Taming Chlorine Azide: Access to 1,2-Azidochlorides from Alkenes

The in situ preparation and trapping of chlorine azide provided a versatile one-pot method for the azidochlorination of alkenes. Gaseous ClN<sub>3</sub> generated from sodium azide, hypochlorite, and acetic acid can be explosive if isolation is attempted. Instead, we generated the reagent in biphasic media in the presence of olefinic compounds dissolved in the organic layer or evenly emulsified throughout the solution in the absence of organic solvent. Under these conditions, ClN<sub>3</sub> is created slowly and trapped immediately at the aqueous–organic interface. The resulting safe and reliable procedure provided 1,2-azidochloride derivatives of a variety of substrates, with evidence for both polar and radical mechanisms. Minor impurities characterized in the product mixtures indicated the presence of alternative reaction pathways deriving primarily from radical intermediates.