Photochemical behavior of thioketenes in solution: Reaction from S2

Sharat Singh, Hildegard Nimmesgern, Ernst Schaumann, Vaidhyanathan Ramamurthy

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Abstract

The higher excited-state reactions of sterically encumbered thioketenes 1a-d in solution were investigated. Substituted thiiranes, thio esters, thioacetophenones, and 1,2-diones are formed on photoexcitation of thioketenes in hydroxylic and nonhydroxylic solvents. Thioketenes while unreactive upon excitation to S1 produce thiiranylidene carbene and zwitterionic intermediates upon excitation to S2. The reactive state is identified to be S2 (ππ*). The excited thioketene resists carbon monosulfide elimination but undergoes rearrangement. The photobehavior of thioketenes, established in solution for the first time, differs significantly from that of ketenes, and it cannot be extrapolated from that of structurally analogous ketenes and allenes.

Original languageEnglish
Pages (from-to)4799-4805
Number of pages7
JournalJournal of Organic Chemistry
Volume50
Issue number24
StatePublished - Dec 1 1985
Externally publishedYes

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ASJC Scopus subject areas

  • Organic Chemistry

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