Abstract
Absolute propagation and termination rate constants have been determined for the autoxidation of some vinyl compounds at 30°. Rates of propagation depend on the structure of both the peroxy radical and the vinyl compound. The reactivity of peroxy radicals towards addition increases as the electron-withdrawing capacity of the α-substituent increases. Rate constants for addition of t-butylperoxy radicals to vinyl compounds, [Formula: see text] fit the equation[Formula: see text]where Es is the estimated stabilization energy of the β-peroxyalkyl radical (in kcal/mol) formed in the addition reaction.
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