1,6-Anhydro-3-deoxy-4-S-ethyl-4-thio-β-D-erythro-hexopyranos-2-ulose (2) reacted with carbon disulphide and iodomethane to furnish 1,6-anhydro-3-[bis(methylthio)methylene]-3-deoxy-4-S-ethyl-4-thio-β-D-erythro-hexopyranos-2-ulose (3). Treatment of2with dimethylformamide dimethyl acetal yielded 1,6-anhydro-3-deoxy-3-(dimethylaminomethylene)-4-S-ethyl-4-thio-β-D-erythro-hexopyranos-2-ulose (4). The reactions of3with malononitrile and hydrazine hydrate furnished 1,6-anhydro-3-[bis-(methylthio)methylene]-2-(dicyanomethylene)-2,3-dideoxy-4-S-ethyl-4-thio-β-D-erythro-hexopyranose (7) and (1R,7R,8R)-2,3,5,6(2,4,5,6)-tetradehydro-7-ethylthio-5-methylthio-3,4-diaza-10,11-dioxatricyclo[6.2.1.02,6]undecane (8a,b), respectively.