| 锗苯与甲醛和二苯甲酮的Diels-Alder反应的计算研究 |
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| 引用本文： | 王岩,周涛,袁红霞. 锗苯与甲醛和二苯甲酮的Diels-Alder反应的计算研究[J]. 计算机与应用化学, 2009, 26(11) |
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| 作者姓名： | 王岩 周涛 袁红霞 |
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| 作者单位： | 信阳师范学院化学化工学院,河南,信阳,464000;信阳师范学院化学化工学院,河南,信阳,464000;信阳师范学院化学化工学院,河南,信阳,464000 |
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| 摘 要： | 采用密度泛函理论(DFT)在B3LYP/6-311G(d,p)水平对锗苯与甲醛和二苯甲酮的Diels-Alder反应的微观机理、势能剖面、取代基效应及溶剂化效应进行了理论计算。结果,所研究的反应均为协同的基元反应,形成Ge-O键的反应中,形成2个新键较大不同步,其它反应的不同步性相对较小。羰基碳原子上的苯基取代基于反应不利,而锗苯分子中锗原子上的C(CH_3)_3与CCl_3取代基则有利。在热力学和动力学上,有锗参与的反应均远比无锗的反应容易,而形成Ge-O键的反应比形成Ge-C键的反应容易,结果与实验一致。四氢呋喃溶剂对所研究反应的势能剖面影响较小。4个形成Ge-O键的反应在四氢呋喃溶剂中进行时,其活化能垒分别为38.03、89.75、29.92和29.87 kJ·mol~(-1)。
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| 关 键 词： | 锗苯 甲醛 二苯甲酮 Diels-Alder反应 反应机理 密度泛函理论 |
Computational studies of the Diels-Alder reactions of germabenzenes with formaldehyde and benzophenone |
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| Wang Yan,Zhou Tao,Yuan Hongxia. Computational studies of the Diels-Alder reactions of germabenzenes with formaldehyde and benzophenone[J]. Computers and Applied Chemistry, 2009, 26(11) |
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| Authors: | Wang Yan Zhou Tao Yuan Hongxia |
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| Affiliation: | College of Chemistry and Chemical Engineering;Xinyang Normal University;Xinyang;464000;Henan;China |
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| Abstract: | The mechanism,potential energy surface,substituent effect and salvation effect of Diels-Alder reactions of germabenzenes with formaldehyde and benzophenone were investigated theoretically using density functional theory(DFT) at the B3LYP/6-311G(d, p) level.It was found that all the studied reactions proceed via a concerted way and the reaction forming one Ge-O bond has much larger asynchronicity in the bond-formation process than other reactions.Phenyl group at C atom of carbonyl disfavors the Diels-Alder r... |
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| Keywords: | germabenzene formaldehyde benzophenone Diels-Alder reaction reaction mechanism density functional theory |
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