Abstract

Using density functional theory with the hybrid functional B3LYP in the 6-311++G(d, p) basis set, the Fukui functions were calculated for hydrogen atoms of CH bonds of 2-butanol in the cases of electrophilic and nucleophilic attacks, transition states were located, and the activation energies and enthalpies were computed for elementary reactions of the electrophilic hydroperoxyl radical (HOO^•) and 2-hydroxy-2-butyl peroxy radical ((CH₃)(C₂H₅)C(OH)OO^•) with CH bonds of all types in 2-butanol. It was shown that the target of the attack of the peroxy radicals on CH bonds of 2-butanol is controlled by the ratio between the electron-donating and electron-accepting abilities of hydrogen atoms of CH bonds of the alcohol. The relationship between the activation energy, the length of the CH bond being cleaved in the transition state, and the nucleophilicity of the formed carbon-centered radical was determined.

中文翻译：

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2-丁醇与氢过氧基和2-羟基-2-丁基过氧自由基的反应

摘要

使用密度泛函理论和杂化官能团B3LYP在6-311 ++ G（d，p）基集中，计算了在亲电子和亲核攻击，过渡情况下2-丁醇CH键氢原子的Fukui函数定位状态，并计算亲电氢过氧自由基（HOO ^•）和2-羟基-2-丁基过氧自由基（（CH ₃）（C ₂ H ₅）C（OH）OO的基本反应的活化能和焓^•）在2-丁醇中具有所有类型的CH键。结果表明，过氧自由基对2-丁醇的CH键的攻击目标是由醇的CH键的氢原子的给电子能力和电子接受能力之比来控制的。确定了活化能，在过渡态中断裂的CH键的长度和形成的碳中心自由基的亲核性之间的关系。