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2022 , Vol. 42 >Issue 12: 4292 - 4299

DOI: https://doi.org/10.6023/cjoc202211002

研究论文

电催化肼、丙二酮和2-溴丙二酸二乙酯三组分合成4-溴吡唑

  • 穆思宇 ,
  • 李红霞 ,
  • 伍智林 ,
  • 彭俊梅 ,
  • 陈锦杨 ,
  • 何卫民
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  • a 南华大学药学院 湖南衡阳 421001
    b 南华大学化学化工学院 湖南衡阳 421001

收稿日期: 2022-11-01

  修回日期: 2022-11-20

  网络出版日期: 2022-11-28

基金资助

湖南省自然科学基金(2021JJ40429); 湖南省教育厅科学研究基金(19B501)

收起

Electrocatalytic Three-Component Synthesis of 4-Bromopyrazoles from Acetylacetone, Hydrazine and Diethyl Bromomalonate

  • Siyu Mu ,
  • Hongxia Li ,
  • Zhilin Wu ,
  • Junmei Peng ,
  • Jinyang Chen ,
  • Weimin He
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  • a School of Pharmaceutical Science, University of South China, Hengyang, Hunan 421001
    b School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan 421001
*E-mail: ;

Received date: 2022-11-01

  Revised date: 2022-11-20

  Online published: 2022-11-28

Supported by

Natural Science Foundation of Hunan Province(2021JJ40429); Research Foundation of Education Bureau of Hunan Province(19B501)

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摘要

吡唑是一类重要的五元氮杂环化合物, 存在于多种天然产物和药物分子中. 4-溴吡唑是一种高价值的吡唑衍生物, 不仅具有多种生物活性和药理活性, 还被广泛用作有机合成中间体, 因此发展新型高效的4-溴吡唑化合物合成方法具有重要的研究意义. 本研究发展了一种电化学促进芳香肼、1,2-丙二酮和2-溴丙二酸二乙酯三组分串联环化-溴化反应合成4-溴吡唑化合物的方法, 并揭示了其反应机理. 反应历程为芳香肼与丙二酮发生环化反应得到吡唑杂环化合物, 其发生溴化反应得到4-溴吡唑. 2-溴丙二酸二乙酯具有较高的氧化态, 防止电解过程中过氧化效应, 避免了过量溴化剂的使用. 我们还将该方法用于其他溴化杂环化合物的合成.

关键词： 有机电合成; 多组分反应; 溴化反应; 4-溴吡唑衍生物

本文引用格式

穆思宇 , 李红霞 , 伍智林 , 彭俊梅 , 陈锦杨 , 何卫民 . 电催化肼、丙二酮和2-溴丙二酸二乙酯三组分合成4-溴吡唑[J]. 有机化学, 2022 , 42(12) : 4292 -4299 . DOI: 10.6023/cjoc202211002

Abstract

Pyrazoles are the most important five-membered N-heterocycles as they are present in many natural products and synthetic drugs. Among various pyrazole derivatives, 4-bromopyrazoles have attracted great attention because they not only display significant biological activities and physicochemical properties but also serve as valuable synthons in organic chemistry. In this manuscript, an efficient and eco-friendly method for the synthesis of various 4-bromopyrazoles through three- component reaction of hydrazine, acetylacetone and 2-bromomalonate was reported and the proposal reaction mechanism was revealed. According to the mechanism, hydrazine reacts with acetylacetone to afford pyrazole firstly, which then converts to 4-bromopyrazole through bromination. This method could also be well applicable for the bromination of other heterocyclic compounds. Given the high oxidation state of diethyl 2-bromomalonate, the peroxidation can be avoided through the electrolysis process, thus the excess amount of brominating agent was not be required.

Key words： electro-organic synthesis; multicomponent reaction; bromination reaction; 4-bromopyrazole derivatives

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