An Investigation on Imine Formation Mechanism of Cyclohexanone and Benzylamine with DFT Study: Significant p-Chloro-Substituted and Metal-Assisted Effects
首发时间:2015-05-04
Abstract:The imine formation mechanism has been investigated using density functional theory at the B3LYP/6-31G* level. The geometries, energies and frequencies of all stationary points were calculated. Our results indicate quantitively that imine formation mechanism proceeds via nucleophilic attack and water elimination, and metal-assisted imine formation only involves nucleophilic attack to ion pair interaction. From the rate-determining step, p-chloro-benzylamine lows energy barrier by 1.1 kJ/mol, which delivers easier imine formation theoretically and accords with experimental description. The imine formation assisted by titanium tetrachloride and zinc dichloride reduces activation energies to 35.6 and -27.0 kJ/mol, respectively, which suggests higher yield.
keywords: DFT Imine Titanium Zinc
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基于DFT方法探究环己酮与苄胺形成亚胺的反应机理:对位氯取代以及金属参与对反应的影响
摘要:本文探讨了环己酮和苄胺参与形成亚胺的反应机理。运用密度泛函理论(DFT)计算了相关几何结构、反应能垒、过渡态频率。主要证明了亚胺的形成是先经历了亲核进攻再脱水的过程,但如果有金属参与时,则发生的是亲核进攻离子对的作用历程。由决速步骤可知,理论上4-氯苄胺拥有较低的能垒(1.1 KJ/mol)以至于它能够更容易与酮作用生成亚胺,而这恰好也与实验所得结论相符合。当有四氯化钛或者二氯化锌参与时,反应活化能会分别降到35.6 KJ/mol和-27.0 KJ/mol,从而明显地提高反应收率。
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No.4639978964856142****
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基于DFT方法探究环己酮与苄胺形成亚胺的反应机理:对位氯取代以及金属参与对反应的影响
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