Heterocyclic steroids: Synthesis of androsteno[17,16‐ d ]pyrazoles and androsteno[17,16‐ e ]pyrimidines

The Vilsmeier‐Haack reaction of 3β‐acetoxyandost‐5‐en‐17‐one ( 1 ) with phosporous oxychloride and dimethylformamide gave 3β‐acetoxy‐17‐chloro‐16‐formylandrosta‐5,16‐diene ( 2 ). Reaction of 2 with hydrazine and phenylhydrazine provided substituted 5‐androsteno[17,16‐ d ]pyrazoles 3 and 4 respectively. Similarly, condensation of 2 with urea and guanidine hydrochloride revealed the formation of the corresponding substituted pyrimidines 5 and 6 respectively.