Synthese et reactivite de derives hybrides quinoleine-oxirane hautement fonctionnalises et etude de la reaction de transposition du groupement nitro en serie imidazolique

Abstract

A series of new highly functionalized epoxide derivatives linked to a quinoline subunit were prepared by oxidation of the corresponding Knoevenagel products (-cyanoacrylates and -cyanoacrylonitriles) with m.CPBA. The addition of appropriate reagents in specified conditions leads to the formation of new compounds derived from -quinolin--aminocids (-aminoamides and -aminoesters), with diversified structures in high yields. The direct addition of 1,2-phenylenediamine on 3-(2-methoxyquinolin-3-yl)oxirane-2,2-dicarbonitriles affords a mixture of quinoxaline- and benzimidazole-quinoline hybrids whose the ratio depends on the solvent used, and without the need for acid halide or catalyst. The study of the transposition reaction of the nitro group in 5-nitro-1-methylimidazoles to the corresponding 4-nitroisomers was examined. This reaction was achieved in nitrobenzene at 160°C using a catalytic amount of methyl iodide, and some novel 4-nitro-2- phenylethanol(styryl)imidazole derivatives were obtained in good to excellent yields (83- 97%). These investigations have allowed us to develop an effective, simple and inexpensive synthetic route toward unknown 4-nitro-2-phenylethanol or styrylimidazole derivatives from their corresponding 5-nitroisomers, which could be prepared independently. This approach should contribute to the synthesis of new 4-nitroimidazole derivatives and can open new prospects for their use in the field of the chemistry of biomolecules. Some prepared compounds were subjected to a comparative analysis of their spectroscopic data (1H NMR, 13C NMR and RX). Extracted informations in particular the crystallographic data of the prepared crystal structures, and their comparison with a reference compound, would be potentially useful in predicting future transformations of these compounds. The structures of all prepared compounds were easily elucidated by the usual spectroscopic methods (IR, 1H NMR, 13C NMR), and some of them were confirmed by elemental analysis and X-ray diffraction.