Patent GB-1008456-A (GB)
Title: New 2-azolyl-5-oxdiazolyl-thiophene derivatives, process for their preparation and their use
IPC: C08K5/45
Filed: 1963-11-25
Abstract: Compounds of the general formula <FORM:1008456/C4-C5/1> wherein W represents a benzene residue which may contain one or more alkyl or alkoxy groups or halogen atoms, R represents a thiophene residue bound in position 2 with the azole ring and in position 5 with the 1,3,4-oxadiazole ring, X is oxygen or an -NH- group, and A is a benzene residue, two vicinal cyclic carbon atoms of which are shared with the azole ring, which benzene ring may contain one or more alkyl or alkoxy groups or halogen atoms (see Division C2), are used as optical brighteners for organic materials.  The compounds may be used in the form of dispersions in dispersing agents such as soaps, soap-like substances, polyglycol ethers of fatty alcohols, sulphite cellulose waste liquor or formaldehyde condensation products of possibly alkylated naphthalenesulphonic acids.  The compounds may be used in conjunction with detergents such as soaps, salts of sulphonate detergents such as sulphonated benzimidazoles substituted on the carbon atom Z by alkyl radicals having at least 10 carbon atoms, salts of monocarboxylic acid esters of 4-sulphophthalic acid with higher fatty alcohols, salts of fatty alcohol sulphonates, alkylarylsulphonic acids or condensation products of higher fatty acids with aliphatic hydroxysulphonic or aminosulphonic acids, and nonionic detergents such as polyglycol ethers derived from ethylene oxide and higher fatty alcohols, alkylphenols or fatty amines.  The detergents may also contain conventional additives such as alkali metal carbonates, phosphates, pyrophosphates, polyphosphates, metaphosphates, silicates, perborates or percarbonates. In an example, acetic acid is also present.  Specification 1,001,956 is referred to.ALSO:In Example 5, a mixture of polyvinyl chloride, dioctyl phthalate, titanium dioxide and one of the compounds listed below, is rolled on a sheeting calender to form a foil.  The compounds referred to are <FORM:1008456/C3/1> and compounds of the general formula <FORM:1008456/C3/2> wherein Y1 and Y2 have the following values: <FORM:1008456/C3/3> <FORM:1008456/C3/4> <FORM:1008456/C3/5> <FORM:1008456/C3/6> <FORM:1008456/C3/7> <FORM:1008456/C3/8> Specification 1,001,956 is referred to.ALSO:The invention comprises compounds of the general formula <FORM:1008456/C2/1> in which A is a benzene residue, two vicinal cyclic carbon atoms of which are shared with the azole ring, which benzene residue may contain one or more alkyl or alkoxy groups or halogen atoms, X is oxygen or an -NH-group, R is a thiophene residue which is linked in position 2 with the azole ring and in position 5 with the 1,3,4-oxadiazole ring, and W is a benzene residue which may contain one or more alkyl or alkoxy groups or halogen atoms.  The compounds may be prepared by reacting a compound of the general formula <FORM:1008456/C2/2> in which W and R are as defined above and Z is a carboxyl group or a functionally converted carboxyl group, e.g. a C1-C4 alkyl ester group or an acid halide group, with a compound of the general formula <FORM:1008456/C2/3> in which A is as defined above, X1 is -OH or -NH2, and -NH2 and X1 are bonded to A in vicinal positions, with or without isolation of the intermediate of the general formula <FORM:1008456/C2/4> in which A, R and W are as defined above and X2 is an oxygen atom or an -NH- group, which may be formed when Z represents an acid halide group.  The starting materials of Formula (4) above may be prepared by reacting a compound of the general formula <FORM:1008456/C2/5> in which R1 is a C1- 4 alkyl ester group and R is a thiophene residue bound in position 2 with the acid halide group and in position 5 with R1, with a compound of the formula <FORM:1008456/C2/6> in which W is as defined above, treating the resultant diacylhydrazine with a water-eliminating agent and, if desired, converting the alkyl ester group into a free carboxyl group or other functionally modified carboxyl group.  The compounds of Formula (7) above may be prepared by treating the appropriate monoalkyl ester of the corresponding thiophene dicarboxylic acid with thionyl chloride.  The compounds of Formula (59) above may be prepared by monoacylating hydrazine with a functional derivative of a carboxylic acid.  The compounds of Formula (4) above may alternatively be prepared by reacting a compound of the general formula <FORM:1008456/C2/7> in which R is a thiophene residue bound in position 2 with the acid hydroxide group and in position 5 with the carboxyl group, with a compound of the formula <FORM:1008456/C2/8> in which W is a defined above, and treating the resulting diacylhydrazine with a water-eliminating agent; when thionyl chloride is used as water-eliminating agent the carboxyl group in position 5 may be converted to an acid chloride group which may then be hydrolysed to give a free carboxyl group or be converted into another functionally modified carboxyl group.  