Nitrogen Radicals as Synthesis Intermediates. N-Halamide Rearrangements and Additions to Unsaturated Hydrocarbons

N-Halamides, R-N(Hal)-X can be rearranged to halo-alkyl isomers in a manner analogous to the free-radical Hofmann-Löffler reaction of protonated N-chloramines. Addition of N-chloramides to unsaturated hydrocarbons also occurs to afford a variety of N-substituted ß-chloroalkyl compounds of the type, or related structures. Both types of reaction are reviewed for halamides with X=-CO-R, -COOR, -SO2-R, and -CN and compared with the corresponding reactions of protonated N-chloramines.