Is the collision induced loss of ethene from the (M – H+)− ion of butyrophenone a γ-hydrogen rearrangement?

Abstract

The (M – H+)− ion of butyrophenone undergoes the following reactions on collisional activation: losses of CH3•, CH4, (C,H5•), C2H4, C3H7•, (CO + CH4), together with formation of C6H5− and C4H5O−. Labelling studies (13C and 2H) show that the losses of CH3•, C3H7• and the formation of C6H5− and C4H5O− are specific and occur without hydrogen scrambling. All other reactions involve prior or accompanying hydrogen rearrangement. In particular, the loss of C2H4 is very complex: it involves loss of ethyl carbon atoms, but all hydrogen atoms are involved via specific rearrangement reactions. The phenyl–alkyl H rearrangements which are noted for this process occur after collisional activation of the (M – H+)− ion.