Insertion of Tetrafluoroethylene and Trifluorochloroethylene into Nitrogen-Chlorine Bonds. A New Route to Perfluoroazaalkenes.

摘要

Insertion of olefins, CF2=CFX (X = CL, F), into the nitrogen-chlorine bonds of dichloro(perfluoroalkyl)amines. R(f)NCL2 (R(f) = CF3, C2,F5), occurs readily, providing an easy, straightforward route to a secondary (polyfluoroalkyl)- or (perfluoroalkyl)chloroamines and tertiary (polyfluoroalkyl)- or (perfluoroalkyl)amines. At 65-70 C, insertion into only one of the nitrogen-chlorine bonds occurs to give R(f)N(CF2CFXCL)CL, while at 90-100 C, insertion into both nitrogen-chlorine bonds produces the tertiary amine R(f)N(CFXCL)2 in good yield. Gas-phase photolysis of R(f)N(CF2CFXCL)CL results in essentially quantitative yields of the respective perfluoroazaalkenes, R(f)N=CF2, and fluorocarbons, CFXCL2 (X = F, CL). Reprints. (jg)