The structure and CH-acidity of CF3-substituted β-thiolactones. A theoretical study |
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Authors: | Yu. A. Borisov A. F. Kolomiets A. V. Fokin |
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Affiliation: | (1) A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul.Vavilova, 117813 Moscow, Russian Federation |
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Abstract: | Ab initio calculations of the molecules of CH3- and CF3-substituted β-propiothiolactones and the productsof their deprotonation were carried out by the restricted Hartree—Fock method with full geometry optimization using the 6–31 G* basis set. Peculiarities of the geometry and electronic structure of the systems in question were established. Only 2-methyl-β-propiothiolactone forms a mesomeric stabilized carbanion in the case of proton abstraction from the α-position of thiolactone cycle. Carbanions of 3-methyl, 2-, and 3-thrifluoromethyl-β-propiothiolactones are stabilized due to the ring opening to form ketene thiolate ions. The CH-acidity of fluorine-containing β-thiolactones is much higher than that of nonfluorinated analogs (the differences in the deprotonation energies are 13.4 to 25.2 kcal mol−1). Deceased. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1719–1725, September, 1998. |
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Keywords: | ab initio calculations α - and β -methyl- and-trifluoromethyl-substituted β -propiothiolactones CH-acidity |
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