Theoretical studies on the aminolysis mechanism of propylene carbonate with ammonia
Theoretical studies on the aminolysis mechanism of propylene carbonate with ammonia
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碳酸丙烯酯与氨氨解机理的理论研究
DOI：
10.1007/s00214-015-1634-6
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发表时间：
2015-02
影响因子：
1.7
通讯作者：
Guoming Liang
中科院分区：
文献类型：
--
作者：
Rong Chen;Xiaoling Luo;Guoming Liang
采用计算技术研究了碳酸丙烯酯氨解反应的可能机理。采用B3 LYP/6-311++G（d，p）和MP2/6-311++G（d，p）方法对所有固定点的优化结构进行了研究。考虑了无催化、碱催化和酸催化的氨解反应。研究了协同反应和加成/消除分步反应两种可能的反应机理，发现分步反应机理的第一阶段均为限速反应.结果表明，非催化氨解协同过程的能垒比分步机理低。对于碱催化和酸催化的氨解反应，中性分步反应比协同反应更有利，各步反应的能垒都比无催化的低。极化连续介质模型的溶剂效应并没有显著改变这一结论。
The possible mechanisms of the aminolysis reaction of propylene carbonate with ammonia were investigated by computational techniques. Optimized structures for all the stationary points were examined by employing the B3LYP/6-311++G(d,p) and MP2/6-311++G(d,p) methods. The uncatalyzed, base-catalyzed and acid-catalyzed aminolysis reactions were taken into account. Two possible mechanisms of the concerted process and the addition/elimination stepwise pathway are investigated, and the first stages of the stepwise mechanism for all pathways are the rate-limiting processes. The results indicate that the concerted process of non-catalyzed aminolysis has lower energy barrier in comparison with the stepwise mechanism. Concerning the base-catalyzed and acid-catalyzed aminolysis, the neutral stepwise pathway is more favorable than the concerted mechanism and the energy barriers of all steps are lower than those of the uncatalyzed aminolysis. The solvent effect by a polarized continuum model does not significantly change the conclusion.
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DOI：
10.1002/jlac.199619961003
发表时间：
1996-10
期刊：
Liebigs Annalen
影响因子：
--
作者：
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通讯作者：
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影响因子：
1.7
作者：
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通讯作者：
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影响因子：
2.3
作者：
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通讯作者：
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DOI：
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发表时间：
1979
期刊：
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影响因子：
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作者：
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通讯作者：
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DOI：
10.1039/b002842h
发表时间：
2001-03
期刊：
Journal of The Chemical Society-perkin Transactions 1
影响因子：
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作者：
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通讯作者：
H. Oh;S. Kim;I. Cho;H. Lee;Ikchoon Lee