NONDISSOCIATIVE PROTON-TRANSFER IN 2-PYRIDONE-2-HYDROXYPYRIDINE - AN ABINITIO MOLECULAR-ORBITAL STUDY
NONDISSOCIATIVE PROTON-TRANSFER IN 2-PYRIDONE-2-HYDROXYPYRIDINE - AN ABINITIO MOLECULAR-ORBITAL STUDY
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DOI：
10.1039/p29870000617
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发表时间：
1987-05-01
期刊：
影响因子：
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通讯作者：
HILLIER, IH
中科院分区：
文献类型：
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作者：
FIELD, MJ;HILLIER, IH
用从头算分子轨道方法研究了2-吡啶酮的内酰亚胺-内酰胺互变异构反应的非解离质子转移机理。已经获得了三种机制的质子转移势能面上的固定点（最小值和鞍点）：（i）分子内机制，（ii）自缔合二聚体内的互变异构互变，以及（iii）涉及一个或两个水分子作为双功能催化剂的机制。后两种机制被认为是更积极的比第一个有利的。本体溶剂的质子转移的能量的这些机制的作用进行了研究。
The lactim–lactam tautomerism of 2-pyridone via non-dissociative proton-transfer mechanisms has been investigated using ab initio MO methods. Stationary points (minima and saddle points) on the potential energy surfaces for proton transfer by three classes of such mechanisms have been obtained: (i) an intramolecular mechanism, (ii) tautomeric interconversion within a self-associated dimer, and (iii) a mechanism involving one or two water molecules as a bifunctional catalyst. The latter two mechanisms were found to be more energetically favourable than the first. The role of bulk solvent on the energetics of proton transfer by these mechanisms has been investigated.