Fluoro-olefin chemistry. Part 15. Thermal reaction of hexafluoropropene with hydrocarbon olefins

Abstract
The thermal reaction of hexafluoropropene with hydrocarbon olefins can give three different types of product, 1,1,2-trifluoro-2-trifluoromethylcyclobutanes, hexafluoroalkenes of the type R1R2CCR3·CH2·CHF·CF2·CF3, and 1,1,2-trifluoro-2-trifluoromethylcyclopentanes. The cyclobutanes are formed via diradical intermediates and the cyclopentanes via intermediate allyl-radical attack on the fluoro-olefin, while the hexafluoroalkenes arise via either of these radical intermediates or by the ‘ene’ reaction. With olefins of the type CH2 CHR (R = Me or Et), cyclobutanes are formed exclusively, while those such as CH2 CMeR (R = Et or Pri) give both cyclobutanes and hexafluoroalkenes. However, the olefins CH2 CMe2, CHMeCMe2, and CMe2 CMe2 afford all three types of product, but only with the alkene CHMeCMe2 is cyclopentane-formation a major reaction (29% at 270 °C and 35% at 220 °C). Certain of the reactions are complicated by hydrocarbon-olefin isomerisation.

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