Citation: Zhou Anxi, Zheng Dagui, Zhu Xianhong, Wang Meimei. SOCl₂/N-Methyl Pyrrolidone-Mediated Beckmann Rearrangement of Ketoximes[J]. Chinese Journal of Organic Chemistry, ;2017, 37(11): 2905-2910. doi: 10.6023/cjoc201706020 shu

SOCl₂/N-Methyl Pyrrolidone-Mediated Beckmann Rearrangement of Ketoximes

Key Laboratory of Applied Organic Chemistry, Higher Institutions of Jiangxi Province, Shangrao Normal University, Shangrao 334001

Corresponding author: Zhou Anxi, zhouanxi@hotmail.com
Received Date: 15 June 2017
Revised Date: 30 July 2017
Available Online: 8 November 2017
Fund Project: Project supported by the Science and Technology Research Projects of the Education Department of Jiangxi Province (Nos. GJJ161059, GJJ151062), the Xinjiang 866 Project of Excellence Talent (No. 2013-37) and the Science and Technology Projects of Shangrao Normal Universitythe Science and Technology Research Projects of the Education Department of Jiangxi Province GJJ161059the Xinjiang 866 Project of Excellence Talent 2013-37the Science and Technology Research Projects of the Education Department of Jiangxi Province GJJ151062

Figures(3)

