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

doi:10.6023/cjoc202107020

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (11): 4353-4360.DOI: 10.6023/cjoc202107020 Previous Articles Next Articles

ARTICLES

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)

1. .pdf(1412KB)

Abstract

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

Cite this article

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.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 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

References 17

[1]	(a) Mantenuto, S.; Ciccolini, C.; Lucarini, S.; Piersanti, G.; Favi, G.; Mantellini, F. Org. Lett. 2017, 19, 608. doi: 10.1021/acs.orglett.6b03775 pmid: 28094964
	(b) Geng, R.; Zhao, Y.; Li, Y.; Liu, X.; Wang, M. Chin. J. Org. Chem. 2019, 39, 3574. (in Chinese) doi: 10.6023/cjoc201906017 pmid: 28094964
	(耿瑞, 赵宇, 李益豪, 刘鑫磊, 王明安, 有机化学, 2019, 39, 3574.) doi: 10.6023/cjoc201906017 pmid: 28094964
	(c) Ma, H.; Guo, C.; Zhan, Z.; Lu, G.; Zhang, Y. X.; Luo, X.; Cui, X.; Huang, G. New J. Chem. 2017, 41, 5280. doi: 10.1039/C7NJ01293D pmid: 28094964
	(d) Zhong, L.; Jiang, T.; Zhang, F.; Fu, Q.; Liu, X.; Xu, T.; Ding, C.; Chen, J.; Yuan, J.; Tan, C. Chin. J. Org. Chem. 2019, 39, 2655. (in Chinese) doi: 10.6023/cjoc201903056 pmid: 28094964
	(钟良坤, 江涛, 张帆, 付庆, 刘幸海, 许天明, 丁成荣, 陈杰, 袁静, 谭成侠, 有机化学, 2019, 39, 2655.) pmid: 28094964
	(e) Cao, M.; Fang, Y.; Wang, Y.; Xu, X.; Xi, Z.; Tang, S. ACS Comb. Sci. 2020, 22, 268. doi: 10.1021/acscombsci.0c00012 pmid: 28094964
	(f) Gong, C. C.; Tan, H. Y.; Zhang, Q. Chin. J. Org. Chem. 2018, 38, 3086. (in Chinese) doi: 10.6023/cjoc201805020 pmid: 28094964
	(龚超超, 谈寒一, 张倩, 有机化学, 2018, 38, 3086.) doi: 10.6023/cjoc201805020 pmid: 28094964
	(g) Chen, M. M.; Shao, L. Y.; Lun, L. J.; Wu, Y. L.; Fu, X. P.; Ji, Y. F. Chin. Chem. Lett. 2019, 30, 702. doi: 10.1016/j.cclet.2018.09.022 pmid: 28094964
[2]	(a) He, Y.; Wang, Y. C.; Hu, K.; Xu, X. L.; Wang, H. S.; Pan, Y. M. J. Org. Chem. 2016, 81, 11813. doi: 10.1021/acs.joc.6b02288
	(b) Murugesan, D.; Mital, A.; Kaiser, M.; Shackleford, D. M.; Morizzi, J.; Katneni, K.; Campbell, M.; Hudson, A.; Charman, S. A.; Yeates, C.; Gilbert, I. H. J. Med. Chem. 2013, 56, 2975. doi: 10.1021/jm400009c
	(c) Zhong, Y. Y.; Yu, L. J.; He, Q. Y.; Zhu, Q. Y.; Zhang, C. G.; Cui, X. P.; Zheng, J. X.; Zhao, S. Q. ACS Appl. Mater. Inter. 2019, 11, 32769. doi: 10.1021/acsami.9b11754
	(d) Shi, Y. J.; Zhou, Q.; Wang, Y.; Qian, H. W.; Ye, L. Y.; Feng, X.; Chen, H.; Li, Y. T.; Dai, H.; Wei, Z. H.; Wu, J. M. Chin. J. Org. Chem. 2018, 38, 2450. (in Chinese) doi: 10.6023/cjoc201806030
