无催化剂一锅法构建取代磺酰吡唑

doi:10.6023/cjoc202104033

有机化学 ›› 2021, Vol. 41 ›› Issue (9): 3710-3716.DOI: 10.6023/cjoc202104033 上一篇下一篇

研究简报

无催化剂一锅法构建取代磺酰吡唑

马豪杰^a^,^b, 周小强^b^,^c, 韩波^a, 李然^a, 侯雪艳^a, 姬星月^a, 张玉琦^a^,^*(), 黄国生^b^,^*(), 王记江^a

a 延安大学化学与化工学院延安大学新能源与新功能材料重点实验室陕西化学反应工程重点实验室陕西延安 716000
b 兰州大学功能有机分子化学国家重点实验室兰州 730000
c 渭南师范学院化学与材料学院陕西渭南 714099

收稿日期:2021-04-16 修回日期:2021-04-27 发布日期:2021-06-22
通讯作者: 张玉琦, 黄国生
基金资助:
国家自然科学基金(21663032); 国家自然科学基金(31701679); 国家自然科学基金(22061041); 延安大学博士科研启动基金(YDBK2019-30); 延安大学博士科研启动基金(YDBK2015-11); 延安市高层次人才专项基金(2019-29); 延安大学大学生创新创业训练计划(D2019016); 陕西省科技厅自然科学基础研究基金(2019JQ-902); 陕西省教育厅自然科学专项研究基金(19JK0287)

A Catalyst-Free One-Pot Protocol for the Construction of Substituted Sulfonyl Pyrazoles

Haojie Ma^a^,^b, Xiaoqiang Zhou^b^,^c, Bo Han^a, Ran Li^a, Xueyan Hou^a, Xingyue Ji^a, Yuqi Zhang^a(), Guosheng Huang^b(), 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 Applied Organic Chemistry, Lanzhou University, Lanzhou 730000
c College of Chemistry and Material, Weinan Normal University, Weinan, Shaanxi 714099

Received:2021-04-16 Revised:2021-04-27 Published:2021-06-22
Contact: Yuqi Zhang, Guosheng Huang
Supported by:
National Natural Science Foundation of China(21663032); National Natural Science Foundation of China(31701679); National Natural Science Foundation of China(22061041); PhD Research Startup Foundation of Yan'an University(YDBK2019-30); PhD Research Startup Foundation of Yan'an University(YDBK2015-11); Municipal Special Fund of Yan'an for High-Level Talents(2019-29); Yan'an University Training Program of Innovation and Entrepreneurship for Undergraduates(D2019016); Natural Science Basic Research Program of Shaanxi Province(2019JQ-902); Scientific Research Program Funded by Shaanxi Provincial Education Department(19JK0287)

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摘要/Abstract

开发了一种新型有效的在无催化剂条件下由苯磺酰肼和戊烷-2,4-二酮构建取代吡唑的方法, 该方法具有官能团适用性好、步骤经济、操作简单、试剂便宜、反应条件温和及可进行按比例放大等优势.

关键词: 无催化剂, 磺酰吡唑, 戊烷-2,4-二酮, 苯磺酰肼

A novel and efficient protocol for the construction of substituted pyrazoles from benzenesulfonohydrazides and pentane-2,4-diones under catalyst-free conditions was developed. This protocol features excellent tolerance to a variety of functional groups, step economy, simple operation with inexpensive reagents, mild reaction conditions, and can be scaled-up.

Key words: catalyst-free, sulfonyl pyrazole, pentane-2,4-dione, benzenesulfonohydrazide

引用此文

马豪杰, 周小强, 韩波, 李然, 侯雪艳, 姬星月, 张玉琦, 黄国生, 王记江. 无催化剂一锅法构建取代磺酰吡唑[J]. 有机化学, 2021, 41(9): 3710-3716.

Haojie Ma, Xiaoqiang Zhou, Bo Han, Ran Li, Xueyan Hou, Xingyue Ji, Yuqi Zhang, Guosheng Huang, Jijiang Wang. A Catalyst-Free One-Pot Protocol for the Construction of Substituted Sulfonyl Pyrazoles[J]. Chinese Journal of Organic Chemistry, 2021, 41(9): 3710-3716.

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图/表 7

Figure 1. Structures of some commercial pyrazoles

Scheme 1. Synthetic approaches toward pyrazoles

Entry	Catalyst	Solvent	Temp./℃	Yield^b/%
1	CBr₄	DMSO	60	50
2	—	DMSO	60	50
3	—	DMA	60	^end
4	—	1,4-Dioxane	60	83
5	—	DMF	60	70
6	—	Toluene	60	94
7	—	CH₃CN	60	97
8	—	DCE	60	92
9	—	H₂O	60	nd
10	—	CH₃CN	40	88
11	—	CH₃CN	80	94
^c12	—	CH₃CN	60	95
^d13	—	CH₃CN	60	96

Table 1. Optimization of reaction conditionsa

Table 2. Synthesis of 3,5-dimethyl-1-(phenylsulfonyl)-1H- pyrazoles from substituted benzenesulfonohydrazides and pentane-2,4-dionea

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

Scheme 2. Gram scale reaction

Scheme 3. Proposed mechanism

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无催化剂一锅法构建取代磺酰吡唑

A Catalyst-Free One-Pot Protocol for the Construction of Substituted Sulfonyl Pyrazoles

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