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

doi:10.6023/cjoc202003047

Chinese Journal of Organic Chemistry ›› 2020, Vol. 40 ›› Issue (9): 2871-2878.DOI: 10.6023/cjoc202003047 Previous Articles Next Articles

丙酮氰醇与3,5-二甲基-N-α,β-不饱和酰基吡唑的反应研究

房观念, 由君, 喻艳超, 荆军凯, 刘波, 武文菊

哈尔滨理工大学化学与环境工程学院黑龙江省绿色化工技术重点实验室哈尔滨 150040

收稿日期:2020-03-19 修回日期:2020-05-22 发布日期:2020-06-20
通讯作者: 由君, 武文菊 E-mail:youjunjun@126.com;wuwenju1017@163.com
基金资助:
国家自然科学基金（No.21908034）、黑龙江省自然科学基金（No.LH2019B010）资助项目.

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

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:2020-03-19 Revised:2020-05-22 Published:2020-06-20
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21908034), and the Natural Science Foundation of Heilongjiang Province (No. LH2019B010).

1. cjoc202003047.pdf(2637KB)

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.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

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.

丙酮氰醇与3,5-二甲基-N-α,β-不饱和酰基吡唑的反应研究

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

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Cunwei Qian, Rong Han, Zhixing Shen, Qian Li, Xuanrong Chen. N-Iodosuccinimide (NIS) Promoted Synthesis of 3-Substituted Indole Derivatives [J]. Chinese Journal of Organic Chemistry, 2022, 42(8): 2496-2503.
[2]	Jingjie Li, Yuhao Wang, Tiantian Meng, Yiyong Huang. Phosphine-Catalyzed Synthesis of 1,3-Dihydro-3-alkylidene-2H-indol-2-ones [J]. Chinese Journal of Organic Chemistry, 2022, 42(7): 2222-2228.
[3]	Zhiwei Ma, Xiaopei Chen, Chuanchuan Wang, Jianling Wang, Jingchao Tao, Quanjian Lü. Chiral Squaramide Catalyzed Enantioselective Michael Addition of Cyclic 1,3-Diketones to β,γ-Unsaturated α-Keto Esters [J]. Chinese Journal of Organic Chemistry, 2022, 42(5): 1520-1526.
[4]	Donglan Liu, Haiyan Xu, Yi Hang, Hongfei Lu. 1,6-Addition of Nitrogen Nucleophile to para-Quinone Methides Catalyzed by Recyclable Bismuth Complex: Facile Access to N-Heterocyclic Substituted Unsymmetric Triarylmethane Derivatives [J]. Chinese Journal of Organic Chemistry, 2022, 42(3): 796-802.
[5]	Anguo Ying, Linsheng Bai, Hailiang Hou, Songlin Xu, Xiaotong Lu, Limin Wang. Research on Thia-Michael Addition Tandem Reactions Catalyzed by AlCl₃@MNPs [J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3843-3852.
[6]	Fang Guo, Jun You, Wenju Wu, Yanchao Yu, Bin Jing, Bo Liu. Study on the Cyanide Substitution Reaction of Acetone Cannolhydrin as Cyanogen Source [J]. Chinese Journal of Organic Chemistry, 2021, 41(5): 1968-1973.
[7]	Fang Li, Yonghe Tang, Rui Guo, Weiying Lin. Development of an Ultrasensitive Mitochondria-Targeted Near Infrared Fluorescent Probe for SO₂ and Its Imaging in Living Cells and Mice [J]. Chinese Journal of Organic Chemistry, 2021, 41(3): 1108-1116.
[8]	Xuehua Liu, Chuanchuan Wang, Xinlu Wang, Zhiwei Ma, Lei Meng, Degang Ding, Juntao Liu, Yajing Chen. Synthesis of Spirobarbiturate Piperidin-2-one Derivatives via Cascade Aza-Michael/Michael Cyclization Reaction [J]. Chinese Journal of Organic Chemistry, 2021, 41(11): 4450-4458.
[9]	Zhou Xiaoqin, Cui Mengyuan, Jia Chengli, Yang Min, Ji Min, Wang Peng. Novel Ratio-Based Fluorescent Probe for Intracellular Cys Detection [J]. Chinese Journal of Organic Chemistry, 2020, 40(8): 2502-2507.
[10]	Zhang Yang, Xing Fen, Feng Zenan, Du Guangfen, Gu Chengzhi, He Lin. N-Heterocyclic Carbene-Catalyzed Double Michael Addition of Cyano Acetates and Dienones: Diastereoselective Synthesis of Multisubstituted Cyclohexanones and Indanes [J]. Chinese Journal of Organic Chemistry, 2020, 40(6): 1608-1617.
[11]	Zhou Huiyuan, Wu Yanlin, Huang Dianhong, Zhang Mingting, Chen Huanming, Qian Mingcheng, Zhao Shuai, Zhang Xinyan, Chen Xin. Synthesis and Anti-tumor Activity of Novel Garcinol Analogs [J]. Chinese Journal of Organic Chemistry, 2020, 40(6): 1578-1587.
[12]	Liu Yaozong, Xu Pengfei, Ma Jianjun, Li Xiaoming, Liang Ruiyuan, Teng Zhijun. Bifunctional Thioureas Catalyzed Asymmetric Michael Addition of 1-Acetylindolin-3-ones to β,γ-Unsaturated α-Keto Esters [J]. Chinese Journal of Organic Chemistry, 2020, 40(5): 1378-1383.
[13]	Wang Xiaogang, Huang Peiqiang. Exploratory Studies on a New Strategy for the Asymmetric Total Synthesis of the Arrow Poison-Frog Alkaloid Batrachotoxin: Asymmetric Synthesis of a Functionalized CD Ring [J]. Chinese Journal of Organic Chemistry, 2020, 40(11): 3858-3865.
[14]	Ma Ben, Wang Ganggang, Zhou Hongyan, Yang Jingya. Alkali Salt-Catalyzed Aza-Michael Addition of 1,2,4-Triazole to α,β-Unsaturated Ketones and Imides [J]. Chinese Journal of Organic Chemistry, 2020, 40(1): 115-124.
[15]	Yang Zhenhua, Zhu Jianan, Wen Caiyue, Ge Yingxiang, Zhao Shengyin. Recent Advances in Functionalization of Double Bond Based on Maleimides [J]. Chin. J. Org. Chem., 2019, 39(9): 2412-2427.