We have the reaction of α-acyl-β-aminovinyl of the 8-azasteroid series with ethanedithiol. The occurrence and orientation of the reaction are determined by structural and steric factors. As applied to derivatives of 8-azasteroids of the D-homo series, the reaction is irreversible and consequently the dithioacetal derivatives of this series are easily hydrolysed under acid and base conditions. Desulfurization over Raney nickel of the 17-dithioacetal derivative of 8-azagona-12,17-dione occirs with simultaneous dehydrogenation of the C ring and leads to the 17-deoxo-9,11-dehydro, ehile desulfurization of the 1-dithioacetal of 8-aza-D-homogona-12,17-a-dione leads to the 12-deoxo derivative. By reaction of the 12-dithioacetal of 8-aza-D-homogona-17a-one with hydroxylamine, we obtained the 12-oximino derivative, which is the result of an unusual reaction at the site of the spiro coupling of the dithiolane ring with the 8-azasteroid ring.