Several 3-substituted 2-azidomethylindoles have been synthesized in high yields either by the reaction of 3-substituted 2-alkylindoles with iodine azide in dry acetonitrile or by treatment of 3-substituted 2-alkyl-3-chloroindolenines with sodium azide in acetic acid. 1, 3-Dipolar cycloaddition of the 2-azidomethylindoles with dimethyl acetylenedicarboxylate gives 2-triazolylmethylindole derivatives. Ozonolysis of 3-phenyl-2-azidomethylindoles in acetic acid gives 2-azidoacetamidobenzophenones, which cyclize to 1, 4-benzodiazepines by treating with triphenylphosphine in toluene at room temperature and then refluxing.