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Compounds 2, 3 and 4 were synthesized and the crystal and molecular structures of 1 and 4 were determined. An hptlc technique for studying the methylation rate of 1 and the oxidation rate of 2 was applied.

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A number of benzenesulfonyl derivatives of benzoimidazol‐2‐ylamine and 1‐methyl‐benzoimidazol‐2‐ylamine were synthesized, their synthesis reactions under different experimental conditions being monitored by hptlc. The crystal and molecular structures of N‐(1‐benzenesulfonyl‐1,3‐dihydrobenzoimidazol‐2‐ylidene)benzenesulfonamide (4) and N‐(1‐benzenesulfonyl‐3‐methyl‐1,3‐dihydro‐benzoimidazol‐2‐ylidene)‐benzenesulfonamide (7) were determined by X‐ray diffraction analysis. The structure of compound 4 is made up of two crystallographically independent molecules and that of compound 7 of one molecule. In both cases, the structure contains the imido form of the molecules. There are strong conjugative effects between the imido groups and the imidazolic rings. Weak intramolecular CH···O hydrogen bonding interactions could influence the molecular conformations.