A McLafferty Rearrangement in an Even-electron System: C3H6 Elimination from the α-Cleavage Product of Tri-n-butylamine

Article abstract of DOI:10.1002/oms.1210260808

It is shown by deuterium labelling, linked-scan measurements and collision activation that the .>⁺ (α-cleavage) ion in the electron impact ionization spectrum of tributylamine loses C3H6 with transfer of one hydrogen specifically from the γ-position.The experimental data point towards a mechanism which involves the intermediate formation of a distonic diradical ion from an excited α-cleavage ion which the eliminates the neutral alkene.