Citation: Zhang Wei, Hu Chenxu, Zhou Xiangge. Synthesis of N, N-Dimethyl Benzamide and Benzonitriles through Copper-Catalyzed One-Pot Reaction[J]. Chinese Journal of Organic Chemistry, ;2017, 37(5): 1246-1251. doi: 10.6023/cjoc201612040 shu

Synthesis of N, N-Dimethyl Benzamide and Benzonitriles through Copper-Catalyzed One-Pot Reaction

College of Chemistry, Sichuan University, Chengdu 610064

Corresponding author: Hu Chenxu, zhouxiangge@scu.edu.cn
Received Date: 12 December 2016
Revised Date: 20 January 2017

Fund Project: Project supported by the National Natural Science Foundation of China J1310008Project supported by the National Natural Science Foundation of China 21472128

Figures(1)

Amide is one of the most important functional groups in nature. Besides the classical synthetic method by using activated acid with amine, several other transition metal-catalyzed protocols have been developed. Aryl nitriles have also attracted substantial attentions as herbicides, natural products, etc. Traditional methods towards aryl nitriles include Sandmeyer and Rosenmund von Braun reaction. In addition of these methods, researchers have explored various kinds of toxic "CN" sources. In continuation of our previous work on copper catalyzed C-CN bond cleavage and C-N formation reactions, herein our recent work of combination of copper-catalyzed amidation of benzyl cyanide and cyanation of aryl iodides by using N, N-dimethyl formamide (DMF) as amide source is reported. A representative procedure for this reaction is as following: benzyl cyanide (1 mmol), iodobenzene (1 mmol), DMF (2 mL), TsOH (1 mmol), Cu₂O (0.2 mmol), 1, 10-phenanthroline (0.4 mmol) were added into a 10 mL of Schlenk tube. The mixture was stirred at 130 ℃ under O₂ atmosphere for 12 h. The reaction mixture was then cooled down to room temperature, quenched with water, and extracted with ethyl acetate. The organic layer was then dried over anhydrous MgSO₄, and the solvent was removed in vacuo. The residue was finally purified by column chromatography on silica gel using petroleum ether-ethyl acetate mixture as eluent. A variety of N, N-dimethyl benzamides and benzonitriles were obtained in yields up to 85% and 75%, respectively.
- copper,
- catalysis,
- one pot reaction,
- amidation,
- cyanation
1. [1]
2. [2]
3. [3]
  Schoenberg, A.; Bartoletti, I.; Heck, R. F. J. Org. Chem. 1974, 39, 3318. doi: 10.1021/jo00937a003
4. [4]
  For some of selected examples, see: (a) Wu, X. F.; Neumann, H.; Beller, M. Chem.-Asian J. 2010, 5, 2168.(b) Tambade, P. J.; Patil, Y. P.; Bhanage, B. M. Appl. Organomet. Chem. 2009, 23, 235.(c) Brennfuhrer, A.; Neumann, H.; Beller, M. Angew. Chem., Int. Ed. 2009, 48, 4114.(d) Martinelli, J. R.; Watson, D. A.; Freckmann, D. M. M.; Barder, T. E.; Buchwald, S. L. J. Org. Chem. 2008, 73, 7102.(e) Bjerglund, K.; Lindhardt, A. T.; Skrydstrup, T. J. Org. Chem. 2012, 77, 3793.(f) Andersen, T. L.; Frederiksen, M. W.; Domino, K.; Skrydstrup, T. Angew. Chem., Int. Ed. 2016, 55, 10396.(g) Hao, W.; Liu, H.; Yin, L.; Cai, M. J. Org. Chem. 2016, 81, 4244.
5. [5]
