a (Hunan Agriculture Biotechnology Research Institute,Hunan Academy of Agricultural Sciences, Changsha 410125, China)
b (Department of Applied Chemistry, College of Science,China Agricultural University, Beijing 100193, China)
c (Laboratory of Integrated Pest Management in Crops, Ministry of Agriculture, Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing 100193, China)
Synthesis, Crystal Structure and Insecticidal Activity of N-(pyridin-2-ylmethyl)-1-phenyl-1,4,5,6,7,8- hexahydrocyclohepta[c]pyrazole-3-carboxamide
DENG Xi-Le;ZHOU Xiao-Mao;WANG Zan-Yong;RUI Chang-Hui;YANG Xin-Ling
a (Hunan Agriculture Biotechnology Research Institute,Hunan Academy of Agricultural Sciences, Changsha 410125, China)
b (Department of Applied Chemistry, College of Science,China Agricultural University, Beijing 100193, China)
c (Laboratory of Integrated Pest Management in Crops, Ministry of Agriculture, Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing 100193, China)
The title compound N-(pyridin-2-ylmethyl)-1-phenyl-1,4,5,6,7,8-hexahydrocy- clohepta[c]pyrazole-3-carboxamide 5 (C21H22N4O, Mr = 346.42) has been synthesized and structurally characterized by IR, 1H NMR, 13C NMR, H RMS and single-crystal X-ray diffraction. The crystal crystallizes in monoclinic system, space group P21/n with a = 8.668(2), b = 22.236(4), c = 9.539(2) Å, β = 108.68(3)°, V = 1786.4(7) Å3, Z = 4, Dx = 1.288 g/cm-3, F(000) = 736, μ(MoKa) = 0.649 mm-1, the final R = 0.0354 and wR = 0.0933 with 3234 observed reflections with I > 2σ(I). The benzene and pyrazole rings are nearly coplanar with a dihedral angle of 50.977(46)°. The dihedral angle between the central pyrazole and pyridine rings is 11.688(46)°. No classical hydrogen bonds were found in the molecules. Two adjacent molecules in crystal packing of compound 5 were linked by two intramolecular hydrogen-bonding interactions C(15)–H(15)•••O(1) to generate a stable structure. Compound 5 had weak insecticidal activity against the diamondback moth (Plutella xylostella), but exhibited good activity against cotton bollworm (Helicoverpa armigera).
This study was financially supported by the National Key Research and Development Plan (No. 2017YFD0200504) and Hunan Provincial Science and Technology Plan Project (No. 2016RS2012)
通讯作者:
yangxl@cau.edu.cn
E-mail: yangxl@cau.edu.cn
引用本文:
邓希乐;周小毛;王赞永;芮昌辉;杨新玲. N-(2-吡啶基甲基)-1-苯基-1,4,5,6,7,8-六氢环庚三烯并吡唑-3-甲酰胺的合成、晶体结构及杀虫活性[J]. 结构化学, 2018, 37(4): 551-556.
DENG Xi-Le;ZHOU Xiao-Mao;WANG Zan-Yong;RUI Chang-Hui;YANG Xin-Ling. Synthesis, Crystal Structure and Insecticidal Activity of N-(pyridin-2-ylmethyl)-1-phenyl-1,4,5,6,7,8- hexahydrocyclohepta[c]pyrazole-3-carboxamide. CHINESE JOURNAL OF STRUCTURAL CHEMISTRY, 2018, 37(4): 551-556.
REFERENCES
(1) Vaidya, A. B.; Morrisey, J. M.; Zhang, Z.; Das, S.; Daly, T. M.; Otto, T. D.; Spillman, N.; Wyvratt J. M.; Siegl, P.; Marfurt, J. Pyrazoleamide compounds are potent antimalarials that target Na(+) homeostasis in intraerythrocytic Plasmodium falciparum. Nat. Commun. 2014, 5, 5521–5521.
(2) Franz, F.; Angerer, V.; Brandt, S. D.; Mclaughlin, G.; Kavanagh, P. V.; Moosmann, B.; Auwärter, V. In vitro metabolism of the synthetic cannabinoid 3,5-AB-CHMFUPPYCA and its 5,3-regioisomer and investigation of their thermal stability. Drug Test. Analysis 2017, 9, 311–316.
(3) Hall, A.; Billinton, A.; Bristow, A. K.; Brown, S. H.; Chowdhury, A.; Cutler, L.; Giblin, G. M. P.; Goldsmith, P.; Hayhow, T. G.; Kilford, I. R. Discovery of brain penetrant, soluble, pyrazole amide EP 1 receptor antagonists. Bioorg. Med. Chem. Lett. 2008, 18, 4027–4032.
