A General Strategy for Elaboration of the Dithiocarbonyl Functionality, -(C=0)SS-: Application to the Synthesis of Bis(chlorocarbonyl)disulfane and Related Derivatives of Thiocarbonic Acids

George Barany, Alayne L. Schroll, Andrew W. Mott, David A. Halsrud

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Abstract

A variety of sulfenyl chlorides have been reacted with a variety of alkoxythiocarbonyl compounds to give adducts which then lose (spontaneously, or upon thermolysis, or in the presence of a Lewis acid catalyst) the alkyl chloride to provide an assortment of dithiocarbonyl compounds in good to excellent yields. The preparations of bis-(chlorocarbonyl)disulfane (1), ((trichloromethyl)dithio)carbonyl chloride (2), ((alkoxycarbonyl)dithio)carbonyl chlorides (3 and 4), and (((alkylthio)carbonyl)dithio)carbonyl chlorides (5 and 6) by this methodology were optimized; some of the (alkoxydichloromethyl)disulfanyl adducts, e.g., ROCCl2SS(C=O)C1 (10) and ROCCl2SS(C=O)OR′ (54), were reasonably stable and could be isolated. All new compounds were characterized by analytical data, 1H and 13C NMR, ER, UV, and mass spectrometry, and high-yield derivatizations with alcohols or N-methylaniline. The reaction with N-methylaniline was also adapted to a rapid, convenient, and precise analytical-scale assay of mixtures of compounds containing acid chloride and/or sulfenyl chloride functionalities. The kinetics, mechanism, and stereochemistry of the dithiocarbonyl synthesis are discussed.

Original languageEnglish (US)
Pages (from-to)4750-4761
Number of pages12
JournalJournal of Organic Chemistry
Volume48
Issue number24
DOIs
StatePublished - Dec 1983

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