Patent GB-879610-A (GB)
Title: Derivatives of thiophene, their production and uses
IPC: C07D413/14
Filed: 1959-08-27
Abstract: <FORM:0879610/IV (a)/1> New fluorescent compounds of the general formula (1), in which A and A1 are benzo groups or mono-methyl substituted benzo groups which have 2 vicinal carbon atoms in common with the fused azole rings and in which X and Y are the same or different and represent either an oxygen atom or a group: <FORM:0879610/IV (a)/2> in which R is hydrogen or an organic substituent, and their quaternary ammonium salts and sulphonation products, are used as brightening agents, e.g. for addition to a solution of acetyl cellulose to be used for spinning to filamentary form or for the production of films.ALSO:The invention comprises thiophene derivatives of the general formula <FORM:0879610/IV (b)/1> in which A and A1 represent benz groups or mono-methyl substituted benz groups which have two vicinal carbon atoms in common with the fused azole rings and in which X and Y are the same or different and each either represents a group >N-R, in which R may be the same or different in the two rings and is hydrogen or an organic substituent, or represents an oxygen atom, and the salts, including the quaternary ammonium salts, of the benzimidazyl derivatives, and the products obtained by the sulphonation by known methods of the said thiophene derivatives, having a sulphonic acid group attached to each of the groups A and A1.  The group R referred to above, when not hydrogen, may be, for example, an acyl radical, an aliphatic or an araliphatic radical, preferably an alkyl, alkenyl or hydroxyalkyl radical containing up to 3 carbon atoms.  The salts of the new imidazole thiophene derivatives may be derived from any organic or inorganic acids.  The new thiophene derivatives are prepared by reacting a compound of the general formula <FORM:0879610/IV (b)/2> in which Q represents NHR or OH and T represents hydrogen or a methyl group, or a salt of a compound of this formula, at elevated temperature and preferably in the presence of dehydration catalysts with thiophene-2.5-dicarboxylic acid or with functional derivatives thereof.  In the case where imidazolyl thiophene derivatives are obtained they may be, if desired, acylated, alkylated, alkenylated, hydroxyalkylated or aralkylated in known manner and/or converted in known manner into quaternary ammonium compounds.  Suitable starting materials in the preparation of the new thiophene derivatives are, for example, in the case of imidazylthiophene compounds, 1.2-diaminobenzene, 1-amino- 2-monomethylaminobenzene and 1-methyl-3.4-diaminobenzene, and in the case of oxazolyl thiophene derivatives, 1-hydroxy-2-amino-4- or 5-methylbenzene.  The preferred temperature range for carrying out the preparation is 160-260 DEG C. and advantageously it is carried out in an inert gas, e.g. nitrogen. Suitable dehydration catalysts are, for example, boric acid and polyphosphoric acids.  Quaternary ammonium salts of the imidazole thiophene derivatives may be obtained by reacting them or their salts with the usual compounds capable of quaternising an imidazole nitrogen atom.  The thiophene derivatives may be sulphonated, for example, by treatment with sulphuric acid monohydrate, chlorosulphonic acid or sulphuric acid containing sulphur trioxide. Examples are given of the preparation of imidazyl thiophene compounds of the formula given in which R is -H, -CH2CHOHCH2OH, -CH2CH2OH, or benzyl and in some of which the benzene nuclei carry a methyl substituent and of oxazolylthiophene compounds in which the benzene rings are unsubstituted or carry methyl substituents.ALSO:New fluorescent compounds of the general formula:-<FORM:879610/IV(c)/1> in which A and A1 are benzo groups or monomethyl substituted benzo groups which have 2 vicinal carbon atoms in common with the fused azole rings and in which X and Y are the same or different and represent either an oxygen atom or a group <FORM:879610/IV(c)/2> in which R is hydrogen or an organic substituent, and their salts and sulphonation products, are used for optically brightening materials, particularly fibrous materials.  They may be used as aqueous solutions or dispersions or as solutions in organic solvents.  They may also be used in the dispersed form, for example as dispersions with soaps, polyglycol ethers of fatty alcohols, waste sulphite liquor or products of condensation of naphthalene sulphonic acids or alkylated naphthalene sulphonic acids with formaldehyde.  They may be used (a) for treating paper by adding them to a paper mass; (b) in mixtures with dyes or as an additive to dye baths, printing, discharge or resist pastes, or for the after-treatment of dyes, prints or discharge prints; (c) in mixtures with chemical bleaches or as additives to bleaching baths or (d) in mixtures with dressing agents such as starch or synthetically obtainable dressings or as additives to solutions used to produce a crease-proof finish.  In examples (a) polyacrylonitrile fabric is treated in a bath containing compounds of the formula given above and a small amount of formic acid, and (b) cotton fabrics are washed with a soap or a synthetic detergent containing 0,005% of one of the new compounds.ALSO:New fluorescent compounds of general formula <FORM:0879610/III/1> in which A and A1 are benz groups or monomethyl substituted benz groups which have 2 vicinal carbon atoms in common with the fused azole rings and in which X and Y are the same or different and represent either an oxygen atom or a group >N - R, in which R is hydrogen or an organic substituent; and their salts and sulphonation products are used as optical brightening agents (a) in dispersions obtained with dispersing agents such as soap, and (b) in combination with detergents in wasting baths.  Suitable detergents are, for example, soaps, salts of sulphonate detergents or non-ionic detergents such as polyglycol ethers, alkyl phenols or fatty amines.