Photochemical, Photophysical, and Theoretical Studies on Cyclobutanethiones: α-Cleavage Reactions

Bantu Nageshwer Rao, Jayaraman Chandrasekhar, Vaidhyanathan Ramamurthy

Research output: Contribution to journalArticle

6 Scopus citations

Abstract

Photophysics and photochemistry of cyclobutanethiones 1-5 have been studied with the view to generalize the α-cleavage reactions of cyclobutanethiones. The above cyclobutanethiones possess a unit intersystem crossing efficiency from S1 to T1, a high self-quenching rate (∼4 × 109 M-1 s-1), and a short triplet lifetime (<0.50 μs). Photolysis of 1-5 yields in benzene a product resulting from 1,3-transposition and in methanol two cyclic thioacetals. The origin of these products is traced to the triplet excited state. A mechanistic scheme involving α-cleavage as the primary photoprocess and diradicals and thiacarbenes as intermediates has been formulated to rationalize the formation of thioacetals and rearranged products. The proposed mechanistic scheme is supported by UHF MINDO/3 calculations performed on four model systems, cyclobutanethiones and 1,3-cyclobutanedithiones 18-21. These calculations indicate that formation of diradical is favored thermodynamically and kinetically for systems analogous to 19 and 21, while rearrangement to thiacarbene is likely only for those similar to 21.

Original languageEnglish (US)
Pages (from-to)745-751
Number of pages7
JournalJournal of Organic Chemistry
Volume53
Issue number4
DOIs
StatePublished - Feb 1 1988
Externally publishedYes

ASJC Scopus subject areas

  • Organic Chemistry

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