New Mechanism for the Reaction of Thianthrene Cation Radical Perchlorate with tert-Butyl Peroxide

Abstract

A new reaction mechanism is proposed for the reaction of thianthrene cation radical perchlorate <TEX>$(Th^{+{\cdot}}CIO_4^-}$</TEX> and tert-butyl peroxide in acetonitrile at room temperature on the basis of experimental and theoretical results. Rapid C-O bond rupture instead of O-O bond cleavage was observed by a good peroxy radical trapping agent, thianthrene cation radical. Products were N-tert-butyl acetamide, thianthrene 5-oxide (ThO), thianthrene 5,5-dioxide <TEX>$(SSO_2)$</TEX>, and thianthrene (Th). Thianthrene 5,10-dioxide (SOSO) was not obtained. A comparative computational study of the cation radical of tert-butyl peroxide is made by using B3LYP and CBS-4. The computational results are helpful to explain the reaction mechanism.