Kinetics of ceric ion oxidation of naphthalene and its derivatives. Formation of the radical cation intermediate in the rate limiting step

Abstract

Ceric ammonium sulfate, CAS, oxidizes naphthalene to 1,4-naphthoquinone in essentially quantitative yield in CH₃CN–dil. H₂SO₄. Stoichiometric studies indicate that 6 mol of CAS are required for the oxidation of 1 mol of naphthalene to 1,4-naphthoquinone. Kinetic investigations reveal that the reaction takes place through initial formation of a 1 : 1 complex of naphthalene and cerium(IV) in an equilibrium step followed by slow decomposition of the complex to naphthalene radical cation. Kinetic results on the effects of acid strength, polarity of the medium, temperature and substituents are in accordance with this mechanism. Further conversion of the radical cation into 1,4-naphthoquinone takes place in fast steps involving a further 5 mol of cerium(IV) and 2 mol of H₂O.