One-Step Synthesis of Dicyano Imidazoles by (NH4)2Ce(NO3)6/HNO3 Promoted Oxidative Cyclocondensation of an Aldehyde and 2,3-diaminomaleonitrile

Document Type : Research Article

Authors

Department of Organic Chemistry, Payame Noor University, P.O. Box 19395-4697 Tehran, I.R. IRAN

10.30492/ijcce.2019.36494

Abstract

The purpose of this study is to obtain a facile, mild, and effective synthetic method for the one-pot synthesis of 2-aryl-4,5-dicarbonitrile imidazole derivatives 3a-q from oxidative cyclo-condensation of aromatic aldehydes and 2,3-diaminomaleonitrile (DAMN) by cerium(IV) ammonium nitrate/nitric acid (CAN/NA) as a novel and efficient oxidation catalyst. This synthetic protocol is cost-effective in addition to other advantages such as rapid transformation with good to excellent yields of products, one-step process and avoiding the pre-functionalization of the starting materials, simple workup procedure and easy operation under mild conditions in comparison previously report. These valuable conditions may be ideally suited for an effective synthesis of dicyano imidazole heterocycles on a larger scale.

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[1] Ali I., Lone, M.N., Aboul-Enein, H.Y., Imidazoles as Potential Anticancer Agents, Med. Chem. Commun., 8: 1742-1773 (2017).
[3] Shargel L., Mutnick‎ A.H., Souney‎ P.F., Swanson L.N., “Comprehensive Pharmacy Review” (7th ed.), LWW, Amazon Basiness, U.S.,ISBN: 9781582557113.
[6] (a) Rani A., Rajoria P., Agarwal S., Imidazolium chloride Immobilized Fly Ash as a Heterogenized Organocatalyst for Esterification Reaction under Microwave Irradiation Heating, Iran. J. Chem. Chem. Eng., (IJCCE), 38(3): 87-96 (2019);
   (b) Shaabani A., Mofakham H., Rahmati A., Farhangi E.,  1-Butyl-3-methylimidazolium Bromide Promoted Selectively Oxidation of Sulfur Compounds by NaBrO3. Iran. J. Chem. Chem. Eng. (IJCCE), 31: 1-8 (2012).
[8] Amini Moghaddam Z., Behmadi H., Poormorteza N., Beyramabadi, S.A., Arian Nezhad, M., A Four Components, One-Pot Synthesis of New Imidazole Molecular Tweezers Based on 2,4,6-Triarylpyridine as Hinge Region. Iran. J. Chem. Chem. Eng. (IJCCE), 36: 11-17 (2017).
[9] Wittine K., Babic M.S., Makuc D., Plavec J., Pavelic S.K., Sedic M., Pavelic K., Leyssen J.P., Neyts J., Balzarini J., Mintas M.,  Novel 1,2,4-Triazole and Imidazole Derivatives of L-Ascorbic and Imino-Ascorbic Acid: Synthesis, Anti-HCV and Antitumor Activity Evaluations. Bioorg. Med. Chem., 20: 3675-3685 (2012).
[10] Nepras M., Almonasy N., Bures F., Kulhánek J., Dvořák M., Michl M., Fluorescence and Photophysical Properties of D-Π-A Push-Pull Systems Featuring a 4,5-Dicyanoimidazole Unit, Dyes Pigments, 91: 466-473 (2011).
[11] Begland R.W., Hartter D.R., Jones F.N., Saw, D.J., Sheppard W.A., Webster O.W., Weigert F.J., Hydrogen Cyanide Chemistry. VIII. New Chemistry of Diaminomaleonitrile. Heterocyclic Synthesis,
J. Org. Chem., 39: 2341-2350 (1974).
[12] Moriya O., Minamide H., Urata Y., A Convenient Synthesis of 2-Aryl-4,5-Dicyanoimidazoles and -Imidazolines from Diaminomaleonitrile, Synthesis, 12: 1057-1058 (1984).
[13] Feldwick G.A., Hatton L.R., Hewett R.H., Pedgrift B.L., Imidazoles and Their Compositions for Plant Growth Regulation.  EP0269238 (1988).
 [14] Patel N.R., Kans S.M. 4, 5-Dicyanoimidazoles and Use as Herbicides. US4220466 (1980).
[16] To Q.H., Lee Y.R., Kim S.H., One-Pot Esterification and Amidation of Phenolic Acids, Tetrahedron, 70: 8108-8107 (2014).
[17] Mitra B., Mukherjee S., Pariyar G.C., Ghosh P., One Pot Three-Component Synthesis of 5-Substituted 1H-Tetrazole from Aldehyde, Tetrahedron Lett., 59: 1385-1389 (2018).
[20] Zaheer Z., Kalam Khan F.A., Sangshetti J.N., Patil R.H., Expeditious Synthesis, Antileishmanial and Antioxidant Activities of Novel 3-Substituted-4-Hydroxycoumarin Derivatives. Chin. Chem. Lett., 27: 287-294 (2016).
[21] Tongkha, S., Radchatawedchakoon W., Kruanetr S., Sakee U., Silica-Supported Ceric Ammonium Nitrate Catalyzed Chemoselective Formylation of Indoles. Tetrahedron Lett., 55: 3909-3912 (2014).
[22] Goswami P., Hazarika S., Das A.M., Chowdhury P., Ceric Ammonium Nitrate (CAN) Catalyzed Baeyer-Villiger Oxidation of Carbonyl Compounds, Specially 20-Oxosteroids, Indian. J. Chem., 43B: 1275-1281 (2004).
[23] Prajapati N.P., Vekariya R.H. Patel H.D., Ceric Ammonium Nitrate (CAN)–Catalyzed Multicomponent Reactions: An Efficient Catalyst for Green Organic Synthesis. Synth Commun., 45: 2399-2425 (2015).
[24] Sridharan V., Menéndez J.C., Cerium(IV) Ammonium Nitrate as a Catalyst in Organic Synthesis. Chem. Rev., 110: 3805-3849 (2010).
[25] Mobinikhaledi A., Foroughifar N., Kalhor M., Mirabolfathy M., Synthesis and Antifungal Activity of Novel 2‐Benzimidazolylimino‐5‐Arylidene‐4‐Thiazolidinones, J. Heterocycl. Chem., 47: 77-80 (2010).
[26] Kalhor M., Mobinikhaledi A., Dadras A., Tohidpour M., Synthesis and Antimicrobial Activity of Some Novel Substituted 1,2,4‐Triazoles Bearing 1,3,4‐Oxadiazoles or Pyrazoles, J. Heterocycl. Chem., 48: 1366-1370 (2011).
[29] Mathur DL., Bakore G.V., Kinetics of Oxidation of Cyclohexanol by Ceric Ammonium Nitrate in aq. HNO3, Z. Naturforsch., 27b: 46-49 (1972).
[30] Johnson RW., Martin Jr D.S., Kinetics of the Oxidation of Cerium(III) by Concentrated Nitric Acid, J. Inorg. Nucl. Chem., 10: 94-102 (1959).