  (a) Ren, W.; Yamane, M. J. Org. Chem. 2009, 74, 8332.(b) Wieckowska, A.; Fransson, R.; Odell, L. R.; Larhed, M. J. Org. Chem. 2011, 76, 978.(c) Dumbris, S. M.; McElwee-White, L. J. Org. Chem. 2009, 74, 8862.
6. [6]
  (a) Wieckowska, A.; Fransson, R.; Odell, L. R.; Larhed, M. J. Org. Chem. 2011, 76, 978.(b) Ren, W.; Yamane, M. J. Org. Chem., 2010, 75, 8410.(c) Roberts, B.; Liptrot, D.; Alcaraz, L.; Luker, T.; Stocks, M. J. Org. Lett. 2010, 12, 4280.(d) Ren, E.; Yamane, M. J. Org. Chem. 2010, 75, 3017.
7. [7]
  Corey, E. J.; Hegedus, L. S. J. Am. Chem. Soc. 1969, 91, 1233. doi: 10.1021/ja01033a044
8. [8]
  (a) Cunico, R. F.; Pandey, R. K. J. Org. Chem. 2005, 70, 9048.(b) Cunico, R. F.; Maity, B. C. Org. Lett. 2003, 5, 4947.(c) Cunico, R. F.; Maity, B. C. Org. Lett. 2002, 4, 4357.
9. [9]
  Lindsay, C. M.; Widdowson, D. A. J. Chem. Soc., Perkin Trans. 1 1988, 569.
10. [10]
  Wan, Y.; Alterman, M.; Larhed, M.; Hallberg, A. J. Comb. Chem. 2003, 5, 82. doi: 10.1021/cc0200843
11. [11]
  (a) Jo, Y.; Ju, J.; Choe, J.; Song, K. H.; Lee, S. J. Org. Chem. 2009, 74, 6358.(b) Ju, J.; Jeong, M.; Moon, J.; Jung, H. M.; Lee, S. Org. Lett. 2007, 9, 4615.(c) Hosoi, K.; Nozaki, K.; Hiyama, T. Org. Lett. 2002, 4, 2849.(d) Chen, J.; Feng, J-B.; Natte, K.; Wu, X. Chem. Eur. J. 2015, 21, 16370.(e) Wu, X.; Zhao, Y.; Ge, H. J. Am. Chem. Soc. 2015, 137, 4924.
12. [12]
13. [13]
  (a) Sandmeyer, T. Ber. Dtsch. Chem. Ges. 1884, 17, 2650.(b) Rosenmund, K. W.; Struck, E. Ber. Dtsch. Chem. Ges. 1919, 52, 1749.
14. [14]
  (a) Zanon, J.; Klapars, A.; Buchwald, S. L. J. Am. Chem. Soc. 2003, 125, 2890.(b) Yang, C.; Williams, J. M. Org. Lett. 2004, 6, 2837.(c) Buono, F. G.; Chidambaram, R.; Mueller, R. H.; Waltermire, R. E. Org. Lett. 2008, 10, 5325.(d) Jia, X.; Yang, D.; Zhang, S.; Cheng, J. Org. Lett. 2009, 11, 4716.(e) Mondal, B.; Acharyya, K.; Howlader, P.; Sarathi Mukherjee, P. J. Am. Chem. Soc. 2016, 138, 1709.(f) Yang, C.; Hu, S.; Wang, X. Org. Biomol. Chem. 2015, 13, 2541.
15. [15]
  Chen, X.; Hao, X. S.; Goodhue, C. E.; Yu, J.-Q. J. Am. Chem. Soc. 2006, 128, 6790. doi: 10.1021/ja061715q
16. [16]
  Ding, S. T.; Jiao, N. J. Am. Chem. Soc. 2011, 133, 12374. doi: 10.1021/ja204063z
17. [17]
  Luo, F.; Chu, C.; Cheng, C. Organometallics 1998, 17, 1025 doi: 10.1021/om970842f
18. [18]
  (a) Sundermeier, M.; Zapf, A.; Beller, M. Angew. Chem., Int. Ed. 2003, 42, 1661.(b) Schareina, T.; Zapf, A.; Cotte, A.; Gotta, M.; Beller, M. Adv. Synth. Catal. 2011, 353, 777.(c) Jiang, Z.; Huang, Q.; Chen, S.; Long, L.; Zhou, X. Adv. Synth. Catal. 2012, 354, 589.(d) Zheng, S.; Yu, C.; Shen, Z. Org. Lett. 2012, 14, 3644.(e) Wen, Q.; Jin, J.; Mei, Y.; Lu, P.; Wang, Y. Eur. J. Org. Chem. 2013, 4032.(f) Kim, J.; Kim, H. J.; Chang, S. Angew. Chem., Int. Ed. 2012, 51, 11948.(g) Malapit, C. A.; Reeves, J. T.; Senanayake, C. H. Angew. Chem., Int. Ed. 2016, 55, 326.(h) Ping, Y.; Ding, Q.; Peng, Y. ACS Catal. 2016, 6, 5989.(i) Mishra, A.; Vats, T. K.; Deb, I. J. Org. Chem. 2016, 81, 6525.
19. [19]
  Hu, C.; Yan, X.; Zhou, X.; Li, Z. Org. Biomol. Chem. 2013, 11, 8179. doi: 10.1039/c3ob41855c
20. [20]
