This compound can be obtained by three related ways: 1) The chlorination of androsta-1,4-diene-3,17-dione (I) with SO2Cl2 in pyridine gives 4-chloroandrosta-1,4-diene-3,17-dione (II), which is brominated with N-bromosuccinimide (NBS) in refluxing carbon tetrachloride yielding the 5-bromo derivative. The reaction of (III) with LiCl and Li2CO3 in hot DMF affords 4-chloroandrosta-1,4,6-triene-3,17-dione (IV), which is finally treated with NH4OH in dioxane at 90 C in a pressure vessel. 2) The reaction of 7alpha-acetoxy-6beta-bromoandrosta-1,4-diene-3,17-dione (V) with sodium azide in hot DMF gives 4-azidoandrosta-1,4,6-triene-3,17-dione (VI), which is then reduced with propane-1,3-dithiol and triethylamine in anhydrous methanol. 3) The reaction of 6beta,7alpha-dibromoandrosta-1,4-diene-3,17-dione (VII) with sodium azide as before also yields the azido derivative (VI).