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有机化学
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有机化学 ›› 2004, Vol. 24 ›› Issue (11): 1478-1481. 上一篇    下一篇

研究简报

液晶材料4-[2-(反-4-丙基环己基)]乙基氟苯的全合成研究

丁晓琴*, 赵立峰, 连兰芬, 陈冀胜   

  1. 北京药物化学研究所 北京 102205
  • 收稿日期:2004-02-09 修回日期:2004-06-09 接受日期:2004-06-09 发布日期:2022-09-21
  • 通讯作者: * E-mail: dingxq@cetin.net.cn

Total Synthesis of Liquid Crystal Material 4-[2-(Trans-4'- propylcyclohexyl)ethyl]-1-fluorobenzene

DING Xiao-Qin*, ZHAO Li-Feng, LIAN Lan-Fen, CHEN Ji-Sheng   

  1. Beijing Institute of Pharmaceutical Chemistry, Beijing 102205
  • Received:2004-02-09 Revised:2004-06-09 Accepted:2004-06-09 Published:2022-09-21

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主要对向列型液晶材料4-[2-(反-4-丙基环己基)]乙基氟苯的全合成进行研究,设计和改进了合成反应的反应条件,提高了收率.最后一步酮基的还原成次甲基采用与乙二硫醇缩合后用Raney镍在无水乙醇条件下进行氢化还原和Wolff-Kishner-黄鸣龙还原反应两种方法,都获得了高纯度的目标化合物.同时,通过使用DFT量子化学从头计算和实验的验证,解释了Wolff-Kishner-黄鸣龙还原反应在合成化合物1过程中产生副产物10 (1-三缩乙二醇取代-4-反式-4'-丙基取代环己烷乙基苯)的原因.通过改进反应条件,将文献报道的一锅一步反应改成一锅两步反应,成功地合成了目标化合物,降低了生产的成本,产品气相色谱纯度达到98％以上,质量完全符合实际的使用要求.

关键词: 向列型液晶材料, 4-[2-(反-4-丙基环己基)]乙基氟苯, 合成, DFT量子化学计算, 还原反应机理

The total synthesis of the nematic liquid crystal material 4-[2-(trans-4'-propylcyclohexyl)ethyl]-1-fluorobenzene through eight steps was reported. In the last step, we used two kinds of reduction methods to transform the carbonyl to methylene and obtained the goal compound. Oneof them was carbonyl reduction by thioacetal hydrogenolysis and the second wasthe Wolff-Kishner-Huangminlong reduction improved from one step to two steps in one pot. Moreover we successfully used the density functional theory (DFT) ab initio quantum chemistry methods to explain the reason of forming the by-product 10, 1-(n-3,6-dioxa-8-hydroxy-octyloxy)-4-[2-(trans-4'-propylcyclo~hexyl)~ethyl]benzene in the process of Wolff-Kishner-Huangminlong reaction. All the calculations in this paper were carriedout by the program of GAUSSIAN 03W.

Key words: nematic liquid crystal material, 4-[2-(trans-4'-propylcyclohexyl)ethyl]-1-fluorobenzene, synthesis, DFT, reduction mechanism for carbonyl to methylene