Redox reactions of 3,5-di-tert-butyl-1,2-benzoquinone. Implications for reversal of paper yellowing

Abstract

One- and two-electron transfer reactions of 3,5-di-tert-butylcatechol and the corresponding quinone were studied by fast kinetic spectroscopy coupled with laser photolysis and pulse radiolysis, and by cyclic voltammetry in aqueous solutions. Photoionization of catechol yields the same semiquinone radical as the formate-radical-induced quinone reduction in the pulse radiolysis experiment. The neutral semiquinone radical deprotonates at pKr = 6.0 ± 0.1, as deduced from the pH induced changes in the radical spectra. The two-electron reduction potentials of quinone and catechol were measured by cyclic voltammetry in aqueous solutions containing 25% methanol in the pH range 3–14. The pH dependence has two linear parts with slopes of 0.056 and 0.03 V/pH, intersecting at pKa = 10.0. This is in excellent agreement with pKa = 10.05 ± 0.05 obtained spectrophotometrically. The reduction potential of 3,5-di-tert-butyl quinone, E7 = 0.01 ± 0.04 V, was obtained from the one-electron transfer equilibrium of the quinone with the oxygen/superoxide redox couple by pulse radiolysis. The rate constant of the reaction of quinone with the superoxide radical, k = 1.2 × 109 M−1 s−1, is higher than those of the superoxide reduction by catechols and phenols (typically ~ 105 M−1 s−1); thus, lignin o-quinones could be efficient scavengers of superoxide under the conditions relevant for the photo-induced yellowing of lignin-rich paper. The reaction with [Formula: see text] effectively bleaches yellow quinone and generates metastable furanone, which hydrolyses to muconic acid, thus completely eliminating yellow quinone. 3,5-Di-tert-butylquinone also undergoes rapid bleaching with ascorbate, k = 600 ± 100 M−1 s−1, in methanol. The reaction has a 1:1 stoichiometry and leads to complete reduction of quinone to catechol with concomitant oxidation of ascorbate to dehydroascorbate. This unusual selectivity and the fact that the reaction of the milder oxidant 3,5-di-tert-butylquinone is an order of magnitude faster than that of stronger oxidant p-benzoquinone (k = 60 ± 10 M−1 s−1) suggest that a nucleophilic attack of quinone at the ascorbate double bond initiates the reaction. Keywords: superoxide, lignin, photochemistry, quinone.