Citation: Xu Min, Shi Daxin, Liu Mingxing, Zhang Qi, Li Jiarong. Study of 1-Methyl-3-propyl-4-aminopyrazole-5-carbonitrile[J]. Chinese Journal of Organic Chemistry, ;2016, 36(7): 1611-1616. doi: 10.6023/cjoc201512042 shu

Study of 1-Methyl-3-propyl-4-aminopyrazole-5-carbonitrile

1.
School of Chemical Engineering and Environment, Beijing institute of Technology, Beijing 100081

Corresponding author: Li Jiarong, jrli@bit.edu.cn
Received Date: 28 December 2015
Revised Date: 10 March 2016

Figures(7)

1-Methyl-3-propyl-4-aminopyrazole-5-carbonitrile was synthesized by using 1-methyl-3-propylpyrazole-5-formic as starting materials in four steps reaction including acylation, dehydration, nitrification and reduction. Then pyrazolopyrimidinone derivatives were obtained from the condensation of 1-methyl-3-propyl-4-aminopyrazole-5-carbonitrile and aldehydes. 1-Methyl-3-propyl-4-nitropyrazole-5-carbonitrile was reduced to amine in the presence of palladium-charcoal. Three intermediate products, hydroxylamine, azoxypyrazole and azopyrazole, were separated and detected with HPLC and HPLC-HRMS during the formation of amine pyrazole. Possible reduction mechanism was proposed. The structures of products were characterized by ¹H NMR, ¹³C NMR, IR spectra and MS.
- 1-methyl-3-propyl-4-aminopyrazole-5-carbonitrile,
- pyrazolopyrimidinone derivative,
- reduction mechanism
1. [1]
  Li, S.-H.; Xu, S.-J.; Tang, Y.-H.; Ding, S.; Zhang, J.-C.; Wang, S.-X.; Zhou, G.-Q.; Zhou, C.-Q.; Li, X.-L. Bioorg. Med. Chem. Lett. 2014, 24, 586.
2. [2]
  Coumar, M. S.; Leou, J. S. J. Med. Chem. 2009, 52, 1050.
3. [3]
  Abu-Melha, S. Arch. Pharm. Chem. Life Sci. 2013, 346, 912.
4. [4]
  Horrocks, P.; Pickard, M. R.; Parekh, H.; Patel, S. P.; Ravindra, B. P. Org. Biomol. Chem. 2013, 11, 4891.
5. [5]
  Palanisamy, P.; Kumaresan, S. RSC Adv. 2013, 3, 4704.
6. [6]
  Chauhan, M.; Kumar, R. Bioorg. Med. Chem. 2013, 21, 5657.
7. [7]
  Gawad, N. M. A. E.; Hassan, G. S.; Georgey, H. H. Med. Chem. Res. 2012, 21, 983.
8. [8]
  Li, X.; Liu, J.-L.; Yang, X.-H.; Lu, X.; Zhao, T.-T.; Cong, H.-B.; Zhu, H.-L. Bioorg. Med. Chem. 2012, 20, 4430.
9. [9]
  Feig, D. I.; Soletsky, B. J. Am. Med. Assoc. 2008, 300, 924.
10. [10]
  Pan, Z.; Scheerens, H.; Li, S.; Schultz, B. E.; Sprengeler, P. A.; Burrill, L. C.; Mendonca, R. V.; Sweeney, M. D.; Scott, K. C. K.; Grothaus, P. G.; Jeffery, D. A.; Spoerke, J. M.; Honigberg, L. A.; Young, P. R.; Dalrymple, S. A.; Palmer, J. T. Chem. Med. Chem. 2007, 2, 58.
11. [11]
12. [12]
13. [13]
14. [14]
15. [15]
16. [16]
  Robert, B.; Moreland, I.; Abdulmaged, T. Life Sci. 1988, 62, 309.
17. [17]
  Terrett, N. K.; Bell, A. S.; Brown, D. Bioorg. Med. Chem. Lett. 1996, 6, 1819.
18. [18]
  Kankan, R. N. R.; Rao, D. R. WO 0119827, 2001 [Chem. Abstr. 2001, 134, 237494].
19. [19]
  Dunn, P. J.; Galvin, S.; Hettenbach, K. Green. Chem. 2004, 6, 43.
20. [20]
  Carlo, M.; Anna, B.; Andrea, L. R.; Monica, B.; Eleonora, A.; Piera, D. M.; Luisa, V.; Isabella, S.; Eliana, C.; Maria, C. G. J. Pharm. Biomed. Anal. 2014, 96, 170.
21. [21]
  Shi, B.-J.; Tang, J.-W.; Qi, B.-X.; Li, R.; Liu, H.-X. Eur. J. Med. Chem. 2015, 90, 889.
22. [22]
