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A perfluoroisopropenyl ether terminated oligo(hexafluoropropylene oxide), a perfluoropolyalkyl ether macromonomer for radical copolymerization, has been prepared. The synthesis was achieved through a carefully controlled defluorination of a highly unstable lithium perfluorocarbanion intermediate. Several undesired pathways were also observed by GC/MS and we report conditions for generating the desired product in 82% yield. [ABSTRACT FROM AUTHOR]

Herein we investigate the propensity of hypervalent iodine based electrophilic trifluoromethylating agents to undergo thermally induced fragmentation of the F3C–I–O motif. For the first time we are able to observe a dissociative electron transfer mechanism using mass spectroscopy techniques to generate and trap CF3 radicals. Consistent with this mechanism, alkyl radical elimination from these reagents is in full support of an intermediate cyclic iodanyl radical and a reagent-specific temperature of maximum radical production was found to correlate with reported solution phase reactivity. [ABSTRACT FROM AUTHOR]

The oxidative activation of the perfluorinated analogue of dimethyl sulfoxide, DMSO-F 6 , by hydroxyl radicals efficiently produces trifluoromethyl radicals based on pulse radiolysis, laboratory scale experiments, and comparison of rates of reaction for analogous radical systems. In comparison to commercially available precursors, DMSO-F 6 proved to be more stable, easier to handle and overall more convenient than leading F 3 C-reagents and may therefore be an ideal surrogate to study F 3 C radicals for time-resolved kinetics studies. In addition, we present an improved protocol for the preparation of this largely unexplored reagent.