- Gas-Solid Reactions: Photochemical Oxidation of Thioketones in the Crystalline State
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Photochemical oxidation of 11 diaryl thioketones (1-11) was conducted in the solid state.Quite interestingly, of these only six were oxidized to the corresponding carbonyl compound whereas the rest were photostable.However, in solution all were readily oxidized.The difference in behaviour between the thioketones in the solid state has been rationalized on the basis of molecular arrangement in the crystal.X-ray crystal structure analyses of four thioketones were carried out in this connection.
- Arjunan, P,Ramamurthy, V,Venkatesan, K
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p. 1765 - 1769
(2007/10/02)
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- Photochemical Oxidation of Thioketones: Steric and Electronic Aspects
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Oxidation of diaryl, aryl alkyl, and dialkyl thioketones by singlet oxygen generated via self-sensitization and other independent methods yielded the corresponding ketone and sulfine in varying amounts.A zwitterionic/diradical intermediate arising out of the primary interaction of singlet oxygen with the thiocarbonyl chromophore is believed to be the common intermediate for the ketone and sulfine.While closure of the zwitterion/diradical to give 1,2,3-dioxathietane would lead to the ketone, competing oxygen elimination is believed to lead to the sulfine.This partitioning is governed by steric and electronic factors operating on the zwitterionic/diradical intermediate.
- Ramnath, N.,Ramesh, V.,Ramamurthy, V.
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p. 214 - 222
(2007/10/02)
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