物理化学学报Issue(2)：422-428,7.DOI:10.3866/PKU.WHXB201512082
2,6-二甲氧基-2-嘧啶氧基-N-芳基苄胺衍生物的酸催化Smiles重排反应动力学
Kinetics of Acid-Catalyzed Smiles Rearrangement of 2,6-Dimethoxy-2-pyrimidinyloxy-N-arylbenzylamine Derivatives
摘要
Abstract
The kinetics of the acid-catalyzed Smiles rearrangement reactions of 2,6-dimethoxy-2-pyrimidinyloxy-N-arylbenzylamine derivatives was investigated. The effects of initial concentrations of hydrochloric acid, solvent, temperature, and substituent on reaction rates were examined. The results show that the rates increase with an increase in the initial concentration of hydrochloric acid. The reactivity order is CH3OH > C2H5OH >CH3SOCH3>CH3CN in a single solvent, but rates markedly increase in mixed CH3OH/H2O (1:1, V/V) and the apparent reaction rate constant (kobs) is 5.27 times that of methanol. The rates for the derivatives are found to increase with an increase in temperature at 25-45 °C, and no significant differences in activation energy (73.99-76.92 kJ∙mol-1), activation enthalpy (71.57-74.38 kJ∙mol-1), and Gibbs free energy (81.51-85.77 kJ∙mol-1) are observed between them, except that there is difference in activation entropy (-24.38--47.11 J∙K-1∙mol-1). There is a good linear relationship between substituents and the apparent reaction rate constants, and it is speculated that electron-withdrawing groups in the benzene ring wil increase the reaction rates. A relevant reaction mechanism is suggested.关键词
动力学/反应机理/2,6-二甲氧基-2-嘧啶氧基-N-芳基苄胺衍生物/Smiles重排/酸催化反应Key words
Kinetics/Reaction mechanism/2,6-Dimethoxy-2-pyrimidinyloxy-N-arylbenzylamine derivatives/Smiles rearrangement/Acid-catalyzed reaction分类
化学化工引用本文复制引用
张培志,叶美君,胡伟莲,吴军..2,6-二甲氧基-2-嘧啶氧基-N-芳基苄胺衍生物的酸催化Smiles重排反应动力学[J].物理化学学报,2016,(2):422-428,7.基金项目
The project was supported by the National Natural Science Foundation of China (31471807) and Special Fund for Agro-scientific Research in the Public Interest, China (201403030).国家自然科学基金(31471807)和公益性行业(农业)科研专项(201403030)资助 （31471807）
