AQUEOUS HIGH-TEMPERATURE CHEMISTRY OF CARBOCYCLE AND HETEROCYCLE .28.REACTIONS OF ARYL SULFOXIDES AND SULFONES IN SUBCRITICAL AND SUPERCRITICAL WATER AT 200-460-DEGREES-C

Diphenyl and methyl phenyl sulfones and sulfoxides and dibenzothiophen e sulfone were treated at 460 degrees C with water, 15% aqueous formic acid, and 15% aqueous sodium formate. Thermal comparisons were run in cyclohexane, and for those compounds and conditions that resulted in fast conversion after 7 min at 460 degrees C, also at lower temperatur es. Sulfoxides are highly reactive, sulfones less so. Reactivity is gr eatest in 15% aqueous sodium formate followed by formic acid for the s ulfones; this reactivity order is inverted for the sulfoxides. In all of the aqueous media, ionic reactions dominate. The sulfoxides are mai nly deoxygenated to the corresponding sulfides, while C-S bond cleavag e is more important for the sulfones. Product slates are identified an d analyzed, and reaction pathways are suggested for the transformation s found.