The mechanism of the formation of gem-disulfenyl dichlorides 2 from active
methylene compounds 1 and sulfur dichloride (via the chlorodithio derivativ
es 12) has been elucidated. Reduction of 2 under a variety of conditions yi
elds, in varying amounts, the corresponding 1,2,4,5-tetrathianes 14 with co
ncomitant formation of the tetrasulfides 15 and/or the desulfurated disulfi
dcs 16. The pyrolysis of 2 and of the corresponding bis(disulfides) 5 leads
to 14, arguably via the corresponding thiosulfines 4. When compounds 2 are
treated with cyanide ions, reduction takes place rather than substitution,
leading to the corresponding 1,2,4-trithiolanes 19. The halogenation of 5
leads to mixtures of hexathiocanes 17, hexathiepanes 18, and tetrathiolanes
7 which, however, could not be obtained in pure form. The single-crystal s
tructures of the key compounds 2a, 5ad, 5bd, and 16b have been determined b
y X-ray diffraction.