film-like structures or by protective layers which contain these triazole compounds; or to the use of the compounds for the stabilising of light-sensitive organic material, the v-triazole compounds being incorporated into this material either homogeneously or on the surface.
  • Annularly-linked v-triazoles especially benzotriazoles, have already frequently been suggested as protective agents against light rays, and, in some cases, have also been put on the market.
  • the compounds according to the invention have, as protective agents against light rays, a better fastness to light and, in some fields of application, a better compatibility with the substrate and better fastness to sublimation.
  • 1,2,4-triazoles have already been suggested as protective agents against light rays.
  • these compounds of this class of substances are, however, not suitable as stabilisers.
  • they On account of their often pronounced acceleration effect on the light-produced yellowing of the substrates, they have hitherto acquired no industrial importance.
  • v-triazoles with an isolated triazole ring are known as protective agents against light rays.
  • 2-phenyl-4-(2'- hydroxybenzoyl)-v-triazoles of the following Formula I have a better protective action, particularly in the longwave UV-range, a lower volatility, and a better compatibility with the substrates than these hitherto known v-triazoles.
  • v-triazoles according to the invention correspond to the general Formula I:
  • R represents hydrogen, alkyl having 1 to 21 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, alkenyl having 3 to 18 carbon atoms, benzyl, alkylbenzyl having 8 to 11 carbon atoms, phenyl or alkylphenyl having 7 to 10 carbon atoms,
  • R represents hydrogen, alkyl having 1 to 22 carbon atoms, A -alkenyl having 3 to 18 carbon atoms, benzyl, alkylbenzyl having 8 to 11 carbon atoms or alkylcarbonyl having 2 to 18 carbon atoms, and
  • R" represents alkyl having 1 to 22 carbon atoms
  • R' represents alkyl having 1 to 22 carbon atoms, chlorine, hydroxyl or alkoxy having 1 to 22 carbon atoms,
  • n 0 to 3
  • n+m shall be 0 to 3.
  • Alkyl groups designated by R in Formula I are, e.g.: methyl, ethyl, butyl, heptyl, undecyl, pentadecyl or heptadecyl.
  • R represents, e.g. cyclohexyl, cyclopentyl or perhydronaphthyl.
  • alkenyl group R represents, e.g. A or A -propenyl or A -hexadecenyl. If a benzyl group R is substituted by alkyl, this can be methyl, ethyl, propyl, butyl or tert.- butyl. If R denotes alkylphenyl, it can be, e.g. 4-methylphenyl, ethylphenyl or 4-tert.-butylphenyl.
  • Alkyl groups denoted by R in Formula I can be, e.g.: methyl, ethyl, propyl, i propyl, butyl, amyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl or docosyl, whereby these alkyl groups can be branched or unbranched.
  • a -alkenyl groups denoted by R are, e.g. A -propenyl, Z-methyl-[M-propenyl] or A -hepdadecenyl. If a benzyl group R is substituted by alkyl, it can be: methyl, ethyl, propyl, butyl or tert.-butyl.
  • the alkylcarbonyl group can be, e.g.: acetyl, propionyl, Z-ethylhexanoyl, caprylol, lauroyl, palmitoyl or stearoyl.
  • R" and R can denote identical or different alkyl groups such as, e.g. methyl, ethyl, i-propyl, n-butyl, tert.-butyl, n-octyl, 1,1,3,3-tetramethylbutyl, dodecyl or octadecyl, and R can be alkoxy such as, e.g. methoxy, ethoxy, butoxy, octoxy, dodecyloxy, or octadecyloXy.
  • R represents hydrogen, alkyl having 1 to 17 carbon atoms, phenyl or alkyl phenyl having 7 to 10 carbon atoms,
  • R represents hydrogen, alkyl having 1 to 18 carbon atoms, A -alkenyl having 3 or 4 carbon atoms, benzyl, alkylbenzyl having 8 to 11 carbon atoms or alkyl-carbonyl having 2 to 18 carbon atoms, and
  • the new compounds of Formula I wherein R represents hydrogen can be obtained by dealkylation of compounds of the general Formula II OH H R C- N B;
  • alkylating agents are: dialkylsulphates such as, e.g. dimethylsulphate or diethylsulphate, l-bromo-, I-chloroalkanes, 2-bromo or 2-chloroal-kanes such as, e.g.
