A green, metal-free, efficient, and simple methodology has been described for the synthesis of a series of biologically and pharmaceutically important nitrogen heterocycles. A variety of 1,3-benzazole compounds are obtained in good to excellent yield by the one-pot reaction between 2-amino/hydroxy/mercapto-anilines with benzylamine under solvent-free conditions using choline chloride (ChCl)-ethylene glycol (EG) (1:2) DES. The inexpensive, biodegradable ChCl-EG (1:2) DES plays the dual role of solvent and catalyst. The DES is recyclable and can be used several times without any significant loss of its activity.

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