(4) Hu, L.; Zheng, Y.; Li, L.; Wang, Y.; Lv, Y.; Qin, X.; Zeng, C. Design, synthesis, and biological activity of phenyl-pyrazole derivatives as BCR-ABL kinase inhibitors. Bioorg. Med. Chem. 2015, 23, 3147–3152.
(5) Wen, J.; Bao, Y.; Niu, Q.; Yang, J.; Fan, Y.; Li, J.; Jing, Y.; Zhao, L.; Liu, D. Identification of N-(6-mercaptohexyl)-3-(4-pyridyl)-1H-pyrazole-5-carboxamide and its disulfide prodrug as potent histone deacetylase inhibitors with in vitro and in vivo anti-tumor efficacy. Eur. J. Med. Chem. 2016, 109, 350–359.
(6) Wu, J.; Song, B. A.; Hu, D. Y.; Yue, M.; Yang, S. Design, synthesis and insecticidal activities of novel pyrazole amides containing hydrazone substructures. Pest. Manag. Sci. 2012, 68, 801–810.
(7) Moberg, W. K.; Major, J.; Seitz, T.; Parra Rapado, L.; Newton, T. W.; Evans, R. R. 5-Trifluoromethylpyrazole amides having herbicidal activity, EP patent, C07d. 2700635 2014-02-26. 82pp.
(8) Mu, J. X.; Shi, Y. X.; Yang, M. Y.; Sun, Z. H.; Liu X. H.; Li, B. J.; Sun, N. B. Design, synthesis, DFT study and antifungal activity of pyrazolecarboxamide derivatives. Molecules 2016, 21, 68.
(9) Deng, X. L.; Xie, J.; Li, Y. Q.; Yuan, D. K.; Hu, X. P.; Zhang, L.; Wang, Q. M.; Chi, M.; Yang, X. L. Design, synthesis and biological activity of novel substituted pyrazole amide derivatives targeting EcR/USP receptor. Chin. Chem. Lett. 2016, 27, 566–570.
(10) Selby, T. P.; Lahm, G. P.; Stevenson, T. M. A Retrospective look at anthranilic diamide insecticides: discovery and lead optimization to chlorantraniliprole and cyantraniliprole. Pest. Manag. Sci. 2017, 73, 658–665.
(11) Yang, X. L.; Deng, X. L.; Zhang, L.; Chi, M.; Yuan, D. K.; Hu, X. P.; Mi, Y. D. Pyrazolocyclo-3-carboxamide analog as pesticide and its preparation. CN patent, C07d. 105367498 2016-03-02. 10pp.
(12) Wu, D.; Jin, F.; Lu, W.; Zhu, J.; Li, C.; Wang, W.; Tang, Y.; Jiang, H.; Huang, J.; Liu, G.; Li, J. Synthesis, structure-activity relationship, and pharmacophore modeling studies of pyrazole-3-carbohydrazone derivatives as dipeptidyl peptidase IV inhibitors. Chem. Biol. Drug Des. 2012, 79, 897–906.
(13) Martins, M. A. P.; Freitag, R. A.; Rosa, A. D.; Flores, A. F. C.; Zanatta, N.; Bonacorso, H. G. Haloacetylated enol ethers. 11. synthesis of 1-methyl- and 1-phenyl pyrazole-3(5)-ethyl esters. a one-pot procedure. J. Heterocyclic Chem. 1999, 36, 217–220.
(14) Sun, Y. F.; Qiao, H. L.; Ling, Y.; Yang, S. X.; Rui, C. H.; Pelosi, P.; Yang, X. L. New analogues of (E)-β-farnesene with insecticidal activity and binding affinity to aphid odorant-binding proteins. J. Agric. Food Chem. 2011, 59, 2456–2461.
(15) Chen, N. C. Bioassay of Pesticides; Beijing Agricultural University Press: Beijing 1991, 161.
(16) Wang, Y.; Shao, H.; Xu, W. R.; Wang, J. W. Synthesis and crystal structure of ethyl 1-(2-bromoethyl)-3-(4-methoxyphenyl)-
1H-pyrazole-5-carboxylate. Chin. J. Struct. Chem. 2012, 31, 110–114.
(17) Li, M.; Wen, L. R.; Fu, W. J.; Hu, F. Z.; Yang, H. Z. Synthesis and structure of 2-isobutyl-6-(2΄,4΄-dichlorophenyl)imidazo[2,1-b]-1,3,4-thiadiazole.
Chin. J. Struct. Chem. 2004, 23, 11–14.
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