	(石玉军, 周钱, 王杨, 钱宏炜, 叶林玉, 冯霞, 陈辉, 李雅婷, 戴红, 魏中昊, 吴锦明, 有机化学, 2018, 38, 2450.) doi: 10.6023/cjoc201806030
[3]	(a) Wang, S. H.; Zhang, B. H.; Chen, J.; Zheng, Y. Y.; Feng, N.; Ma, A. J.; Xu, X. T.; Abdullah, M. A. Chin. J. Org. Chem. 2020, 40, 15. (in Chinese) doi: 10.6023/cjoc201906007 pmid: 15214796
	(王少华, 张帮红, 陈洁, 郑莹莹, 冯娜, 马爱军, 徐学涛, Abdullah, M. A., 有机化学, 2020, 40, 15.) doi: 10.6023/cjoc201906007 pmid: 15214796
	(b) Li, Y.; Wan, J. P. Chin. J. Org. Chem. 2020, 40, 3889. (in Chinese) doi: 10.6023/cjoc202005026 pmid: 15214796
	(李毅, 万结平, 有机化学, 2020, 40, 3889.) doi: 10.6023/cjoc202005026 pmid: 15214796
	(c) Liu, J. J.; Sun, J.; Fang, Y. B.; Yang, Y. A.; Jiao, R.H.; Zhu, H. L. Org. Biomol. Chem. 2014, 12, 998. doi: 10.1039/c3ob41953c pmid: 15214796
	(d) Ouyang, G.; Cai, X. J.; Chen, Z.; Song, B. A.; Bhadury, P. S.; Yang, S.; Jin, L. H.; Xue, W.; Hu, D. Y.; Zeng, S. J. Agric. Food Chem. 2008, 56, 10160. doi: 10.1021/jf802489e pmid: 15214796
	(e) Tanitame, A.; Oyamada, Y.; Ofuji, K.; Fujimoto, M.; Iwai, N.; Hiyama, Y.; Suzuki, K.; Ito, H.; Terauchi, H.; Kawasaki, M.; Nagai, K.; Wachi, M.; Yamagishi, J. J. Med. Chem. 2004, 47, 3693. pmid: 15214796
	(f) Tian, L. H.; Wan, J. P.; Sheng, Sh. R. ChemCatChem. 2020, 12, 2533. doi: 10.1002/cctc.v12.9 pmid: 15214796
[4]	(a) Abd El Razik, H. A.; Badr, M. H.; Atta, A. H.; Mouneir, S. M.; Abu-Serie, M. M. Arch. Pharm. 2017, 350, e1700026.
	(b) Bhosle, M. R.; Mali, J. R.; Pal, S.; Srivastava, A. K.; Mane, R. A. Bioorg. Med. Chem. Lett. 2014, 24, 2651. doi: 10.1016/j.bmcl.2014.04.064
	(c) El-Sayed, M. A. A.; Abdel-Aziz, N. I.; Abdel-Aziz, A. A. M.; El-Azab, A. S.; ElTahir, K. E. H. Bioorg. Med. Chem. 2012, 20, 3306.
	(d) Bekhit, A. A.; Abdel-Aziem, T. Bioorg. Med. Chem. 2004, 12, 1935. doi: 10.1016/j.bmc.2004.01.037
	(e) Zhang, M.; Zheng, D. D.; Ni, Y. D.; Liang, K.; Xun, X.; Hu, L. P.; Chen, Q. W.; Yang, B.; Liang, Zh. P.; Ding, Y.; Shi, J.; Dai, H. Chin. J. Org. Chem. 2020, 40, 1772. (in Chinese) doi: 10.6023/cjoc202001028
	(张敏, 郑丹丹, 倪亚丹, 梁凯, 荀校, 胡兰萍, 陈庆文, 杨冰, 梁志鹏, 丁颖, 石健, 戴红, 有机化学, 2020, 40, 1772.) doi: 10.6023/cjoc202001028
	(f) Li, Y.; Wan, J. P.; Liu, Y. Y. ChemistrySelect 2020, 5, 9431. doi: 10.1002/slct.v5.30
[5]	Cox, S. R.; Lesman, S. P.; Boucher, J. F.; Krautmann, M. J.; Hummel, B. D.; Savides, M.; Marsh, S.; Fielde, A.; Stegemann, M. R. J. Vet. Pharmacol. Ther. 2010, 33, 461. doi: 10.1111/j.1365-2885.2010.01165.x pmid: 20840390
[6]	Kidwai, M.; Jain, A.; Poddar, R. J. Organomet. Chem. 2011, 696, 1939. doi: 10.1016/j.jorganchem.2010.09.012
