The chemical generation of superoxide ion, and its relative reactivity (versus hydroperoxide ion and hydroxide ion) with halocarbons, esters, and nitriles in aprotic media /.
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| Other Authors: | , , |
| Format: | Thesis Book |
| Language: | English |
| Published: |
1990.
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| Subjects: | |
| Online Access: | Link to ProQuest copy Link to OAKTrust copy ProQuest, Abstract |
| 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-... |
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| Item Description: | "Major subject: Chemistry." Typescript (photocopy). Vita. |
| Physical Description: | xiv, 97 leaves : illustrations ; 29 cm |
| Bibliography: | Includes bibliographical references. |