JOCR  >> Vol. 4 No. 1 (March 2016)

    Silver-Promoted Cyclization of α-Aminoacetophenone with NH4PF6: Synthesis of 2-Arylformylimidazole Derivatives

  • 全文下载: PDF(487KB) HTML   XML   PP.6-12   DOI: 10.12677/JOCR.2016.41002  
  • 下载量: 1,516  浏览量: 5,051  


王祚辉,程晓雪,王 浩,凌心茹,赵晨晨,胡茂林:温州大学化学与材料工程学院,浙江 温州

α-氨基芳乙酮咪唑缩合反应环化反应氧化脱胺α-Aminoacetophenone Imidazole Condensation Cyclization Oxidative Deamination



A new method for AgOAc-oxidative cyclization of α-aminoacetophenones with NH4PF6 leading to 2-arylformylimidazoles derivatives has been developed. Under the optimal reaction conditions, a wide range of 2-arylformylimidazoles derivatives were synthesized in moderate to good yields ranging from 52% to 93%. These products were confirmed by IR, NMR and MS. The results show that this method has advantages such as the availability for raw materials and simple chemical operations.

王祚辉, 程晓雪, 王浩, 凌心茹, 赵晨晨, 胡茂林. 银促进的α-氨基芳乙酮与NH4PF6的缩合环化反应:2-芳甲酰基咪唑衍生物的合成研究[J]. 有机化学研究, 2016, 4(1): 6-12.


