ON THE REACTIVITY OF CFNH3-NCH2X (N = 0, 1, 2, AND 3, AND X = H OR HALOGEN ATOM)

Theoretical and experimental data are presented which concern the properties and reactivity of CFnH3-nCH2X (X = H, Cl, Br, and I; n = 0, 1, 2, and 3). Anomalous behavior is shown for CF3CH2X (X = Cl, Br, and I). This includes (i) tertiary amines do not react with CF3CH2X to form a quaternary salt; (ii) the C-13 NMR chemical shift is more than 20 ppm upfield than expected; and (iii) AM1 semi-empirical molecular orbital calculations predict C-C heterolytic bond cleavage is preferred to C-X heterolytic bond cleavage. Regarding (iii) experimental data indicate a small preference for C-X bond cleavage, but the difference may be within the error bars for some of the enthalpies.