  Cristau, H. J.; Ouali, A.; Spindler, J. F.; Taillefer, M. Chem. Eur. J. 2005, 11, 2483. doi: 10.1002/(ISSN)1521-3765
21. [21]
  Lamani, M.; Prabhu, K. R. Angew. Chem., Int. Ed. 2010, 49, 6622. doi: 10.1002/anie.201002635
22. [22]
  Suzuki, Y.; Moriyama, K.; Togo, H. Tetrahedron 2011, 67, 7956. doi: 10.1016/j.tet.2011.08.028
23. [23]
  Enthaler, S. Chem. Eur. J. 2011, 17, 9316. doi: 10.1002/chem.v17.34
24. [24]
  Bai, C. H.; Yao, X. F.; Li Y. W. ACS Catal. 2015, 5, 884. doi: 10.1021/cs501822r
25. [25]
  Motoyama, Y.; Mitsui, K.; Ishida, T.; Nagashima, H. J. Am. Chem. Soc. 2005, 127, 13150.
26. [26]
  Hu, L.; Liu, X.; Liao, X. B. Angew. Chem., Int. Ed. 2016, 55, 9743. doi: 10.1002/anie.201604406
27. [27]
  Priyadarshini, S.; Joseph, P. J. A.; Kantam, M. L. RSC Adv. 2013, 3, 18283.
28. [28]
  Chen, W. F.; Li, K. B.; Hu, Z. Q.; Wang, L. L.; Lai, G. Q.; Li, Z. F. Organometallics 2011, 30, 2026. doi: 10.1021/om200080f
29. [29]
  Sawant, D. N.; Wagh, Y. S.; Bhatte, K. D.; Bhanage, B. M. J. Org. Chem. 2011, 76, 5489. doi: 10.1021/jo200754v
30. [30]
  Liu, Z. J.; Zhang, J.; Chen, S. L.; Shi, E.; Xu, Y.; Wan, X. B. Angew. Chem., Int. Ed. 2012, 51, 3231. doi: 10.1002/anie.v51.13
1. [1]
  Shiyan Cheng , Yonghong Ruan , Lei Gong , Yumei Lin . Research Advances in Friedel-Crafts Alkylation Reaction. University Chemistry, 2024, 39(10): 408-415. doi: 10.12461/PKU.DXHX202403024
2. [2]
  Xudong Lv , Tao Shao , Junyan Liu , Meng Ye , Shengwei Liu . Paired Electrochemical CO₂ Reduction and HCHO Oxidation for the Cost-Effective Production of Value-Added Chemicals. Acta Physico-Chimica Sinica, 2024, 40(5): 2305028-0. doi: 10.3866/PKU.WHXB202305028
3. [3]
  Ran Yu , Chen Hu , Ruili Guo , Ruonan Liu , Lixing Xia , Cenyu Yang , Jianglan Shui . Catalytic Effect of H₃PW₁₂O₄₀ on Hydrogen Storage of MgH₂. Acta Physico-Chimica Sinica, 2025, 41(1): 100001-0. doi: 10.3866/PKU.WHXB202308032
4. [4]
  Xiaogang Liu , Mengyu Chen , Yanyan Li , Xiantao Ma . Experimental Reform in Applied Chemistry for Cultivating Innovative Competence: A Case Study of Catalytic Hydrogen Production from Liquid Formaldehyde Reforming at Room Temperature. University Chemistry, 2025, 40(7): 300-307. doi: 10.12461/PKU.DXHX202408007
5. [5]
  Jinyao Du , Xingchao Zang , Ningning Xu , Yongjun Liu , Weisi Guo . Electrochemical Thiocyanation of 4-Bromoethylbenzene. University Chemistry, 2024, 39(6): 312-317. doi: 10.3866/PKU.DXHX202310039
6. [6]
  Renxiao Liang , Zhe Zhong , Zhangling Jin , Lijuan Shi , Yixia Jia . A Palladium/Chiral Phosphoric Acid Relay Catalysis for the One-Pot Three-Step Synthesis of Chiral Tetrahydroquinoline. University Chemistry, 2024, 39(5): 209-217. doi: 10.3866/PKU.DXHX202311024
7. [7]
  Dong Xiang , Kunzhen Li , Kanghua Miao , Ran Long , Yujie Xiong , Xiongwu Kang . Amine-Functionalized Copper Catalysts: Hydrogen Bonding Mediated Electrochemical CO₂ Reduction to C₂ Products and Superior Rechargeable Zn-CO₂ Battery Performance. Acta Physico-Chimica Sinica, 2024, 40(8): 2308027-0. doi: 10.3866/PKU.WHXB202308027
8. [8]