  • l-bromoethane 1-chloropropane, 2-bromopropane, l-bromobutane, 1-bromo-3,3-dimethylpropane, 1- chloro-3,3-dimethylbutane, l-bromohexane, l-bromooctane, l-bromodecane, l-bromododecane, l-bromotetradecane, l-bromohexadecane or l-bromooctadecane, benzyl chloride, 4-tert.-butylbenzyl chloride, alkenylbromides or -chlorides such as, e.g. allyl chloride, allyl bromide, methallyl chloride or methallyl bromide.
  • acylating agents are: acetic anhydride, aliphatic carboxylic acid chlorides such as, eg propionic acid chloride, valeric acid chloride, 2-ethylcaproic acid chloride, caprylic acid chloride, lauric acid chloride, palmitic acid chloride or stearic acid chloride.
  • the alkylation operations are performed in solvents, such as, e.g. alcohols, ketones or dimethylacetamide, in the presence of acid acceptors such as, e.g. potassium carbonate, potassium hydroxide, or sodium methylate.
  • solvents such as, e.g. alcohols, ketones or dimethylacetamide
  • acid acceptors such as, e.g. potassium carbonate, potassium hydroxide, or sodium methylate.
  • Used as compounds of Formula IV are, e.g.. resorcinolmonomethyl ether, resorcinol-dimethyl ether, resorcinoldiethyl ether, resorcinol-dibutyl ether, resorcinol-dihexyl ether, resorcinol-dioctyl ether, resorcinol-didodecyl ether.
  • the compounds of Formula III can be obtained by the following reactions:
  • the compounds of Formula IIIa are produced, e.g. by reaction of Z-arylazomalonaldehydeoximes with agents splitting off Water, preferably acetic anhydride under the Perkin reaction conditions.
  • the compounds of Formula 1111 are produced, e.g. by the simultaneous reaction of 2-arylazoacylacetic esters with ammonia and copper-(II)-salts, such as, e.g. copper- (II)-chloride-monohydrate, in alcohol at temperatures of around C. under pressure.
  • the compounds of the general Formula I wherein R represents hydrogen, alkyl having 1 to 22 carbon atoms, benzyl, alkylbenzyl having 8 to 11 carbon atoms, or alkylcarbonyl having 2 to 18 carbon atoms can also be produced by a Fries rearrangement of a compound of the general formula i R C-O- OR l i I can n/
  • the v-triazoles of Formula I according to the invention are, at room temperature and particularly when in fine dispersion, practically colourless to slightly yellow solids.
  • v-triazoles according to the invention to be preferred as light-filters are the ones producing the maximum light absorption.
  • the main carriers for the compounds of Formula I according to the invention are organic synthetic materials, i.e. polymeric organic compounds, that is, thermoplastic and also thermosetting polymers.
  • organic synthetic materials i.e. polymeric organic compounds, that is, thermoplastic and also thermosetting polymers.
  • suitable are both fully synthetic polymers and natural polymers, as well as polymer-homologous chemical modification products thereof.
  • pure addition polymers and pure condensation polymers are particularly suitable, but also condensation polymers crosslinked by addition polymerisation.
  • the addition polymers suitable as carrier materials for the new protective agents against light rays can be put into the following main types:
  • Polymerisable ethylenic unsaturated halogenated hydrocarbon compounds especially vinyl chloride, vinyl fluoride and vinylidene chloride.
  • Polymerisable hydrocarbons with double-bond capable of addition especially styrene, isobutylene, ethylene and propylene, whereby both the atactic and the isotactic polymerisation forms are suitable.
  • one-Unsaturated polymerisable carboxylic acids and functional derivatives thereof such as acrylic acid, methacrylic acid, acrylonitrile, alkyl esters, particularly lower alkyl esters, and amides of acrylic and methacrylic acid, e.g. the methyl, ethyl, and butyl esters of methacrylic acid and acrylic acid.
  • acyl derivatives of ethylenic unsaturated alcohols and amines especially those of organic carboxylic acids, whereby are suitable acyl radicals of alkanoic and alkenoic carboxylic acids having up to 18 carbon atoms, and of aromatic monocyclic carboxylic acids such as benzoic acids and phthalic acids, as well as acyl radicals of cyclic carbonic acid imides, such as, e.g. those of cyanuric acid.
