3-Heteraglutaraldehydes. Part II. Tetrahydrothiophen-3,4-diol 1,1-dioxides and the chemistry of their oxidation product, 3-thiaglutaraldehyde 3,3-dioxide, and its derivatives

Abstract

Reproducible methods are described for the preparation of 3,4-epoxytetrahydrothiophen 1,1-dioxide and trans-tetrahydrothiophen-3,4-diol 1,1-dioxide by acid-catalysed reactions of 2,5-dihydrothiophen 1,1-dioxide with hydrogen peroxide. Earlier confusing accounts of the effect of acetic and formic acids have been clarified. The trans- as well as the more reactive cis-diol was oxidised by periodate to 2,2′-sulphonyldiacetaldehyde. In reaction with nitrogen-, sulphur-, or oxygen-containing nucleophiles, the dialdehyde formed crystalline linear derivatives and the only cyclic compounds readily obtained were 2-acetoxy-6-phenylthio-1,4-oxathian 4,4-dioxide and 1,4-dithian-2,6-diol 4,4-dioxide. 2,2′-Sulphonyldi(acetaldehyde oxime) was dehydrated to sulphonyldiacetonitrile, also prepared by oxidation of the known thiodiacetonitrile. An alternative approach to the dialdehyde by addition of sulphuryl chloride to ethyl vinyl ether was unsuccessful.