Amine-Induced Reactions of Diacyl Peroxides

Article abstract of DOI:10.1021/jo00293a021

The decompositions of 3-chlorobenzoyl cyclobutylformyl peroxide (3a), and 3-chlorobenzoyl cyclopropylacetyl peroxide (3b) induced by 1-azabicyclo<2.2.2>octane (Q), N¹,N¹,N⁴,N⁴-tetramethyl-1,4-benzenediamine (W), 1,4-diazabicyclo<2.2.2>octane (DABCO), and N,N-dimethylaniline (DMA) were investigated.Peroxides 3 were selected for study because distinctive product patterns were expected from decompositions induced by the alternative S_N2 and SET pathways.Q and W were selected as amines likely to react by the S_N2 and SET pathways, respectively.Q reacted with3 to give products characteristic of the intermediacy of an ion pair (general structure: R₃NOCOC4H7⁺ArCO2^-) formed by the S_N2 pathway, while W reacted with 3 to give rapid formation of the C4H7CO2 radical, indicative of an SET pathway.Based on the results with Q and W, we interpret the results with DABCO and DMA to indicate that both induce the decomposition of 3 by the S_N2 pathway.Thus, peroxides 3 have been shown to be structurally sensitive to the modes of their induced decomposition, and are, potentially, mechanistic probes for ascertaining the mechanism of induced peroxide decomposition by closed-shell molecules.