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化学学报
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化学学报 ›› 2004, Vol. 62 ›› Issue (20): 2003-2006. 上一篇    下一篇

研究论文

SnCl4和DMF作用下1-三氯锡烷基2,3-丁二烯与甲醛反应机理的理论研究

徐开来1, 谢代前1,2, 鄢国森1   

  1. 1. 四川大学化学学院, 成都, 610064;
    2. 南京大学化学系, 理论与计算化学研究所, 南京, 210093
  • 投稿日期:2004-02-10 修回日期:2004-06-30 发布日期:2014-02-17
  • 通讯作者: 谢代前,E-mail:dqxie@nju.edu.cn;Fax:025-3596131 E-mail:dqxie@nju.edu.cn
  • 基金资助:
    国家自然科学基金(No.30370337),教育部"高校青年教师奖"和南京大学引进人才启动基金资助项目.

Theoretical Studies on Mechanism of Reaction of 1-Trichlorostannyl-2,3-butadiene with Formaldehyde Involving SnCl4 and DMF

XU Kai-Lai1, XIE Dai-Qian1,2, YAN1   

  1. 1. Deparment of Chemistry, Sichuan University, Chengdu 610064;
    2. Institute of Theoretical and Computational Chemistry, Department of Chemistry, Nanjing University, Nanjing 210093
  • Received:2004-02-10 Revised:2004-06-30 Published:2014-02-17

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用密度泛函理论方法在B3LYP/6-31G**水平上研究了SnCl4和DMF作用下1-三氯锡烷基-2,3-丁二烯与甲醛的反机理.优化得到各驻点的几何构型,通过振动分析和内禀反应坐标对过渡态进行了确认.计算得到两条反应路径.研究表明,反应具有很强的选择性,主要得到DMF作用下1-三氯锡烷基-2,3-丁二烯与甲醛直接反应的产物.计算结果与实验事实一致.

关键词: 1-三氯锡烷基-2, 3-丁二烯, 甲醛, DMF, SnCl4, B3-LYP

The mechanism of the reaction of 1-trichlorostannyl-2,3-butadiene with formaldehyde involving SnCl4 and DMF has been studied by using the density functional method at the B3LYP/6-31G** level. The structures and energies of the stationary points were calculated to produce the activation barriers. The transition states were confirmed by using vibration analysis and IRC calculations. Two reaction pathways were obtained and discussed. The results show that the reactions take place with high regioselectivity and mainly produce the product of the reaction of the 1-trichlorostannyl-2,3-butadiene with formaldehyde involving DMF, in good agreement with the available experiments.

Key words: 1-trichlorostannyl-2,3-butadiene, formaldehyde, DMF, SnCl4, B3L YP