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Chinese Journal of Organic Chemistry >

2020 , Vol. 40 >Issue 9: 2871 - 2878

DOI: https://doi.org/10.6023/cjoc202003047

Study on the Reaction of Acetone Cyanohydrin with 3,5-Dimethyl-N-α,β-unsaturated Acyl Pyrazole

  • Fang Guannian ,
  • You Jun ,
  • Yu Yanchao ,
  • Jing Junkai ,
  • Liu Bo ,
  • Wu Wenju
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  • Key Laboratory of Green Chemical Engineering and Technology of Heilongjiang Province, College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin 150040

Received date: 2020-03-19

  Revised date: 2020-05-22

  Online published: 2020-06-19

Supported by

Project supported by the National Natural Science Foundation of China (No. 21908034), and the Natural Science Foundation of Heilongjiang Province (No. LH2019B010).

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Abstract

Cyano compounds are a class of organic compounds with great value. Two different kinds of reactions have been reported using acetone cyanohydrin as reagent and substituted 3,5-dimethyl-N-α,β-unsaturated acyl pyrazole as substrate. The reaction pathway depends on the basic catalysts used when aromatic substituted 3,5-dimethyl-N-α,β-unsaturated acyl pyrazole was used as the substrate. Michael addition reaction occurred in the presence of MgBu2 with the product yield up to 95%, while alcoholysis reaction of amide occurred in the presence of 1,1,3,3-tetramethylguanidine (TMG), producing β-substituted phenyl cyanoacrylates with 84% yield. However, fatty substituted 3, 5-dimethyl-N-α,β-unsaturated acyl pyrazole and acetone cyanohydrin underwent Michael addition reaction in the presence of MgBu2 or TMG, the product yield was up to 99%. The possible reaction mechanism when using different basic catalysts was discussed.

Key words： acetone cyanohydrin; 3,5-dimethyl-N-α,β-unsaturated acyl pyrazole; Michael addition; β-substituted phenyl cyanoacrylate

Cite this article

Fang Guannian , You Jun , Yu Yanchao , Jing Junkai , Liu Bo , Wu Wenju . Study on the Reaction of Acetone Cyanohydrin with 3,5-Dimethyl-N-α,β-unsaturated Acyl Pyrazole[J]. Chinese Journal of Organic Chemistry, 2020 , 40(9) : 2871 -2878 . DOI: 10.6023/cjoc202003047

References

[1] Veum, L.; Hanefeld, U. Chem. Commun. 2006, 825.
[2] Gregory; Robert, J. H. Chem. Rev. 1999, 99, 3649.
[3] Zhang, W. J.; Huo, F. J.; Yin, C. X. Mater. Chem. 2018, 6, 6919.
[4] Wang, J.; Liu, H. Chin. J. Org. Chem. 2012, 32, 1643(in Chinese). (王江, 柳红, 有机化学, 2012, 32, 1643.).
[5] Elliott, M.; Farnham, A. W.; Janes, N. F. Pestic. Sci. 1978, 9, 112.
[6] Ping, Y. Y.; Ding, Q. P.; Peng, Y. Y. J. ACS. Catal. 2016, 6, 5989.
[7] Lapworth, A. J. Chem. Soc. 1903, 995.
[8] Beletskaya, I. P.; Sigeev, A. S.; Peregudov, A. S. J. Org. Chem. 2004, 7, 19.
[9] Zanon, J.; Klapars, A.; Buchwald, S. L. J. Am. Chem. Soc. 2003, 125, 2890.
[10] Dong, L. C.; Crowe, M.; West, J.; Ammann, J. R. Tetrahedron. Lett. 2004, 45, 2731.
[11] Belokon, Y. N.; Blacker, A. J.; Clutterbuck, L. A.; Hogg, D.; North, M.; Reeve, C. Eur. J. Org. Chem. 2006, 4609.
[12] Sakai, Y.; Mitote, J.; Matsumoto, K. Chem. Commun. 2010, 46, 5787.
[13] Meninno, S.; Naddeo, S.; Varricchio, L. Org. Chem. Front. 2018, 10, 1039.
[14] Liu, X. S.; Li, M.-M.; You, J.; Liu, B. Chin. J. Org. Chem. 2017, 37, 86(in Chinese). (刘迅绅, 李美美, 由君, 刘波, 有机化学, 2017, 37, 86.)
[15] Li, P.; Hu, X.; Dong, X. Q.; Zhang, X. Chem. Commun. 2016, 52, 11677.
[16] Huo, H.; Harms, K.; Meggers, E. J. Am. Chem. Soc. 2016, 138:6936.
[17] Lin, X.; Tang, Y.; Yang, W.; Tan, F.; Lin, L.; Liu, X.; Feng, X. J. Am. Chem. Soc. 2018, 140, 3299.
[18] Sakaguchi, Y.; Kurono, N.; Yamauchi, K.; Ohkuma, T. Org. Lett. 2014, 16, 808.
[19] Wet-Osot, S.; Pattarawarapan, M.; Phakhodee, W. Tetrahedron Lett. 2015, 56, 7172.
[20] Zhang, W.; Shi, M. Org. Biomol. Chem. 2006, 4, 1671.
[21] Chen, H.; Chen, D. H.; Huang, P. Q. Sci. China Chem. 2020, 63, 370.
[22] Zheng, Y. Q.; Yao, Y. Q.; Ye, L.; Shi, Z. C.; Li, X. F.; Zhao, Z. G.; Li, X. Y. Tetrahedron 2015, 72, 973.
[23] Zhang, J. L.; Liu, X. H.; Wang, R. Chem.-Eur. J. 2014, 20, 4911.
[24] Flammang, R.; Abdelouahab, F. B. B.; Munkengeshayi, K. Bull. Soc. Chim. Belg. 1992, 101, 215.
[25] Kashima, C.; Harada, H.; Kita, I.; Fukuchi, I.; Hosomi, A. Synthesis 1994, 1, 61.
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