Patent GB-786234-A (GB)
Title: Improvements relating to substituted ureidocoumarin compounds and their use
IPC: C07D311/16
Filed: 1955-11-10
Abstract: The invention comprises coumarin derivatives of the formula: <FORM:0786234/IV (b)/1> where R1 is NH2 or the residue of a primary or secondary amine and R2 is phenyl which may be substituted by halogen or alkyl.  These are made by condensing (a) a benzaldehyde 2-substituted by hydroxyl or group convertible thereto (e.g. alkoxy) and 4-substituted by acylamino or nitro with (b) phenyl-acetic acid or a derivative thereof (e.g. ester or nitrile) which may be nuclearly substituted by halogen or alkyl, to give the corresponding a b -di-phenylacrylic derivative, if necessary liberating the 2-hydroxyl group, ring-closing to the coumarin, converting the acylamino or nitro group to amino and reacting the latter either with a suitable carbamic acid derivative to give the urea direct or with phosgene to form the isocyanate and treating this with ammonia or a primary or secondary amine.  Dealkylation of the 2-alkoxy group can be effected with aluminium chloride or with hydrogen bromide in acetic acid and this often closes the coumarin ring simultaneously. If not ring-closure can be brought about with a hydrogen halide in a lower fatty acid, zinc chloride or phosphoric acid.  The 4-acylamino group may itself be a ureido group in which case the conversion to amino and re-acylation is omitted.  Examples are given of the preparation of compounds of the above formula in which R2 is amino, methylamino, dimethylamino, ethylamino, propylamino, ethanolamino, dimethylaminoethylamino and dimethylaminopropylamino and R2 is phenyl, p-tolyl and p-chlorophenyl.  A table is given of further products in which R1 is methoxypropylamino, isopropanolamino, methylethanolamino, carboxymethylamino, sulphoethylamino, sulphoanilino and sulphotoluidino.  The preparation of the following intermediates is described: 2 - methoxy - 4 - acetylamino benzaldehyde (by N - acetylation), a  - phenylb  - (2 - methoxy - 4 - acetylaminophenyl)acrylonitrile, 3 - phenyl - 7 - aminocoumarin, 3-phenyl - 1 - acetylaminocoumarin (the last two being interconverted), a  - phenyl - b  - (2 - hydrdroxy - 4 - acetylaminophenyl) - acrylamide, a (p - chlorophenyl) - b  - (2 - methoxy - 4 - acetylaminophenyl) - acrylonitrile, 3 - (p - chlorophenyl) - 7 - aminocoumarin, a  - (p - tolyl) - b (2 - methoxy - 4 - acetylaminophenyl) - acrylonitrile, 3 - (p - tolyl) - 7 - aminocoumarin, 3-phenylcoumarin - 7 - isocyanate, 3 - (p - chlorophenyl) - coumarin - 7 - isocyanate and 3 - (p-totyl) - coumarin - 7 - isocyanate.ALSO:Coumarin derivatives of the formula: <FORM:0786234/IV (b)/1> where R1 is NH2 or the residue of a primary or secondary amine and R2 is phenyl (which may be substituted by halogen or alkyl) are used for the optical brightening of textile materials.  In examples: (1) wool flannel is treated with a bath containing N - (b  - hydroxyethyl) - N1-(3 - phenyl - coumarinyl - 7) - urea and Glauber's salt; (2) nylon is treated with the same compound or with the N-methyl analogue; (3) woollen goods are treated with a bath as in (1) containing also sodium dodecyl sulphate; (4) polyacrylonitrile is treated with N-(b -dimethylaminoethyl) - N1 - (3 - phenyl - coumarinyl-7)- urea in an acetic acid bath.  Other compounds are also mentioned as suitable for the above materials and also for polyurethane, cellulose and cellulose acetate fibres.ALSO:Coumarin derivatives of the formula: <FORM:0786234/IV (a)/1> where R1 is NH2 or the residue of a primary or secondary amine and R2 is phenyl (which may be substituted by halogen or alkyl) are incorporated in synthetic polymers such as polyvinyl chloride, polyacryonitrile, polystyrene or polyethylene and worked up to give fluorescent plastic foils. Many suitable compounds are mentioned.