A mild, convenient, and economical approach for the construction of amides and lactams from ketoximes via Beckmann rearrangement by using a new type of Vilsmeier reagents generated in situ from thionyl chloride and 1-methyl-pyrrolidin-2-one was reported. Various amides and lactams bearing different substituents were obtained in good to excellent yields under mild conditions, and the gram scale reaction was achieved without the loss of the yield. Moreover, it can be used in the synthesis of 2-methylbenzoxazole from 1-(2-hydroxyphenyl)ethanone oxime.
- Beckmann rearrangement,
- vilsmeier reagent,
- ketoximes,
- amides
1. [1]
  For reviews, see: (a) Gawly, R. E. Org. React. 1988, 35, 1 and references therein.
  (b) Smith, M. B.; March, J. In Advanced Organic Chemistry, 5th ed., John Wiley and Sons, New York, 2001, p. 1415 and references cited therein.
  (c) Beckmann, E.; Ber. Dtsch. Chem. Ges. 1886, 19, 988.
  (d) Blatt, A. H. Chem. Rev. 1933, 12, 215.
  (e) Arisawa, M.; Yamaguchi, M. Org. Lett. 2001, 3, 311.
  (f) Ramalingan, C.; Park, Y.-T. J. Org. Chem. 2007, 72, 4536.
  (g) Li, J.; Cheng, C.; Zhang, X.; Li, Z.; Cai, F.; Xue, Y.; Liu, W. Chin. J. Chem. 2012, 30, 1687.
2. [2]
  For selected examples of catalytic Beckmann rearrangement, see:
  (a) Narasaka, K.; Kusama, H.; Yamashita, Y.; Sato, H. Chem. Lett. 1993, 489.
  (b) Ichihashi, H.; Kitamura, M. Catal. Today 2002, 73, 23.
  (c) Yadav, J. S.; Reddy, B. V. S.; Madhavi, A. V.; Ganesh, Y. S. S. J. Chem. Res., Synop. 2002, 236.
  (d) Srinvas, K. V. N. S.; Reddy, E. B.; Das, B. Synlett 2002, 625.
  (e) Ikushima, Y.; Sato, O.; Sato, M.; Hatakeda, K.; Arai, M. Chem. Eng. Sci. 2003, 58, 935.
  (f) Fernández, A. B.; Boronat, M.; Blasco, T.; Corna, A. Angew. Chem. Int. Ed. 2005, 44, 2370.
  (g) Kopple, K. D.; Katz, J. J. J. Org. Chem. 1959, 24, 1975.
  (h) Sato, H.; Yoshioka, H.; Izumi, Y. J. Mol. Catal. A: Chem. 1999, 149, 25.
3. [3]
  Xu, F.; Wang, N.-G.; Tian, Y.-P.; Chen, Y.-M.; Liu, W.-C. Synth. Commun. 2012, 42, 3532. doi: 10.1080/00397911.2011.585270
4. [4]
  Furuya, Y.; Ishihara, K.; Yamamoto, H. J. Am. Chem. Soc. 2005, 127, 11240. doi: 10.1021/ja053441x
5. [5]
  Zhu, M.; Cha, C.; Deng, W.-P.; Shi, X.-X. Tetrahedron Lett. 2006, 47, 4861. doi: 10.1016/j.tetlet.2006.05.029
6. [6]
  Yadav, L. D. S.; Patel, R.; Srivastava, V. P. Synthesis 2010, 1771.
7. [7]
  (a) Hashimoto, M.; Obora, Y.; Sakaguchi, S.; Ishii, Y. J. Org. Chem. 2008, 73, 2894.
  (b) Dong, J. D. Master's Thesis, East China University of Science and Technology, 2009, p. 21~31.
8. [8]
  Augustine, J. K.; Kumar, R.; Bombrun, A.; Mandal, A. B. Tetrahedron Lett. 2011, 52, 1074. doi: 10.1016/j.tetlet.2010.12.090
9. [9]
  Pi, H.-J.; Dong, J.-D.; An, N.; Du, W.; Deng, W.-P. Tetrahedron 2009, 65, 7790. doi: 10.1016/j.tet.2009.07.036
10. [10]
  Srivastava, V. P.; Patel, R.; Garima; Yadav, L. D. S. Chem. Commun. 2010, 46, 5808. doi: 10.1039/c0cc00815j
11. [11]
  Vanos, C. M.; Lambert, T. H. Chem. Sci. 2010, 1, 705. doi: 10.1039/c0sc00421a
12. [12]
  Luca, L. D.; Giacomelli, G.; Porcheddu, A. J. Org. Chem. 2002, 67, 6272. doi: 10.1021/jo025960d
13. [13]
  Narahari, S. R.; Reguri, B. R.; Mukkanti, K. Tetrahedron Lett. 2011, 52, 4888. doi: 10.1016/j.tetlet.2011.07.045
14. [14]
