The rate constants for rearrangement of the 2,2,5,5-tetramethyl-3-hexyn-1-yl radical to the 2,6,6-trimethyl-4-heptyn-2-yl radical have been measured from 45 to 88 °C by kinetic epr spectroscopy. The temperature dependence can be represented by[Formula: see text]where θ = 2.3RT kcal mol−1. This rearrangement, which must involve an intermediate vinyl radical of the methylenecyclopropane type, is much slower than analogous rearrangement of homoallyl radicals but comparable in rate to rearrangement of homobenzyl (neophyl) radicals.
No takes yet. Share an insight, caveat, or question.
Ingold et al. (1980) studied this question.