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The electronic structures of several alkyl peroxides including the carbonyl group, i. e., performic acid, peracetic acid and their methyl esters, are investigated by the extended Hiickel method proposed by Hoffmann. The structure of the bond between peroxy oxygens, the intramolecular hydrogen bonding in peracid, the pyrolysis of peracid which is caused by the fact that the bond strength between peroxy oxygen atoms is weakened by an intramolecular hydrogen bonding, and the reaction mechanism of both the epoxidation of olefin by peracid and the ionic decomposition of peresters by basic catalysts can be successfully explained on the basis of the calculated results.
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Yonezawa et al. (1967) studied this question.
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