A mild oxidation of 1,2,3,5,6,11b-hexahydroimidazo[1,2-d][1,4]benzoxazepines using KMnO 4 in DMF at room temperature produces a mixture of unsaturated and partially unsaturated [1,4]benzoxazepines in very good yields. Condensation of 2-(2-bromoethoxy)benzaldehydes with either o-phenylenediamine or ethylenediamine in the presence of oxidative reagents such as sodium metabisulfite in acetonitrile at reflux temperature produces a series of [1,4]benzoxazepines, in a simple way and in good yields. Structures of all the synthesized compounds were established in detail via NMR, HRMS spectra and single-crystal X-ray diffraction analyses.