Abstract: | Using the principles of the quasi-equilibrium theory, substituent effects, deuterium labeling and comparison of compound behavior, we provide strong evidence for aryl participation in the expalsion of Br· from the molecular ion of β-phenylethyl bromide and eleven of its ringsubstitued derivatives. This reaction shows a kinetic behavior which is typical of rearrangements, its activation energy is lower than that of similar reactions where participation is partially or completely precluded and substitute effects are not only consistent with a particular process, but are also consistent with those predicted from solution chemistry. |