Cyanuric Chloride Catalysis and Solvent Effect Leading to a Mild and Efficient Beckmann Rearrangement of Ketoximes

doi:10.6023/cjoc202008018

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (2): 688-694.DOI: 10.6023/cjoc202008018 Previous Articles Next Articles

Article

三聚氯氰催化及溶剂效应实现温和高效的酮肟贝克曼重排反应

周婷婷¹, 刘霞¹, 叶子航¹, 周奕鹏¹, 杨雅淇¹, 徐清¹^,^*()

1 温州大学化学与材料工程学院浙江温州 325035

收稿日期:2020-08-12 修回日期:2020-09-18 发布日期:2020-09-30
通讯作者: 徐清
作者简介:
* Corresponding author. E-mail: qing-xu@wzu.edu.cn
基金资助:
国家自然科学基金(21672163); 浙江省自然科学基金杰出青年基金(LR14B020002)

Cyanuric Chloride Catalysis and Solvent Effect Leading to a Mild and Efficient Beckmann Rearrangement of Ketoximes

Tingting Zhou¹, Xia Liu¹, Zihang Ye¹, Yipeng Zhou¹, Yaqi Yang¹, Qing Xu¹^,^*()

1 College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang 325035

Received:2020-08-12 Revised:2020-09-18 Published:2020-09-30
Contact: Qing Xu
Supported by:
the National Natural Science Foundation of China(21672163); the Natural Science Foundation of Zhejiang Province for Distinguished Young Scholars(LR14B020002)

1. cjoc202008018.pdf(2330KB)

Abstract

By using hexafluoroisopropanol as the solvent, a low loading of cyanuric chloride could effectively catalyze the Beckmann rearrangement of ketoximes to obtain the corresponding amide products under mild conditions, such as room temperature and air atmosphere. The effect of hexafluoroisopropanol was greatly different from that of other solvents. This method has the advantages of simple operation, low catalyst loading, recoverability of solvent, mild conditions, good tolerance of the functional groups, broad substrate scope and high product yields. It is a relatively green and practical method for the preparation of amide compounds.

Key words: ketoxime, Beckmann rearrangement, cyanuric chloride, hexafluoroisopropanol, mild condition, amide

Cite this article

Tingting Zhou, Xia Liu, Zihang Ye, Yipeng Zhou, Yaqi Yang, Qing Xu. Cyanuric Chloride Catalysis and Solvent Effect Leading to a Mild and Efficient Beckmann Rearrangement of Ketoximes[J]. Chinese Journal of Organic Chemistry, 2021, 41(2): 688-694.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 5

