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| 3-甲基环状乙撑磷酸二酯醇解的反应途径的理论研究 | |
| 引用本文： | 夏福婷,朱华,薛英,郭勇,谢代前.3-甲基环状乙撑磷酸二酯醇解的反应途径的理论研究[J].化学学报,2009,67(9). |
| 作者姓名： | 夏福婷 朱华 薛英 郭勇 谢代前 |
| 作者单位： | 1. 四川大学化学学院,成都,610064 2. 四川大学化学学院,成都,610064;四川大学生物治疗国家重点实验室,成都,610064 3. 南京大学化学化工学院,理论与计算化学研究所,南京,210093 |
| 基金项目： | 四川省应用基础研究项目，四川省国际合作项目 |
| 摘 要： | 采用密度泛函理论和MP2方法研究了3-甲基环状乙撑磷酸二酯(MEP)与甲醇的反应途径:(Ⅰ)CH3O-+MEP;(Ⅱ)CH3OH+MEP;(Ⅲ)CH3O-+HMEP(MEP的质子化形式);(Ⅳ)CH3OH+HMEP.在B3LYP/6-31++G(d,p)水平上优化了四条反应途径的反应物、中间体、过渡态及产物的几何构型,并在同水平上进行了自然电荷分析,然后在MP2/6-311++G(3df,2p)水平上计算了各驻点的单点能.采用极化连续介质模型(PCM)研究了各途径在苯、甲醇和水溶液中的溶剂化效应.计算结果表明,溶剂效应使途径(Ⅰ)的自由能垒降低,而使途径(Ⅱ)和(Ⅳ)的决速步骤的自由能垒升高.在气相和苯溶剂中途径(Ⅳ)是反应的优势途径,在甲醇和水溶剂中途径(Ⅰ)则成为最优.研究结果进一步表明实验条件下途径(Ⅱ)与(Ⅳ)对总醇解反应的贡献相当. |
| 关 键 词： | 3-甲基环状乙撑磷酸二酯 甲醇解反应 反应途径 溶剂效应 |
Theoretical Study on Reaction Pathways for Methanolysis of 3-Methyl Cyclic Ethylene Phosphate |
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| Xia,Futing,Zhu,Hua,Xue,Ying,Guo,Yong,Xie,Daiqian.Theoretical Study on Reaction Pathways for Methanolysis of 3-Methyl Cyclic Ethylene Phosphate[J].Acta Chimica Sinica,2009,67(9). | |
| Authors: | Xia Futing Zhu Hua Xue Ying Guo Yong Xie Daiqian |
| Institution: | a College of Chemistry;Sichuan University;Chengdu 610064;b State Key Laboratory of Biotherapy;Chengdu 610064;c Institute of Theoretical and Computational Chemistry;College of Chemistry and Chemical Engineering;Nanjing University;Nanjing 210093 |
| Abstract: | The density functional theory and MP2 method were employed to study the reaction pathways of methanolysis of 3-methyl cyclic ethylene phosphate (MEP): (I) CH3O-+MEP; (II) CH3OH+MEP; (III) CH3O-+HMEP (protonated form of MEP); (IV) CH3OH+HMEP. The geometries for the reactants, intermediates, transition states and products were optimized at B3LYP/6-31++G(d,p) level, and the natural charge was analyzed at the same level. The single point energy of each stationary point was calculated at MP2/6-311++G(3df,2p) lev... |
| Keywords: | 3-methyl cyclic ethylene phosphate methanolysis reaction pathway solvent effect |
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