摘要 A pair of Z-E enaminonitrile isomerisms 2-(3,4-dimethoxyphenyl)-3-((3-methoxyphenyl)ami- no)acrylonitrile (C18H18N2O3, Mr = 310.34) were synthesized and separated by flash column chromatography, and their structures were determined by IR, 1H NMR, 13C NMR, MS and single-crystal X-ray diffraction. The crystal of compound 2a belongs to the monoclinic system, space group C2/c with a = 33.805(7), b = 5.4496(12), c = 18.401(4) Å, β = 112.45(2)º, V = 3133.1(12) Å3, Z = 8, μ = 0.091 mm-1, Dc = 1.143 gcm-3, the final R = 0.0491 and wR = 0.1439 for 2764 observed reflections (I > 2σ(I)). The crystal of compound 2b belongs to the triclinic system, space group P1, with a = 8.8403(7), b = 9.0390(6), c = 12.0044(74) Å, α = 72.075(5), β = 86.291(5), γ = 81.216(5)º, V = 901.82(10) Å3, Z = 2, T = 293(2) K, μ = 0.079 mm-1, Dc = 1.143 gcm-3, the final R = 0.0474 and wR = 0.1377 for 3176 observed reflections (I > 2σ(I)). The crystal packing of 2a and 2b is governed by intermolecular N(2)–H(2)···N(1) and N(2)–H(2)···O(2) interactions respectively to stabilize the structure.
Abstract：A pair of Z-E enaminonitrile isomerisms 2-(3,4-dimethoxyphenyl)-3-((3-methoxyphenyl)ami- no)acrylonitrile (C18H18N2O3, Mr = 310.34) were synthesized and separated by flash column chromatography, and their structures were determined by IR, 1H NMR, 13C NMR, MS and single-crystal X-ray diffraction. The crystal of compound 2a belongs to the monoclinic system, space group C2/c with a = 33.805(7), b = 5.4496(12), c = 18.401(4) Å, β = 112.45(2)º, V = 3133.1(12) Å3, Z = 8, μ = 0.091 mm-1, Dc = 1.143 gcm-3, the final R = 0.0491 and wR = 0.1439 for 2764 observed reflections (I > 2σ(I)). The crystal of compound 2b belongs to the triclinic system, space group P1, with a = 8.8403(7), b = 9.0390(6), c = 12.0044(74) Å, α = 72.075(5), β = 86.291(5), γ = 81.216(5)º, V = 901.82(10) Å3, Z = 2, T = 293(2) K, μ = 0.079 mm-1, Dc = 1.143 gcm-3, the final R = 0.0474 and wR = 0.1377 for 3176 observed reflections (I > 2σ(I)). The crystal packing of 2a and 2b is governed by intermolecular N(2)–H(2)···N(1) and N(2)–H(2)···O(2) interactions respectively to stabilize the structure.
基金资助: This project was supported by the National Natural Science Foundation of China (No. 21362007)
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引用本文:
郑彬;王淑琴;张晓婷;黄婉云. Syntheses and Crystal Structures of a Pair of Z-E Enaminonitrile Isomerisms[J]. 结构化学, 2021, 40(6): 821-826.
ZHENG Bin;WANG Shu-Qin;ZHANG Xiao-Ting;HUANG Wan-Yun. Syntheses and Crystal Structures of a Pair of Z-E Enaminonitrile Isomerisms. CHINESE JOURNAL OF STRUCTURAL CHEMISTRY, 2021, 40(6): 821-826.
REFERENCES
(1) Bondock, S.; Fadaly, W.; Metwally, M. A. Enaminonitrile in heterocyclic synthesis: synthesis and antimicrobial evaluation of some new pyrazole, isoxazole and pyrimidine derivatives incorporating a benzothiazole moiety. Eur. J. Med. Chem. 2009, 44, 48134818.
(2) Fadda, A. A.; Elattar, K. M. Design and synthesis of some enaminonitrile derivatives of antipyrine as potential novel anti-inflammatory and analgesic agents. J. Biosci. Med. 2015, 3, 114123.
(3) Shaaban, M. R.; Saleh, T. S.; Farag, A. M. Synthesis and antimicrobial evaluation of new thiophene and 1,3,4-thiadiazole derivatives. Heterocycles 2009, 78, 151159.
(4) Alblewi, F. F.; Okasha, R. M.; Hritani, Z. M.; Mohamed, H. M.; El-Nassag, M. A. A.; Halawa, A. H.; Mora, A.; Fouda, A. M.; Assiri, M. A.; Al-Dies, A. A. M.; Afifi, T. H.; El-Agrody, A. M. Antiproliferative effect, cell cycle arrest and apoptosis generation of novel synthesized anticancer heterocyclic derivatives based 4H-benzo[h] chromene. Bio. Chem. 2019, 87, 560571.
(5) Zhu, Y. Z.; Li, Y. H.; Xiang, S. Q.; Fan, W. B.; Jin, J.; Huang, D. G. Utilization of nitriles as the nitrogen source: practical and economical construction of 4-amino-pyrimidine and β-enaminonitrile skeletons. Org. Chem. Front. 2019, 6, 30713077.
(6) Anwer, K. E.; Sayed, G. H. Conventional and microwave reactions of 1,3-diaryl-5,4-enaminonitrile-pyrazole derivative with expected antimicrobial and anticancer activities. J. Hetero. Chem. 2020, 57, 23392353.
(7) Yoshizawa, K.; Toyota, S.; Toda, F. Efficient solvent-free Thorpe reactions. Green Chem. 2002, 4, 6870.
(8) Ghorai, M. K.; Talukdar, R.; Tiwari, D. P. An efficient synthetic route to carbocyclic enaminonitriles via Lewis acid catalysed domino-ring-opening-cyclisation (DROC) of donor-acceptor cyclopropanes with malononitrile. Chem. Commun. 2013, 49, 82058207.
(9) Sim, J.; Viji, M.; Rhee, J.; Jo, H.; Cho, S. J.; Park, Y.; Seo, S. Y.; Jung, K. Y.; Lee, H.; Jung, J. K. γ-Functionalization of α,β-unsaturated nitriles under mild conditions: versatile synthesis of 4-aryl-2-bromopyridines. Adv. Synth. Catal. 2019, 361, 54585465.
(10) Okasha, R. M.; Alblewi, F. F.; Afifi, T. H.; Naqvi, A.; Fouda, A. M.; Al-Dies, A. M.; ElAgrody, A. M. Design of new benzo[h]chromene derivatives: antitumor activities and structure-activity relationships of the 2,3-positions and fused rings at the 2,3-positions. Molecules 2017, 22, 479496.
(11) Kim, S.; Hong, S. H. Copper-catalyzed N-aryl-β-enaminonitrile synthesis utilizing isocyanides as the nitrogen source. Adv. Synth. Catal. 2015, 357, 10041012.
(12) Liu, J. Q.; Liu, Z. H.; Liao, P. Q.; Zhang, L.; Tu, T.; Bi, X. H. Silver-catalyzed cross-coupling of isocyanides and active methylene compounds by a radical process. Angew. Chem. Int. Ed. 2015, 54, 1061810622.
(13) Wang, H. L.; Xu, H.; Li, B.; Wang, B. Q. Annulation of β-enaminonitriles with alkynes via Rh(III)-catalyzed C–H activation: direct access to highly substituted 1-naphthylamines and naphtho[1,8-bc]pyridines. Org. Lett. 2018, 20, 56405643.
(14) Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Cryst. 2015, C71, 38.
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