Collect. Czech. Chem. Commun. 2008, 73, 1655-1662

Radical Addition of Diethyl Carbonate to Pentafluoropropen-2-yl Benzoate

Akihiro Hosoyaa, Tadashi Naritaa,* and Hiroshi Hamanab

a Department of Applied Chemistry, Graduate School of Engineering, Saitama Institute of Technology, 1690 Fusaiji, Fukaya 369-0293, Japan
b Department of Life Science and Green Chemistry, Saitama Institute of Technology, 1690 Fusaiji, Fukaya 369-0293, Japan


The reactivity in radical addition of diethyl carbonate to pentafluoropropen-2-yl benzoate [CF2=C(CF3)OCOC6H5] (BPFP) was investigated to afford the one-to-one addition product by the carbon-carbon bond formation in the presence of dibenzoyl peroxide at 80 °C. The reaction took place predominantly on the methylene group of diethyl carbonate. The mechanism of the hydrogen abstraction from diethyl carbonate followed by the addition to BPFP was proposed. This might be the first example that shows an addition of an organic compound bearing carbonyl group to a polyfluorinated vinyl compound. The method may be a facile way to prepare pentafluoroalkyl-substituted organic compounds by the formation of carbon-carbon bonds with the aid of fluorine atoms. The radical addition reaction of dipropyl carbonate, ethyl methyl carbonate, dibenzyl carbonate and ethylene carbonate to BPFP showed no peaks assignable to addition products by the analysis of reaction systems with GC-MS.

Keywords: Radical additions; Pentafluoropropen-2-yl benzoate; Diethyl carbonate; Fluorinated alkenes; Perfluoroalkenyl building blocks.

References: 16 live references.