Patent GB-973320-A (GB)
Title: New coumarin compounds
IPC: C08K5/00
Filed: 1962-08-20
Abstract: The invention comprises fluorescent substantially colourless, nitro-group free coumarin compounds of the general formula <FORM:0973320/C1/1> wherein A stands for the residue of a benzene or naphtholene ring and Z stands for the residue of a 5- or 6-membered heterocyclic ring system in which the hetero atom is a nitrogen atom and which may also bear a fused hydrocarbon ring, and the quaternization products thereof, and the method of preparation thereof wherein a nitro-group free aromatic aldehyde of the benzene or naphtholene series carrying a hydroxyl group in the ortho-position or one of its substitution products is reacted with a five or six membered heterocyclic compound which contains at least one nitrogen atom in the ring and carries the radical of acetic acid or of one of its functional derivatives on a nitrogen atom present in the ring and may also carry a fused hydrocarbon ring, except that when the functional derivative of the acetic acid is acetonitrile, the nitrile group of the intermediate is first hydrolyzed and then cyclized and, if desired, the compound obtained is quaternized. Preferred coumarin-compounds are those of the formulae <FORM:0973320/C1/2> and <FORM:0973320/C1/3> where R1 and R2 represent, independently, hydroxyl, C1-C4 alkpxy, acyloxy, amino or acylamino groups and R1 may also be a hydrogen atom, R3 and R4 represent, independently, hydrogen atoms or C1-C4 alkoxy or C2-C6 carbalkoxy groups and X represents the group <FORM:0973320/C1/4> or where Y1 and Y2 represent either, independently, hydrogen atoms or alkoxyalkyl radicals, the alkoxy radicals having 1 to 4 carbon atoms, or together the group -CH2CH2.CH2.CH2- o -CH=CH-CH=CH-, and quaternization compounds thereof. Compounds of the Formula I may be sulphonated.ALSO:Spinning and casting compositions for polyacrylonitrile contain, as optical brightening agents, fluorescent, substantially colourless nitro-group free coumarins of the general formula <FORM:0973320/C3/1> wherein A represents the residue of a benzene or naphthalene ring and Z represents the residue of a 5 or 6 membered heterocyclic ring system in which the hetero-atom is a nitrogen atom and which may also bear a fused hydrocarbon ring and quaternization products thereof.  In an example, polyacrylonitrile is spun from a solution in dimethyl formamide containing 3-(11)-triazolyl-(11 21, 31)-7-methoxy coumarin; such that the product contains 0.25% by weight of the coumarin.ALSO:Fluorescent, substantially colourless, nitro-group free coumarin compounds of the formula <FORM:0973320/D1-D2/1> wherein A represents the residue of a benzene or naphthalene ring and Z represents the residue of a 5 or 6 membered heterocyclic ring system in which the hetero atom is a nitrogen atom and which may also bear a fused hydrocarbon ring, and the quaternisation products thereof are optical brightening agents for natural fibres such as wool, and for polyacrylonitrile, cellulose esters, polyesters, polyamides, polyurethanes, and polyacrylonitrile, and polystyrene.  The aromatic rings in the compounds of formula given above may be substituted by halogen atoms or alkyl, aralkyl, aryl, hydroxy, alkoxy, aralkoxy, aryloxy, acyloxyl, or carbamyloxy groups or -NHCO-alkyl, -NHCO-aryl, -NH . CO . NH- alkyl, -NH . CO . NH- aryl, carbolkoxy, or cyano-groups or carbonamide or sulphonamide groups which can be substituted by alkyl, aralkyl or aryl radicals, acid groups, for example, sulphonic or carboxylic acids, and basic groups, for example, amino or quaternary ammonium groups.  The heterocylic ring system represented by the symbol Z may be substituted by, for example, alkoxyalkyl.  The coumarins may be applied in the conventional manner, e.g. in solution in water or organic solvents or in the form of aqueous dispersion, suitable dispersing agents being the condensation products of naphthalene sulphonic acid and formaldehyde.  In examples, the coumarins are used in aqueous solutions which contain in addition oleyl alcohol sulphonate, a surface active-paraffin sulphonate, formic acid and oxalic acid and sodium chlorite.