  Chen, Y.-Y.; Qiu, J.-S.; Wang, X.-K.; Xiu, J.-H. J. Catal. 2006, 242, 227.
23. [23]
  Shen, J.-H.; Chen, Y.-W. J. Mol. Catal. A: Chem. 2007, 273, 265.
24. [24]
  Vilella, I. M. J.; Miguel, S. R.; Scelza, O. A. Chem. Eng. J. 2005, 114, 33.
25. [25]
  Takasaki, M.; Motoyama, Y.; Higashi, K.; Yoon, S. H.; Mochida, I.; Nagashima, H. Org. Lett. 2008, 10, 1601.
26. [26]
  Sonavane, S. U.; Gawande, M. B.; Deshpande, S. S.; Venkataraman, A.; JayaraM, R. V. Catal. Commun. 2007, 8, 1803.
27. [27]
  Liu, X.-Z.; Lu, S.-W. J. Mol. Catal. A: Chem. 2004, 212, 127.
28. [28]
  Rai, G.; Jeong, J. M.; Lee, Y. S.; Kim, H. W.; Lee, D. S.; Chung, J. K.; Lee, M. C. Tetrahedron Lett. 2005, 46, 3987.
29. [29]
  Pradhan, N.; Pal, A.; Pal, T. Colloids Surf., A 2002, 196, 247.
30. [30]
  Yang, X. J.; Chen, B.; Zheng, L. Q.; Wu, L. Z.; Tung, C. H. Green Chem. 2014, 16, 1082.
31. [31]
  Göksu, H.; Ho, S. F.; Metin, Ö.; Korkmaz, K.; Garcia, A. M.; Gültekin, M. S.; Sun, S. ACS Catal. 2014, 4, 1777.
32. [32]
  Shanthi, K.; Viswanathan, B.; Selvam, P.; Sangeetha, P.; Rama Rao, K. S. Appl. Catal. A: Gen. 2009, 353, 160.
33. [33]
  Li, F.; Frett, B.; Li, H.-Y. Synlett 2014, 25, 1403.
34. [34]
  Genc, H. Catal. Commun. 2015, 67, 64.
35. [35]
  Göksu, H. New J. Chem. 2015, 39, 8498.
36. [36]
  Quinn, J. F.; Bryant, C. E.; Golden, K. C.; Gregg, B. T. Tetrahedron Lett. 2010, 51, 786.
37. [37]
  Wei, Z.-Z.; Wang, J.; Mao, S.-J.; Su, D.-F.; Jin, H.-Y.; Wang, Y.-H.; Xu, F.; Li, H.-R.; Wang, Y. ACS Catal. 2015, 5, 4783
38. [38]
  Bouchenafa-Saïb, N.; Grange, P.; Verhasselt, P.; Addoun, F.; Dubois, V. Appl. Catal. A: Gen. 2005, 286, 167.
39. [39]
40. [40]
41. [41]
42. [42]
43. [43]
  Liu, M.-X.; Li, J.-R.; Zheng, K.; Yao, H.; Zhang, Q.; Shi, D.-X. Tetrahedron 2015, 71, 7658.
44. [44]
  Collins, M. R.; Natarajan, V. US 20070249637, 2007 [Chem. Abstr. 2006, 144, 433108].
45. [45]
  Németh, J.; Kiss, Á.; Hell, Z. React. Kinet., Mech. Catal. 2014, 111, 115.
46. [46]
  Corma, A.; Concepcion, P.; Serna, P. Angew. Chem., Int. Ed. 2007, 46, 7266.
47. [47]
  Visentin, F.; Puxty, G.; Kut, O. M.; Hungerbuehler, K. Ind. Eng. Chem. Res. 2006, 45, 4544.
48. [48]
  Blaser, H. U. Science 2006, 313, 312
49. [49]
  Nemtseva, M. P.; Lefedova, O. V.; Zuenko, M. A.; Antina, L. A. Zh. Fiz. Khim. 2004, 78, 1571.
50. [50]
  Figueras, F.; Coq, B. J. Mol. Catal. A: Chem. 2001, 173, 223.
51. [51]
  Studer, M.; Neto, S.; Blaser, H. U. Top. Catal. 2000, 13, 205.
52. [52]
  Siegrist, U.; Baumeister, P.; Blaser, H. U. Chem. Ind. 1998, 75, 207.
53. [53]
  Burge, H. D.; Collins, D. J. Ind. Eng. Chem. Prod. Res. Dev. 1980, 19, 389.
54. [54]
  Haber, F. Z. Elektrochem. 1898, 22, 506.
55. [55]
  Höller, B. V.; Wegricht, D.; Yuranov, I.; Kiwi-Minsker, L.; Renken, A. Chem. Eng. Technol. 2000, 23, 251.
56. [56]
  Makaryan, I. A.; Savchenko, V. I. Stud. Surf. Sci. Catal. 1993, 75, 2439.
57. [57]
  Gelder, E. A.; Jackson, S. D.; Lok, C. M. Chem. Commun. 2005, 4, 522.
58. [58]
  Kunio, S.; Junichi, I.; Minoru, F. Chem. Pharm. Bull. 1984, 32, 1568.
59. [59]
  Magnus, A. M.; Staszak, A. M.; Udodong, E. U.; Wepsiec, P. J. Org. Process Res. Dev. 2006, 10, 899.
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