References 31

[1]	(a) Li X.; Xiog W.; Zheng Y. Pharm. J. Chin. People's Liberation Army 2007, 23, 56. (in Chinese) pmid: 3D0BC9F6-3830-4FFC-B889-FDF93A78D197
	李晓慧, 熊伟, 郑应华, 解放军药学学报, 2007, 23, 56.). pmid: 3D0BC9F6-3830-4FFC-B889-FDF93A78D197
	(b) Zheng Y.; Guo Q.; Yu Z. Fine Chem. Intermed. 2015, 45, 1. (in Chinese) pmid: 3D0BC9F6-3830-4FFC-B889-FDF93A78D197
	郑玉国, 郭晴晴, 余忠林, 精细化工中间体, 2015, 45, 1.). pmid: 3D0BC9F6-3830-4FFC-B889-FDF93A78D197
	(c) Huang P. Acta Chim. Sinica 2018, 76, 357. (in Chinese) doi: 10.6023/A18020054 pmid: 3D0BC9F6-3830-4FFC-B889-FDF93A78D197
	黄培强, 化学学报, 2018, 76, 357.). doi: 10.6023/A18020054 pmid: 3D0BC9F6-3830-4FFC-B889-FDF93A78D197
[2]	Zhou Y; Lu J.; Zhu M. Synth. Fiber Ind. 2015, 38, 51. (in Chinese)
	周云, 卢建国, 朱明乔, 合成纤维工业, 2015, 38, 51.).
[3]	(a) Chen H.; Dai W.; Chen Y.; Xu Q.; Chen J.; Yu L.; Zhao Y.; Ye M.; Pan Y. Green Chem. 2014, 16, 2136. doi: 10.1039/C3GC42310G pmid: 658EE764-0E13-4DDC-81E2-574167568B82
	(b) Li Y.; Chen H.; Liu J.; Wan X.; Xu Q. Green Chem. 2016, 18, 4865. doi: 10.1039/C6GC01565D pmid: 658EE764-0E13-4DDC-81E2-574167568B82
	(c) Ma X.; Li B.; Xiao Y.; Yu X.; Su C.; Xu Q. Chin. J. Org. Chem. 2017, 37, 2034. (in Chinese) doi: 10.6023/cjoc201703028 pmid: 658EE764-0E13-4DDC-81E2-574167568B82
	马献涛, 李波, 肖映林, 余小春, 苏陈良, 徐清, 有机化学, 2017, 37, 2034.). doi: 10.6023/cjoc201703028 pmid: 658EE764-0E13-4DDC-81E2-574167568B82
[4]	Beckmann E. Chem. Ber. 1886, 89, 988.
[5]	Donaruma L.G.; Heldt W.Z. Org. React. 1960, 11, 1.
[6]	Zhang J.; Liu Y.; Feng W.; Wu Y. Chin. J. Org. Chem. 2019, 39, 961. (in Chinese) doi: 10.6023/cjoc201809031 pmid: 2B7A4B17-F226-47D9-8C56-090326A190D3
	张健, 刘园园, 冯维春, 武玉民, 有机化学, 2019, 39, 961.). doi: 10.6023/cjoc201809031 pmid: 2B7A4B17-F226-47D9-8C56-090326A190D3
[7]	Rohokale S.V.; Kote S.R.; Deshmukh S, R.; Thopate, S.R.Chem. Pap. 2014, 68, 575.
[8]	Guo S.; Du Z.; Zhang S.; Li D.; Li Z.; Deng Y. Green Chem. 2006, 8, 296. doi: 10.1039/B513139A
[9]	Li D.; Mao D; Li J.; Zhou Y.; Wang J. Appl. Catal., A 2016, 510, 125. doi: 10.1016/j.apcata.2015.11.014
[10]	(a) Liu L.-F.; Liu H.; Pi H.-J.; Yang S.; Yao M.; Du W.; Deng W.-P. Synth. Commun. 2011, 41, 553. doi: 10.1080/00397911003629416
	(b) An N.; Pi H.; Liu L.; Du W.; Deng W. Chin. J. Chem. 2011, 29, 947. doi: 10.1002/cjoc.201190193
[11]	Li Z.; Lu Z.; Ding R.; Yang J. J. Chem. Res. 2006, 2006, 668. doi: 10.3184/030823406779173523
[12]	Yan P.; Batamack P.; Prakash G. K. S.; Olah G.A. Catal. Lett. 2006, 103, 165. doi: 10.1007/s10562-005-7149-3
[13]	Zhang X.; Mao D.; Leng Y.; Zhou. Y.; Wang, J.Catal Lett. 2013, 143, 193. doi: 10.1007/s10562-012-0939-5
[14]	Furuya Y.; Ishihara K.; Yamamoto H. J. Am. Chem. Soc. 2005, 127, 11240. doi: 10.1021/ja053441x
[15]	(a) Betti C.; Landini D.; Maia A.; Pasi M. Synlett 2008, 908.
	(b) Maia A.; Albanese D. C. M.; Landini D. Tetrahedron 2012, 68, 1947. doi: 10.1016/j.tet.2011.12.051
[16]	Hashimoto M.; Obora Y.; Ishii Y. Org. Process Res. Dev. 2009, 13, 411. doi: 10.1021/op800258s
[17]	Srivastava V.P.; Patel R.; Garima; Yadav, L. D. S.Chem. Commun. 2010, 46, 5808. doi: 10.1039/c0cc00815j
[18]	Kalkhambkar R.G.; Savanura H.M. RSC Adv. 2015, 5, 60106. doi: 10.1039/C5RA07789C
[19]	Patil D.; Dalal D. Synth. Commun. 2013, 43, 118. doi: 10.1080/00397911.2011.592747
[20]	(a) Ikushima Y.; Hatakeda K.; Sato O.; Yokoyama T.; Arai M. J. Am. Chem. Soc. 2000, 122, 1908. doi: 10.1021/ja9925251
	(b) Yamaguchi Y.; Yasutake N.; Nagaoka M. J. Mol. Struct.: THEOCHEM 2003, 639, 137. doi: 10.1016/j.theochem.2003.08.064
[21]	Mao D.; Lu G.; Chen Q. React. Kinet. Catal. Lett. 2002, 75, 75. doi: 10.1023/A:1014849501999
[22]	Yang Q.-L.; Li Y.-Q.; Ma C.; Fang P.; Zhang X.-J.; Mei T.-S. J. Am. Chem. Soc. 2017, 139, 3293. doi: 10.1021/jacs.7b01232
[23]	Kim B.R.; Sung G.H.; Kim J.-J.; Yoon Y.-J. J. Korean Chem. Soc. 2013, 57, 295. doi: 10.5012/jkcs.2013.57.2.295
[24]	Xie F.; Du C.; Pang Y.; Lian X.; Xue C.; Chen Y.; Wang X.; Cheng M.; Guo C.; Lin B.; Liu Y. Tetrahedron Lett. 2016, 57, 5820. doi: 10.1016/j.tetlet.2016.11.054
[25]	Zhi P.; Xi Z.-W.; Wang D.-Y.; Wang W.; Liang X.-Z.; Tao F.-F.; Shen R.-P.; Shen Y. New J. Chem. 2019, 43, 709. doi: 10.1039/C8NJ05288C
[26]	Jefferies L.R.; Weber S.R.; Cook S.P. Synlett 2015, 26, 331. doi: 10.1055/s-00000083
[27]	Beinker P.; Hanson J.R.; Meindl N.; Medina I. C. R.J. Chem. Res. ( S ) 1998, 204.
[28]	Gao Y.; Liu J.; Li Z.; Guo T.; Xu S.; Zhu H.; Wei F.; Chen S.; Hailemariam G.; Guo K. J. Org. Chem. 2018, 83, 2040. doi: 10.1021/acs.joc.7b02983
[29]	Pelagalli R.; Chiarotto I.; Feroci M.; Vecchio S. Green Chem. 2012, 14, 2251. doi: 10.1039/c2gc35485c
[30]	Choudhary V.R.; Dumbre D.K. Catal. Commun. 2011, 12, 1351. doi: 10.1016/j.catcom.2011.05.015
[31]	Sharley D. D. S.; Williams J. M. J.Chem. Commun. 2017, 53, 2020. doi: 10.1039/C6CC09023K