  • suitable acyl radicals of alkanoic and alkenoic carboxylic acids having up to 18 carbon atoms and of aromatic monocyclic carboxylic acids such as benzoic acids and phthalic acids, as well as acyl radicals of cyclic carbonic acid imides, such as, e.g. those of cyanuric acid.
  • allyl phthalate, polyallyl melamines, vinyl acetate, vinyl stearate, vinyl benzoate and vinyl maleate are examples of allyl phthalate, polyallyl
  • Polymerisable hydrocarbons with conjugated double bonds such as butadiene, isoprene, chloroprene.
  • Homoand copolymers of epoxides especially of bisepoxides, which are formed by acidor base-catalytic hardening.
  • Suitable in this class are polymerisates of bisglycidyl ethers of geminal bis-(p-hydroxyphenyl)-alkanes and -cycloalkanes.
  • Addition products of isocyanates with hydroxyl and/or amino compounds particularly such ones of dior polyisocyanates with bior polyvalent hydroxyl or amino compounds.
  • This class embraces the polyurethanes and polyureas which are formed by reaction of diisocyanates with polyesters and/or polyethers containing hydroxyl groups.
  • condensation polymers suitable as carrier materials for the v-triazoles according to the invention are, among others, especially polyesters and polyamides. To be mentioned thereby are, in particular, linear thermoplastic polycondensates which, on the one hand, are derived from dicarboxylic acids and organic dihydroxy derivatives or organic diamines, and, on the other hand, from hydroxyor aminocarboxylic acids.
  • Preferred linear polycondensates are the fibre-forming polymers of w,w-dicarboxylic acids and w,w-dihydroxy compounds, or w,w'-diamines, as well as those of whydroxycarboxylic acids or of w-aminocarboxylic acids, particularly such polymers derived from saturated aliphatic, cycloaliphatic and carbocyclic non-annularly-linked aromatic carboxylic acids.
  • linear condensation products of the following components: adipic acid hexamethylenediamine, sebacic acid hexamethylenediamine, terephthalic acid ethylene glycol, terephthalic acid-1,4-dimethylol-cycloh'exane, IO-aminodecanecarboxylic acid, (l'l-aminoundecyclic acid).
  • C.oss-linked polycondensates as carrier materials are thermosetting and are formed, in particular, by condensation of aldehydes with polyvalent compounds capable of condensation. Mention is made for formaldehyde condensates with phenols, ureas and melamines.
  • polyester resins i.e. copolymerisates of polyesters of unsaturated organic carboxylic acids, which contain double bonds capable of addition, with polyvalent, especially bivalent alcohols, whereby, optionally, these polyesters are modified, on the one hand, with dicarboxylic acids not capable of addition, and, on the other hand, with vinyl or vinylidenemonomers.
  • Suitable monomers are preferably olymerisable mixtures of condensates of maleic acid, itaconic acid, citraconic acid with bivalent alcohols, preferably the water-addition-products of ethyleneand propylene oxide, such as ethylene glycol, propylene glycol and diethylene glycol and, optionally, further dicarboxylic acids of the aliphatic-alicyclic and monocyclic-aromatic series, or their anhydrides such as succinic acid anhydride, phthalic acid anhydride, and/or adipic acid, and of styrene and/or methyl methacrylate.
  • This monomer mixture of the unsaturated polyesters and vinyland/or vinylidenemonomers (often called liquid polyester resin) is preferably cross-linked by radical polymerisation initiators.
  • the natural polymers which are suitable as carrier materials for the 2 phenyl-4-(2'-hydroxybenzoyl)-v-triazoles according to the invention are, in particular, polysaccharides such as cellulose, or also rubber and proteins.
  • polymerhomologously chemically modified synthetic polymers mention is made, in particular, of the reaction products of polyvinyl alcohols with aldehydes such as polyvinylbutyral, and of the saponification products of polyvinyl esters.
  • Polymerhomologously chemically modified natural polymers as carrier materials for the new protective agents against light rays are, in particular, cellulose esters and cellulose ethers, such as cellulose esters of acetic acid, propionic acid, benzoic acid, having, on average, 1 to 3 acyl groups per glucose unit.
