Patent GB-927533-A (GB)
Title: Derivatives of ªÐ-[coumarinyl-(3)]-phenyl carbamic acid
IPC: C08K5/16
Filed: 1959-12-17
Abstract: A dispersion for use in brightening fibres and fabrics comprises an aqueous solution of equal parts by weight of a fatty alcohol sulphate and a fatty alcohol polyglycol ether to which is added (e.g. as a solution in dioxane) a para-(coumarinyl3)-phenyl carbonate or urea brightening agent of the formula:  <FORM:0927533/III/1> wherein X represents -OR or -NR1R2, R denoting an alkyl, aralkyl or aryl radical, any of which may bear optional substituents such as halogen, alkoxy or dialkylamino, and R1 and R2 independently represent hydrogen or an alkyl, aralkyl or aryl radical, any of which may bear optional substituents such as halogen, hydroxy, alkoxy or sulphonic acid groups, and wherein the phenyl-coumarinyl inacty may be substituted by, for example, halogen, alkyl, cyano, alkylsulphone, sulphonamide, carboxy or sulphonic acid groups.  The pH of the dispersion may be adjusted by the addition of acetic acid.ALSO:Spinning or pouring masses serving for the production of synthetic fibres, filaments or foils from materials such as polyacrylonitrile, cellulose acetate, polyamides and polyesters are brightened by the addition of para-(coumarinyl-3)-phenyl carbamate or urea brightening agents of the formula:- <FORM:0927533/IV(a)/1> wherein X represents -OR or -NR1R2, R denoting an alkyl, aralkyl or aryl radical, any of which may bear optional substituents such as halogen, alkoxy or dialkylamino, and R1 and R2 independently represent hydrogen or an alkyl, aralkyl or aryl radical, any of which may bear optional substituents such as halogen, hydroxy, alkoxy or sulphonic acid groups, and wherein the phenyl-coumarinyl moiety may be substituted by, for example, halogen, alkyl, cyano, alkylsulphone, sulphonamide, carboxy or sulphonic acid groups.  The above brightening agents may also be prepared in situ in the materials to be brightened.  Thus para-(coumarinyl-3)-phenyl isocyanates may be added to such materials together with alcohols or phenols of the formula R.OH or amines of the formula NH.R1R2.  The isocyanate reactant may also be introduced as an addition compound with a phenol or a compound containing a reactive methylene group, such as malaic acid diethyl ester.  Prior to the formation of polymers using glycol or diamine reaction components, the isocyanate reactants may be added to the pre-polymer mix, so that during the polymerization process it reacts with some of the glycol or diamine component to give the required brightening agent.  In an example a mixture of polyacrylonitrile and brightening agent in dimethyl formamide is spun using a dry spinning process and the resulting filaments are stretched in boiling water prior to heating in a bath containing sodium chlorite and oxalic acid.ALSO:The invention comprises para-coumarinyl-3)-phenyl carbamate or urea brightening agents of the formula:-  <FORM:0927533/IV(a)/1> wherein X represents -OR or -NR1R2, R denoting an alkyl, aralkyl or aryl radical, any of which may bear optional substituents such as halogen, alkoxy or dialkylamino, and R1 and R2 independently represent hydrogen or an alkyl, aralkyl or aryl radical, any of which may bear optional substituents such as halogen, hydroxy, alkoxy or sulphonic acid groups, and wherein the phenylcoumarinyl moiety may be substituted by, for example, halogen, alkyl, cyano, alkylsulphone, sulphonamide, carboxy or sulphonic acid groups. The above compounds are prepared by reacting 3-(para-aminophenyl)-coumarin or derivatives thereof bearing substituents in the phenyl or coumarin radicals with the chloroformic acid esters of alcohols or phenols corresponding to the formula R.OH or with pyrocarbonic acid esters of alcohols of the formula R.OH. Alternatively, the above compounds may be prepared by reacting para-(coumarinyl-3)-phenyl isocyanate or derivatives thereof bearing substituents in the phenyl or coumarin radicals with alcohols or phenols of the formula R.OH, or with amines of the formula HNR1R2. The above compounds may also be prepared in situ in the materials to be brightened.  Thus the above-mentioned isocyanates may be added to such materials together with alcohols or phenols of the formula R.OH or amines of the formula NH.R1R2.  The isocyanate may also be introduced as an addition compound with a phenol or a compound containing a reactive methylene group, such as malonic acid diethyl ester.  Prior to the formation of polymers using glycol or diamine reaction components, the isocyanate reactants may be added to the pre-polymer mix, so that during the polymerization process it reacts with some of the glycol or diamine component to give the required brightening agent.  3-(Para-aminophenyl)- coumarin starting materials are prepared by reduction of the corresponding 3-(para-nitrophenyl)-coumarins.  3-(Para-nitrophenyl)-coumarins are prepared by condensing para-nitrophenyl-acetonitrile with appropriate ortho-hydroxybenzaldehydes followed by cyclization in glacial acetic acid or by coupling an appropriate coumarin with diazotised para-nitraniline.ALSO:Fibres, fabrics, foils or filaments of polyacrylonitrile, cellulose acetate, polyamides and polyesters are brightened by treatment with aqueous or organic solutions, aqueous dispersions or detergents containing para-(coumavinyl-3)-phenyl carbamate or urea brightening agents of the formula <FORM:0927533/IV(a)/1> wherein X represents -OR or -NR1R2, R denoting an alkyl, aralkyl or aryl radical, any of which may bear optional substituents such as halogen, alkoxy or dialkylamino, and R1 and R2 independently represent hydrogen or an alkyl, aralkyl or aryl radical, any of which may bear optional substituents such as halogen, hydroxy, alkoxy or sulphonic acid groups, and wherein the phenyl-coumarinyl moiety may be substituted by, for example, halogen, alkyl, cyano, alkylsulphone, sulphonamide, carboxy or sulphonic acid groups.  In examples (1) polyacrylonitrile is spun from a solution in dimethyl formamide also containing one of the above brightening agents, the fibres are stretched in boiling water and are then heated in a bath containing sodium chlorite and oxalic acid before rinsing and drying; (2) fibres or fabrics of polyacrylonitrile, cellulose acetate and polyamides are heated with a mixture of dioxane, brightening agents, water, fatty alcohol sulphonate, fatty alcohol polyglycol ether and optional acetic acid, followed by rinsing and drying; and (3) fibres or fabrics of polyacrylonitrile and polyamides are heated with aqueous acetic acid solutions of brightening agents, followed by rinsing and drying.