C,N-二甲基硝酮与丙烯腈1,3-偶极环加成反应的理论研究  

Theoretical Study on the 1,3-dipolar Cycloaddition Reaction of C,N-dimethyl Nitrone and Acrylonitrile

作　　者：汪晓敏[1] 姜妲[2] 唐明生[1] 

机构地区：[1]郑州大学化学系,郑州450001 [2]东北大学材料与冶金学院,沈阳110004

出　　处：《郑州大学学报（理学版）》2006年第2期96-100,共5页Journal of Zhengzhou University:Natural Science Edition

基　　金：国家自然科学基金资助项目;编号20272054

摘　　要：用分子轨道理论在B3LYP/6-31G*水平上对C,N-二甲基硝酮与丙烯腈的1,3-偶极环加成反应进行了理论计算.当C,N-二甲基硝酮向丙烯腈靠近时反应先生成3种不同的氢键复合物,其相对能量分别为-24.14,-23.43和-21.63 kJ.mol-1.随着反应的进行,3种氢键复合物转化为相应endo-4、exo-4、endo-5、exo-5四种不同产物的过渡态,4种反应途径的能垒分别为55.86,60.96,58.16和58.83 kJ.mol-1.研究结果表明该反应区域选择性和立体选择性都不明显,4种反应都很容易进行,最终得到endo-4、exo-4、endo-5、exo-5四种产物的混合物.The 1,3-dipolar cycloaddition reaction of C, N-dimethyl nitrone with acrylonitrile has been caculated at B3LYP/6-31G＇ level using molecular orbital theory. Three H-bond complexes are first produced when C, N-dimethyl nitrone approaches acrylonitrile. Their relative energies are -24. 14, -23.43 and -21.63 kJ/mol. These three H-bond complexes lead to four transition states endo-4, exo-4, endo-5 and exo-5 as the reactions proceed and the energy barriers of four reactions are 55.86,60.96,58.16 and 58.83 kJ/mol respectively. The calculation results show that the reactions haven＇t obvious regioselectivity and steroselectivity. Four products are all produced easily. The final products are the mixture of endo-4,exo-4,endo-5 and exo-5.

关 键 词：硝酮 1 3-偶极环加成反应 过渡态 密度泛函理论 

分 类 号：O641[理学—物理化学]