Abstract: A series of N-2,4-dinitrobenzenesulfenylbenzimidazoles has been prepared by the reaction of 2,4-dinitrobenzenesulfenylchloride with a series of 2-alkyl benzimidazoles and 5(6)-chloro-2-alkyl-benzimidazoles. Dynamic NMR spe-ctroscopy was used to measure the torsional barriers about the N-S bond,which were in the range of c.a. 19-20 kcal/mol. The torsional barriers reported here are among the highest yet observed for torsion about sulfenamide bonds.