Preparation of organic sulfur compounds

摘要

Thio-ethers and secondary mercaptans are prepared by reacting H2S with ethylenically unsaturated compounds in the presence of catalytic amounts of (1) a diamino sulphide, or (2) sulphur with certain basic compounds. The ethylenically unsaturated compounds are of the general formula wherein x and y are integers of 0-5; R is hydrogen or alkyl, preferably C1-C5; R1 and R2 are hydrogen or alkyl, preferably C1-C5, and can be linked by a covalent bond providing x + y = 2 or more; R3 is hydrogen, alkyl, preferably C1-C5, an -OR group, or, if the catalyst is to be sulphur, an -N(R)2 group. The diamino sulphides are of the formula wherein the R4 group, which may be the same or different, are alkyl, aryl, cycloalkyl, aralkyl, or alkaryl, preferably C1-C8, and n is 1 or 2, and they are suitably used at 0.25-15 g./mole with reference to the ethylenically unsaturated compound. They may be employed with basic catalysts, viz. ammonia, primary, secondary, or tertiary alkyl amines, alkyl being C1-C8, suitably at levels of 0.25-30 g./mole. Alternatively, sulphur, at 0.25-5 g./mole with a basic substance which is as above, or alkali metal hydroxide, at 0.25-30 g./mole, is employed; when the ethylenically unsaturated compound is an amine, additional base is not essential. Reaction temperature is 25-150 DEG C., and H2S is used at 1-10 moles/mole of unsaturated compound; solvents or diluents (e.g. water or low M.W. alcohols, ethers, ketones &c.) may be present. Examples are given for reaction of the following with H2S: (1) allyl alcohol; (2) octene-1; and (3) allylamine; using various catalyst systems. Also the catalyst, bis-(dimethylamino) disulphide is prepared, by reaction of dimethylamine with sulphur mono-chloride in the presence of sodium hydroxide.