Patent GB-892767-A (GB)
Title: New 1:3:4-oxdiazoles and process for their manufacture
IPC: A61Q17/04
Filed: 1959-02-06
Abstract: 1:3:4-Oxdiazoles free from hydroxyl groups and acid groups imparting solubility in water, substituted in each of the 2- and 5- positions by a residue of the benzene series, one of the benzene residues being substituted in the o-position by a lower alkoxy group, and optionally having other substituents, e.g. alkyl groups, chlorine atoms or phenyl groups, with the proviso that each aliphatic substituent (including the alkoxy group) contains less than 4 carbon atoms, are used as light-screening agents in various substrata to protect them from ultra-violet light or for incorporation in films which are used to protect the substrate. Among the substances which may be protected are oils, fats and waxes, such as edible oils and fats; candles; wood stains; floor polishes; dyed or natural soaps; and shampoos.ALSO:1:3:4-Oxdiazoles free from hydroxyl groups and acid groups imparting solubility in water, substituted in each of the 2- and 5- positions by a residue of the benzene series, one of the benzene residues being substituted in the o-position by a lower alkoxy group, and optionally having other substituents, e.g. alkyl groups, chlorine atoms or phenyl groups, with the proviso that each aliphatic substituent (including the alkoxy group) contains less than 4 carbon atoms, are used as light-screening agents in various substrata to protect them from ultra-violet light or for incorporation in films which are used to protect the substrata. They may be added, for example, to the spinning mass of acetylcellulose (including cellulose triacetate) or to the mass from which fully synthetic fibres are made, e.g. polyamide melts p  or polyacrylonitrile spinning masses, prior to, in the course of, or subsequently to the polycondensation or polymerization.  They may also be added to lacquers and films, e.g. those made from acetyl cellulose, cellulose propionate, cellulose butyrate, nitrocellulose, vinyl acetate, polyvinyl chloride, copolymers of vinyl chloride and vinylidene chloride, alkyd lacquers, polyethylene, polyamides, polyacrylonitrile, polyesters and in transparent foils of regenerated cellulose or acetyl cellulose. They may also be added to natural or synthetic resins, e.g. epoxy resins, polyester resins, vinyl resins, polystyrene resins, alkyd resins, phenol-, urea- and melaminealdehyde resins, emulsions of synthetic resins, synthetic resins reinforced with glass fibres and natural or synthetic rubber-like materials such as rubber, balata gum, gutta-percha, polychloroprene, olefinic polysulphides, polybutadiene, butadiene-styrene copolymers and butadiene-acrylonitrile copolymers.  Specification 816,750 is referred to.ALSO:The invention comprises 1,3,4-oxdiazoles which are free from hydroxy groups and acid groups imparting solubility in water, and are substituted in each of the 2- and 5-positions by a residue of the benzene series one and only one, of these residues containing a lower alkoxy group in the o-position to a carbon atom bound to the oxdiazole ring, and in which all aliphatic residues present in the molecule (including the alkoxy group) contain less than 4 carbon atoms.  They may be produced by treating a diacylhydrazine of formula <FORM:0892767/IV (b)/1> in which R1 and R2 are residues of the benzene series one of which contains a lower alkoxy group in o-position to the -CO group and in which any alkyl residue contains less than 4 carbon atoms, with a non-sulphonating agent capable of eliminating water, e.g. anhydrous aluminium chloride, phosgene, phosphorus trichloride, pentachloride or oxychloride or, preferably, thionyl chloride.  The diacylhydrazines used as starting materials may be made by condensing a monoacyl hydrazine of formula <FORM:0892767/IV (b)/2> (which itself may be made by monoacylating hydrazine with a functional derivative of benzoic acid) with an acid halide of formula <FORM:0892767/IV (b)/3> Further substituents may be present in residues R1 and R2, e.g. lower alkyl groups, halogen atoms and phenyl radicals.  