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Photochemical Behavior of Thioketenes in Solution: Reaction from $S_2$

Singh, Sharat and Nimmesgern, Hildegard and Schaumann, Ernst and Ramamurthy, Vaidhyanathan (1985) Photochemical Behavior of Thioketenes in Solution: Reaction from $S_2$. In: Journal of Organic Chemistry, 50 (24). pp. 4799-4805.

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The higher excited-state reactions of sterically encumbered thioketenes la-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 $S_1$ produce thiiranylidene carbene and zwitterionic intermediates upon excitation to $S_2$. The reactive state is identified to be $S_2 (\pi \pi^*)$. 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.

Item Type: Journal Article
Publication: Journal of Organic Chemistry
Publisher: American Chemical Society
Additional Information: Copyright of this article belongs to American Chemical Society
Department/Centre: Division of Chemical Sciences > Organic Chemistry
Date Deposited: 10 Apr 2008
Last Modified: 19 Sep 2010 04:44
URI: http://eprints.iisc.ac.in/id/eprint/13660

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