Selective Formation of Five-Membered Heterocyclic Products by Anodic Oxidation of Alkyl Isothiocyanates (RNCS)in Dichloromethane and Their Thermal Isomerization and Decomposition

James Y. Becker, Shimon Yatziv

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Abstract

Anodic oxidation of primary and secondary alkyl isothiocyanates (RNCS) in dichloromethane yielded two isomers of five-membered heterocyclic products, 4-alkyl-5-(alkylimino)-1,2,4-dithiazolidine-3-one 2 and 2,4-dialkyl-5-oxo-l,2,4-thiadiazolidine-3-thione 3. Their relative ratio was found to be dependent on the length or bulkiness of the alkyl group in RNCS. Isomer 2 was favorable for R = Me and Et and exclusive for R = n-Pr, n-Bu, and cyclohexyl. Upon GLC injection (at 150–200 °C), compounds of type 2 isomerized completely to 3 (when R = Me, Et), mostly to 3 and partially decomposed to RN=C=NR (11) (when R = n-Pr, n-Bu), and exclusively decomposed to 11 for R = cyclohexyl. Tertiary RNCS did not yield cyclic products but instead underwent chlorination to substitute a hydrogen (or “NCS” group) by chlorine. Plausible mechanistic schemes are suggested and discussed.

Original languageEnglish
Pages (from-to)1744-1748
Number of pages5
JournalJournal of Organic Chemistry
Volume53
Issue number8
DOIs
StatePublished - 1 Apr 1988

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