The compounds of Formula (4) above may also be prepared by reacting a compound of the general formula <FORM:1008456/C2/9> in which W is as defined above and R is a thiophene residue bound in position 2 with H and in position 5 with the 1,3,4-oxadiazole ring, with hydrogen chloride and formaldehyde or paraformaldehyde, or with dichloromethyl ether, hydrolysing the chloromethyl group in the product of general formula <FORM:1008456/C2/100> to a hydroxymethyl group, which group is then oxidized to a carboxyl group and then, if desired, esterified or converted into another functionally modified carboxyl group.  The compounds of the invention, of Formula (1) above, may also be prepared by reacting a compound of the general formula <FORM:1008456/C2/111> with a compound Formula (59) above, wherein A and X have as first defined above and R is a thiophene ring bound in position 2 with the azole ring and in position 5 with the acid halide group, and treating the resulting diacylhydraxine with a water-eliminating agent; another process involves reacting a compound of the formula <FORM:1008456/C2/122> in which A, R and X are as defined for Formula (21) above, with a compound of Formula (60) and treating the resulting diacylhydrazine with a water-eliminating agent.  The compounds of Formulae (21 and (22) above may be prepared by condensing a compound of Formula (7) above with a compound of Formula (5) above to give a compound of the general formula <FORM:1008456/C2/133> in which A, R and R1 are as defined above and X2 represents an oxygen atom or an -NH-group, which compound is then converted into the corresponding mono-azolyl-thiophene compound by heating with a water-eliminating agent, and the C1-C4 alkyl ester group (R1) is converted into an acid halide or an acid hydrazide group.  The compounds of Formula (21) and (22) above may also be prepared by reacting a compound of the general formula <FORM:1008456/C2/144> in which A and X are as defined above and R is a thiophene residue bound in position 2 with the azole ring and in position 5 with H, with hydrogen chloride and formaldehyde or paraformaldehyde or with dichloromethyl ether, hydrolysing the chloromethyl group in the product of the general formula <FORM:1008456/C2/155> oxidizing the hydroxymethyl group to a carboxyl group, and converting this group to an acid halide group and theme, if required, to the acid hydrazide group.  Examples are given. Specification 1,001,956 is referred to.ALSO:Compounds of the general formula <FORM:1008456/D1-D2/1> wherein W represents a benzene residue which may contain one or more alkyl or alkoxy groups or halogen atoms, R represents a thiophene residue bound in position 2 with the azole ring and in position 5 with the 1,3,4-oxadiazole ring, X is oxygen or an NH-group, and A is a benzene residue, two visual carbon atoms of which are shared with the azole ring, which benzene ring may contain one or more alkyl or alkoxy groups or halogen atoms, (see Division C2) are used as optical brighteners for organic materials. The material may be impregnated at an elevated temperature, for example 50 to 100 DEG C., with a solution, preferably aqueous, or a dispersion of the compound, followed by squeezing or certifying the material and then drying it. Solutions of the brightness in organic solvents may also be used. The brightness may be used in admixture with clinical bleaches or as additives to bleaching baths, in conjunction with detergents, in admixture with starch or synthetic dressing agents, or as additives to a liquor for producing an anti-crease effect. Materials to be brightened may be, for example: (A) textile materials in the form of fibres, filaments, yarns, woven or knitted fabrics, or felt, the materials consisting of wool, silks, cotton, hemp, flax, linen, jute, ramie, rayon, visions, cellulose butyrate, acetylcellulose, polyacrylonitrile, polyvinylidene chloride, polyvinyl chloride, polyethylene, polypropylene, polyesters and polyamides; (B) other fibrous materials such as feathers, hairs, felts, hides, leathers, straw, wood, woodpulp, paper, cardboard and hardboard.  In Example 3, a polyamide fabric such as spun nylon is immersed in a bath consisting of water, a dispersant (adduct of ethylene oxide and octadecyl alcohol), 40% acetic acid and the compound of formula <FORM:1008456/D1-D2/2> and is then boiled, rinsed and dried.  Similar results are obtained when the compound is replaced by the compounds of formulae 34 and 38 below and when a polyester fabric is treated with the compound of Formula 43 below. In Example 4, a polypropylene fabric is treated in a similar bath, which contains no acetic acid, with the compounds of Formulae 39 and 44 below, rinsed and dried.  The compounds referred to alone in connection with Examples 3 and 4 are of the general formula <FORM:1008456/D1-D2/3> wherein Y1 and Y2 have the following values <FORM:1008456/D1-D2/4> <FORM:1008456/D1-D2/5> <FORM:1008456/D1-D2/6> <FORM:1008456/D1-D2/7> <FO