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2020 , Vol. 40 >Issue 9: 2871 - 2878

DOI: https://doi.org/10.6023/cjoc202003047

研究论文

丙酮氰醇与3,5-二甲基-N-α,β-不饱和酰基吡唑的反应研究

  • 房观念 ,
  • 由君 ,
  • 喻艳超 ,
  • 荆军凯 ,
  • 刘波 ,
  • 武文菊
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  • 哈尔滨理工大学化学与环境工程学院 黑龙江省绿色化工技术重点实验室 哈尔滨 150040

收稿日期: 2020-03-19

  修回日期: 2020-05-22

  网络出版日期: 2020-06-19

基金资助

国家自然科学基金（No.21908034）、黑龙江省自然科学基金（No.LH2019B010）资助项目.

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Study on the Reaction of Acetone Cyanohydrin with 3,5-Dimethyl-N-α,β-unsaturated Acyl Pyrazole

  • Fang Guannian ,
  • You Jun ,
  • Yu Yanchao ,
  • Jing Junkai ,
  • Liu Bo ,
  • Wu Wenju
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  • Key Laboratory of Green Chemical Engineering and Technology of Heilongjiang Province, College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin 150040

Received date: 2020-03-19

  Revised date: 2020-05-22

  Online published: 2020-06-19

Supported by

Project supported by the National Natural Science Foundation of China (No. 21908034), and the Natural Science Foundation of Heilongjiang Province (No. LH2019B010).

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摘要

氰基化合物是一类具有重要价值的有机物.研究了以丙酮氰醇为反应试剂，以取代的3，5-二甲基-N-α，β-不饱和酰基吡唑为底物时发生在不同位点的两种反应.研究结果表明，芳香取代的3，5-二甲基-N-α，β-不饱和酰基吡唑为底物时，使用不同的碱性催化剂会发生两种不同类型的反应：MgBu2存在时体系发生Michael加成反应，产物收率最高可达95%；在四甲基胍（TMG）存在时体系发生酰胺的醇解反应，生成β-取代苯基丙烯酸氰醇酯，收率最高达84%.脂肪取代的3，5-二甲基-N-α，β-不饱和酰基吡唑与丙酮氰醇在MgBu2或TMG存在下均发生Michael加成反应，产率最高为99%.讨论了使用不同碱性催化剂时的反应机理.

关键词： 丙酮氰醇; 3,5-二甲基-N-α,β-不饱和酰基吡唑; Michael加成反应; β-取代苯基丙烯酸氰醇酯

本文引用格式

房观念 , 由君 , 喻艳超 , 荆军凯 , 刘波 , 武文菊 . 丙酮氰醇与3,5-二甲基-N-α,β-不饱和酰基吡唑的反应研究[J]. 有机化学, 2020 , 40(9) : 2871 -2878 . DOI: 10.6023/cjoc202003047

Abstract

Cyano compounds are a class of organic compounds with great value. Two different kinds of reactions have been reported using acetone cyanohydrin as reagent and substituted 3,5-dimethyl-N-α,β-unsaturated acyl pyrazole as substrate. The reaction pathway depends on the basic catalysts used when aromatic substituted 3,5-dimethyl-N-α,β-unsaturated acyl pyrazole was used as the substrate. Michael addition reaction occurred in the presence of MgBu2 with the product yield up to 95%, while alcoholysis reaction of amide occurred in the presence of 1,1,3,3-tetramethylguanidine (TMG), producing β-substituted phenyl cyanoacrylates with 84% yield. However, fatty substituted 3, 5-dimethyl-N-α,β-unsaturated acyl pyrazole and acetone cyanohydrin underwent Michael addition reaction in the presence of MgBu2 or TMG, the product yield was up to 99%. The possible reaction mechanism when using different basic catalysts was discussed.

Key words： acetone cyanohydrin; 3,5-dimethyl-N-α,β-unsaturated acyl pyrazole; Michael addition; β-substituted phenyl cyanoacrylate

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