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

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

Cite this article

Siyu Mu, Hongxia Li, Zhilin Wu, Junmei Peng, Jinyang Chen, Weimin He. Electrocatalytic Three-Component Synthesis of 4-Bromopyrazoles from Acetylacetone, Hydrazine and Diethyl Bromomalonate[J]. Chinese Journal of Organic Chemistry, 2022, 42(12): 4292-4299.

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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