  Srivastava, V. P.; Yadav, A. K.; Yadav, L. D. S. Synlett 2014, 665.
15. [15]
  Zheng, D.; Zhou, A.; Zhu, X.; Zheng, H.; Sun, X. Chin. J. Org. Chem. 2016, 36, 137(in Chinese).
16. [16]
  Arrieta, A.; Aizpurua, J. M.; Palomo, C.; Tetrahedron Lett. 1983, 25, 3365.
17. [17]
  (a) An, N.; Tian, B.-X.; Pi, H.-J.; Eriksson, L. A.; Deng, W.-P. J. Org. Chem. 2013, 78, 4297.
  (b) Tian, B.-X.; An, N.; Deng, W.-P.; Eriksson, L. A. J. Org. Chem. 2013, 78, 6782.
18. [18]
  Cantillo, D.; Gutmann, B.; Kappe, C. O. J. Am. Chem. Soc. 2011, 133, 4465. doi: 10.1021/ja109700b
19. [19]
  Ramalingan, C.; Park, Y.-T. J. Org. Chem., 2007, 72, 4536. doi: 10.1021/jo070297k
20. [20]
  Smith, Jr, W. T.; King, G. G. J. Org. Chem. 1959, 24, 976. doi: 10.1021/jo01089a023
21. [21]
  Clayden, J.; Stimsonab, C. C.; Keenan, M. Chem. Commun. 2006, 1393.
22. [22]
  Murai, N.; Komatsu, M.; Yagii, T.; Nishihara, H.; Ohahiro, Y.; Agawa, T. J. Org. Chem. 1977, 42, 847. doi: 10.1021/jo00425a018
23. [23]
  Comerford, J. W.; Clark, J. H.; Macquarie, D. J.; Breeden, S. W. Chem. Commun. 2009, 2562.
24. [24]
  Zhang, Z.; Yu Y.; Liebeskind, L. S. Org. Lett. 2008, 10, 3005. doi: 10.1021/ol8009682
25. [25]
  Ignatenko, V. A.; Deligonul, N.; Viswanathan, R. Org. Lett. 2010, 12, 3594. doi: 10.1021/ol1012372
26. [26]
  Saha, P.; Ramana, T.; Purkait, N.; Ali, M. A.; Paul, R.; Punniyamurthy, T. J. Org. Chem. 2009, 74, 8719. doi: 10.1021/jo901813g
1. [1]
  Yongqing Kuang , Jie Liu , Jianjun Feng , Wen Yang , Shuanglian Cai , Ling Shi . Experimental Design for the Two-Step Synthesis of Paracetamol from 4-Hydroxyacetophenone. University Chemistry, 2024, 39(8): 331-337. doi: 10.12461/PKU.DXHX202403012
2. [2]
  Jiabo Huang , Quanxin Li , Zhongyan Cao , Li Dang , Shaofei Ni . Elucidating the Mechanism of Beckmann Rearrangement Reaction Using Quantum Chemical Calculations. University Chemistry, 2025, 40(3): 153-159. doi: 10.12461/PKU.DXHX202405172
3. [3]
  Chi Li , Jichao Wan , Qiyu Long , Hui Lv , Ying Xiong . N-Heterocyclic Carbene (NHC)-Catalyzed Amidation of Aldehydes with Nitroso Compounds. University Chemistry, 2024, 39(5): 388-395. doi: 10.3866/PKU.DXHX202312016
4. [4]
  Hao Wu , Zhen Liu , Dachang Bai . ¹H NMR Spectrum of Amide Compounds. University Chemistry, 2024, 39(3): 231-238. doi: 10.3866/PKU.DXHX202309020
5. [5]
  Meijin Li , Xirong Fu , Xue Zheng , Yuhan Liu , Bao Li . The Marvel of NAD⁺: Nicotinamide Adenine Dinucleotide. University Chemistry, 2024, 39(9): 35-39. doi: 10.12461/PKU.DXHX202401027
6. [6]
  Hong Zheng , Xin Peng , Chunwang Yi . The Tale of Caprolactam Cyclic Oligomers: The Ever-changing Life of “Princess Cyclo”. University Chemistry, 2024, 39(9): 40-47. doi: 10.12461/PKU.DXHX202403058
7. [7]
  Yuena Yu , Fang Fang . Microwave-Assisted Synthesis of Safinamide Methanesulfonate. University Chemistry, 2024, 39(11): 210-216. doi: 10.3866/PKU.DXHX202401076
8. [8]
  Xinghai Li , Zhisen Wu , Lijing Zhang , Shengyang Tao . Machine Learning Enables the Prediction of Amide Bond Synthesis Based on Small Datasets. Acta Physico-Chimica Sinica, 2025, 41(2): 100010-. doi: 10.3866/PKU.WHXB202309041
9. [9]
  Caixia Lin , Ting Liu , Zhaojiang Shi , Hong Yan , Keyin Ye , Yaofeng Yuan . Innovative Experiment of Electrochemical Dearomative Spirocyclization of N-Acyl Sulfonamides. University Chemistry, 2025, 40(4): 359-366. doi: 10.12461/PKU.DXHX202406107
