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Title: Photochemical Ring-Opening and Intramolecular Hydrogen Shift Reactions in Sulfur Analogues of α-Pyrone
Authors: Breda, S. 
Reva, I. 
Lapinski, L. 
Cristiano, M. L. S. 
Frija, L. 
Fausto, R. 
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.
DOI: 10.1021/jp061139k
Rights: openAccess
Appears in Collections:FCTUC Química - Artigos em Revistas Internacionais

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