  • compositions according to the invention constitute in the compositions according to the invention, the polymers being either on their own or in admixtures, the carriers of the new protective agents against light rays.
  • Particularly valuable compositions according to the invention contain, as carriers of the new protective agents against light rays, cellulose esters, polyester resins, polymethacrylic acid esters, polyvinyl chloride, polyethylene and polypropylene.
  • carrier materials for the new protective agents against light rays are, in addition to the above mentioned polymeric carriers, natural as well as synthetic light-sensitve waxes, fats and oils, and also complex systems such as photographic material, emulsions containing light-sensitive fatty substances, emulsions or dispersions of the aforementioned polymers.
  • the molecular weight of the aforestated polymers is of secondary importance, as long as it within the limits necessary for the characteristic mechanical properties of the respective polymers. Depending on the polymers, it can be 1,000 to several millions.
  • 2-phenyl-4-(2'-hydroxylbenzoyl)-v-triazoles into these polymers is effected, for example, depending on the nature of the polymers, by at least one of these compounds and, optionally, further additives such as, e.g.
  • softeners, antioxidants, other protective agents against light rays, heatstabilisers, and pigments being worked into the melt by methods usual in engineering, either before or after moulding, or by dissolving in the corresponding monomer before polymerisation, or by dissolving of the polymer and additives in solvents which are subsequently evaporated oif.
  • the new protective agents against light rays may also be applied from baths, e.g. from aqueous dispersions, or from solution in organic solvents, to polymer granulateand to thinner carrier structures, such as to films or threads.
  • antioxidants such as pheno compounds, for example:
  • Aryl esters of optionally substituted benzoic acids such as, for example, phenylsalicylate; octylphenylsalicylate; benzoylresorcinol; 3,5di-tert.butyl-4-hydroxybenzoic acid-2,4-di-tert.-butyl-phenyl ester; dibenzoylresorcinol;
  • (e) Acrylates, for example, a-cyano-fi,fi-diphenylacrylic acid ethylor isooctyl-ester; a-carbomethoxycinnamic acid methyl ester; a-cyano- 3-methyl-p-methoxycinnamic acid methylor butyl-ester; N-(dcarbomethoxywinyl)-2- methylindoline;
  • Nickel compounds for example, nickel complexes of 2,2'-thiobis-(4-di-tert.octylphenol), such as the 1:1 and 2:1 complex, optionally with other ligands such as nbutylamine; nickeldibutyldithiocarbamate; nickel salts of 4-hydroxy-3,5-di-tert.butylbenzylphosphonic acid monoalkyl esters such as methyl-, ethylor butyl-ester, the nickel complex of 2-hydroxy-4-methylacetophenoneoxime;
  • nickel complexes of 2,2'-thiobis-(4-di-tert.octylphenol) such as the 1:1 and 2:1 complex
  • other ligands such as nbutylamine; nickeldibutyldithiocarbamate; nickel salts of 4-hydroxy-3,5-di-tert.butylbenzylphosphonic acid monoalkyl esters such as methyl-, ethylor butyl-ester
  • the lauryl, stearyl, myrystyl or tridecyl ester salts of Z-mercaptobenzimidazoles, e.g. zinc salt; diphenylthiourea; phosphites such as triphenylphosphite; diphenylalkylphosphites; phenyldialkylphosphites; trinonylphenylphosphite; trilaurylphosphite; trioctadecylphosphite; 3,9-diisodecyloxy-2,4,8,10- tetraoxa 3,9 diphosphaspiro-(5,5)-undecane; tri-(4-hydroxy-3,5-di-tert.butylphenyl)-phosphite.
  • salts of Z-mercaptobenzimidazoles e.g. zinc salt
  • diphenylthiourea phosphites such as triphenylphosphit
  • stabilisers such as potassium, barium, cadmium, magnesium, calcium or zinc salts of organic acids, e.g. stearates or laurates; basic or neutral lead salts of organic or inorganic acids; tin-containing stabilisers such as dibutyl tin laurates, -maleates or -n1arcaptides; hexamethylphosphoric acid triamide; copper salts such as copper acetates or copper-I- or copper-lI-halides, optionally in combination with alkali halides, -hypophosphites, -phosphites and -phosphates or free phosphorous acids or phosphoric acid; manganese-I-I-salts, such as the chloride, hypophosphite or phosphate, optionally in combination with other hydrophosphites, phosphites and phosphates; dicyandiamide; diphenylurea.
