Treatment of D-homo-17-oxaandrosta-1,4,6-triene-3,17a-dione (I) with refluxing thioacetic acid (II) yields either 7-alpha-(acetylthio) derivative (III) or 1alpha,7alpha-bis(acetylthio) derivative (IV). The desired product can then be obtained either by treatment of (III) with NaOH in THF or by reaction of (IV) with sodium methylate in methanol.