Examples are given of the preparation of 2-[21 - methoxyphenyl-(11)]-5-phenyl - 1, 3, 4 - oxdiazole; 2 - [21 - methoxy - phenyl - (11)] - 5 - [411 - methylphenyl - 1, 3, 4 - oxdiazole; 2 - [21 - methoxyphenyl - (11)] - [411 - chlorphenyl - (111)] - 1, 3, 4 - oxdiazole; 2 - [21 - methoxyphenyl - (11)] - 5 - [411 - methoxy - phenyl - (111)] - 1, 3, 4 - oxdiazole; 2 - [21 - methoxyphenyl - (11)] - 5 - [111, 1111 - diphenyl - (411)] - 1, 3, 4 - oxdiazole; 2 - [21 - methoxy - 41 - methylphenyl - (11)] - 5 - phenyl - 1, 3, 4 - oxdiazole; 2 - [21 - methoxy - 41 - methylphenyl - (11)] - 5 - [411 - methylphenyl - (111)] - 1, 3, 4 - oxdiazole; 2 - [21 - methoxy - 41 - methylphenyl - (11)] - 5 - [411 - chlorphenyl - (111)] - 1, 3, 4 - oxdiazole; 2 [ [21 - methoxy - 41 - methylphenyl - (11)] - 5 - (411 - methoxyphenyl - (111)] - 1, 3, 4 - oxdiazole; and 2 - [21 - methoxy - 41 - methyl - phenyl - (11)] - 5 - [111, 1111 - diphenyl - (411)] - 1,3,4-oxdiazole.  Specification 816,750 is referred to.ALSO:1 : 3 : 4-Oxdiazoles free from hydroxyl groups and acid groups imparting solubility in water, substituted in each of the 2- and 5-positions by a residue of the benzene series, one of the benzene residues being substituted in the o-position by a lower alkoxy group, and optionally having other substituents, e.g. alkyl groups, chlorine atoms or phenyl groups, with the proviso that each aliphatic substituent (including the alkoxy group) contains less than 4 carbon atoms, are used as light-screening agents in various materials to protect them from ultra-violet light.  These compounds may be incorporated with a material by means of a dyeing process or in a "filter coating" to protect a material placed immediately beneath or some distance from it.  Materials that can be protected are textile materials in general, e.g. fibres, filaments, yarns, woven or knitted fabrics or felt and finished products made therefrom, consisting of natural materials of animal or vegetable origin, semi-synthetic materials such as regenerated cellulose, rayon or spun rayon, or synthetic materials obtained by polymerisation or copolymerisation.  The protective compounds may also be added to coating and dressing agents for textiles, e.g. those based on starches, casein or synthetic resins made from vinyl acetate or derivatives of acrylic acid.ALSO:1 : 3 : 4-Oxdiazoles free from hydroxyl groups and acid groups imparting solubility in water, substituted in each of the 2- and 5-positions by a residue of the benzene series, one of the benzene residues being substituted in the o-position by a lower alkoxy group, and optionally having other substituents, e.g. alkyl groups, chlorine atoms or phenyl groups, with the proviso that each aliphatic substituent (including the alkoxy group) contains less than 4 carbon atoms, are used as light-screening agents in various substrata to protect them from ultra-violet light or for incorporation in films which are used to protect the substrata. They may be used, for example, for the protection of butter, feathers, hairs, pelts, hides, straw and wood, or for incorporation in cosmetics such as perfumes, bath salts, skin and face creams, lipsticks, powder, brilliantines, hair sprays, insect repellants and sunburn lotions and oils. Examples are given of the production of sunburn preparations and insect repellants containing one of the substituted 1 : 3 : 4-oxdiazoles defined above with: (a) adipic acid isopropyltetrahydrofurfuryl ester and glycerol monostearate in alcoholic solution; (b) trichloromonofluromethane, dichlorodifluoromethane, ethanol and perfume oil; (c) adipic acid isopropyltetrahydrofurfuryl ester, benzoic acid diethylamide and dimethylphthalade dissolved in peanut oil and paraffin oil; (d) glycerol monostearate, cetyl alcohol, sodium cetyl sulphate, stearic acid and glycerol; and (e) adipic acid isopropyl tetrahydrofurfuryl ester, toluic acid diethylamide, cetyl alcohol, petroleum oil, beeswax, lanolin, cocoa butter, water and sodium benzoate.