Reactivity of the C-H bonds of methyl hexanoate toward the tert-butylperoxy radical

Abstract

The kinetics of oxygen uptake and the kinetics of accumulation of methyl hexanoate oxidation products in the presence of tert-butyl hydroperoxide have been investigated to determine the partial rate constants for the interaction of the tert-butylperoxy radical with C-H bonds of the ester at 373 K. The ester group deactivates the C-H bonds in the 2- and 3-positions and does not deactivate the same bonds in the 5-position, which are similar in reactivity to the methylenic C-H bonds of hydrocarbons. The C-H bonds of the methoxyl group of methyl hexanoate are substantially more reactive than the C-H bonds of the methyl group.