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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (15): 1743-1750. 上一篇    下一篇

研究论文

2-[(4-氯苯基亚氨基)甲基]-8-羟基喹啉质子转移的理论研究

杨国辉1, 李言信1, 颜世海*,1,2, 代丽1, 赵斌*,1   

  1. (1曲阜师范大学化学与化工学院 曲阜 273165)
    (2中国科学院青岛生物能源与过程研究所 青岛 266101)
  • 投稿日期:2010-12-03 修回日期:2011-02-26 发布日期:2011-04-07
  • 通讯作者: 赵斌 E-mail:liyanxin04@163.com
  • 基金资助:

    山东省优秀中青年科学家科研奖励基金;曲阜师范大学校级基金

Theoretical Study on Proton Transfer of 2-[(4-Chlorophenylimino)- methyl]-8-hydroxyquinoline

Yang Guohui1; Li Yanxin1; Yan Shihai*,1,2; Dai Li1; Zhao Bin*,1   

  1. (1 Chemistry and Chemical Engineering Institute, Qufu Normal University, Qufu 273165)
    (2 Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101)
  • Received:2010-12-03 Revised:2011-02-26 Published:2011-04-07
  • Supported by:

    the Science-Technology Foundation for Middle-Aged and Young Scientist of Shandong Province, China

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1208

被引次数

13

研究了2-[(4-氯苯基亚氨基)甲基]-8-羟基喹啉的三种质子转移途径: 分子内质子转移、水分子辅助质子转移和甲醇分子辅助质子转移. 以该席夫碱化合物的晶体结构作为模型, 在B3LYP/6-31＋G(d)水平上, 优化得到稳定态和过渡态的几何构型. 对三类质子转移前后的结构、能量、红外光谱、化学位移进行研究, 结果表明水分子辅助质子转移和甲醇分子辅助质子转移中, 水和甲醇分子利用氢键作用参与质子转移过程, 形成七元环状过渡态, 大大降低了反应的能垒, 有利于质子的转移, 氢键在降低活化能方面起着重要作用.

关键词: 2-[(4-氯苯基亚氨基)甲基]-8-羟基喹啉, 质子转移, 过渡态, 氢键, 活化能

The intramolecular proton transfer (PT), the water-assisted PT, and the methanol-assisted PT of 2-[(4-chlorophenylimino)methyl]-8-hydroxyquinoline are investigated. Based on the crystal structure of the Schiff base compounds, the intramolecular PT, the water-assisted PT, and the methanol-assisted PT of 2-[(4-chlorophenylimino)methyl]-8-hydroxyquinoline are investigated at B3LYP/6-31＋G(d) basis set level. The primary geometry structures, infrared frequencies, energies as well as the NMR data are compared. It implies that both the water and methanol are involved in the proton transfer processes through hydrogen bonds, and seven-membered cyclic transition states are formed, which are favorable for PT owing to their capability to reduce significantly the PT energy barriers. The H-bonds play a key role in decreasing the activation energy.

Key words: 2-[(4-chlorophenylimino)methyl]-8-hydroxyquinoline, proton transfer, transition state, hydrogen bond, activation energy