10. [10]
  Minna Ma , Yujin Ouyang , Yuan Wu , Mingwei Yuan , Lijuan Yang . Green Synthesis of Medical Chemiluminescence Reagents by Photocatalytic Oxidation. University Chemistry, 2024, 39(5): 134-143. doi: 10.3866/PKU.DXHX202310093
11. [11]
  Zitong Chen , Zipei Su , Jiangfeng Qian . Aromatic Alkali Metal Reagents: Structures, Properties and Applications. University Chemistry, 2024, 39(8): 149-162. doi: 10.3866/PKU.DXHX202311054
12. [12]
  Lihui Jiang , Wanrong Dong , Hua Yang , Yongqing Xia , Hongjian Peng , Jun Yuan , Xiaoqian Hu , Zihan Zeng , Yingping Zou , Yiming Luo . Study on Extraction of p-Hydroxyacetophenone. University Chemistry, 2024, 39(11): 259-268. doi: 10.12461/PKU.DXHX202402056
13. [13]
  Shiyi WANG , Chaolong CHEN , Xiangjian KONG , Lansun ZHENG , Lasheng LONG . Polynuclear lanthanide compound [Ce₄^ⅢCe₆^Ⅳ(μ₃-O)₄(μ₄-O)₄(acac)₁₄(CH₃O)₆]·2CH₃OH for the hydroboration of amides to amine. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 88-96. doi: 10.11862/CJIC.20240342
14. [14]
  Jingjing QING , Fan HE , Zhihui LIU , Shuaipeng HOU , Ya LIU , Yifan JIANG , Mengting TAN , Lifang HE , Fuxing ZHANG , Xiaoming ZHU . Synthesis, structure, and anticancer activity of two complexes of dimethylglyoxime organotin. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1301-1308. doi: 10.11862/CJIC.20240003
15. [15]
  Tao Wen , Tao Zhang , Changguo Sun , Jinyu Liu . Preparation of Dess-Martin Reagent and Its Application in Oxidizing Cyclohexanol. University Chemistry, 2024, 39(5): 20-26. doi: 10.3866/PKU.DXHX202309055
16. [16]
  Wanmin Cheng , Juan Du , Peiwen Liu , Yiyun Jiang , Hong Jiang . Photoinitiated Grignard Reagent Synthesis and Experimental Improvement in Triphenylmethanol Preparation. University Chemistry, 2024, 39(5): 238-242. doi: 10.3866/PKU.DXHX202311066
17. [17]
  Yue Zhao , Yanfei Li , Tao Xiong . Copper Hydride-Catalyzed Nucleophilic Additions of Unsaturated Hydrocarbons to Aldehydes and Ketones. University Chemistry, 2024, 39(4): 280-285. doi: 10.3866/PKU.DXHX202309001
18. [18]
  Liangzhen Hu , Li Ni , Ziyi Liu , Xiaohui Zhang , Bo Qin , Yan Xiong . A Green Chemistry Experiment on Electrochemical Synthesis of Benzophenone. University Chemistry, 2024, 39(6): 350-356. doi: 10.3866/PKU.DXHX202312001
19. [19]
  Guojie Xu , Fang Yu , Yunxia Wang , Meng Sun . Introduction to Metal-Catalyzed β-Carbon Elimination Reaction of Cyclopropenones. University Chemistry, 2024, 39(8): 169-173. doi: 10.3866/PKU.DXHX202401060
20. [20]
  Feng Han , Fuxian Wan , Ying Li , Congcong Zhang , Yuanhong Zhang , Chengxia Miao . Comprehensive Organic Chemistry Experiment: Phosphotungstic Acid-Catalyzed Direct Conversion of Triphenylmethanol for the Synthesis of Oxime Ethers. University Chemistry, 2025, 40(3): 342-348. doi: 10.12461/PKU.DXHX202405181

Get Citation

PDF

XML

Metrics

PDF Downloads(20)
Abstract views(4667)
HTML views(246)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

SOCl2/N-Methyl Pyrrolidone-Mediated Beckmann Rearrangement of Ketoximes

Metrics

通讯作者: 陈斌, bchen63@163.com

SOCl₂/N-Methyl Pyrrolidone-Mediated Beckmann Rearrangement of Ketoximes