Abstract
17-Oxo-5-androsten-3-beta-yl acetate (1) on base catalysed reaction with aromatic aldehydes gave the chalcones, 17-oxo-5-androsten-16-benzyliden-3-beta-yl acetate (2a-e). The Schmidt reaction of the chalcones (2a-e) using sodium azide and concentrated sulphuric acid in benzene solution gave the lactams, 17a-aza-17-oxo-D-homo-5-androsten-16-benzyliden-3-beta-yl acetate (3a-e). However, the Schmidt reaction with excess of hydrazoic acid and in presence of boron trifluoride etherate afforded D-homo-5-androsteno[17a, 17-d]tetrazole-16-benzyliden-3-beta-yl acetate (5a-e) and 13,17-seco-13-azido-5-androsten-16-benzyliden-16-nitrile-3-beta-yl acetate (4a-e). The chalcones (2a-e) on oximation gave respective ketoximes (6a-e), which on Beckmann rearrangement using thionyl chloride at low temperature, gave the lactams (3a-e) and ene-nitriles, 13,17-seco-16-cyano, 5,13(18)-androstadien-16-benzyliden-3-beta-yl acetate (9a-e).