Patent GB-990397-A (GB)
Title: New azolylthiophene compounds useful as optical brightening agents and process for their production
IPC: C08G18/80
Filed: 1962-07-18
Abstract: The invention comprises azolylthiophene compounds of formula <FORM:0990397/C2/1> in which R1 is a benzene or naphthalene residue, R represents a thiophene residue linked in 2-position to R1 and 5-position to the azole ring, R2 is a benzene or naphthalene residue, and X is an oxygen or sulphur atom, an NH group or a group <FORM:0990397/C2/2> in which A is an alkyl, alkenyl, a hydroxyalkyl or a cyanoalkyl group of up to 4 carbon atoms or an aralkyl or carboxylic acyl group.  The preferred compounds are those of formula <FORM:0990397/C2/3> in which U1 and U2 are the same or different and each represents a hydrogen or halogen, e.g. Cl or F, atom, or a C1-C4 alkyl or alkoxy group; U3 represents a hydrogen or a C1-C4 alkoxy group; W1 is a hydrogen or halogen atom, phenyl, phenylalkyl, alkoxy, a saturated C1-C12 non-aromatic hydrocarbon residue, cyanoalkyl, carboxyalkyl or a carbalkoxyalkyl group having up to 12 carbon atoms; W2 and W3 are the same or different and each represents a hydrogen atom or a C1-C4 alkyl group or together with the 2 vicinal carbon atoms of the benzene ring form a six-membered alicyclic ring; Z1 and Z2 are the same or different and each represents a hydrogen atom or a C1-C7 hydrocarbon residue, and X stands for an oxygen atom, the -NH- group or a group -NA- in which A has the above meaning. The new compounds may be made by reacting a monocarboxylic acid R1-R-COOH, or a functional derivative of such an acid, at elevated temperature and in the presence of a condensation catalyst with an ortho-amino compound of formula <FORM:0990397/C2/4> and, if desired, when X represents an -NH- group, treating the resulting azolylthiophene with an alkylating, alkenylating, hydroxyalkylating, cyanoalkylating, acylating or aralkylating agent.  Suitable condensation catalysts are, for example, boric acid, sulphonic acids of the benzene series, polyphosphoric acids and zinc chloride.  A high-boiling organic solvent may also be present in the reaction mixture.ALSO:Azolylthiophene compounds of the formula <FORM:0990397/C3/1> in which R1 is an benzene or naphthalene residue, R represents a thiophene nucleus linked in the 2-position to R1 and the 5-position to the azole ring, R2 is a benzene or naphthalene residue and X is an oxygen or sulphur atom or an -NH- group or a group <FORM:0990397/C3/2> In which A is an alkyl, alkenyl, hydroxyalkyl or cyanoalkyl group of up to 4 carbon atoms or an aralkyl or carboxylic acyl group, are used as optical brightening agents for polymers. They are, for example, incorporated in films of (a) polyethylene; (b) polyvinyl chloride containing dioctyl phthalate and titanium dioxide; and (c) polyacrylonitrile; and in a polyester granulate from polyterephthalic acid ethylene glycol ester and in a polyamide prepared from hexamethylene diamine adipate in chip form.ALSO:Azolylthiophene compounds of the formula <FORM:0990397/C4-C5/1> in which R1 is a benzene or naphthalene residue, R represents a thiophene nucleus linked in the 2- position to R1 and the 5-position to the azole ring, R2 is a benzene or naphthalene residue, and X is an oxygen or sulphur atom or an -NH-group or a group <FORM:0990397/C4-C5/2> in which A is a C1-C4 alkyl, alkenyl, hydroxyalkyl or cyanoalkyl group or an aralkyl or cyanoalkyl group, are used as optical brightening agents in detergent compositions.  The detergent and brightening agent may be added separately to the wash liquor.  Suitable detergents are, for example, soaps; salts of sulphonated detergents, e.g. sulphonated benzimidazoles substituted by higher alkyl groups at the 2-carbon atom; salts of monocarboxylic acid esters of 4-sulphophthalic acid with higher fatty alcohols; salts of fatty alcohol sulphonates; alkylaryl sulphonic acids; 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. In an example a soap (Na salt of higher fatty acids) is prepared containing 0.5% of a compound of the above formula and is used for washing acetate rayon and cotton.ALSO:Azolylthiophene compounds of the formula <FORM:0990397/D1-D2/1> in which R1 is a benzene or naphthalene residue, R is a thiophene nucleus linked in the 2-position to R1 and the 5-position to the azole ring, R2 is a benzene or naphthalene nucleus and x is <FORM:0990397/D1-D2/2> , <FORM:0990397/D1-D2/3> , -NH- or a group <FORM:0990397/D1-D2/4> in which A is a C1-C4 alkyl, alkenyl, hydroxyalkyl or cyanoalkyl group or an aralkyl or cyanoalkyl group, are used as optical brightening agents in the treatment of textiles.  They may be used as admixture with dressing agents such as starches or synthetic dressings or may be added to liquors used to produce anti-crease effects.  In examples the new compounds are used to treat (a) polyacrylonitrile fibre fabric, (b) a fabric of polyester fibres and (c) a polyamide fabric. The brightening agents are used in an aqueous solution which may contain a dispersant.