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Mechanism of the reaction of radicals with peroxides and dimethyl sulfoxide in aqueous solution

机译：自由基与水溶液中的过氧化物和二甲亚砜反应的机理

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摘要

The reactions of methyl and methylperoxyl radicals derived from dimethyl sulfoxide (DMSO) with hydrogen peroxide, peroxymonocarbonate (HCO4-), and persulfate were studied. The major reaction observed for the hydroperoxides was the abstraction of the hydrogen atom by the radicals. The radicals interact with a lone pair of electrons on the peroxide to produce methanol and formaldehyde. Furthermore, the results indicate that in RO2H and RO2R', electron-withdrawing groups cause a considerable increase in the reactivity of the peroxides towards the radicals and not only towards nucleophiles. The HO2 center dot/O-2(center dot-) and CO3 center dot- radicals react with DMSO to produce methyl radicals. Thus, the formation of the (CH3)-C-center dot radicals in the presence of DMSO is not proof of the formation of the (OH)-O-center dot radicals in the system. These reactions must be considered when radical processes, such as in biological and catalytic systems, are studied. Especially, the plausible role of HCO4- ions in biological systems as a source of oxidative stress cannot be overlooked.
机译：研究了由二甲基亚砜（DMSO）衍生的甲基和甲基过氧自由基与过氧化氢，过氧一碳酸根（HCO4-）和过硫酸根的反应。观察到的氢过氧化物的主要反应是自由基对氢原子的提取。自由基与过氧化物上的孤对电子相互作用，生成甲醇和甲醛。此外，结果表明，在RO2H和RO2R'中，吸电子基团导致过氧化物不仅对亲核试剂对自由基的反应性显着提高。 HO2中心点/ O-2（中心点）和CO3中心点自由基与DMSO反应生成甲基。因此，在DMSO存在下（CH3）-C-中心点自由基的形成不能证明系统中（OH）-O-中心点自由基的形成。在研究自由基过程（例如生物和催化系统）时，必须考虑这些反应。尤其是，不可忽视HCO4-离子在生物系统中作为氧化应激源的合理作用。

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