有机化学 ›› 2012, Vol. 32 ›› Issue (04): 794-798.DOI: 10.6023/cjoc1109212 上一篇    下一篇

研究简报

氯化亚铜催化3-氯-1-丁烯异构为1-氯-2-丁烯研究

董建勋a, 阎智峰b, 石玉坤a, 胡晓静a, 丁真贞a, 赵伟玲a, 宋娟娟a, 黄唯平a   

  1. a 南开大学化学系 天津 300071;
    b 河南省伟华安全科技有限公司 郑州 450000
  • 收稿日期:2011-09-21 修回日期:2011-11-12 出版日期:2012-04-25 发布日期:2012-04-24
  • 通讯作者: 黄唯平 E-mail:huangw@eyou.com
  • 基金资助:

    国家自然科学基金(No. 21071086)资助项目.

Cuprous Chloride Catalyzed Isomerization of 3-Chloro-1-butene to Crotyl Chloride

Dong Jianxuna, Yan Zhifengb, Shi Yukuna, Hu Xiaojinga, Ding Zhenzhena, Zhao Weilinga, Song Juanjuana, Huang Weipinga   

  1. a College of Chemistry, Nankai University, Tianjin 300071;
    b Henan Weihua Safety Assessment Company Limited, Zhengzhou 450000
  • Received:2011-09-21 Revised:2011-11-12 Online:2012-04-25 Published:2012-04-24
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21071086).

采用一价铜盐为催化剂、二甲基甲酰胺为溶剂, 在均相体系中催化3-氯-1-丁烯异构化生成1-氯-2-丁烯. 考察了溶剂、反应温度、催化剂种类和加入量对反应的影响, 研究发现反应温度和催化剂的加入量对异构化反应有较大影响.在最优条件3-氯-1-丁烯1 mL, 二甲基甲酰胺 9 mL, CuCl 0.10 g, 60 ℃反应5 h, 产物和原料的浓度比为3.88 mmol·L-1. 采用在线红外光谱对反应过程进行监测, 检测到有红外吸收峰在反应过程中先增加后减少的变化过程, 提出了可能的反应机理.

关键词: 3-氯-1-丁烯, 1-氯-2-丁烯, 氯化亚铜, 异构化

The isomerization of 3-chloro-1-butene to crotyl chloride was carried out in the homogeneous catalytic system containing cuprous salt and dimethylformamide. Factors such as solvent, temperature, and content of catalyst that influence the reaction were investigated. The type of solvent and content of catalyst had great effect on the isomerization. Equilibrium constant of the title reaction reached 3.88, which was kept for 5 h at 60 ℃ under the optimal condition. The process of isomerization was monitored with in-situ FTIR-ATR and the possible reaction mechanism was suggested in this paper.

Key words: 3-chloro-1-butene, crotyl chloride, cuprous chloride, isomerization