Citation: 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 shu

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

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

Corresponding author: You Jun, youjunjun@126.com Wu Wenju, wuwenju1017@163.com
Received Date: 19 March 2020
Revised Date: 22 May 2020
Available Online: 19 June 2020
Fund Project: the National Natural Science Foundation of China 21908034the Natural Science Foundation of Heilongjiang Province LH2019B010Project supported by the National Natural Science Foundation of China (No. 21908034), and the Natural Science Foundation of Heilongjiang Province (No. LH2019B010)

Figures(1)

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.
- acetone cyanohydrin,
- 3, 5-dimethyl-N-α, β-unsaturated acyl pyrazole,
- Michael addition,
- β-substituted phenyl cyanoacrylate
1. [1]
  Veum, L.; Hanefeld, U. Chem. Commun. 2006, 825.
2. [2]
  Gregory; Robert, J. H. Chem. Rev. 1999, 99, 3649. doi: 10.1021/cr9902906
3. [3]
  Zhang, W. J.; Huo, F. J.; Yin, C. X. Mater. Chem. 2018, 6, 6919. doi: 10.1039/C8TB02205D
4. [4]
  Wang, J.; Liu, H. Chin. J. Org. Chem. 2012, 32, 1643(in Chinese).
5. [5]
  Elliott, M.; Farnham, A. W.; Janes, N. F. Pestic. Sci. 1978, 9, 112. doi: 10.1002/ps.2780090204
6. [6]
  Ping, Y. Y.; Ding, Q. P.; Peng, Y. Y. J. ACS. Catal. 2016, 6, 5989. doi: 10.1021/acscatal.6b01632
7. [7]
  Lapworth, A. J. Chem. Soc. 1903, 995.
8. [8]
  Beletskaya, I. P.; Sigeev, A. S.; Peregudov, A. S. J. Org. Chem. 2004, 7, 19.
9. [9]
  Zanon, J.; Klapars, A.; Buchwald, S. L. J. Am. Chem. Soc. 2003, 125, 2890. doi: 10.1021/ja0299708
10. [10]
  Dong, L. C.; Crowe, M.; West, J.; Ammann, J. R. Tetrahedron. Lett. 2004, 45, 2731. doi: 10.1016/j.tetlet.2004.02.040
11. [11]
  Belokon, Y. N.; Blacker, A. J.; Clutterbuck, L. A.; Hogg, D.; North, M.; Reeve, C. Eur. J. Org. Chem. 2006, 4609.
12. [12]
  Sakai, Y.; Mitote, J.; Matsumoto, K. Chem. Commun. 2010, 46, 5787. doi: 10.1039/c0cc00588f
13. [13]
  Meninno, S.; Naddeo, S.; Varricchio, L. Org. Chem. Front. 2018, 10, 1039. doi: 10.1039/C8QO00357B
14. [14]
  Liu, X. S.; Li, M.-M.; You, J.; Liu, B. Chin. J. Org. Chem. 2017, 37, 86(in Chinese).
15. [15]
  Li, P.; Hu, X.; Dong, X. Q.; Zhang, X. Chem. Commun. 2016, 52, 11677. doi: 10.1039/C6CC04987G
16. [16]
  Huo, H.; Harms, K.; Meggers, E. J. Am. Chem. Soc. 2016, 138:6936. doi: 10.1021/jacs.6b03399
17. [17]
  Lin, X.; Tang, Y.; Yang, W.; Tan, F.; Lin, L.; Liu, X.; Feng, X. J. Am. Chem. Soc. 2018, 140, 3299. doi: 10.1021/jacs.7b12486
18. [18]
  Sakaguchi, Y.; Kurono, N.; Yamauchi, K.; Ohkuma, T. Org. Lett. 2014, 16, 808. doi: 10.1021/ol403545b
19. [19]
  Wet-Osot, S.; Pattarawarapan, M.; Phakhodee, W. Tetrahedron Lett. 2015, 56, 7172. doi: 10.1016/j.tetlet.2015.11.038
20. [20]
  Zhang, W.; Shi, M. Org. Biomol. Chem. 2006, 4, 1671. doi: 10.1039/b602197b
21. [21]
  Chen, H.; Chen, D. H.; Huang, P. Q. Sci. China Chem. 2020, 63, 370. doi: 10.1007/s11426-019-9665-5
22. [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. [23]
  Zhang, J. L.; Liu, X. H.; Wang, R. Chem.-Eur. J. 2014, 20, 4911. doi: 10.1002/chem.201304835
24. [24]
  Flammang, R.; Abdelouahab, F. B. B.; Munkengeshayi, K. Bull. Soc. Chim. Belg. 1992, 101, 215.
25. [25]
  Kashima, C.; Harada, H.; Kita, I.; Fukuchi, I.; Hosomi, A. Synthesis 1994, 1, 61.
1. [1]
  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
2. [2]
  Xudong Liu , Huili Fan , Junping Xiao , Min Yang , Yan Li . Teaching Approaches to the A_E + A_N Mechanism of Electrophilic Addition Reactions between Olefins and Inorganic Acids in Organic Chemistry. University Chemistry, 2025, 40(7): 367-372. doi: 10.12461/PKU.DXHX202409041
3. [3]
  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
4. [4]
  Yuanyuan Ping , Wangqing Kong . 光催化碳氢键官能团化合成1-苯基-1,2-乙二醇. University Chemistry, 2025, 40(6): 238-247. doi: 10.12461/PKU.DXHX202408092
5. [5]
