Citation: YI Yanhui, WANG Xunxun, WANG Li, YAN Jinhui, ZHANG Jialiang, GUO Hongchen. Plasma-Triggered CH₃OH/NH₃ Coupling Reaction for Synthesis of Nitrile Compounds[J]. Acta Physico-Chimica Sinica, ;2018, 34(3): 247-255. doi: 10.3866/PKU.WHXB201708171 shu

Plasma-Triggered CH₃OH/NH₃ Coupling Reaction for Synthesis of Nitrile Compounds

YI Yanhui ^1,, ,
WANG Xunxun ¹ ,
WANG Li ¹ ,
YAN Jinhui ¹ ,
ZHANG Jialiang ² ,
GUO Hongchen ^1,,

1.
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning Province, P. R. China
2.
School of Physics and Optoelectronic Engineering, Dalian University of Technology, Dalian 116024, Liaoning Province, P. R. China

Corresponding author: YI Yanhui, yiyanhui@dlut.edu.cn GUO Hongchen, hongchenguo@163.com
Received Date: 22 June 2017
Revised Date: 8 August 2017
Accepted Date: 10 August 2017
Available Online: 17 March 2017
Fund Project: The project was supported by the Natural Science Foundation of China 21503032The project was supported by the Natural Science Foundation of China (21503032) and China Postdoctoral Science Foundation (2015M580220, 2016T90217)China Postdoctoral Science Foundation 2016T90217China Postdoctoral Science Foundation 2015M580220

