María Victoria Roux, Manuel Temprado, Pilar Jiménez, Rafael Notario, Ramón Guzman-Mejía, Eusebio Juaristi
Instituto de Química Física Rocasolano, CSIC, Serrano 119, 28006 Madrid, Spain.
The Journal of organic chemistry 2006 Mar 31This work reports the enthalpies of formation in the condensed and gas state of 1,4-dithiacyclohexane 1,1-dioxide (1,4-dithiane sulfone, 5), derived from the enthalpy of combustion in oxygen, measured by a rotating bomb calorimeter and the variation of vapor pressures with temperatures determined by the Knudsen effusion technique. The theoretically estimated enthalpy of formation was calculated from high-level ab initio molecular orbital calculations at the G2(MP2) level. The theoretical calculations appear to be in very good agreement with experiment. A comparison of the conversion of thiane sulfone 3 to 1,3-dithiane sulfone 4 and 1,4-dithiane sulfone 5 clearly shows the 1,3 isomer to be 6.7 kJ mol(-1) less stable, probably owing to diminished electrostatic repulsion between the sulfur heteroatoms in 1,4-sulfone 5.
María Victoria Roux, Manuel Temprado, Pilar Jiménez, Rafael Notario, Ramón Guzman-Mejía, Eusebio Juaristi. Calorimetric and computational study of 1,4-dithiacyclohexane 1,1-dioxide (1,4-dithiane sulfone). The Journal of organic chemistry. 2006 Mar 31;71(7):2581-6
PMID: 16555808
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