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http://hdl.handle.net/10316/17918
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. | 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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J.Physical Chemistry A, 110 (2006) 6415.pdf | 423.54 kB | Adobe PDF | View/Open |
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