V. Petrov, W. Marshall
Nov 1, 2012
Citations
0
Influential Citations
12
Citations
Journal
Journal of Fluorine Chemistry
Abstract
Abstract It was demonstrated that the fluoride anion catalyzed reaction of 2,2,4,4-terakis(trifluoromethyl)dithienane-1,3 ( 1 , cyclic dimer of hexafluorothioacetone) with ketene dimethylacetal ( 2 , 1,1-dimethoxy ethylene) leads to the formation of 2,2-bis(trifluoromethyl)-3,3-bis(methoxy)thietane ( 3 ), rather than expected 2,2-bis(trifluoromethyl)-4,4-bis(methoxy)thietane isomer ( 4 ). Compound 3 is a kinetic product and upon storage at ambient temperature undergoes quantitative isomerization into 4 . The isomerization proceeds through the formation of free hexafluorothioacetone, which was trapped as cycloadduct with quadricyclane. It was also demonstrated that the ethylene 2 is able to react with dimer 1 in the absence of the catalyst. The reaction results in unusual ring opening process producing (2,2-dimethoxyvinyl)(1,1,1,3,3,3-hexafluoro-2-(1,1,1,3,3,3-hexafluoropropan-2-yl)thio)propan-2-yl)sulfane ( 11 ).