Entry	Cat. (mol%)	Solvent	T^b/℃	t/h	Yield^c/%
1	AlCl₃ (20)	CH₃CN	100	6	88
2	ZnCl₂ (20)	CH₃CN	100	6	56
3	FeCl₃ (20)	CH₃CN	100	6	71
4	MoO₃ (20)	CH₃CN	100	6	Trace
5	MnO₂ (20)	CH₃CN	100	6	Trace
6	T_SCl (20)	CH₃CN	100	6	69
7	Phosphonitrilic chloride trimer (20)	CH₃CN	100	6	81
8	Cyanuric chloride (20)	CH₃CN	100	6	84
9	Cyanuric chloride (20)	CH₃CN	100	2	86
10	Cyanuric chloride (20)	DMF	100	2	66
11	Cyanuric chloride (20)	DCE	100	2	75
12	Cyanuric chloride (20)	THF	100	2	76
13	Cyanuric chloride (20)	TFA	100	2	93
14	Cyanuric chloride (20)	HFIP	100	2	95
15	Cyanuric chloride (20)	HFIP	60	2	96
16	Cyanuric chloride (10)	HFIP	60	2	94
17^d	Cyanuric chloride (10)	HFIP	60	2	90
18^d	Cyanuric chloride (10)	HFIP	45	2	91
19^d	Cyanuric chloride (5)	HFIP	45	2	80
20^d	Cyanuric chloride (5)	HFIP	r.t.	2	75
21^d	Cyanuric chloride(1)	HFIP	r.t.	24	95
22^d	Cyanuric chloride (0.5)	HFIP	r.t.	24	89
23^d	Cyanuric chloride (0.3)	HFIP	r.t.	24	77
24^d	—	HFIP	r.t.	24	36

Entry	Cat. (mol%)	Solvent	T^b/℃	t/h	Yield^c/%
1	AlCl₃ (20)	CH₃CN	100	6	88
2	ZnCl₂ (20)	CH₃CN	100	6	56
3	FeCl₃ (20)	CH₃CN	100	6	71
4	MoO₃ (20)	CH₃CN	100	6	Trace
5	MnO₂ (20)	CH₃CN	100	6	Trace
6	T_SCl (20)	CH₃CN	100	6	69
7	Phosphonitrilic chloride trimer (20)	CH₃CN	100	6	81
8	Cyanuric chloride (20)	CH₃CN	100	6	84
9	Cyanuric chloride (20)	CH₃CN	100	2	86
10	Cyanuric chloride (20)	DMF	100	2	66
11	Cyanuric chloride (20)	DCE	100	2	75
12	Cyanuric chloride (20)	THF	100	2	76
13	Cyanuric chloride (20)	TFA	100	2	93
14	Cyanuric chloride (20)	HFIP	100	2	95
15	Cyanuric chloride (20)	HFIP	60	2	96
16	Cyanuric chloride (10)	HFIP	60	2	94
17^d	Cyanuric chloride (10)	HFIP	60	2	90
18^d	Cyanuric chloride (10)	HFIP	45	2	91
19^d	Cyanuric chloride (5)	HFIP	45	2	80
20^d	Cyanuric chloride (5)	HFIP	r.t.	2	75
21^d	Cyanuric chloride(1)	HFIP	r.t.	24	95
22^d	Cyanuric chloride (0.5)	HFIP	r.t.	24	89
23^d	Cyanuric chloride (0.3)	HFIP	r.t.	24	77
24^d	—	HFIP	r.t.	24	36

