CBr4促进的分子间环化反应: 高效合成取代N-酰基吡唑

doi:10.6023/cjoc202107020

有机化学 ›› 2021, Vol. 41 ›› Issue (11): 4353-4360.DOI: 10.6023/cjoc202107020 上一篇下一篇

研究论文

CBr₄促进的分子间环化反应: 高效合成取代N-酰基吡唑

马豪杰^a, 孙洲^b, 刘金磊^a, 张夏^b, 崔华莉^a, 张玉琦^a^,^*(), 王记江^a

a 延安大学化学与化工学院新能源与新功能材料重点实验室陕西省化学反应工程重点实验室延安 716000
b 齐鲁工业大学前沿交叉学科研究院生物基材料与绿色造纸国家重点实验室济南 250353

收稿日期:2021-07-07 修回日期:2021-07-26 发布日期:2021-08-24
通讯作者: 张玉琦
作者简介:
† 共同第一作者.
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); 陕西省科技资源开放共享平台(2021PT-004); 陕西省教育厅重点科学研究计划(20JS154); 山东省自然科学基金(ZR2020QB042)

CBr₄-Mediated Intermolecular Cyclization Reaction: Efficient Synthesis of Substituted N-Acylpyrazoles

Haojie Ma^a, Zhou Sun^b, Jinlei Liu^a, Xia Zhang^b, Huali Cui^a, Yuqi Zhang^a(), Jijiang Wang^a

a 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, Shaanxi 716000
b State Key Laboratory of Biobased Material and Green Papermaking, Academy of Advanced Interdisciplinary Studies, Qilu University of Technology, Jinan 250353

Received:2021-07-07 Revised:2021-07-26 Published:2021-08-24
Contact: Yuqi Zhang
About author:
† These authors contributed equally to this work.
Supported by:
PhD Research Startup Foundation o 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); Open Sharing Platform for Scientific and Technological Resources of Shaanxi Province(2021PT-004); Key Scientific Research Project of Shaanxi Provincial Education Department(20JS154); Natural Science Foundation of Shandong Province(ZR2020QB042)

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摘要/Abstract

报道了CBr₄促进的苯甲酰肼和2,4-戊二酮分子间环化高产率地合成(3,5-二甲基-1H-吡唑-1-基)(苯基)-甲酮. 该方法具有条件温和、良好的官能团耐受性、环境友好、操作简单、成本低、步骤经济、可进行按比例放大等优点, 为广泛应用于药物、生物活性分子和农药中的吡唑类化合物的合成提供了一种实用而有吸引力的策略.

关键词: 苯甲酰肼, 2,4-戊二酮, N-酰基吡唑, 四溴化碳

Synthesis of (3,5-dimethyl-1H-pyrazol-1-yl)(phenyl)-methanones in excellent yields by CBr₄ mediated intermolecular cyclization of benzohydrazide and pentane-2,4-dione has been reported. The method shows various advantages such as mild conditions, good functional group tolerance, environmental friendliness, easy operation with cheap reagents, step economy and can be scaled-up, offering a useful and attractive strategy to synthesize N-acylpyrazoles, which is widely presented in drugs, biologically active molecules and pesticides.

Key words: benzohydrazides, pentane-2,4-diones, N-acylpyrazoles, CBr₄

引用此文

马豪杰, 孙洲, 刘金磊, 张夏, 崔华莉, 张玉琦, 王记江. CBr₄促进的分子间环化反应: 高效合成取代N-酰基吡唑[J]. 有机化学, 2021, 41(11): 4353-4360.

Haojie Ma, Zhou Sun, Jinlei Liu, Xia Zhang, Huali Cui, Yuqi Zhang, Jijiang Wang. CBr₄-Mediated Intermolecular Cyclization Reaction: Efficient Synthesis of Substituted N-Acylpyrazoles[J]. Chinese Journal of Organic Chemistry, 2021, 41(11): 4353-4360.

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图/表 8

Figure 1. Structures of some important pyrazoles

Scheme 1. Novel routes to synthesize pyrazoles

Entry	CBr₄	Solvent	Temp./℃
1	1	DMSO	60	53
2	1	DMF	60	85
3	1	Toluene	60	15
4	1	DCE	60	95
5	1	CH₃CN	60	98
6	0.5	CH₃CN	60	76
7	1.5	CH₃CN	60	93
8	1	CH₃CN	r.t.	20
9	1	CH₃CN	40	96
10	1	CH₃CN	80	95
11^c	1	CH₃CN	60	70
12^d	1	CH₃CN	60	95

Table 1. Optimization of reaction conditionsa

Table 2. Synthesis of (3,5-dimethyl-1H-pyrazol-1-yl)(phenyl)- methanones from substituted benzohydrazides and pentane-2,4- dionea

Table 3. Synthesis of (3,5-dimethyl-1H-pyrazol-1-yl)(phenyl)- methanones from benzohydrazide and substituted pentane-2,4- dionesa

Scheme 2. Gram scale reaction

Scheme 3. Control experiments

Scheme 4. Proposed mechanism

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CBr₄促进的分子间环化反应: 高效合成取代N-酰基吡唑

CBr₄-Mediated Intermolecular Cyclization Reaction: Efficient Synthesis of Substituted N-Acylpyrazoles

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