New Synthetic Approach to PolyfluorinatedCarbonates

Transesterification of commercial titanium(IV) alkoxides with 2,2,3,3-tetrafluoropropan-1-ol, followed by in situ transesterification of mixed titanium(IV) alkoxides thus formed with diphenyl carbonate, afforded alkyl 2,2,3,3-tetrafluoropropyl carbonates and bis(2,2,3,3-tetrafluoropropyl) carbonate in up to 60% yield. The degree of transesterification decreased in the series (i-PrO)4Ti > (EtO)4Ti > (BuO)4Ti and did not exceed 68%. The selectivity for alkyl 2,2,3,3-tetrafluoropropyl carbonates and bis(2,2,3,3-tetrafluoropropyl) carbonate was found to change depending on the composition of mixed titanium(IV) alkoxide formed in situ.