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A new application of silica chloride as an easily available and reusable solid acid catalyst for the synthesis of benzimidazole and its derivatives through the condensation of o-phenylenediamines and orthoesters under thermal and solvent-free conditions is described. This novel and eco-friendly method is very cheap and has many advantages including excellent yields, short reaction time, and simple work-up procedure. Copyright © 2012 SIOC, CAS, Shanghai & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.