The Role of Hydrogen Bond in the Mechanism of Autocatalytic Reaction between Acetic Anhydride and tert-Butyl Hydroperoxide

Abstract

The role of hydrogen bonding in the autocatalytic reaction of acetic anhydride with tert-butyl hydroperoxide in CC1₄ has been elucidated. The stage-by-stage mechanisms of formation of hydrogen-bonded complexes. Structure and energy parameters of stable conformers of the compounds and energy of the major and transition states have been determined by means of B3LYP/aug-cc-pVDZ and B3LYP/aug-cc-pVTZ methods. The contribution of the O···HO hydrogen bonds in the stabilization of the complexes has been determined using the noncovalent interactions index. 1-Hydroxy-1-alkylperoxy compound is the most stable intermediate.