No abstract

No abstract

The aliphatic ethylene sulphides often undergo the same ring-opening reactions as do the ethylene oxides, but polymerisation usually prevents the isolation of much of the initial product of ring fission. However, good yields of 2-chlorothiols and 2-chlorothio-esters are obtained by reaction with concentrated hydrochloric acid and acyl chlorides ; potassium thioalkoxides and potassium hydrogen sulphide combine readily t o form the expected mercapto-sulphides and dithiols ; and acetic acid gives a low yield of the 2-mercaptoalkyl acetate.A characteristic feature of aliphatic ethylene sulphides is the inability of the 3-membered ring to exist with the sulphur atom in the higher-valent state; ring opening always occurs when the preparation of these derivatives is attempted. Sulphoxides and sulphones are not formed, and triethyl-and triphenyl-phosphine and triethyl phosphite remove the sulphur atom to form the iP:S compound. Methyl iodide breaks up ethylene sulphides, the larger ones giving good yields of trimethylsulphonium iodide, the smaller ones mixtures of salts containing small amounts of this iodide. THE only survey of ethylene sulphides seems to be in the monograph by A. Schonberg in AhrensVortriige, Heft 19, Enke, 1933, on " Thioketone, Thioacetale und Aethylensulfide," where, however, the section (pp. 66 to 72) on ethylene sulphides is almost entirely confined to aromatic derivatives.It has latterly been realised that ethylene sulphides may have industrial applications, e.g., as synthetic polymers, and during the last eight years the results of some technical studies have been described in patents. The present investigation of aliphatic ethylene sulphides deals partly with their preparation, but is chiefly concerned with their reactions and properties, many of which could not have been deduced, by analogy, from a knowledge of the chemistry of ethylene oxides.Pqtuzrution of Ethylene SuZphides.-The first preparations of authentic ethylene sulphides are due to Delkpine (Bull.

No abstract

Alkali thioalkoxides react with extreme ease with ethylene oxides to form the 2-hydroxyalkyl sulphides, and alkali sulphides react in a similar manner. With a simple ethylene oxide, potassium o-aminothiophenoxide gives a dihydrobenz-1 : 4-thiazineJ and with a glycidic ester forms a 3-ketodihydrobenz-1 : 4-thiazine substituted in the 2-positionJ and this compound is readily hydrolysed to the 3-ketodihydrobenzthiazine. Ethylene oxide reacts with thiosulphates as well as with neutral sulphites to form an isethionate. Some simple ethylene oxides are converted into the corresponding sulphides not only by thiourea but by a number of compounds containing the S:C*NH, or H S C N H groups, such as xanthamide, thioacetamide, and thiobarbituric acid. Thiourea with stilbene oxide yields stilbene and sulphur and no stilbene sulphide, and this type of reaction, sometimes accompanied by the formation of thiazolidine compounds, can occur with ethylene oxides containing an acyl group.THIS paper describes the continuation and extension of the work of Culvenor, Davies, and Pausacker (J., 1946, 1050) on the reactions of some simple ethylene oxide types with thiourea, xanthates, and related compounds. It has now been found that cyclohexene oxide or epichlorohydrin reacts not only with thiourea and thiocarbanilide but also with xanthamide, thioacetamide, thiobenzamide, and thiobarbituric acid to form the ethylene sulphide and the oxygen analogue of the thio-compound used.Thiourea with butadiene monoxide and 4-methylcyclohexene oxide gives the expected sulphides, but stilbene oxide yields only stilbene, sulphur, and urea, no cyclic compound being detected. Apparently, unlike the stable tetraphenylethylene sulphide (Schonberg and Barak, J , , 1939, 1074), stilbene sulphide is unstable. The presence of strongly polar groups in ethylene oxides hinders the formation of ethylene sulphides when thiourea in alcoholic or aqueousalcoholic solution is used. Benzylideneacetone oxide (4-phenyl-3 : 4-epoxybutan-2-one) gives a yellow amorphous solid containing nitrogen and sulphur. Bodforss (Ber., 1918, 51, 212) found that 1-benzoyl-2-m-nitrophenylethylene oxide gave a nitrothia.zolidine, m. p. 176", but a repetition of his work shows that only a small amount of this is formed, most of the pure product obtained being m-nitrobenzylideneacetophenone. This, and selenium, are the products from 1-benzoyl-2-m-nitrophenylethylene oxide and potassium selenocyanate, and similarly stilbene oxide yields stilbene and selenium only.The condensation of alcoholic thiourea with ethyl dimethylglycidate produces a thiazolidine derivative, m. p. 285", which is being investigated, while with ethyl phenylglycidate at ordinary temperatures the products are ethyl cinnamate, sulphur, and urea. Xanthamide, thioacetamide, and thiobenzamide also give ethyl cinnamate and sulphur. Ethylene oxides are most reactive towards solutions of alkali hydrogen sulphides and alkali derivatives of thiols. Thus cyclohexene oxide and potassium hydrogen sulphide in the cold give 2-merca~tocy...