Photochemical, photophysical, and theoretical studies on cyclobutanethiones..alpha.-Cleavage reactions
- Rao, Bantu Nageshwer
- Chandrasekhar, Jayaraman
- Ramamurthy, Vaidhyanathan
DOIAbstract
Photophysics and photochemistry of cyclobutanethiones 1-5 have been studied with the view to generalize\ud the a-cleavage reactions of cyclobutanethiones. The above cyclobutanethiones possess a unit intersystem crossing\ud efficiency from S1 to T1, a high self-quenching rate (-4 X lo9 M-' s-'), and a short triplet lifetime (<0.50 ws).\ud 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 a-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 me...
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