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首页> 外文期刊>RSC Advances >Theoretical insights into the reaction mechanism between tetrachloro-o-benzoquinone and N-methyl benzohydroxamic acid
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Theoretical insights into the reaction mechanism between tetrachloro-o-benzoquinone and N-methyl benzohydroxamic acid

机译：四氯- o -苯醌与 N -甲基苯并异羟肟酸反应机理的理论见解

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Acquiring the detailed reaction mechanism between halogenated quinones and hydroxamic acids is crucial for better understanding of the potential applications of benzohydroxamic acids in the detoxification of the carcinogenic polyhalogenated quinoid metabolites of pentachlorophenol. In this study, the reaction mechanism between tetrachloro-o-benzoquinone (o-TCBQ) and N-methyl benzohydroxamic acid (N-MeBHA) has been systematically investigated at the B3LYP/6-311++G(d,p) level. It was found that o-TCBQ can react with the anion of N-MeBHA (N-MeBHA?) under mild conditions. As the first step of reaction, a molecular complex is formed between o-TCBQ and N-MeBHA? followed by the nucleophilic attack of the O atom of N-MeBHA? at the C atom attached to the Cl atom of o-TCBQ, resulting in the formation of an unstable intermediate containing an N–O bond. Subsequently, the unstable intermediate decomposes via the homolytic cleavage of the N–O bond to produce N-centered and O-centered radicals. For the O-centered radical, it can isomerize to a C-centered form upon structural relaxation. Finally, these radicals react with each other to form the major C–N bonding products and minor C–O bonding products. In addition, it was found that the reactivity of o-TCBQ with N-MeBHA is higher than that of tetrachloro-p-benzoquinone (p-TCBQ).
机译：获得卤代醌和异羟肟酸之间的详细反应机理对于更好地了解苯并异羟肟酸在五氯苯酚的致癌多卤代醌类代谢物解毒中的潜在应用至关重要。在这项研究中，四氯- o -苯醌（ o -TCBQ）与 N -甲基苯并异羟肟酸（ N -MeBHA）已在B3LYP / 6-311 ++ G（d，p）水平上进行了系统研究。发现 o -TCBQ可以与 N -MeBHA（ N -MeBHA ？ sup> ）。反应的第一步是在 o -TCBQ和 N -MeBHA ？ 之间形成分子复合物通过 N -MeBHA ？ 的O原子对与 o的Cl原子相连的C原子的亲核攻击em> -TCBQ，导致形成含有N-O键的不稳定中间体。随后，不稳定中间体通过N–O键的同质裂解分解产生N中心和O中心自由基。对于以O为中心的基团，在结构弛豫时它可以异构化为以C为中心的形式。最后，这些自由基彼此反应形成主要的C–N键合产物和次要的C–O键合产物。此外，还发现 o -TCBQ与 N -MeBHA的反应性比四氯- p -苯醌（< em> p -TCBQ）。

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