109577-03-9Relevant academic research and scientific papers
Does an Oxygen Function Stabilize the Sulfonyl Carbanion? Metalation of 1,3-Oxathiane 3,3-Dioxides
Fuji, Kaoru,Usami, Yoshihide,Sumi, Kenzo,Ueda, Masaru,Kajiwara, Kanji
, p. 1655 - 1658 (1986)
1,3-Oxathiana 3,3-dioxides were lithiated not at C-2 but at C-4 preferentially, which revealed that the oxygen function destabilizes the sulfonyl carbanion in this ring system.
Calorimetric and computational study of 1,3-and 1,4-oxathiane sulfones
Roux, Maria Victoria,Temprado, Manuel,Jimenez, Pilar,Notario, Rafael,Guzman-Mejia, Ramon,Juaristi, Eusebio
, p. 1143 - 1147 (2007/10/03)
(Chemical Equation Presented) The enthalpies of formation in the condensed and gas states, ΔfH°m(cd) and ΔfH°m(g), of 1,3- and 1,4-oxathiane sulfones were derived from their respective enthalpies of combustion in oxygen, measured by a rotating bomb calorimeter and the variation of vapor pressures with temperatures determined by the Knudsen effusion technique. Standard ab initio molecular orbital calculations at the G2(MP2) and G3 levels were performed, and a theoretical study on molecular and electronic structure of the compounds has been carried out. Calculated ΔfH°m(g) values at the G3 level using atomization reactions agree well with the experimental ones. These experimental and theoretical studies support that the destabilization found in 1,3-oxathiane sulfone, 11.2 kJ mol-1 respecting to 1,4-oxathiane sulfone, is due to the electrostatic repulsion between the negative charges of the axial oxygen of the sulfone and the oxygen of the ring and apparently masks any stabilization originating from the hyperconjugative nO → σ*C-SO2 stereoelectronic interaction.
