Patent GB-444501-A (GB)
Title: Improvements in the manufacture and production of organic sulphur compounds
IPC: C07C317/00
Filed: 1934-10-25
Abstract: Organic sulphur compounds are manufactured by causing vinyl sulphones or sulphoxides containing but one vinyl group attached to a sulphur atom and corresponding to the general formula CH2 = CH.SO2.R or CH2 = CH.SO.R, where R is an alkyl group containing at least 6 carbon atoms or the radicle of a cyclic compound, e.g. hexyl, dodecyl, octodecyl, octodecenyl, an aryl group, such as phenyl, the radicle of a polynuclear isocyclic compound, such as naphthyl, or of a heterocyclic compound, an aralkyl group, such as benzyl or phenylethyl, or a cycloaliphatic radicle, which radicles may contain further substituents, e.g. halogens or alkyl, hydroxyalkyl, nitro, hydroxy, sulphonic or carboxylic groups, to react with compounds containing at least one SH-group, e.g. hydrogen sulphide, alkyl or hydroxyalkyl mercaptans, such as ethyl, propyl, isobutyl, octodecyl or octodecenyl mercaptan, monothioalkylene glycols, dithioalkylene glycols, monothioglycerines, dithioglycerines, and trithioglycerines, aromatic mercaptans such as thiophenol, thiocresols, disulphhydrylbenzene and polysulphhydrylbenzenes, -naphthalenes, -anthracenes and -anthraquinones, mono- and polysulphhydryls of other isocyclic and heterocyclic compounds such as mercaptobenzothiazole and mercaptobenzimidazole, aralkylsulphhydryls such as phenylethylmercaptan, cycloaliphatic mercaptans such as cyclohexylmercaptan, or substitution products of these compounds containing halogen atoms, tertiary combined nitrogen atoms, or alkyl, hydroxylalkyl, nitro, hydroxyl, carboxylic or sulphonic groups, e.g. ethyl-, hydroxyethyl-, nitro-, hydroxy- or dialkylaminothiophenols, -thionaphthols, -sulphydrylanthracenes and -anthraquinones, thioglycollic and thiosalicylic acids and their esters, sulphydrylbenzene-, -naphthalene-, -anthracene-or -benzanthronesulphonic acids; also compounds which also contain at least one nitrogen atom combined with one or more hydrogen atoms, in which case a simultaneous action may take place as described in Specification 442,525.  The reaction may be effected at elevated temperatures, e.g. 60--200 DEG  C., particularly 100--160 DEG  C., at ordinary or increased pressure, if desired in the presence of diluents such as alcohols (ethyl, propyl or benzyl), ketones (acetophenone), ethers (dibenzyl ether), hydrocarbons (toluene, xylene) or halogenated hydrocarbons (chlorobenzene), and advantageously in the presence of substances of basic character as catalysts, e.g. small amounts of alkali metal or alkaline-earth metal oxides, hydroxides, sulphides, carbonates, acetates, phenolates, alcoholates and mercaptides, zinc oxide, cadmium oxide, zinc or cadmium salts of organic acids, especially acetic acid, or organic bases such as pyridine or dimethyl aniline.  The products may be used as dyestuff intermediates, in some cases as dyestuffs themselves, as assistants in the textile industry or for combating animal or vegetable pests.  The products may be oxidized to compounds containing more than one sulphoxide or sulphone group.  Examples describe the interaction of: (1) vinyl-p-tolylsulphone and hydrogen sulphide in the presence of sodium ethylate; (2) vinyl-p-tolylsulphone and ethyl mercaptan in the presence of sodium methylate; (3) vinyl-p-tolylsulphone and p-thiocresol; (4) vinyl-p-tolylsulphone and 2-mercapto-5-chlorotoluene, if desired in the presence of alkali or alkaline-earth metals or sodium, potassium or calcium alcoholates; (5) vinyl-p-tolylsulphone and 1-chloro-8-mercaptonaphthalene; (6) vinyl-p-tolylsulphone and thioglycollic acid in the presence of sodium carbonate; (7) vinyl-p-tolylsulphone and mercaptobenzothiazole, preferably in the presence of sodium ethylate or sodium or potassium hydroxide; (8) vinyl-p-tolylsulphone and 1- or 2-mercaptoanthraquinone in the presence of sodium ethylate; (9) 1-chloro-8-naphthylvinylsulphoxide and p-thiocresol in the presence of sodium methylate; (10) vinyloctodecylsulphoxide, or other vinyl sulphoxides, e.g. vinylhexyl or dodecylsulphoxide, and thioglycollic acid; also other vinyl sulphoxides, e.g. vinyl-p-tolylsulphoxide, and other compounds containing SH-groups, e.g. hydrogen sulphide or mercaptobenzothiazole.  Specification 442,524 also is referred to.  A sample has been furnished under Sect. 2 (5) of a product obtained by reacting vinyl-p-tolylsulphone with o-aminomercaptobenzene.  The Provisional Specification comprises the use of alkenyl sulphones and sulphoxides in general, and contains an example in which vinylethylsulphoxide is reacted with p-thiocresol.