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本文运用密度泛函理论(DFT)计算,系统研究了碱促均裂芳香取代合成6-酰基菲啶的反应机理.计算结果表明,叔丁氧自由基和苯甲醛间的自由基传递反应是整个反应的决速步骤.随后酰基自由基对氰基的亲核进攻以及自由基环化过程是快速步骤.此外,我们还利用Hammett曲线研究了反应过程中不同位置上取代基的电子效应.研究结果表明,氰基对位上被吸电子基团取代时有利于酰基自由基的亲核进攻,酰基对位被给电子基团取代时有助于自由基环化过程的发生.
In this paper, the reaction mechanism of alkali-catalyzed aromatic substitution of 6-acylphenanthridine was systematically investigated by using density functional theory (DFT). The calculation results show that the free radical transfer reaction between tert-butoxy and benzaldehyde is the whole Followed by the radical step of the reaction.Afterwards, the nucleophilic attack of cyanoacyl by acyl free radical and the process of free radical cyclization are fast steps.In addition, we also use the Hammett curve to study the electronic effect of the substituents at different positions during the reaction.Results It is indicated that the cyano group is favored to nucleophilic attack of the acyl radicals when it is substituted by an electron withdrawing group and the acyl group is assisted by the electron group to substitute for the cyclization of free radicals.