全文下载：2013060551
徐文媛，唐静，徐娜娜，杜瑞焕
（华东交通大学 基础科学学院，江西 南昌 330013）
摘要： 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。
关键词：(E)-1,3-丁二烯磷酸二乙酯亚硝基甲烷；Diels-Alder反应；DFT
中图分类号：O 64.12文献标志码： A
Theoretical Calculation of Hetero Diels-Alder Reaction Between (E)-Diethylbuta-1,3-dienylphosphonate and Nitrosomethane
XU Wen-yuan，TANG Jing，XU Na-na, DU Rui-huan
(School of Basic Science,EastChinaJiaotongUniversity,Nanchang330013,China)
Abstract: 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.
Key words: (E)-diethylbuta-1,3-dienylphosphonate; nitrosomethane; Diels-Alder reaction; DFT
收稿日期：2012-12-26
基金项目：国家自然科学基金项目(21163005，31160187).
作者简介：徐文媛(1975—)，女，教授.
