Liquid-phase free-radical isomerization of cyclic acetals

1,3-Dioxacyclanes are converted to esters in the presence of di-tert-butyl peroxide. The reaction is described by the kinetic equation of an unbranched chain reaction with quadratic chain termination. It is shown that five-membered acetals are more reactive than seven- and six-membered acetals. The introduction of hydrocarbon groups in the 2 position of the ring increases the reactivity. It is concluded that the primary site of attack by the alkyl radical is the methylene or methylidyne group adjacent to the two heteroatoms.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1171–1175, September, 1976.