Patent GB-813843-A (GB)
Title: Process for improving the appearance of polymeric synthetic substances, and the resulting products
IPC: D06L4/629
Filed: 1956-03-02
Abstract: Compounds of the general formula <FORM:0813843/IV (b)/1> or tautometic forms thereof, in which R1 and R2 are alkyl groups of 1 to 4 C atoms, R3 to R10 are hydrogen or substituents, which are both nonionogenic and non-chromophoric, X is sulphur or a hydrocarbon radical having the bonds shown at the same carbon atom, and Y is the anion of an inorganic or organic acid, may be obtained by condensing o - methyl - N - alkyl cyclammonium salts with o-alkylmercapto-N-alkyl cyclammonium salts while splitting off alkyl mercaptan.  Thus, N-alkyl-2-methyl benzoxazolium salts (which may be substituted in the benzene ring) may be condensed in the presence of dimethyl or diethyl sulphate with 2-methylmercaptobenzthiazoles, or 2-methylmercaptobenzoxazoles may be condensed with 2-methyl-N-benzthiazolium salts or with 2-methyl indolenines.  R3 to R10 may be methyl, ethyl, isopropyl, tert.-butyl, tert.-amyl, benzyl, phenyl, fluorine, chlorine, methoxy, ethoxy, benzyloxy, phenyloxy, alkyl sulphonyl, aryl sulphonyl, cyano, acylamino, acyloxy, acid ester or acid amide groups.  X may be dimethyl methylene and Y may be the anion of a halogen hydracid, sulphuric acid, sulphuric acid half ester or benzene or toluene sulphonic acid.  In examples: (1) (3-methyl-benzthiazolo)-(3-methyl or 3,5-dimethylbenzoxazolo)-monomethine cyanine-p-toluene sulphonate is obtained by quaternizing, at 120-130 DEG  C., 2-methyl-benzthiazole with p-toluenesulphonic acid methyl ester and condensing with 2-methylmercaptobenzoxazole or 2-methylmercapto-5-methylbenzoxazole and p-toluene sulphonic acid methyl ester at 140-150 DEG  C., methyl mercaptan being split off; alternatively, 2-methyl benzoxazole or 2,5-dimethyl-benzoxazole may be quaternized with p-toluene-sulphonic acid methyl ester and then condensed with 2-methylmercapto-benzthiazole and p-toluene sulphonic acid methyl ester; (2) (1,3,3-trimethyl-indolo)-(3 - methyl - or 3,5 - dimethylbenzoxazolo) - monomethine cyanine acetate is obtained by quaternizing, at 120-125 DEG  C., 2-methylmercaptobenzoxazole or 2-methylmercapto-5-methylbenzoxazole with p-toluene sulphonic acid methyl ester and condensing at 150-155 DEG  C. with 2,3,3-trimethyl-indolenine or with 1,3,3-trimethyl-2-methylene indole and p-toluene sulphonic acid methyl ester while splitting off methyl mercaptan.  Other compounds which may be prepared are those in which R1 and R2 are methyl, X is S, Y is a para-toluene sulphonate anion, R3, R4 and R6-10 are hydrogen and R5 is chlorine, phenyl, sulphonamide, N : N-dimethylsulphonamide, methyl sulphone or methoxy; R1 and R2 are methyl, X is S, R3-10 are hydrogen and Y is a benzenesulphonate or a sulphate anion; R1 and R2 are propyl, X is S, R3, R4 and R6-10 are hydrogen, Y is a para-toluene sulphonate anion and R5 is hydrogen or methyl; R1 and R2 are ethyl, R3 and R5 are methyl, R4 and R6-10 are hydrogen, X is S and Y is a benzenesulphonate anion; R1 and R2 are methyl, R3, R4 and R6-10 are hydrogen, Y is a para-toluene sulphonate anion, X is dimethyl methylene and R5 is methoxy, phenyl, sulphonamide, N : N-dimethyl-sulphonamide and methyl sulphone; R1 and R2 are methyl, R8 is chlorine, R3, R4, R6, R7, R9 and R10 are hydrogen, X is dimethylmethylene, Y is a para-toluenesulphonate anion and R5 is hydrogen or methyl; and R1 and R2 are methyl, R3, R4, R6, R7, R9 and R10 are hydrogen, X is S, Y is a para-toluenesulphonate anion, R5 is hydrogen or methyl and R8 is chlorine or methyl.  