Facile Synthesis of 1,4,2‐Dioxazines Using Aromatic Chlorooximes and 2‐Chloroethanol/2‐Chlorophenols

Abstract A facile and mild strategy for the synthesis of 5,6‐dihydro‐1,4,2‐dioxazines by the reaction of aromatic chlorooximes with 2‐chloroethanol in presence of NaH at room temperature in a short period of time is developed. This strategy is further extended for the synthesis of substituted 1,4,2‐dioxazines using aromatic chlorooximes and 2‐chlorophenols. Similarly, 5,6‐dihydro‐1,4,2‐dioxazepine was also synthesized using aromatic chlorooxime and 3‐bromopropanol. The developed protocol is simple, efficient and produces environmentally benign byproducts.