| 5-醛基-1,2,3-三唑互变异构的理论研究 |
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| 引用本文： | 姜恒香,国永敏,李宝宗.5-醛基-1,2,3-三唑互变异构的理论研究[J].化学研究,2007,18(2):69-72. |
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| 作者姓名： | 姜恒香 国永敏 李宝宗 |
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| 作者单位： | 苏州大学,独墅湖校区化学化工学院,江苏,苏州,215123 |
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| 基金项目： | 国家自然科学基金(20673075)，江苏高校国家级有机化学重点学科培育点经费资助 |
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| 摘 要： | 用密度泛函B3LYP/6-311++G**方法,对气相和水相中的5-醛基-1,2,3-三唑互变异构体进行了几何构型全自由度优化,获得了它们在气相和水相中的几何结构和电子结构.讨论了不同的取代基团和溶剂化效应对互变异构体的几何结构、能量以及互变异构反应活化能的影响.并进一步研究了N1-H、N2-H和N3-H型三唑之间的互变异构机理:(a)分子内质子转移;(b)水助质子转移.计算结果表明,途径(b)所需要的活化能较小,平均为101.31kJ/mol,途径(a)为211.70kJ/mol.
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| 关 键 词： | 5-醛基-1 2 3-三唑 互变异构 过渡态 质子迁移 密度泛函理论 |
| 文章编号： | 1008-1011（2007）02-0069-04 |
| 修稿时间： | 2007-01-11 |
DFT Studies on the Tautomerization of 5-Formyl-1,2,3-triazoles |
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| JIANG Heng-xiang,GUO Yong-min,LI Bao-zong.DFT Studies on the Tautomerization of 5-Formyl-1,2,3-triazoles[J].Chemical Research,2007,18(2):69-72. |
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| Authors: | JIANG Heng-xiang GUO Yong-min LI Bao-zong |
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| Institution: | School of Chemistry and Chemical Engineering , Suzhou University, Suzhou 215123, Jiangsu, China |
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| Abstract: | Molecular structures of 5-formyl-1,2,3-triazoles tautomers were calculated by the B3LYP method at the 6-311 G level both in the gaseous and aqueous phases with full geometry optimization. The geometrical and electronic structure of the tautomers of 5-substituted 1,2,3-triazoles and their transition states were obtained. The influence of the different 5-substituents and solvent effect on the geometrical structure, energy, and activated energy were discussed. The reaction mechanisms of tautomers of 5-substituted 1,2,3-triazoles were also studied. There are two reaction pathways: (a) intramolecular proton transfer; (b) water-assisted intermolecular transfer. The calculated results showed that process (b) has lower activation energy than (a). |
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| Keywords: | 5-formyl-1 2 3-triazole tautomer transition state proton transfer DFT |
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