  • tin-containing stabilisers such as dibutyl tin
  • Inorganic fillers e.g. asbestos, glass fibres, kaolin, talcum.
  • the light-sensitive materials can be protected from the harmful action of light also by them being coated with a protective layer, e.g. with a lacquer, containing at least one 2-phenyl-4-(2'-hydroxybenzo yl)-v-triazole according to the invention; or by them being covered with structures containing such protective agents against light rays, e.g. structures such as films, discs or plates.
  • a protective layer e.g. with a lacquer, containing at least one 2-phenyl-4-(2'-hydroxybenzo yl)-v-triazole according to the invention
  • structures containing such protective agents against light rays e.g. structures such as films, discs or plates.
  • the amount of added protective agent against light rays is advantageously 1030% (relative to the protective layer material) for protective layers of less than 0.01 mm. thickness and for protective layers of 0.0l0.1 mm. thickness.
  • reaction solution After cooling to room temperature, the reaction solution is hydrolysed with ice/hydrochloric acid, and the solvent removed by steam distillation. After washing with water and drying of the crude product, recrystallisation from glacial acetic acid is carried out and 2- phenyl-4-(2-hydroxy 4 methoxybenzoyl)-1,2,3-(2H)- triazole, M.P. 173-175, obtained as yellowish crystals; -max.
  • (2H) -triazole An amount of 28.1 g. of 2-phenyl-4-(2-hydroxy-4-methoxybenzoyl) 1,2,3 (2H)-triazole (Example 1) is suspended in 300 ml. of benzene; to the suspension are added, with stirring, 40 g. of powdered aluminium chloride, the whole is heated to reflux temperature, and this temperature maintained for 2 hours. After cooling to room temperature, hydrolysis is performed with ice/hydrochloric acid, the solvent removed by steam distillation, the fine-grained yellow reaction product washed with water, dried, and recrystallised from chlorobenzene.
  • the protective agents against light rays given under 6.7 and 6.9 were obtained by demethylation of 6, 6.4 or 6.6, corresponding to the data in Example 2.
  • reaction solution is acidified with dilute hydrochloric acid; the reaction product is then precipitated with water, Washed, and recrystallised from acetonitrile.
  • 2-phenyl-4-(2-hydroxy 4 dodecyloxybenzoyl)-5-methyl-1,2,3-(2H)-triazole M.P. IDS-109, as slightly yellow coloured crystals; A 342 m E 16,280.
  • EXAMPLE 8 A solution of 15 g. of acetyl cellulose having on average 2.5 acetoxy groups per glucose unit, and 0.075 g. of one of the UV-absorbers listed in the following table in g. of acetone is spread out on a glass plate to form a film.
  • the cellulose acetate films obtained after evaporation of the acetone are dried firstly at room temperature, and then in an oven at 60. Specimens of these 0.04 mm.-thick UV-filters are exposed, for measurement of the fastness to light of the UV-absorbers, for 500 hours in a Fade-O- Meter, and then examined with respect to their residual UV-absorption.
  • the obtained results are given in the following table.
  • the applied polyester resin was produced as follows: To a mixture of g. of ethylene glycol and 292 g. of diethylene glycol is added in portions, at 80, a mixture of 343 g. of maleic acid anhydride and 428 g. of tetrachlorophthalic acid anhydride. After the air has been expelled in the reaction vessel by nitrogen, the temperature is raised in the course of 1 hour to 150", then in the course of 9 hours to 210, and this temperature is maintained for a further hour. The mass is afterwards cooled to 180, vacuum is applied, and the pressure slowly reduced to 100 torr. These conditions are maintained until the acid number of the reaction mixture has sunk to below 50.
  • An amount of 100 g. of the thus obtained polyester is mixed with 50 g. of styrene, and the mixture is polymcriscd under the above described conditions.
  • such sheets can be used as UV-filters.
  • EXAMPLE 1 Processed on a two-roller-mill in the usual manner into the form of sheet is a mixture of:
  • EXAMPLE 12 100 parts of polyethylene having a density of 0.917 are homogeneously mixed at 180 in a Brabender-plastograph with 0.5 parts of a UV-absorber from. the following table, and
  • the thus obtained mass is pressed in a platen press at to form 1 mm. thick sheets.
