CAJ | 학술논문

应用量子化学中的密度泛函（B3LYP/6-311G（d,p））和二级微扰（MP2/6-311G（d,p））方法对肟和环戊二烯的杂Diels-Alder反应机理进行了计算.结果表明,碳氮键先于碳碳键生成,碳氮键和碳碳键的生成与断裂属非同步的协同过程,C-O键在反应中钝化,不参与反应;反应符合前线轨道理论,利于反应进行;从热力学和动力学角度分析,此反应可以进行,优化计算的结果意义较大;反应计算数据与已有实验结果一致.
응용양자화학중적밀도범함（B3LYP/6-311G（d,p））화이급미우（MP2/6-311G（d,p））방법대우화배무이희적잡Diels-Alder반응궤리진행료계산.결과표명,탄담건선우탄탄건생성,탄담건화탄탄건적생성여단렬속비동보적협동과정,C-O건재반응중둔화,불삼여반응;반응부합전선궤도이론,리우반응진행;종열역학화동역학각도분석,차반응가이진행,우화계산적결과의의교대;반응계산수거여이유실험결과일치.
B3LYP/6-311G（d,p） theory and MP2/6-311G（d,p） theory were used to calculate the Hetero-Diels-Alder reaction’s mechanism of oxime and cyclopentadiene.The results indicate that C-N bonds’ formation was prior to C-C bonds’;the formation and fracture of C-N bonds and C-C bonds were asynchronous collaborative processes;C-O bond which was passivated did not participate in the reaction.Reactions agree with frontier orbital theory which is favorable for the hetero-Diels-Alder reaction’s progress.From the perspective of thermodynamics and kinetics,the reaction is feasible and the optimization results are of great significance.Reaction’s calculated data is in full agreement with literature’s.