  Yinuo Wang , Siran Wang , Yilong Zhao , Dazhen Xu . Selective Synthesis of Diarylmethyl Anilines and Triarylmethanes via Multicomponent Reactions: Introduce a Comprehensive Experiment of Organic Chemistry. University Chemistry, 2024, 39(8): 324-330. doi: 10.3866/PKU.DXHX202401063
9. [9]
  Zhiquan Zhang , Baker Rhimi , Zheyang Liu , Min Zhou , Guowei Deng , Wei Wei , Liang Mao , Huaming Li , Zhifeng Jiang . Insights into the Development of Copper-Based Photocatalysts for CO₂ Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2406029-0. doi: 10.3866/PKU.WHXB202406029
10. [10]
  Jiapei Zou , Junyang Zhang , Xuming Wu , Cong Wei , Simin Fang , Yuxi Wang . A Comprehensive Experiment Based on Electrocatalytic Nitrate Reduction into Ammonia: Synthesis, Characterization, Performance Exploration, and Applicable Design of Copper-based Catalysts. University Chemistry, 2024, 39(6): 373-382. doi: 10.3866/PKU.DXHX202312081
11. [11]
  Zhen Yao , Bing Lin , Youping Tian , Tao Li , Wenhui Zhang , Xiongwei Liu , Wude Yang . Visible-Light-Mediated One-Pot Synthesis of Secondary Amines and Mechanistic Exploration. University Chemistry, 2024, 39(5): 201-208. doi: 10.3866/PKU.DXHX202311033
12. [12]
  Lili Jiang , Shaoyu Zheng , Xuejiao Liu , Xiaomin Xie . Copper-Catalyzed Oxidative Coupling Reactions for the Synthesis of Aryl Sulfones: A Fundamental and Exploratory Experiment for Undergraduate Teaching. University Chemistry, 2025, 40(7): 267-276. doi: 10.12461/PKU.DXHX202408004
13. [13]
  Yan Li , Xinze Wang , Xue Yao , Shouyun Yu . 基于激发态手性铜催化的烯烃E→Z异构的动力学拆分——推荐一个本科生综合化学实验. University Chemistry, 2024, 39(5): 1-10. doi: 10.3866/PKU.DXHX202309053
14. [14]
  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
15. [15]
  Pengzi Wang , Wenjing Xiao , Jiarong Chen . Copper-Catalyzed C―O Bond Formation by Kharasch-Sosnovsky-Type Reaction. University Chemistry, 2025, 40(4): 239-244. doi: 10.12461/PKU.DXHX202406090
16. [16]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
17. [17]
  Lancanghong Chen , Xingtai Yu , Tianlei Zhao , Qizhi Yao . Exploration of Abnormal Phenomena in Iodometric Copper Quantitation Experiment. University Chemistry, 2025, 40(7): 315-320. doi: 10.12461/PKU.DXHX202408089
18. [18]
  Guangming YIN , Huaiyao WANG , Jianhua ZHENG , Xinyue DONG , Jian LI , Yi'nan SUN , Yiming GAO , Bingbing WANG . Preparation and photocatalytic degradation performance of Ag/protonated g-C₃N₄ nanorod materials. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1491-1500. doi: 10.11862/CJIC.20240086
19. [19]
  Mengyang LI , Hao XU , Zhonghao NIU , Chunhua GONG , Weihui ZHONG , Jingli XIE . Highly effective catalytic synthesis of β-amino alcohols by using viologen-polyoxometalate hybrid materials. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1294-1300. doi: 10.11862/CJIC.20250080
20. [20]
  Yukun Chang , Haoqin Huang , Baolei Wang . Preparation of Trans-Cinnamic Acid via “One-Pot” Protocol of Aldol Condensation-Hydrolysis Reaction: Recommending an Improved Organic Synthesis Experiment. University Chemistry, 2024, 39(4): 322-328. doi: 10.3866/PKU.DXHX202309095

Get Citation

PDF

XML

Metrics

PDF Downloads(3)
Abstract views(2078)
HTML views(129)

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