Abstract
With dioxygen-saturated (1 atm, 2.1 mM) dimethyl sulfoxide solutions that contain aniline (1-15 mM), the addition of excess hydroxide ion (10:1 HO-/PhNH2) yields approximately two superoxide ions (O2-), one azobenzene, and one hydrogen peroxide per two aniline molecules [2 PhNH2 + 2 HO- + 3 O2 [arrow] 2 O2- + PhN=NPh + HOOH + 2 H2O]. Similar stoichiometries and yields of O2- are achieved with the N-substituted anilines; the relative reaction rates are in the order PhNHNH2> PhNHPh> PhNHMe> PhNH2. The apparent yield of O2- is low when PhNHNH2 is the substrate, because the latter reduces O2- to HOO-. With hydroxylamines and excess HO- dioxygen is reduced to O2- [2 H2NOH + 4 O2 + 4 HO- [arrow] 2 O2- + HOOH + 2 NO2- + 4 H2O], but the yield is low because O2- reacts with excess H2NOH to give NO and HOO-. Although the combination of H2NNH2, O2, and HO- is unreactive, the addition of anthraquinone (AQ) or its ethyl derivative (Et-AQ) catalyzes the stoichiometric production of O2-...
Jeon, Seungwon (1990). The chemical generation of superoxide ion, and its relative reactivity (versus hydroperoxide ion and hydroxide ion) with halocarbons, esters, and nitriles in aprotic media. Texas A&M University. Texas A&M University. Libraries. Available electronically from
https : / /hdl .handle .net /1969 .1 /DISSERTATIONS -1190572.