Specification 424,559, [Group IV], is referred to.ALSO:Materials consisting wholly or in part of acrylonitrile in polymeric or copolymeric form are treated with from 0.001 to 0.2 per cent, calculated on the weight of the material, of a compound of the general formula <FORM:0813843/IV (c)/1> or a tautomeric form thereof, wherein R1 and R2 are alkyl groups of 1 to 4 carbon atoms, R3 to R10 are hydrogen or non-ionic and non-chromophoric substituents, X is sulphur or a hydrocarbon radical containing the bonds shown at the same carbon atom and Y is an anion of an organic or inorganic acid.  The material treated may be textile fibres and the compound may be in aqueous solution.  R3 to R10 may be methyl, ethyl, isopropyl, tert.-butyl, tert.-amyl, benzyl, phenyl, fluorine, chlorine, methoxy, ethoxy, benzyloxy, phenyloxy, alkyl sulphonyl, aryl sulphonyl, cyano, acylamino, acyloxy, acid ester or acid amide groups, X may be dimethyl methylene and Y may be the anion of a halogen hydracid, sulphuric acid, sulphuric acid half ester or benzene or toluene sulphonic acid.  In Example (1) polyacrylonitrile yarn is treated with (3-methyl-benzthiazolo)-(3-methyl-benzoxazolo)-monomethine cyanine-p-toluene sulphonate in aqueous solution containing acetic acid at 50 DEG  C. raised to 100 DEG  C.  Other examples give similar treatments with different compounds.  The compounds may be prepared by condensing o-methyl-N-alkyl cyclammonium salts with o-alkyl-mercapto-N-alkyl cyclammonium salts while splitting off alkyl mercaptan.  Thus, N-alkyl-2 methyl benzoxazolium salts (which may be substituted in the benzene ring) may be condensed in the presence of dimethyl or diethyl sulphate with 2-methyl mercaptobenzthiazoles, or 2-methylmercaptobenzoxazoles may be condensed with 2-methyl-N-benzthiazolium salts or with 2-methyl indolenines.  In examples: (1) (3 - methyl - benzthiazolo) - (3 - methyl or 3.5 - dimethyl benzoxazolo) - monomethine cyanine-p-toluene sulphonate is obtained by quaternizing, at 120-130 DEG  C., 2-methyl-benzthiazole with p-toluene sulphonic acid methyl ester and condensing with 2-methylmercapto-benzoxazole or 2 - methylmercapto - 5 - methyl-benzoxazole and p-toluene sulphonic acid methyl ester at 140-150 DEG  C., methyl mercaptan being split off; alternatively, 2-methyl benzoxazole or 2.5-dimethyl-benzoxazole may be quaternized with p-toluene sulphonic acid methyl ester and then condensed with 2-methylmercapto-benzthiazole and p-toluene sulphonic acid methyl ester; (2) (1.3.3-trimethylindolo) - (3 - methyl- or 3.5 - dimethyl - benz -oxazolo)-monomethine cyanine acetate is obtained by quaternizing, at 120-125 DEG  C., 2-methylmercapto - benzoxazole or 2 - methylmercapto - 5 - methyl benzoxazole with p-toluene sulphonic acid methyl ester and condensing at 150-155 DEG  C. with 2.3.3-trimethyl indolenine or with 1.3.3-trimethyl-2-methylene indole and p-toluene sulphonic acid methyl ester while splitting off methyl mercaptan.  A long list of other compounds is given.  The method of obtaining the compounds is as described in Specification 424,559, [Group IV].