1,1- OR 1,3-ADDITION MECHANISM OF OLEFIN EPOXIDATION WITH ORGANIC PEROXY ACIDS . A MOLECULAR ORBITAL STUDY

The electronic structure of the peroxy acid molecule in its intramolecularly hydrogen bonded (B) and dipolar (B+) form has been investigated using the semiempirical Pariser-Parr-Pople SCF-MO method. On the basis of the π-electron distribution and the observed relatively small difference between the total energies of both molecular species (EB - EB - 0.03 eV), it was concluded that both proposed mechanisms, namely 1,1 and 1,3 addition, are theoretically possible, the first mechanism being more probable in nonpolar and the second in polar media. © 1969, American Chemical Society. All rights reserved.