Role of Hydrogen Bonding in the Oxidation of Thianthrene 5-Oxide with Peroxy Acids

The oxidation of thianthrene 5-oxide, i.e., a mechanistic probe for the assessment of the electronic character of various oxidants, with peroxybenzoic acids in various oxygen bases as solvents was investigated. The nucleophilicity (X(SO)) of peroxy acids was increasing with increasing basicity of the oxygen base. A good linear correlation was observed by plotting X(SO) values vs either the Kamlet-Taft beta values or the OOH (1)H NMR chemical shifts of m-chloroperoxybenzoic acid (m-CPBA) in solvents of various basicity. These observations, together with the results of IR and (1)H NMR spectroscopic studies of peroxybenzoic acids, and DFT (B3LYP/6-311++G) studies of the intramolecular hydrogen bonding in peroxyformic, peroxyacetic, and m-CPBA, as well as the intermolecular hydrogen bonding in the complexes of the these peroxy acids with dimethyl ether as a model oxygen base, support the involvement of the peroxy acid-oxygen base complexes in the transition states of these reactions. The increased nucleophilicity (X(SO)) of peroxy acids in basic solvents is most likely due to the increased negative charge on the terminal "electrophilic" peroxycarboxylic oxygen atom (OH), and/or the increased LUMO and HOMO energies of the peroxy acid in the complexes, as compared to those parameters in the intramolecularly hydrogen-bonded form of peroxy acids, believed to be operative in inert solvents.