Quantum-chemical study on the reaction of phenyl isocyanate with linear methanol associates. Addition at the C=N bond
Quantum-chemical study on the reaction of phenyl isocyanate with linear methanol associates. Addition at the C=N bond
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DOI：
10.1134/s107042800809011x
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发表时间：
2008-10
影响因子：
0.8
通讯作者：
A. Samuilov;L. Zenitova;Y. Samuilov;A. Konovalov
中科院分区：
文献类型：
--
作者：
A. Samuilov;L. Zenitova;Y. Samuilov;A. Konovalov
在B3 LYP/6-311++G（df，p）水平上的量子化学计算表明，异氰酸苯酯与甲醇缔合物的反应涉及反应前和反应后络合物的形成.反应通过晚期不对称环状过渡态进行。能垒的高度随着醇的缔合度的增加而降低。异氰酸苯酯与甲醇反应的吉布斯自由能的相对变化也随着醇缔合度的增加而变小。
Quantum-chemical calculations at the B3LYP/6-311++G(df,p) level of theory showed that reactions of phenyl isocyanate with methanol associates involve formation of pre-and post-reaction complexes. The reactions proceed through late asymmetric cyclic transition states. The height of the energy barrier decreases as the degree of association of the alcohol increases. The relative change in the Gibbs energy in the reaction of phenyl isocyanate with methanol also becomes smaller as the degree of alcohol association increases.