Nucleophilic Displacements of Imidazoles. I. Oxygen, Nitrogen and Carbon Nucleophiles

Abstract
4(5)-Bromo-and-iodo-imidazoles, activated by an adjacent nitro substituent, undergo nucleophilic displacement with methoxide, phenoxide, cyclic secondary amines and cyanide. The regiochemistry of the reactions of 5-iodo-4-nitroimidazole with methoxide has been confirmed by spectroscopic and X-ray methods, and a number of erroneous structures from the literature have been revised. Some apparently anomalous reactions of methoxide with 5-halo-1,2-dimethyl-4-nitroimidazoles, and cyanide with 4-halo-1-methyl-5-nitroimidazole have been noted. The crystal and molecular structure of 5-methoxy-1-methyl-l4-nitroimidazole has been determined by direct methods. Crystals are monoclinic, P21/c, a 10.929(3), b 8.899(2), c 7.290(2) .ANG.; .beta. 92.87(2).degree.; Z 4. The structure was refined to R = 0.095 for 818 reflections (I > 2 .sigma. I).

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