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

The reactivity in radical addition of diethyl carbonate to pentafluoropropen-2-yl benzoate [CF 2 =C(CF 3 )OCOC 6 H 5 ] (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.

[1]  M. Ue,et al.  Electrolytic behavior and application to lithium batteries of monofluorinated dimethyl carbonate , 2006 .

[2]  H. Hamana,et al.  Oligomer preparation from hexane by radical polyaddition with bis(alpha-trifluoromethyl-beta,beta-difluorovinyl) terephthalate. , 2004, Chemical communications.

[3]  H. Hamana,et al.  On the structure of the radical addition product of 2-benzoxypentafluoropropene with 1,4-dioxane , 2004 .

[4]  T. Narita.  Novel fluorinated polymers by radical polyaddition: Inspiration and progress , 2004 .

[5]  H. Hamana,et al.  Novel fluorinated polymer from 18-crown-6 by radical polyaddition , 2003 .

[6]  Marshall C. Smart,et al.  Improved performance of lithium-ion cells with the use of fluorinated carbonate-based electrolytes , 2003 .

[7]  H. Hamana,et al.  Novel fluorinated hybrid polymer by radical polyaddition of bis(α-trifluoromethyl-β, β-difluorovinyl) terephthalate onto dialkoxydialkylsilanes , 2002 .

[8]  H. Hamana,et al.  Radical polyaddition reaction of bis(α-trifluoromethyl-β,β-difluorovinyl) terephthalate onto diformylalkane , 2002 .

[9]  H. Hamana,et al.  Radical polyaddition reaction of bis(α-trifluoromethyl-β, β-difluorovinyl) terephthalate with ethylamine compounds , 2002 .

[10]  H. Hamana,et al.  Radical addition reaction of 2-benzoyloxypentafluoropropene onto cycloalkanes , 1999 .

[11]  H. Hamana,et al.  Radical polyaddition of bis(α-trifluoromethyl-β-difluorovinyl) terephthalate with 1,4-dioxane , 1998 .

[12]  K. Tomooka,et al.  Unique radical addition reactions onto perfluoro-enol esters , 1995 .

[13]  D. Dixon,et al.  Ketone perfluoro enolates: regioselective and stereoselective synthesis, unique reactivities, and electronic properties , 1990 .

[14]  T. Nakai,et al.  Perfluoro-enolate chemistry: facile generation and unique reactivities of metal F-1-propen-2-olates , 1988 .