Sulphides divinyl

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. 

With Potassium Hydroxide, (a) In Alcoholic Solution. By the action of a 20% solution of potassium hydroxide in alcohol, dichloroethyl sulphide is converted into divinyl sulphide ... 

Divinyl sulphide is also formed by the abstraction of two molecules of water from one of thiodiglycol. On treatment with gaseous hydrochloric acid, it forms aa dichloroethyl sulphide, a colourless liquid with a penetrating odour, which boils at 58 5° C. at 15 mm. mercury and has a density of 1-1972 at 15° C. On treatment of divinyl sulphide in aqueous solution with hydriodic acid, 8/3 diiodoethyl sulphide is formed (see p. 244). With chlorine various chlorinated compounds are formed, for instance, a/3 dichloroethyl vinyl sulphide ... 

Divinyl sulphide is formed quantitatively according to Helfrich when dichloroethyl sulphide is treated with sodium ethylate,... 

It is produced in the reaction between dichloroethyl sulphide and the Grignard reagent (see p. 248), and also, together with dithiane methiodide, by the action of methyl iodide on dichloroethyl or dibromoethyl sulphide. It has also been obtained by the action of hydriodic acid on an aqueous solution of divinyl sulphide. ... 

Divinyl ether itself presents a fairly complex case one detailed study claimed that the decomposition of the ether-phosphorus pentachloride complex with SO2 yields the phosphonic dichlorides 78-80 together with vinyl dichlorophosphate whilst a more recent study demonstrated that treatment of the intermediate complex with SO2 yielded 81, and with Asp3 yielded 82 in each case, a co-product was [2-(l-chloroethoxy)vinyl]phosphon-ic dichloride (78). The action of phosphorus pentachloride on the sulphide 83 presumably proceeds through 84, although in the work-up procedures thus far adopted, dehydrohalo-genation occurs to give 85 (R = Cl) ... 

The iV-acyl-imine (426) cyclo-adds to aromatic aldehydes and nitriles to give 1,3,5-dioxazines and 1,3,5-oxadiazines, respectively. Treatment of divinyl sulphide with thiourea affords the 1,3,5-dithiazine (427). ... 

DiethyI-2,4-dimethyl-3-siIathietan is prepared from divinyl sulphide by its reaction with diethylsilane. Tetramethyl-2,4-disila-l,3-dithietan disproportionates with octamethyl-l,4-dithia-2,3,5,6-tetrasilacyclohexane to give hexamethyl-1,3-dithia-2,4,5-trisilacyclopentane. ... 

Typical reactions of mustard with nucleophiles are shown in Figure 5. Strong bases such as KOH will cause elimination of HCl from the material to yield divinyl sulphide. One equivalent of base will cause elimination in one mustard sidearm resulting in a vinyl chlorethyl thioether which itself can undergo a whole series of hydrolytic equilibria. Mustard will react with primary amines to produce cyclic products and will also react with higher amines and amino acids. Mustard reacts with sulphide ion to produce a cyclic dithiane. This material is of interest since it is a useful analytical indicator of the former presence of mustard in old environmental samples and munitions. 

Addition to Multiple Bonds. Kinetic measurements of the addition of acrylic acid and its methyl ester have shown this reaction to be first-order in both thiourea and alkenes. Divinyl sulphides (27) and (28) are formed from the corresponding alkynes and thioureas, but rearrangement is observed in the reaction with diphenylacetylene to give (PhaC=CH)2S. S-Vinyl-isoselenourea (29) is obtained from the addition of selenourea to I,3-diphenylprop-2-yn-l-one,... 

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