Nitriles are very important for the synthesis of fine chemicals and medicines. However, many nitriles are not widely available, as their synthesis processes pose a serious risk to the environment. Herein, we report that a spontaneous CH₃OH/NH₃ coupling reaction can directly synthesize N, N-dimethyl cyanamide[(CH₃)₂NCN], amino acetonitrile [NH₂CH₂CN], and N, N-dimethyl amino acetonitrile [(CH₃)₂NCH₂CN], when a mixture of methanol and ammonia is transferred into the plasma state via a dielectric barrier discharge. The effects of the plasma reactor configuration, discharge conditions, reaction conditions, and packing materials on the methanol conversion as well as the product selectivity were systematically investigated. Experimental results indicate that, under optimized conditions, a nitrile compound selectivity of 22.1% with a methanol conversion of 51.5% could be achieved. Analysis by optical emission spectroscopy indicates that the C≡N species in CH₃OH/NH₃ plasma could be a key reactive intermediate aiding in the synthesis of nitrile compounds. The CH₃OH/NH₃ plasma coupling reaction process is an environment-friendly methodology for the synthesis of (CH₃)₂NCN, NH₂CH₂CN, and (CH₃)₂NCH₂CN, and is a potential novel pathway for the synthesis of fine chemicals like methanol and ammonia.
- DBD plasma,
- Methanol,
- Ammonia,
- Coupling reaction,
- Nitrile compounds
1. [1]
  Fatiadi, A. J. Preparation and Synthetic Applications of Cyano Compounds; Wiley: New York, 1983.
2. [2]
  Fleming, F. F.; Yao, L; Ravikumar, P. C.; Funk, L; Shook, B. C. J. Med. Chem. 2010, 53, 7902. doi: 10.1021/jm100762r doi: 10.1021/jm100762r
3. [3]
  Sundermeier, M.; Zapf, A.; Mytyala, S. Baumann, W.; Sans, J.; Weiss, S.; Beller, M. J. Chem. Eur. 2003, 9, 1828. doi: 10.1002/chem.200390210 doi: 10.1002/chem.200390210
4. [4]
  Movassaghi, M.; Hill, M. D. Nat. Protoc. 2007, 2, 2018. doi: 10.1038/nprot.2007.280 doi: 10.1038/nprot.2007.280
5. [5]
  Yang, J.; Karver, M. R.; Li, W.; Sahu, W.; Devaraj, N. K. Angew. Chem. Int. Ed.2012, 51, 5222. doi: 10.1002/anie.201201117 doi: 10.1002/anie.201201117
6. [6]
  Yu, S.; Xiong, M.; Xie, X.; Liu, Y. Angew. Chem. Int. Ed. 2014, 53, 11596. doi: 10.1002/anie.201407221 doi: 10.1002/anie.201407221
7. [7]
  Lu, S.; Wang, J.; Cao, X.; Li, X.; Gu, H. Chem. Commun. 2014, 50, 3512. doi: 10.1039/C3CC48596J doi: 10.1039/C3CC48596J
8. [8]
  Kim, J.; Hong, S. H. Org. Lett. 2014, 16, 4404. doi: 10.1021/ol501835t doi: 10.1021/ol501835t
9. [9]
  Fleming, F. F. Nat. Prod. Rep. 1999, 16, 597. doi: 10.1039/A804370A doi: 10.1039/A804370A
10. [10]
  Dornan, P.; Rowley, C. N.; Priem, J.; Barry, S. T.; Burchell, T. J.; Woo, T. K.; Richeson, D. S. Chem. Commun. 2008, 3645. doi: 10.1039/B803732A doi: 10.1039/B803732A
11. [11]
  Lin, L. L.; Zhou, W.; Gao, R.; Yao, S.; Zhang, X.; Xu, W.; Zheng, S.; Jiang, Z.; Yu, Q.; Li, Y. W.; Shi, C.; Wen, X. D.; Ma, D. Nature 2017, 544, 80. doi: 10.1038/nature21672 doi: 10.1038/nature21672
12. [12]
  Natte, K.; Neumann, H.; Beller, M.; Jagadeesh, R. V. Angew. Chem. Int. Ed. 2017, 56, 6384. doi: 10.1002/anie.201612520 doi: 10.1002/anie.201612520
13. [13]
  Khare, R.; Liu, Z. H.; Han, Y.; Bhan, A. J. Catal. 2017, 348, 300. doi: 10.1016/j.jcat.2017.02.022 doi: 10.1016/j.jcat.2017.02.022
14. [14]
  Hwang, A.; Kumar, M.; Rimer, J. D.; Bhan, A. J. Catal. 2017, 346, 154. doi: 10.1016/j.jcat.2016.12.003 doi: 10.1016/j.jcat.2016.12.003
15. [15]
  Hu, S.; Zhang, Q.; Yin, Q.; Zhang, Y. F.; Gong, Y. J.; Zhang, Y.; Wu, Z. J.; Dou, T. Acta Phys. -Chim. Sin. 2015, 31, 1374. doi: 10.3866/PKU.WHXB201504302
16. [16]
  Zhang, J.; Yuan, Q. C.; Zhang, J. L.; Li, T.; Guo, H. C. Chem. Commun. 2013, 49, 10106. doi: 10.1039/C3CC45877F). doi: 10.1039/C3CC45877F
17. [17]
  Wang, L.; Yi, Y. H.; Zhao, Y.; Zhang, R.; Zhang, J. L.; Guo, H. C. ACS Catal. 2015, 5, 4167. doi: 10.1021/acscatal.5b00728 doi: 10.1021/acscatal.5b00728
18. [18]
  Wang, L.; Zhao, Y.; Liu, C. Y.; Gong, W. M.; Guo, H. C. Chem. Commun. 2013, 49, 3787. doi: 10.1039/C3CC41301B doi: 10.1039/C3CC41301B
19. [19]
  Sun, S. Q.; Yi, Y. H.; Wang, L.; Zhang, J. L.; Guo, H. C. Acta Phys. Chim. Sin.2017, 33, 1123. doi: 10.3866/PKU.WHXB201703301
20. [20]
  Fan, J. X.; Yu, H. B; Zang, J. Z.; Xing, S. J. Industrial Catalysis 2013, 21 (5), 7.
21. [21]
  Qiang, L. P.; Chen, Y. B.; Cao, W.; Zhao, S. F. J. Fine and Specialty Chemical 2012, 20, 15.
22. [22]
  Shadrin, D. V.; Daut, V. A.; Ozhegov, A. I.; Gusev, A. L.; Avramenko, EH.V.RU 2198887-C1, 2003.
23. [23]
  Pan, W. X.; Feng, J.; Wen, T.; Wu, X. H.: Method for One-step Synthetising Nitrile and Amino-acetic Acid by Methanol Ammoniation Dehydrogenation. CN 101597240 A, 2009
24. [24]
  Wang, Z. M. The synthesis of 2, 6-Dimethylpyridine. M. S. Dissertation, Zhejiang University, Hangzhou, 2003.
25. [25]
  Muller, U.; Schulz, G. J. Chem. Phys. 1992, 96, 5924. doi: 10.1063/1.462661 doi: 10.1063/1.462661
26. [26]
  Worsley, M. A.; Bent, S. F.; Fuller, N. C. M.; Dalton, T. J. Appl. Phys. 2006, 100 (8), 083301. doi: 10.1063/1.2358303 doi: 10.1063/1.2358303
27. [27]
  Petrović. Z. L.; Phelps, A. V. Phys. Rev. E 2009, 80, 016408. doi: 10.1103/PhysRevE.80.016408 doi: 10.1103/PhysRevE.80.016408
28. [28]
  Watson, J. K. G.; Majewski, W. A.; Glownia, J. H. J. Mol. Spectrosc. 1986, 115, 82. doi: 10.1016/0022-2852(86)90277-8 doi: 10.1016/0022-2852(86)90277-8
29. [29]
  Herzberg, G.; Ramsay, D. A. J. Chem. Phys. 1952, 20, 347 doi: 10.1063/1.1700418 doi: 10.1063/1.1700418
30. [30]
  Vandevelde, T.; Nesladek, M.; Ouaeyhaegens, C.; Stals, L. Thin Solid Films 1996, 290-291, 143.doi: 10.1016/S0040-6090(96)09189-4 doi: 10.1016/S0040-6090(96)09189-4
31. [31]
  Glarborg, P.; Miller, J. A.; Kee, R. J. Combust. Flame 1986, 65, 177. doi: 10.1016/0010-2180(86)90018-0 doi: 10.1016/0010-2180(86)90018-0
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Plasma-Triggered CH₃OH/NH₃ Coupling Reaction for Synthesis of Nitrile Compounds