Patent GB-1001956-A (GB)
Title: New oxdiazole-thiophene derivatives, process for their preparation and their use
IPC: D06L3/12
Filed: 1963-11-27
Abstract: Compounds of the general formula <FORM:1001956/C4-C5/1> wherein W represents an alkonylbenzene, biphenylyl or naphthalene residue, R represents a thiophene residue bound in position 2 with Z and in position 5 with the 1,3,4-oxadiazole ring, and Z represents a carboxyl group or a functionally converted carboxyl group (see Division C2) are used as optical brighteners.  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 2 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 non-ionic 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 Example (3), a treatment bath consists of water, a dispersant (adduct of ethylene oxide and octadecyl alcohol), and the compound of formula <FORM:1001956/C4-C5/2> or the compound of formula <FORM:1001956/C4-C5/3>ALSO:The invention comprises compounds of the general formula <F\1> in which W represents an alkoxybenzene, biphenylyl or naphthalene residue, R represents a thiophene residue bound in position 2 with Z and in position 5 with the 1: 3: 4-oxdiazole ring, and Z represents a carbonyl group or a functionally converted carbonyl group.  The compounds are prepared (a) by reacting a thiophene acid halide of the formula <F\2> with a monoacyl-hydrazine of the formula <F\3> and treating the resulting diacyl-hydrazine of the formula <F\4> with a water-separation agent; (b) by reacting a compound of the formula <F\5> with a compound of the formula <F\6> and treating the resulting diacyl-hydrazine of the formula <F\7> with a water-eliminating agent; or (c) by reacting a compound of the formula <F\8> with hydrogen chloride and formaldehyde or paraformaldehyde or with dichloromethyl ether to give a compound of the formula <F\9> the chloromethyl group is hydrolysed to the hydroxymethyl group and this is then oxidized to the carbonyl group, R and W being as defined above, R1 being a C1 to C4 alkyl ester group.  The group Z in the product may, when it is an ester group, be hydrolysed to give the acid or may be converted into a different ester group or other functionally modified carbonyl group.  When the group Z is a free carbonyl group it may be esterified or converted into another functionally modified carboxyl group. The thiophene acid halides of formula (3) above may be prepared by the reaction of thionyl chloride with the monomethyl or monoethyl ester of the appropriate thiophene-2: 5-dicarboxylic acid.  The monoacyl-hydrazines of formula (4) above may be prepared by monoacylating hydrazine with a functional derivative of a carboxylic acid.  Examples are given.ALSO:Compounds of the general formula <FORM:1001956/D1-D2/1> wherein W represents an alkoxybenzene, biphenylyl or naphthalene residue, R represents a thiophene residue bound in position 2 with Z and in position 5 with the 1, 3, 4-oxadiozole ring, and Z represents a carboxyl group or a functionally converted carboxyl group (see Division C2) are used as optical brighteners for organic materials.  The compounds may be applied to the material by impregnation with a solution or dispersion of the compound followed by squeezing or centrifuging the material and then drying it.  The material may also be treated with dispersions of the compounds in dispersing agents such as soaps, soap-like substances, polyglycol ethers of fatty alcohols, sulphite cellulose waste liquor or formaldehyde condensation products of possibly alkylatic naphthalenesulphonic acids: (a) in admixture with chemical bleaches or as additives to bleaching baths; (b) in admixture with dressing agents such as starch or synthetic dressing agents; the compound may be added, for example to a liquor used for producing an anti-crease effect; (c) in conjunction with detergents. 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, for example, wool, silk, cotton, hemp, flax, linen, jute, ramie, rayon, viscoses, cellulose butyrate, acetylcellulose, polyacrylonitrile, polyvinylidene chloride, polyvinyl chloride, polyethylene, polypropylene, polyesters and polyamides; (B) other fibrous materials such as feather, hairs, pelts, hides, leathers, straw, wood, woodpulp, paper, cardboard and hardboard.  In Example 3, a polyamide fabric such as spun nylon is immersed in a bath p  consisting of water, a dispersant (adduct of ethylene oxide and octadenyl alcohol), and the compound of formula <FORM:1001956/D1-D2/2> and is then boiled, rinsed and dried.  Similar results are obtained when the compound is replaced by the compound of formula <FORM:1001956/D1-D2/3>