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Paper | Regular issue | Vol 51, No. 1, 1999, pp.51-59
Published online, 1st January, 1970
DOI: 10.3987/COM-98-8324
Catalytic Thione-Thiol Rearrangement of Xanthates by 4-Dialkylaminopyridine

Hidetoshi Nakagawa, Masashi Eto, and Kazunobu Harano*

*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan

Abstract

Pyridines bearing electron-donating substituents are useful catalysts for the rearrangement of O,S-dialkyl xanthates (1) to S,S-dialkyl dithiocarbonates (2). The rearrangement was analyzed by semiempirical and ab initio molecular orbital methods. The transition-structure analyses indicate that the pyridine-ring nitrogen of dialkylarninopyridine rather than the dialkylamino nitrogen attacks the O-alkyl carbon of xanthates. The reaction proceeds through an SN2 mechanism to give the dithiolcarbonate anion (RSCOS-) which acts as an actual catalyst.