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有机化学
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有机化学 ›› 2006, Vol. 26 ›› Issue (01): 77-81. 上一篇    下一篇

研究论文

1,3-二甲氧甲酰-4,6-二氰基噻吩并[3,4-c]噻吩的合成和密度泛函理论研究

耿蓉霞*，何佑秋，申伟   

  1. (西南师范大学化学化工学院 重庆 400715)
  • 收稿日期:2005-01-14 修回日期:2005-07-29 发布日期:2005-12-31
  • 通讯作者: 耿蓉霞

ynthesis and Density Functional Theory Study of 1,3-Dimethoxy-carbonyl-4,6-dicyan-othieno[3,4-c]thiophene

GENG Rong-Xia*,HE You-Qiu,SHEN Wei   

  1. (School of Chemistry and Chemical Engineering, Southwest China Normal University, Chongqing 400715)
  • Received:2005-01-14 Revised:2005-07-29 Published:2005-12-31
  • Contact: GENG Rong-Xia

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设计采用新颖的Pummerer-氰化路线和用亚硫酰氯作S-转移试剂的路线合成了第一例全部连吸电子基的噻吩并[3,4-c]噻吩. 用1H NMR, 13C NMR, FTIR, 元素分析和X射线衍射分析进行了表征. 用B3LYP/6-31G*及B3LYP/6- 311＋＋G**方法全优化计算了1,3-二甲氧甲酰-4,6-二氰基吩并[3,4-c]噻吩分子, 得到几何构型、总能量、标准熵、标准焓和标准自由能, 计算构型与X射线衍射测定结果非常吻合. 并用电荷分布讨论了有关非经典噻吩并[3,4-c]噻吩体系的稳定性, 计算结果能很好地解释有关实验现象.

关键词: Pummerer-氰基化, 电荷分布, S-转移反应, 噻吩并[3,4-c]噻吩, 密度泛函理论

By adopting novel Pummerer-cyanation route and by using thionyl chloride as S-transfer reagent, the first thieno[3,4-c]thiophene bearing all electron withdrawing groups (EWGs) has been synthesized. The molecular structure was identified and characterized by 1H NMR, 13C NMR, FTIR spectra, elemental analysis and X-ray diffractional method. The molecular structure of 1,3-dimethoxycarbonyl-4,6-di- cyanothieno[3,4-c]thiophene was calculated by DFT method at B3LYP/6-31G* and B3LYP/6-311＋＋G** levels. The structure, total energy, standard entropy, standard enthalpy and standard free energy were obtained, in which the calculated molecular configuration was very close to the experimental analysis of X-ray diffraction. The data of charge distribution were also used to discuss the stability of the series of nonclassical condensed thieno[3,4-c]thiophene. The calculation results can be better used to explain some experimental phenomena.

Key words: thieno[3,4-c]thiophene, density functional theory, charge distribution, S-transfer reaction, Pummerer-cyanation