Patent GB-914347-A (GB)
Title: Improvements relating to fluorescent coumarin derivatives, quaternary ammonium saltsthereof, and their use
IPC: C07D407/04
Filed: 1959-06-18
Abstract: Polyvinyl chloride, polyvinylidene chloride and polystyrene are dyed yellow to orange shades or are given fluorescent properties by the incorporation of a compound of the formula:- <FORM:0914347/IV(a)/1> where A and B are each bivalent carbocyclic aromatic radicals consisting of at most two fused rings and bound at adjacent ring carbon atoms and X is sulphur or a secondary or tertiary amino group, or of quaternary ammonium compounds thereof of the formula:- <FORM:0914347/IV(a)/2> where Y is an alkyl or substituted alkyl group of 1-4 carbon atoms or a benzyl radical and Z1 is an anion.  In an example (1), a pigment of the above formula, copper phthalocyanine or a monoazo pigment, polyvinyl chloride, dioctyl phthalate and dibutyl tin laurate are mixed, plasticized and extruded to give foils having blue-green or yellow-green shot effects.ALSO:The invention comprises coumarin compounds of the formula:-  <FORM:0914347/IV (b)/1> where A and B each represent a bivalent carboxylic aromatic radical consisting of at most two fused rings and bound at adjacent ring carbon atoms and X is sulphur or a secondary or tertiary amino group, and quaternary ammonium salts thereof of the formula:- <FORM:0914347/IV (b)/2> where Y is an alkyl or substituted alkyl radical of 1-4 carbon atoms or a benzyl radical and Z1 is an anion. The compounds are made by condensing a carbocyclic aromatic aldehyde containing at most two fused rings and a possibly etherified hydroxy group in the orthoposition with a compound of the formula:- <FORM:0914347/IV (b)/3> where Q is a carboxylic acid, carbalkoxy, carbamyl or cyano group, saponifying any ortho-alkoxy group to an ortho-hydroxy group and cyclizing the product to a 2-pyrone compound, and if desired reacting the latter with alkylating agents to form the quaternary ammonium salts.  The compounds may also be made by reacting a compound of the formula:-  <FORM:0914347/IV (b)/4> where R is a carboxylic acid, carboxylic acid halide, carboxylic acid ester or a carbamyl group with an o-phenylene diamine, o-amino-N-alkyl-aniline or o-amino-thiophenol in which the benzene ring may be substituted or may contain a fused benzene ring and if desired reacting the product with alkylating agents to form the quaternary ammonium salt.  A and B are preferably substituted or unsubstituted benzo radicals and the anion Z1 may be chloride, bromide, iodide, sulphate, alkyl, phenyl or p-toluene sulphonate or the double salts of zinc or cadmium chloride with the chloride ion. Examples are given.  The compounds are fluorescent compounds or yellow dyestuffs.  In Examples (1-3), a -benzimidazolyl-(2)-acrylonitriles substituted in b -position by an o-hydroxyphenyl, p-methoxy-, -ethoxy-, -diethylamino- or -acetylamino-o-hydroxyphenyl or b -hydroxy-a -naphthyl radical are made by condensing 2-(cyanomethyl)-benzimidazole with the appropriate o-hydroxy-benzaldehyde or with b -hydroxy-a -naphthaldehyde.  In a further example (8), N-ethyl-N1-(7-dimethylaminocoumarinoyl-3)-o-phenylene diamine is made by condensing 7-N-dimethylamino-coumarin-3-carboxylic acid ethyl ester with N-ethyl-o-phenylene diamine.ALSO:The invention comprises yellow dyestuffs and fluorescent compounds of the formula:- <FORM:0914347/IV (b)/1> where A and B each represent a bivalent carboxylic aromatic radical consisting of at most two fused rings and bound at adjacent ring carbon atoms and X is sulphur or a secondary or tertiary amino group, and quaternary ammonium salts thereof of the formula:- <FORM:0914347/IV (b)/2> where Y is an alkyl or substituted alkyl radical of 1-4 carbon atoms or a benzyl radical and Z1 is an anion.  The compounds are made by condensing a carbocyclic aromatic aldehyde containing at most two fused rings and a possibly etherified hydroxy group in the ortho-position with a compound of the formula:- <FORM:0914347/IV (b)/3> where Q is a carboxylic acid, carbalkoxy, carbamyl or cyano group, saponifying any ortho-alkoxy group to an ortho-hydroxy group and cyclising the product to a 2-pyrone compound, and if desired quaternising the latter.  The compounds may also be made by reacting a compound of the formula:- <FORM:0914347/IV (b)/4> where R is a carboxylic acid, halide or ester group or a carbamyl group with an o-phenylene diamine, o-amino-N-alkyl-aniline or o-amino-thiophenol in which the benzene ring may be substituted or may contain a fused benzene ring and if desired quaternising the product.  Examples are given.  The dyes dye polymeric and copolymeric acrylonitrile fibres (see also Group IV(a)).