[7]	Lange, J. H. M.; van Stuivenberg, H. H.; Coolen, H. K. A. C.; Adolfs, T. J. P.; McCreary, A. C.; Keizer, H. G.; Wals, H. C.; Veerman, W.; Borst, A. J. M.; de Looff, W.; Verveer, P. C.; Kruse, C. G. J. Med. Chem. 2005, 48, 1823. pmid: 15771428
[8]	(a) Szabo, G.; Fischer, J.; Kis-Varga, A.; Gyires, K. J. Med. Chem. 2008, 51, 142. doi: 10.1021/jm070821f pmid: 17321742
	(b) Navidpour, L.; Amini, M.; Shafaroodi, H.; Adbi, K.; Ghaheremani, H. M.; Dehpour, R. A.; Shafiee, A. Bioorg. Med. Chem. Lett. 2006, 16, 4483. pmid: 17321742
	(c) Jorand-Lebrun, C.; Brondyk, B.; Jing, L.; Magar, S.; Murray, R.; Reddy, A.; Shroff, H.; Wands, H.; Weiser, Q.; Xu, W.; McKenna, S.; Brugger, N. Bioorg. Med. Chem. Lett. 2007, 17, 2080. pmid: 17321742
[9]	(a) Zeng, J. L.; Xu, Z. H.; Ma, J. A. Chin. J. Org. Chem. 2020, 40, 1105. (in Chinese) doi: 10.6023/cjoc201912024
	(曾俊良, 许志红, 马军安, 有机化学, 2020, 40, 1105.) doi: 10.6023/cjoc201912024
	(b) Zhu, Y.; Zheng, D. D.; Miao, H. Y.; Qian, C.; Dai, H.; Liang, K.; Zhou, B. B.; Shi, Y. J.; Xun, X.; Wang, Y. Chin. J. Org. Chem. 2020, 40, 4315. (in Chinese) doi: 10.6023/cjoc202008031
	(朱玥, 郑丹丹, 缪何一, 钱程, 戴红, 梁凯, 周贝贝, 石玉军, 荀校, 王阳, 有机化学, 2020, 40, 4315.) doi: 10.6023/cjoc202008031
[10]	Chen, X.; She, J.; Shang, Z.; Wu, J.; Wu, H.; Zhang, P. Synthesis 2008, 3478.
[11]	Polsheettiwar, V.; Varma, S. R. Tetrahedron Lett. 2008, 49, 397.
[12]	Xiong, W.; Chen, J. X.; Liu, M. C.; Ding, J. C.; Wu, H. Y.; Su, W. K. J. Braz. Chem. Soc. 2009, 20, 367. doi: 10.1590/S0103-50532009000200023
[13]	Texier-Boullet, F.; Klein, B.; Hamelin, J. Synth. Commun. 1986, 409.
[14]	(a) Yang, G. P.; He, X.; Yu, B.; Hu, C. W. Appl. Organomet. Chem. 2018, 32, 4532.
	(b) Wang, H. F.; Sun, X. L.; Zhang, S. L.; Liu, G. L.; Wang, C. J.; Zhu, L. L.; Zhang, H. Synlett 2018, 29, 2689. doi: 10.1055/s-0037-1610330
	(c) Venkateswarlu, V.; Kour, J.; Aravinda Kumar, K. A.; Verma, P. K.; Lakshma Reddy, G.; Hussain, Y.; Tabassum, A.; Balgotra, S.; Gupta, S.; Hudwekar, A. D.; Vishwakarma, R. A.; Sawant, S. D. RSC Adv. 2018, 8, 26523. doi: 10.1039/C8RA04550J
[15]	Curini, M.; Rosati, O.; Campagna, V.; Montanari, F.; Cravatto, G.; Boclini, M. Synlett 2005, 2927.
[16]	Wang, Z.; Qin, H. Green Chem. 2004, 6, 90. doi: 10.1039/b312833d
[17]	Polshettiwar, V.; Varma, R. S. Tetrahedron 2010, 66, 1091. doi: 10.1016/j.tet.2009.11.015

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

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 8

References 17

Related Articles 0

Recommended Articles

Metrics

Comments

CBr4促进的分子间环化反应: 高效合成取代N-酰基吡唑