(E)-1,3-丁二烯磷酸二乙酯和亚硝基甲烷杂D-A反应机理的理论计算

Theoretical Calculation of Hetero Diels-Alder Reaction Between (E)-Diethylbuta-1,3-dienylphosphonate and Nitrosomethane

采用密度泛函理论(DFT)在B3LYP/6-311G(d,p)水平上,对(E)-1,3-丁二烯磷酸二乙酯和亚硝基甲烷杂Diels-Alder反应机理进行了理论计算。结果表明:反应为协同过程,C—O、C—N键的生成和断裂协同进行;亚硝基甲烷平行接近(E)-1,3-丁二烯磷酸二乙酯,使得轨道最大重叠;反应是放热的,符合实验结果;前线轨道理论、热力学和动力学对本体系的研究结果一致。

The theoretical calculation of hetero Diels-Alder reaction between （E）-diethylbuta-1,3-dienylphosphonate and nitrosomethane was carried out by DFT method at B3LYP/6-311G（d,p） level.The results showed that the reaction was a concerted reaction,and the formation and breaking of C-O and C-N bonds were concerted.Nitrosomethane approaches parallelly to （E）-diethylbuta-1,3-dienylphosphonate to make the orbits reach maximum overlapping sequence.The reaction is in agreement with frontier orbital theory.The reaction is exothermic,which is in accordance well with experimental observations.The studying results of this reaction using thermodynamics,kinetics and frontier orbital theory are consistent.