高等学校化学学报

高等学校化学学报 ›› 2009, Vol. 30 ›› Issue (10): 2059.

• 研究论文 • 上一篇    下一篇

亚硝基化合物与甲醛的反应机理和溶剂效应的理论研究

郑天龙, 黎安勇   

  1. 西南大学化学化工学院, 重庆 400715
  • 收稿日期:2008-05-06 出版日期:2009-10-10 发布日期:2009-10-10
  • 通讯作者: 黎安勇, 男, 博士, 教授, 主要从事量子化学研究. E-mail: aylifnsy@swu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号： 20873013)资助.

Theoretical Studies on Mechanism and Solvent Effects of Reactions of Nitrosobenzene and 2-Methyl-2-nitrosopropane with Formaldehyde

ZHENG Tian-Long, LI An-Yong*   

  1. School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China
  • Received:2008-05-06 Online:2009-10-10 Published:2009-10-10
  • Contact: LI An-Yong. E-mail: aylifnsy@swu.edu.cn
  • Supported by:

    国家自然科学基金(批准号： 20873013)资助.

PDF (PC)

被引次数

3

摘要：

采用密度泛函方法B3LYP/6-311++G(d,p)研究了亚硝基苯C6H5—NO和2-甲基-2-亚硝基丙烷(CH3)3C—NO与甲醛分别在气相和溶剂中的反应机理. 在气相中均找到两条反应通道, 即协同机理和分步机理, 均生成实验产物氧肟酸, 而且分步机理均为优势通道; 除2-甲基-2-亚硝基丙烷的反应没有协同途径外, 在溶剂中反应机理与气相中的类似. 采用导电极化连续介质模型分别研究了在乙腈与水溶液中反应的溶剂化效应, 发现这些溶剂可降低反应的活化能, 但降低的程度比较小, 反应速率变化不大.

关键词: 密度泛函理论方法; 亚硝基苯; 2-甲基-2-亚硝基丙烷; 甲醛; 溶剂效应; 极化连续介质模型

Abstract:

The DFT method B3LYP/6-311++G(d,p) was used to study mechanism of reactions of nitrosobenzene and 2-methyl-2-nitrosopropane with formaldehyde in gas phase and solvents. In gas phase, there are two reaction paths, the concerted and stepwise mechanisms, both of which produce the experimental product, hydroxamic acid; the stepwise mechanism is predominant. The solvent effects were studied with the conductor-like polarizable continuum model respectively in the solvents acetonitrile and water, and we found that the solvent effects reduce the activation energy, but the reduction is small, these reactions are not sensitive to the solvent polarity.

Key words: Density function theory method; Nitrosobenzene; 2-Methyl-2-nitrosopropane; Formaldehyde; Solvent effect; Polarizable continuum model

TrendMD: