Spectroscopic evidence for 1,2-diiminoethane – a key intermediate in imidazole synthesis

Abstract

Simple imines and diimines are common building blocks in organic synthesis, but the compound class is spectroscopically not well characterized. Herein we report the formation of the simplest diimine, namely 1,2-diiminoethane, as well as spectroscopic characterization by cryogenic matrix isolation IR and UV/Vis spectroscopy. Three conformers of 1,2-diiminoethane form after UV irradiation of 1,2-diazidoethane by N₂ extrusion at 3 K in solid argon and can be photochemically interconverted. In a matrix isolation pyrolysis experiment at 600 °C with 1,2-diazidoethane as the starting material we observe hydrogen cyanide and formaldimine as the main decomposition products. All experimental findings are supported by deuterium labeling experiments and B3LYP/6-311++G(2d,2p) calculations. Irradiation of 1,2-diazidoethane in aqueous solution leads to the formation of imidazoles as indicated by NMR spectroscopy and GC-MS analysis. Our results underline the key role of diimines as building blocks in N-heterocyclic chemistry.