Hydrogen Abstraction from Amines: Formation of Aminyl vs. α-Aminoalkyl Radicals

Article abstract of DOI:10.1021/ja00345a051

A series of electron paramagnetic experiments were carried out which showed that dialkylaminyl radicals do not readily attack dialkylamines to form α-aminoalkyl radicals.These results disprove earlier conclusions that such processes were the major pathways for formation of α-aminoalkyl radicals in free radical reactions involving dialkylamines.By contrast, tert-butoxyl radicals were found to efficiently abstract hydrogen from amines.Rate constants for C-H and N-H abstraction by tert-butoxyl were respectively 6.5 x 10⁷ and 1.1 x 10⁷ for Me2NH, 6.6 x 10⁷ and 1.0 x 10⁷ for Et2NH, 1.3 x 10⁷ and 3 x 10⁶ for n-PrNH2, 7 x 10⁶ and 3 x 10⁶ for n-BuNH2, and 3.3 x 10⁶ for t-BuNH2 (units M^-1 s^-1).