Acta Chimica Sinica ›› 2005, Vol. 63 ›› Issue (23): 2163-2168. Previous Articles     Next Articles

水溶液中亚硝基甲烷与甲醛肟之间互变异构反应的理论研究

梁国明1, 任译2   

  1. 1. 重庆师范大学化学学院, 重庆, 400047;
    2. 四川大学化学学院, 成都, 610064
  • 投稿日期:2004-11-16 修回日期:2005-06-29 发布日期:2014-02-14
  • 通讯作者: yiren57@sina.com
  • 作者简介:任译,E-mail:yiren57@sina.com
  • 基金资助:

    重庆市教委科技(No.kj050805)资助项目.

Theoretical Study of the Tautomerization of Nitromethane to Formaldoxime in Aqueous Solution

LIANG Guo-Ming1, REN Yi2   

  1. 1. College of Chemistry, Chongqing Normal University, Chongqing 400047;
    2. College of Chemistry, Sichuan University, Chengdu 610064
  • Received:2004-11-16 Revised:2005-06-29 Published:2014-02-14

The mechanism of the tautomerization of nitromethane to formaldoxime in aqueous solution has been investigated at the level of B3LYP/6-311++G** using the supramolecular/continuum model. Calcu-lated results indicate that the isomerization of nitromethane to more stable trans-formaldoxime can proceed via two different reaction channels, but the favorable reaction pathway in aqueous is different from the one in the gas phase. It is more favorable that the tautomeric reaction involves the formation of cis-formaldoxime and a subsequent rotation about the N—O bond to form the trans-formaldoxime in aqueous solution. More-over, the activation energies were reduced from 240.6 and 196.2 kJ/mol in the gas phase to 61.7 and 92.1 kJ/mol in aqueous solution, respectively, due to the catalysis of water.

Key words: nitromethane, formaldoxime, water-catalyzed tautomerization, density functional theory