The mechanism of the formation of gem-disulfenyl dichlorides 2 from active methylene compounds 1 and sulfur dichloride (via the chlorodithio derivatives 12) has been elucidated. Reduction of 2 under a variety of conditions yields, in varying amounts, the corresponding 1,2,4,5-tetrathianes 14 with concomitant formation of the tetrasulfides 15 and/or the desulfurated disulfides 16. The pyrolysis of 2 and of the corresponding bis(disulfides) 5 leads to 14, arguably via the 2583 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 structures of the key compounds 2a, 5ad, 5bd, and 16b have been determined by X-ray diffraction.investigation we hoped to be able to shed new light on this reaction sequence.3. Assuming that compounds 2 should be convenient precursors for the formation of dithiiranes 3 and thiosulfines 4, [3] cf. Equation (1), we wished to elaborate this aspect further.4. Cleavage of the 2,2-bis(acyldithio) derivatives 5 (R ϭ COMe or COPh; readily prepared from 2 and the corresponding thiocarboxylic acids) with chlorine should yield the unprecedented 2,2-bis(chlorodithio) compounds 6,
The pyridine-catalyzed reaction between a number of propanedioic acid derivatives 1 and thionyl chloride has been investigated in detail. Contrary to popular belief the straightforward formation of the corresponding α-chloro sulfenyl chlorides 2 is the exception rather than the rule. The propanediamide 2e, not available by the ''standard'' reaction of Our renewed interest in active methylene compound 1 derived α-chloroalkanesulfenyl chlorides 2, [1Ϫ6] [see Equation (1)] stems from the following considerations: 1) Compounds 2 are in principle convenient intermediates for the generation of transient dithiiranes/thiosulfines 3/ 4, [3,7] i.e. via their conversion with thiocarboxylic acids to Scheme 1 [a]
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