三聚氯氰催化及溶剂效应实现温和高效的酮肟贝克曼重排反应

Cyanuric Chloride Catalysis and Solvent Effect Leading to a Mild and Efficient Beckmann Rearrangement of Ketoximes

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 5

References 31

Related Articles 15

Recommended Articles

Metrics

Comments

Entry	Yield^b/%	Entry	Yield^b/%
1	95	12	91
2	95 (2b/2b': 52/48)	13	82
3	92	14	81
4	89	15	84
5	96	16	96
6	89	17	91
7	92	18^c	71
8	98	19^c	72
9	89	20c	77

[1]	Yang Li, Yanan Dong, Yuehui Li. Efficient Synthesis of Nitrile Compounds through Amide Conversion via N-Boroamide Intermediates [J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 638-643.
[2]	Penghui Li, Qingyang Xie, Fuxian Wan, Yuanhong Zhang, Lin Jiang. Synthesis and Fungicidal Activity of Novel Substituted Pyrimidine-5-carboxamides Bearing Cyclopropyl Moiety [J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 650-656.
[3]	Baochang Gao, Yu Shi, Yuan Tian, Zhiguo Zhang, Jingru Zhang, Yufeng Sun, Guoliang Mao, Lingyan Dai. Synthesis of 4-Methyl-2-oxo-6-arylamino-2H-pyran-3-carbonitrile Derivatives [J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 644-649.
[4]	Suyan Tao, Zixin Xiang, Junjie Bai, Xiao Wan, Xiaobing Wan. Amide Hydrolysis Reaction Using tert-Butyl Nitrite [J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 550-560.
[5]	Gangzhong Jiang, Jiaxing Lin, Xiaoguang Bao, Xiaobing Wan. Isoamyl Nitrite Activated Primary Sulfonamide to Sulfonyl Bromide and Sulfonyl Chloride [J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 533-549.
[6]	Lijun Xu, Zongjun Li, Fushe Han, Xiang Gao. N,N-Dimethylformamide-Promoted Synthesis of Fullerene-Fused Oxazoline Derivatives [J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 242-250.
[7]	Bozhen Wang, Jie Zhang, Chunhui Nian, Mingming Jin, Miaomiao Kong, Wulan Li, Wenfei He, Jianzhang Wu. Synthesis and Antitumor Activity of 3,4-Dichlorophenyl Amides [J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 232-241.
[8]	Zhiyou Huang, Ping Yang, Bo He, Wenxia Ou, Siyu Yuan. Design and Synthesis of Morpholine Sulfonamide Compound and Its Inhibition on Soybean Seed Germination [J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 309-315.
[9]	Wenfeng Bei, Jian Pan, Dongmei Ran, Yilin Liu, Zhen Yang, Ruokun Feng. Cobalt-Catalyzed [4+2] Annulation of Indole Carboxamide with Diynes and Monoacetylene: Direct Access to γ-Carbolinones [J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3226-3238.
[10]	Jing Tang, Wenkun Luo, Jun Zhou. Advances in the Synthesis of Azaspiro[4.5]trienones [J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3006-3034.
[11]	Xiantao Ma, Xiaoyu Yan, Yingying Zhu, Shuanglin Niu, Yuxuan Wang, Chao Yuan. Water-Promoted Green Synthesis of Heteroaryl Thioether [J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 2136-2142.
[12]	Zhijun Ren, Weiwei Luo, Jun Zhou. Recent Progress in Silver-Mediated Tandem Cyclization of N-Arylacrylamides [J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 2026-2039.
[13]	Yu Wang, Yifang Chen, Xin Luo, Zhifu Xing, Ju Peng, Jixiang Chen. Design, Synthesis and Nematicidal Activity of Novel 2-Cyanoacrylate (Amide) Derivatives [J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 2206-2216.
[14]	Wenhan Yang, Jiwen Jiao, Xiaoming Wang. Merging Electron Transfer Activation with 1,2-Metalate Migration: Deoxygenative Silylation of Amides [J]. Chinese Journal of Organic Chemistry, 2023, 43(5): 1857-1867.
[15]	Yang Liu, Xiang Huang, Min Wang, Jian Liao. Enantioselective Copper-Catalyzed Mannich-Type Reaction of Cycic Ketimines and β,γ-Unsaturated N-Acylpyrazoles [J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1499-1509.