Patent GB-613983-A (GB)
Title: Manufacture of dyestuffs
Filed: 1946-07-03
Abstract: New dyestuffs are made by treating compounds of the anthraquinone series and related types as hereinafter defined which carry one or more chloromethyl or bromomethyl groups by known methods for replacing the chlorine or bromine atoms of the chloromethyl or bromomethyl groups by sulphonium salt groups. The compounds of the anthraquinone series and related types referred to in this Specification are the coloured compounds which may be represented by the formula <FORM:0613983/IV (c)/1> wherein A and B may be the same or different and may be carbon, nitrogen or sulphur atoms which form part of one or more ring systems condensed with one or both of the phenylene nuclei X and Y, or may be oxygen atoms, and wherein the phenylene nuclei X and Y may carry further substituents other than sulphonic or carboxylic acid groups, or may carry rings condensed with two adjacent carbon atoms of X or Y, provided that when the number of aromatic and quinonoid rings in the condensed ring systems is less than 6 then a heterocyclic ring which forms part of the condensed ring system must carry at least one pendent aryl nucleus (free from sulphonic or carboxylic acid groups) connected directly, or X or Y or any of the condensed rings must carry at least one pendent aryl nucleus (free from sulphonic or carboxylic acid groups) connected through an -O-, -S-, -NH, -NH-CO- or -CO-NH- linkage. Examples of starting materials which may be used in this invention include mono- and bis-(chloromethyl) - acedianthrone, bis - (chloromethyl) - dibenzanthrone, bis - (chloromethyl)-isodibenzanthrone, chloromethyl - indanthrone, the chloromethyl derivative of 8 : 17-di-p-toluidinoindanthrone, the bis-chloromethyl derivative of 2 : 8-diphenyl-11 : 21(N) : 51 : 61(N)-anthraquinonedithiazole and bis - (chloromethyl) - 1 : 4 - dianiline-, 1 : 4-di-p-toluidino-and 1 : 4-di-m-xylidine-anthraquinone, bis-(chloromethyl-perylene-3 : 4 : 9 : 10-tetracarboxy-di-(phenylimide).  The starting materials for use in this invention may be made by reacting the compounds of the anthraquinone series and related types with dichloro-or dibromodimethyl ether in the presence of a condensing agent such as for example sulphuric acid.  Examples of suitable methods are: (1) causing the chloro- or bromo-methyl derivative to react with an alkali metal derivative of a mercaptan and then treating the so-obtained sulphide with such an ester as is known to convert suphides into ternary sulphonium salts, for example with dimethyl sulphate or methyl p-toluenesulphonate.  Suitable mercaptans which may be used in this process include for example methyl-mercaptan, n-butyl mercaptan, cyclohexyl mercaptan, benzyl mercaptan, thiophenol and p-thiocresol; (2) causing the chloro- or bromo-methyl derivative to react with thiourea, treating the product with alkali, reacting the alkali metal salt of the mercaptomethyl derivative so obtained with a dialkyl sulphate to form the alkyl sulphide and reacting the alkyl sulphide with dimethyl sulphate or methyl p-toluene-sulphonate to form the ternary sulphonium salt.  In examples, perylene-3.4.9.10-tetracarboxy - di(phenylimide) are reacted with the sodium compounds of (1) methyl mercaptan; (2) n-butylmercaptan; (3) benzyl mercaptan; (4) p-thiocresol, followed in each case by treatment with dimethyl sulphate or methyl-p-toluenesulphonate.  Also in examples: (5) bis-(chloromethyl) - isodibenzanthrone is reacted with sodium methyl mercaptide followed by treatment with dimethyl sulphate; (6) the isothiouronium salt of bis-(chlormethyl)-isodibenzanthrone is warmed with caustic soda solution, and then treated with dimethyl sulphate and sodium m-nitrobenzenesulphonate, followed by conversion with more dimethyl sulphate into the sulphonium compound.