THE PREPARATION OF 1,2,3,5-DITHIADIAZOLIUM CHLORIDES FROM THE REACTION OF NITRILE SULFIDES WITH THIAZYL CHLORIDE

Adamantyl-1,3,4-oxathiazol-2-one has been prepared for the first time and from it l-adamantyl nitrile sulphide has been generated. Characterisation data are presented, including the X-Ray crystal structure of the oxathiazolone. (Crystal data for C12H15NO2S: monoclinic, space group P2(1)/c, a = 11.334(2) Angstrom, b = 7.344(1) Angstrom, c = 14.373(2) Angstrom, beta = 107.74(1)degrees, V = 1139.5(3) Angstrom(3), Z = 4, R = 0.042). The planar heterocyclic ring is similar to structures observed in the gas phase for other oxathiazolone derivatives. The nitrile sulphide was reacted with dimethyl-acetylene dicarboxylate in situ to give an isothiazole derivative. The X-Ray crystal structure of 3-adamantyl-4,5-bis(methoxycarbonyl)-isothiazole has been obtained. (Crystal data for C17H21NO4S: monoclinic, space group P2(1)/n, a = 7.305(4) Angstrom, b = 7.339(4) Angstrom, c = 31.552(4) Angstrom, beta = 92.75(3)degrees, V = 1690(1) Angstrom(3), Z = 4, R = 0.079). A general cycloaddition reaction was discovered between the nitrile sulphides and thiazyl chloride to give 1,2,3,5-dithiadiazolium chlorides. The structure of the new 4-adamantyl-1,2,3,5-dithiadiazolium chloride was confirmed by reduction to the 4-adamantyl-1,2,3,5-dithiadiazolyl for which the X-Ray crystal structure has been determined. (Crystal data for C11H15N2S2: monoclinic, space group C2, a = 10.284(4) Angstrom, b = 8.651(2) Angstrom, c = 13.669(2) Angstrom, beta = 112.83(1)degrees, V = 1120.9(4) Angstrom(3), Z = 4, R = 0.042). The radical adopts a twisted dimer structure in the solid state which is similar to the structures observed for other alkyl derivatives.