Construction of Substituted N-Phenylpyrazoles via a Catalyst- Free and Additive-Free Intermolecular Cyclization Process

doi:10.6023/cjoc202201017

Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (6): 1843-1848.DOI: 10.6023/cjoc202201017 Previous Articles Next Articles

NOTES

无催化剂和无添加剂条件下分子间环化构建取代N-苯基吡唑

马豪杰^*(), 周风院, 刘金磊, 韩波, 杨华, 张玉琦^*(), 王记江

延安大学化学与化工学院陕西省化学反应工程重点实验室新能源与新功能材料重点实验室延安 716000

收稿日期:2022-01-12 修回日期:2022-02-23 发布日期:2022-03-21
通讯作者: 马豪杰, 张玉琦
基金资助:
延安大学博士科研启动基金(YDBK2019-30); 延安市高层次人才专项基金(2019-29); 陕西省教育厅自然科学专项研究基金(21JK0979); 国家级大学生创新创业训练计划(202110719022); 榆林市自然科学基金(CXY-2020-065)

Construction of Substituted N-Phenylpyrazoles via a Catalyst- Free and Additive-Free Intermolecular Cyclization Process

Haojie Ma(), Fengyuan Zhou, Jinlei Liu, Bo Han, Hua Yang, Yuqi Zhang(), Jijiang Wang

Key Laboratory of New Energy & New Functional Materials, Shaanxi Key Laboratory of Chemical Reaction Engineering, College of Chemistry and Chemical Engineering, Yan'an University, Yan'an 716000

Received:2022-01-12 Revised:2022-02-23 Published:2022-03-21
Contact: Haojie Ma, Yuqi Zhang
Supported by:
PhD Research Startup Foundation of Yan'an University(YDBK2019-30); Municipal Special Fund of Yan'an for High-Level Talents(2019-29); Scientific Research Program Funded by Shaanxi Provincial Education Department(21JK0979); National College Students’ Innovation and Entrepreneurship Training Program(202110719022); Natural Science Foundation of Yulin City(CXY-2020-065)

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Abstract

A simple and practical protocol for the construction of substituted N-phenylpyrazoles from phenylhydrazine and pentane-2,4-dione under catalyst-free and additive-free conditions was demonstrated. The catalyst-free and additive-free process has advantages of operational simplicity, good functional group tolerance, step economy, scaled-up synthesis and high yields, which render this strategy to be more useful in the synthesis of pyrazole drugs, biologically active molecules and pesticides.

Key words: catalyst-free, additive-free, N-phenylpyrazole, phenylhydrazine, pentane-2,4-dione

Cite this article

Haojie Ma, Fengyuan Zhou, Jinlei Liu, Bo Han, Hua Yang, Yuqi Zhang, Jijiang Wang. Construction of Substituted N-Phenylpyrazoles via a Catalyst- Free and Additive-Free Intermolecular Cyclization Process[J]. Chinese Journal of Organic Chemistry, 2022, 42(6): 1843-1848.

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Fig. & Tab. 7

Figure 1. Some important pyrazoles

Scheme 1. Approaches toward pyrazoles

Entry	Solvent	Temp./℃	Yield^b/%
1	DMSO	60	46
2	DMF	60	30
3	CH₃CN	60	99
4	Toluene	60	58
5	DCE	60	73
6	CH₃CN	40	92
7 8^c 9^d	CH₃CN CH₃CN CH₃CN	80 60 60	96 98 96

Table 1. Optimization of reaction conditionsa

Table 2. Synthesis of 3,5-dimethyl-1-phenyl-1H-pyrazoles from substituted benzohydrazides and pentane-2,4-dionea

Table 3. Synthesis of 3,5-dimethyl-1-phenyl-1H-pyrazoles from benzohydrazide and substituted pentane-2,4-dionesa

Scheme 2. Gram scale reaction

Scheme 3. Proposed mechanism

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无催化剂和无添加剂条件下分子间环化构建取代N-苯基吡唑

Construction of Substituted N-Phenylpyrazoles via a Catalyst- Free and Additive-Free Intermolecular Cyclization Process

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Fig. & Tab. 7

References 19

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