  • EXAMPLE 14 Bleached maple-veneer is coated with a wood-lacquer of the following composition:
  • the ceresin, petrolatum and lanolin are melted together and the protective agent against light rays dissolved in the melt.
  • the mineral oil is thereupon added at 70, and subsequently the water slowly worked in at the same temperature. Stirring is continued until the temperature has fallen to below 50, whereupon the perfume is added.
  • EXAMPLE 16 A sprayable cosmetic protective agent against light rays is obtained by dissolving in parts of ethanol,
  • the solution can be sprayed from an aerosol container.
  • the usual commercial fluorine-containing propellants e.g. Freon-products of the firm Du Pont, U.S.A.
  • R represents hydrogen, alkyl having 1 to 21 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, alkenyl having 3 to 18 carbon atoms, benzyl, alkylbenzyl having 8 to 11 carbon atoms, phenyl or alkylphenyl having 7 to 10 carbon atoms,
  • R represents hydrogen, alkyl having 1 to 22 carbon atoms, A -alkenyl having 3 to 18 carbon atoms, benzyl, alkylbenzyl having 8 to 11 carbon atoms or alkylcarbonyl having 2 to 18 carbon atoms, and
  • R" represents alkyl having 1 to 22 carbon atoms
  • R represents the same as R", hydroxyl or alkoxy having 1 to 22 carbon atoms,
  • n 0 or 1
  • R represents hydrogen, alkyl having 1 to 17 carbon atoms
  • R represents hydrogen, alkyl having 1 to 18 carbon atoms
  • R" represents alkyl having 1 to 18 carbon atoms
  • R' represents the same as R", hydroxyl or alkoxy having 1 to 8 carbon atoms, and n represents 0 to 3, m represents 0 or 1, and n+m represents 0 to 3.
  • R represents hydrogen, alkyl having 1 to 17 carbon atoms, or phenyl
  • R represents hydrogen, alkyl having 1 to 18 carbon HZOIIIS, A -alkenyl having 3 or 4 carbon atoms, benzyl, alkylbenzyl having 8 to 11 carbon atoms, or alkylcarbonyl having 3 to 18 carbon atoms, and
  • R" represents butyl or chlorine
  • R' represents the same as R", hydroxyl or alkoxy
  • n 0 to 2
  • n 0 or 1
  • n+m represents 0 to 2.

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  • Medicinal Chemistry (AREA)
  • Dermatology (AREA)
  • Epidemiology (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00122132A 1970-03-11 1971-03-08 Triazolyl ketones Expired - Lifetime US3749732A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH360170A CH524662A (de) 1970-03-11 1970-03-11 Verwendung von 2-Phenyl-4-(2'-hydroxybenzoyl)-v-triazolen als Lichtschutzmittel für nichttextile organische Materialien

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US3749732A true US3749732A (en) 1973-07-31

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US00122132A Expired - Lifetime US3749732A (en) 1970-03-11 1971-03-08 Triazolyl ketones

Country Status (6)

Country Link
US (1) US3749732A (OSRAM)
CH (1) CH524662A (OSRAM)
DE (1) DE2111538A1 (OSRAM)
FR (1) FR2084419A5 (OSRAM)
GB (1) GB1317232A (OSRAM)
NL (1) NL7103208A (OSRAM)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4140674A (en) * 1974-07-01 1979-02-20 Eastman Kodak Company Heterocyclic phenyl ester ultraviolet stabilizers and their use in organic compositions
US4290974A (en) * 1978-07-11 1981-09-22 L'oreal Oxybenzylidene-bornanones, their preparation and their use in cosmetics

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4140674A (en) * 1974-07-01 1979-02-20 Eastman Kodak Company Heterocyclic phenyl ester ultraviolet stabilizers and their use in organic compositions
US4290974A (en) * 1978-07-11 1981-09-22 L'oreal Oxybenzylidene-bornanones, their preparation and their use in cosmetics

Also Published As

Publication number Publication date
CH524662A (de) 1972-06-30
GB1317232A (en) 1973-05-16
FR2084419A5 (OSRAM) 1971-12-17
NL7103208A (OSRAM) 1971-09-14
DE2111538A1 (de) 1971-09-30

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