环氧化物与氮亲核试剂反应机理的研讨.pdf

环氧化物与氮亲核试剂反应机理的研究 林雪飞*，方 帆 （曲靖师范学院化学与生命科学系，云南曲靖 655011 ，E-mail:xflin99@ ） 摘 要 用量子化学半经验AM1 和密度泛B3LYP/6-31G**方法对环氧化物和氮亲核试剂的反应进行研究，对其反应过程 中的过渡态、中间体和最后的产物进行了计算。根据优化所得到这些分子的几何构型，从空间位阻和电子效应两方 面对它们进行了分析和讨论，以期从理论上揭示取代基对环氧化物开环的影响，且通过热力学和动力学两个角度分 析了标题物反应。结果表明，氮亲核试剂由于位阻和电子两方面的作用，使其容易从空间位阻小的方向进攻，从速 率和产率两方面考虑也有利于从位阻小的位置得到产物。同时在计算的过程中，找到了此反应进程中过渡态和中间 体，证实此反应为SN2类型，这在有机合成上是一个重要的反应，尤其是合成具有光学活性的氨基醇类物质。以上研 究计算的结果与实验结果得出的结论基本一致。 关键词：环氧化物；氮亲核试剂；几何构型；量子化学 Study on the Reaction Mechanism of Epoxide and Nitrogen Nucleophiles Abstract: This paper studies the reaction mechanism of epoxide and nitrogen nuleophiles by using quantum chemistry methods. Molecular energies, charge distribution and the frontier orbital energies of these substances are obtained after the geometries of the reactants, intermediates, transition states and products have been optimized. Based on the computation, two products which are isomer in the reaction are analyzed from kinetic and thermodynamic viewpoints. The result shows that the product P1 can be obtained more easily than the product P2 in the reaction, because the activation energy of P1 is smaller than that of P2. Moreover, the yield of the P1 is bigger than that of the P2 as a result of their different △G, the △G of the product P1 is smaller than that of the product P2. In the process of calculation, the reaction path has also been studied in detail. Two transition states and an intermediate are found in the process of the reaction. The optimized geometries of the transition states have further been conformed vibrational frequency analysis; there is only an imaginary frequency. The computation can be expected to provide a theoretical guide for synthesizing aminoalcohol compounds in organic synthesis. Keyword: Epoxides; Nitrogen nucleophiles; Geometry; Quantum