Synthesis of benzimidazoles in high-temperature waterThis work was presented at the Green Solvents for Catalysis Meeting held in Bruchsal, Germany, 13–16th October 2002.Electronic supplementary information (ESI) available: analytical data for compounds 3a–f and 5g–j. See http://www.rsc.org/suppdata/gc/b2/b212394k/

Abstract

The objective of this research was to conduct constructive organic chemistry in water and to achieve yields that were comparable to, or better than, those in conventional media. The synthesis of 2-phenylbenzimidazole from 1,2-phenylenediamine and benzoic acid was chosen as a benchmark reaction. The reaction parameters, such as temperature, density and reaction time, have been systematically studied to understand whether the solvent properties of high-temperature water can have a positive effect on the chemistry. The reaction was performed in a new design of batch-type autoclave and was also monitored in situ by UV-vis spectroscopy. By tuning the parameters, the yield has been optimised to around 90%. The optimised conditions were then applied to related benzimidazoles, some of which crystallised from solution in situ to yield single crystals that were sufficiently pure to be analysed directly by X-ray diffraction, without any further purification.