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|Title:||Photochemical Ring-Opening and Intramolecular Hydrogen Shift Reactions in Sulfur Analogues of α-Pyrone||Authors:||Breda, S.
Cristiano, M. L. S.
|Issue Date:||May-2006||Publisher:||American Chemical Society||Serial title, monograph or event:||J. Phys. Chem. A||Volume:||110||Abstract:||A combined matrix isolation FTIR and theoretical DFT(B3LYP)/6-311++G(d,p) study of the photochemistry of sulfur analogues of α-pyrone [2H-thiopyran-2-one (TP) and 2H-pyran-2-thione (PT)] was carried out. The vibrational spectra of monomers of the compounds isolated in low-temperature argon matrixes were studied experimentally and assigned completely on the basis of theoretical calculations. UV irradiation (λ > 337 nm) of the studied compounds isolated in low-temperature matrixes results mainly in the ring-opening reaction by means of the cleavage of the α-bond. Other photoprocesses, not involving the α-bond-cleavage step (such as generation of Dewar valence isomer), correspond to the minor reaction channels in both studied compounds. The ring-opening photoreaction in PT represents the first reported case of an α-bond cleavage in a compound with a CS group attached to a six-membered ring, in which the internal strain practically does not exist, whereas the corresponding reaction in TP (a cleavage of a C−S bond in the α position with respect to a carbonyl group) is now reported for the first time. Following the ring-opening reactions, isomerization processes and intramolecular hydrogen shift reactions were observed, enabling production of TP from PT and vice versa. A detailed study of such processes was undertaken, and kinetical and mechanistical data are presented and discussed.||URI:||http://hdl.handle.net/10316/17918||DOI:||10.1021/jp061139k||Rights:||openAccess|
|Appears in Collections:||FCTUC Química - Artigos em Revistas Internacionais|
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