Microwave-Assisted Synthesis of Novel Functionalized Ketenimines and Azadienes via a Solvent-Free Reaction of Isatoic Anhydride, Alkyl-Isocyanides and Dialkyl Acetylenedicarboxylates

Document Type: Research Article

Author

Department of Chemistry, Shahr-e-Qods Branch, Islamic Azad University,Tehran, I.R. IRAN

Abstract

Ketenimines and azadienes are transient intermediates in organic chemistry especially in elimination-addition processes and in the formation of heterocyclic systems. These compounds play a considerable role as intermediates in the synthesis of heterocyclic ring systems. In this present research synthesis of novel ketenimines and azadienes via multicomponent reactions (MCRs) based on alkyl-Isocyanides is reported. Following our ongoing interest in isocyanide-based MCRs, we reported stereoselective reactions between 4H-3,1-benzoxazine-2,4(1H)-dione (isatoic anhydride) with dialkylacetylenedicarboxylates in the presence of alkyl isocyanides under solvent-free microwave conditions which leads to novel functionalized ketenimines and azadienes in a green route. The results show that the microwave-assisted leaching process has advantages over the conventional ones, concerning energy-consumption, processing time, and environmental protection.

Keywords

Main Subjects


[1] Tierney J.P., Lidström p., "Microwave Assisted Organic Synthesis", John Wiely & Sons, Inc., U.S.A (2009).

[2] Van der Eycken E.,  Kappe C.O., "Microwave Assisted Synthesis of Heterocycles", Springer, U.S.A (2006).

[3] Papadaki E., Delaude  L., Magrioti V., Microwave-Assisted Synthesis of Hydroxymethyl Ketones Using Azolium-2-Carboxylate Zwitterions as Catalyst Precursors, Tetrahedron, 73(52): 7295-7300 (2017).

[5] Poursattar Marjani A., Khalafy J., Chitan M., Mahmoodi S., Microwave-Assisted Synthesis of Acridine-1,8(2H,5H)-diones via a One-pot, Three Component Reaction, Iran. J. Chem. Chem. Eng. (IJCCE), 36(2): 1-6 (2017).

[6] Kadi H., Moussaoui R., Sadia D., Microwave Assisted Extraction of Olive Oil Pomace by Acidic Hexane, Iran. J. Chem. Chem. Eng. (IJCCE), 35(4): 7295-7300 (2016).

 [7] Domling A. and Ugi, I., Multicomponent Reactions with Isocyanides Angew Chem. Int. Ed. Eng., 39(18): 3918-3169 (2000).

[10] Reichen W.,Oxygen, Nitrogen and Sulfur-Substituted Heteroallenes, Chem. Rev., 78(5): 569-588 (1978).

[11] Motoyoshiya J., Teranishi A., Mikoshiba R., Yamamoto I., Gotoh H., c-Phosphonoketenimines, Characterization and Synthetic Application to Heterocycles, J. Org. Chem., 45(26): 5385–5387 (1980).

[12] Yavari I., Arab-Salmanabadi S., Aminkhani A., Synthesis of Functionalized Azadienes from Aminobenzothiazole, Acetylenic Esters and Isocyanides, Chinese Chem. Lett., 23(1): 49–52 (2012).

[13] Cristau H.J., Jouanin I., Taillefer M., New Synthesis of Diphenyl-N-(substituted)ketenimines from Diaminophosphonium Diazaylides, J. Organomet. Chem., 584(1): 68–72 (1999).

[14] Krow, G., Synthesis and Reactions of Ketenimines, Angew Chem. Int. Ed. Eng., 10(7): 435-449 (1971).

[15] Yavari, I., Djahaniani, H., Nassiri F., Synthesis of Highly Functionalized 1-Azadienes and Ketenimines, Monatshefte für Chemie / Chemical Monthly, 135(5): 543-548 (2004).

[16] Alajarin, M., Vidal A., Ortin M.M., First Radical Addition onto Ketenimines: a Novel Synthesis of Indoles, Tetrahedron Lett., 44(15): 3027-3030 (2003).

[19] Getzmann R., Moller M.H., Rodewald U., Frohlich R., Grehl M., Wurthwein, E.U, Metallated Ketenimines: Deprotonation of N-Isopropyl-Diphenylketenimine and Subsequent Trapping Reactions with Electrophiles A Theoretical and Experimental Study, Tetrahedron, 51(13): 3767-3786 (1995).

[20] Yavari I., Arab-Salmanabadi S., Aminkhani A., Synthesis of Functionalized 5H-spiro[furan-2,2′-indene]-1′,3′,5-triones from Primary Amines, Acetylenic Esters and Ninhydrin,  J. Iranian Chem. Soc., 9(3): 503-506 (2012).

[21] Nair V.J., Rajesh C., Vinod A.U., Bindu S., Sreekanth A.R., Mathess J.S., Balagopal L., Strategies for Heterocyclic Construction via Novel Multicomponent Reactions Based on Isocyanides and Nucleophilic Carbenes, Acc. Chem. Res., 36(12): 899-907 (2003).