Calorimetric and computational study of 1,4-dithiacyclohexane 1,1-dioxide (1,4-dithiane sulfone).

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 31

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This 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.

Citation

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