Reactions of Unsaturated Sulphides

Cleavage of alkenyl sulphides into alkenethiolates with sodium in liquid ammonia, and further studies (see Vol. 1, p. 53) of the conversion of an alkynyl sulphide R S-C=C R into the thioamide R CHa CS -NR 2 by heating with a secondary amine to 150 have been reported. Sulphide cleavage into (R C=C S - R C=C=S) precedes addition of the amine, and the reaction product is R C(NR 2)==CH SR for primary alkyl substrates, for which the reaction conditions are too mild to cause C—S bond cleavage. 

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Benzoyl hydroperoxide was used for the conversion of divinyl sulphide into divinyl sulphoxide by Levin as early as 1930. In 1954 Bateman and Hargrave reported that saturated sulphides may be oxidized to sulphoxides by means of cyclohexyl or t-butyl hydroperoxide. These authors found that in both polar and non-polar solvents oxygen transfer occurred to give quantitative yields of sulphoxides over a wide range of experimental conditions according to equation 7. It was also reported that a quantitative yield of sulphoxides was obtained from the reaction of unsaturated sulphides with t-butyl and cyclohexyl hydroperoxides in methanol. With t-butyl hydroperoxide in benzene the sulphoxide yield was in no case stoichiometric, varying from 90 to 5% under the condition chosen. 

Thioaldehydes and Thioketones. (i) Synthesis of simple aliphatic thioalde-hydes and thioketones by reductive cleavage reactions of unsaturated sulphides. (ii) Photochemistry of thioketones. (iii) Synthesis of... 

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