[1] 伍晓春. 咪唑类化合物的合成与应用研究[J]. 精细与专用化学品, 2010, 18(7): 51-55.
[2] 刘凤珍, 吴炎, 赵智斌, 谢淑英, 张锐, 高嵩. 氯沙坦降压疗效及对血管活性物质的影响[J]. 高血压杂志, 2000, 8(1): 43-44.
[3] Brogden, R.N., Heel, R.C., Speight, T.M. and Avery, G.S. (1978) Cimetidine: A Review of Its Pharmacological Properities and Therapeutic Efficacy in Peptic Ulcer Disease. Drugs, 15, 93-131.
[4] Zhou, R. and Skibo, E.B. (1996) Chemistry of the Pyrrolo[1,2-a]benzimidazole Antitumor Agents: Influence of the 7- su-bstituent on the Ability to Alkylate DNA and Inhibit Topoisomerase II. Journal of Medicinal Chemistry, 39, 4321- 4331.
[5] Skibo, E.B., Gordon, S., Bess, L., Boruah, R. and Heileman, M.J. (1997) Studies of Pyrrolo[1,2-a]benzimidazolequi- None DT-Diaphorase Substrate Activity, Topoisomerase II Inhibition Activity, and DNA Reductive Alkylation. Journal of Medicinal Chemistry, 40, 1327-1339.
[6] Craigo, W.A., Le Sueur, B.W. and Skibo, E.B. (1999) Design of Highly Active Analogues of Thepyrrolo[1,2-a]ben- zimidazole Antitumor Agents. Journal of Medicinal Chemistry, 42, 3324-3333.
[7] Kirchner, C. and Krebs, B. (1987) Pentacoordinate Zinc Complexes of Imidazole Nitrogen Donors as Structural Models for the Active Site in Enzymes: Preparation and Crystal Structures of (μ-2,2'-Biimidazolet)tetrakis(2,2'-biimidazole) dizinc(II) Tetraperchlorate Trihydrate and Bis(2,2'-biimidazole)(formato)zinc(II) perchlorate. Inorganic Chemistry, 26, 3569-3576.
[8] 李云中, 侯自杰. 具有生物活性的咪唑类化合物的合成研究[J]. 有机化学, 2003(23): 426.
[9] 马文展, 刘少文, 胡建. 咪唑及其衍生物的合成[J]. 化学试剂, 1997, 19(5): 281-285.
[10] Gridnev, A.A. and Mihaltseva, I.M. (1994) Synthesis of 1-Alkylimidazoles. Synthetic Communications, 24, 1547-1555.
[11] Sharma, S.D., Hazarika, P. and Konwar, D. (2008) An Effi-cient and One-Pot Synthesis of 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted Imidazoles Catalyzed by InCl3•3H2O. Tetrahedron Letters, 49, 2216-2220.
[12] Maleki, B. and Ashrafi, S.S. (2014) N-Bromosuccinimide Catalyzed Three Component One-Pot Efficient Synthesis of 2,4,5-triaryl-1H-imidazoles from Aldehyde, Ammonium Acetate, and 1,2-diketone or α-Hydroxyketone. Journal of the Mexican Chemical Society, 58, 76-81.
[13] Mulliez, E. (1989) Synthesis of Polyimidazolesas Biomimetic Ligands Formetalloprotein Activesite Modeling. Tetrahedron Letters, 30, 6169-6172.
[14] Uno, K., Niume, K., Iwata, Y., Toda, F. and Iwakura, Y. (1977) Synthesis of Polybenzimidazoles with Sulfonic Acid Groups. Journal of Polymer Science—Polymer Chemistry Edition, 15, 1309-1318.
[15] 赵晶, 盛丽, 徐宏杰, 房建华, 印杰. 新型磺化聚苯并咪唑的合成及性能[J]. 高等学校化学学报, 2012, 33(3): 645-648.
[16] Nunami, K., Yamada, M., Fukui, T. and Matsumoto, K. (1994) A Novel Synthesis of Methyl 1,5-disubstitutedimida- zole-4-carboxylates Using 3-bromo-2-isocyanoacrylates. The Journal of Organic Chemistry, 59, 7635-7642.
[17] Pawar, V.G., De Borggraeve W.M., Robeyns, K., Meervelt, L.V., Compernollea, F. and Hoornaerta, G. (2006) Synthesis of 1,5-disubstituted 4-haloimidazoles from α-Aminonitriles. Tetrahedron Letters, 47, 5451-5453.
[18] Bleicher, K.H., Gerber, F., Wüthrich, Y., Alanine, A. and Caprettab, A. (2002) Parallel Synthesis of Substituted Imidazoles from 1,2-aminoalcohols. Tetrahedron Letters, 43, 7687-7690.
[19] Lantos, I., Zhang, W.Y., Shui, S.Q. and Eggleston, D.S. (1993) Synthesis of Imidazoles via Hetero-Cope Rearran- gements. The Journal of Organic Chemistry, 58, 7092-7095.
[20] Zaman, S., Mitsuru, K. and Abell, A.D. (2005) Synthesis of Trisubs-tituted Imidazoles by Palladium-Catalyzed Cyclization of O-Pentafluorobenzoylamidoximes: Application to Amino Acid Mimetics with a C-Terminal Imidazole. Organic Letters, 7, 609-611.
[21] Durán, R., Zubía, E., Ortega, M.J., Naranjo, S. and Salyá, J. (1999) Novel Alkaloids from the Red Ascidian Botryllus Leachi. Tetrahedron, 55, 13225-13232.
[22] Sonia, M., Javier, S. and Jesus Angel, D. (2006) Phenolic Marine Natural Products as Aldose Reductase Inhibitors. Journal of Natural Products, 69, 1485-1487.
[23] Zuliani, V., Cocconcelli, G., Fantini, M., Ghiron, C. and Rivara, M. (2007) A Practical Synthesis of 2,4(5)- diarylimidazoles from Simple Building Blocks. The Journal of Organic Chemi-stry, 72, 4551-4553.
[24] Khalili, B., Tondro, T. and Hashemi, M.M. (2009) Novel One-Pot Synthesis of (4 or 5)-aryl-2-aryloyl-(1H)-imidazoles in Water and Tauto-Isomerization Study Using NMR. Tetrahedron, 65, 6882-6887.
[25] Batanero, B., Escudero, J. and Barba, F. (1999) Cathodic Reduction of Phenacyl Azides. Organic Letters, 1, 1521-1522.
[26] Chen, J., Chen, W., Yu, Y.P. and Zhang, G.L. (2013) One-Pot Synthesis of Disubstitutedimidazole Derivatives from α-Azido Ketones Catalyzed by Potassium Ethylxanthate. Tetrahedron Letters, 54, 1572-1575.
[27] Srinivasan, M., Perumal, S. and Selvaraj, S. (2006) A Facile Stereoselective Synthesis of (Z)-1,3-diaryl-2-(N- methylanilin-o)-2-propen-1-ones. ARKIVOC, 2006, 21-27.