有机化学 ›› 2015, Vol. 35 ›› Issue (1): 121-128.DOI: 10.6023/cjoc201406051 上一篇    下一篇

研究论文

碳酸铯催化吡唑与α,β-不饱和酮的氮杂Michael反应

杨靖亚a, 马奔a, 周红艳b, 占宝华a, 李政a   

  1. a 西北师范大学化学化工学院 兰州 730070;
    b 甘肃农业大学理学院 兰州 730070
  • 收稿日期:2014-06-30 修回日期:2014-09-24 出版日期:2015-01-25 发布日期:2014-10-09
  • 通讯作者: 杨靖亚 E-mail:yangjy@nwnu.edu.cn
  • 基金资助:

    国家自然科学基金(Nos. 21362034, 21162026)、高等学校博士学科点专项科研基金(No. 20136203120005)、甘肃省自然科学基金(No. 1107RJZ189)、西北师范大学青年教师科研能力提升计划(No. NWNU-LKQN-11-15)和甘肃农业大学科技创新基金(No. GAU-CX1115)资助项目.

Cesium Carbonate Catalyzed Aza-Michael Addition of Pyrazole to α,β-Unsaturated Ketones

Yang Jingyaa, Ma Bena, Zhou Hongyanb, Zhan Baohuaa, Li Zhenga   

  1. a College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070;
    b College of Science, Gansu Agricultural University, Lanzhou 730070
  • Received:2014-06-30 Revised:2014-09-24 Online:2015-01-25 Published:2014-10-09
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21362034, 21162026), the Research Fund for the Doctoral Program of Higher Education of China (No. 20136203120005), the Provincial Natural Science Foundation of Gansu Province (No. 1107RJZ189), the Program for Improving Scientific Research Ability of Young Teachers of Northwest Normal University (No. NWNU-LKQN-11-15) and the Science and Technology Innovation Fund of Gansu Agricultural University (No. GAU-CX1115).

发展了一种碳酸铯催化吡唑与α,β-不饱和酮的氮杂Michael反应新方法. 在5 mol% Cs2CO3存在下, 于1,4-二氧六环中回流反应7~12 h, 以86%~95%的产率得到21种β-(N1-吡唑基)酮. 此法对芳香类和脂肪类α,β-不饱和酮均适用良好, 易实现克级放大. 产物可容易地转化为相应的γ-氨基醇. 发展的方法同样适用于吡唑与丙烯酸甲酯和硝基苯乙烯的氮杂Michael反应.

关键词: Michael加成, 含氮杂环, α,β-不饱和酮, 催化, 碳酸铯

A Cs2CO3-catalyzed aza-Michael reaction of pyrazole to α,β-unsaturated ketones has been developed. With 5 mol% Cs2CO3 as catalyst, a series of β-N1-pyrazoly ketones were achieved in 86%~95% yields after 7~12 h in refluxing dioxane. Both aromatic and aliphatic α,β-unsaturated ketones as well as methacrylate and nitrostyrene are well tolerated. Broad scope of substrate and easily scale up make this protocol really practical. Furthermore, the product could be facilely transformed into corresponding γ-amino alcohol.

Key words: Michael addition, nitrogen heterocycles, α,β-unsaturated ketones, catalysis, cesium carbonate