  Zijian Zhao , Yanxin Shi , Shicheng Li , Wenhong Ruan , Fang Zhu , Jijun Jiang . A New Exploration of the Preparation of Polyacrylic Acid by Free Radical Polymerization Based on the Concept of Green Chemistry. University Chemistry, 2024, 39(5): 315-324. doi: 10.3866/PKU.DXHX202311094
6. [6]
  Yifeng TAN , Ping CAO , Kai MA , Jingtong LI , Yuheng WANG . Synthesis of pentaerythritol tetra(2-ethylthylhexoate) catalyzed by h-MoO₃/SiO₂. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2155-2162. doi: 10.11862/CJIC.20240147
7. [7]
  Lirui Shen , Kun Liu , Ying Yang , Dongwan Li , Wengui Chang . Synthesis and Application of Decanedioic Acid-N-Hydroxysuccinimide Ester: Exploration of Teaching Reform in Comprehensive Applied Chemistry Experiment. University Chemistry, 2024, 39(8): 212-220. doi: 10.3866/PKU.DXHX202312035
8. [8]
  Yikai Wang , Xiaolin Jiang , Haoming Song , Nan Wei , Yifan Wang , Xinjun Xu , Cuihong Li , Hao Lu , Yahui Liu , Zhishan Bo . 氰基修饰的苝二酰亚胺衍生物作为膜厚不敏感型阴极界面材料用于高效有机太阳能电池. Acta Physico-Chimica Sinica, 2025, 41(3): 2406007-. doi: 10.3866/PKU.WHXB202406007
9. [9]
  Xiaoyang Li , Xiaowei Huang , Yimeng Zhang , Huan Liu , Shao Jin , Junpeng Zhuang . Comprehensive Chemical Experiments on the Synthesis of 1,3-Dibromo-5,5-Dimethylhydantoin and Its Application as a Brominating Reagent. University Chemistry, 2025, 40(7): 286-293. doi: 10.12461/PKU.DXHX202408035
10. [10]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
11. [11]
  Aili Feng , Xin Lu , Peng Liu , Dongju Zhang . Computational Chemistry Study of Acid-Catalyzed Esterification Reactions between Carboxylic Acids and Alcohols. University Chemistry, 2025, 40(3): 92-99. doi: 10.12461/PKU.DXHX202405072
12. [12]
  Peng XU , Shasha WANG , Nannan CHEN , Ao WANG , Dongmei YU . Preparation of three-layer magnetic composite Fe₃O₄@polyacrylic acid@ZiF-8 for efficient removal of malachite green in water. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 544-554. doi: 10.11862/CJIC.20230239
13. [13]
  Ronghao Zhao , Yifan Liang , Mengyao Shi , Rongxiu Zhu , Dongju Zhang . Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 305-313. doi: 10.3866/PKU.DXHX202309101
14. [14]
  Xinhao Yan , Guoliang Hu , Ruixi Chen , Hongyu Liu , Qizhi Yao , Jiao Li , Lingling Li . Polyethylene Glycol-Ammonium Sulfate-Nitroso R Salt System for the Separation of Cobalt (II). University Chemistry, 2024, 39(6): 287-294. doi: 10.3866/PKU.DXHX202310073
15. [15]
  Zhaoxuan ZHU , Lixin WANG , Xiaoning TANG , Long LI , Yan SHI , Jiaojing SHAO . Application of poly(vinyl alcohol) conductive hydrogel electrolytes in zinc ion batteries. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 893-902. doi: 10.11862/CJIC.20240368
16. [16]
  Hongmei Chai , Yixia Ren , Xiangyang Hou , Long Tang , Jiawei Xie . 智能手机光传感的“丙酮碘化反应”实验改进. University Chemistry, 2025, 40(6): 193-200. doi: 10.12461/PKU.DXHX202407086
17. [17]
  Yiling Wu , Peiyao Jin , Shenyue Tian , Ji Zhang . The Star of Sugar Substitutes: An Interview of Erythritol. University Chemistry, 2024, 39(9): 22-27. doi: 10.12461/PKU.DXHX202404034
18. [18]
  Zhuoming Liang , Ming Chen , Zhiwen Zheng , Kai Chen . Multidimensional Studies on Ketone-Enol Tautomerism of 1,3-Diketones By ¹H NMR. University Chemistry, 2024, 39(7): 361-367. doi: 10.3866/PKU.DXHX202311029
19. [19]
  Caixia Lin , Ting Liu , Zhaojiang Shi , Hong Yan , Keyin Ye , Yaofeng Yuan . Innovative Experiment of Electrochemical Dearomative Spirocyclization of N-Acyl Sulfonamides. University Chemistry, 2025, 40(4): 359-366. doi: 10.12461/PKU.DXHX202406107
20. [20]
  Aiyi Xin , Jiawei Li , Xinyang Ran , Chuanjiang Fu , Zhiguo Wang . Collaborative Science and Education Based Experimental Design in Organic Chemistry: A Case Study of the Nucleophilic Substitution Reaction of 2-Hydroxymethyl-4,6-Di-Tert-Butylphenol. University Chemistry, 2025, 40(5): 366-375. doi: 10.12461/PKU.DXHX202407031

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(1098)
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