Synthesis of New Pyrazole and Pyrimidine Steroidal Derivatives

摘要

The synthesis of steroidal heterocycles containing the pyrazole and pyrimidine ring fused to the 16,17-position of the steroid nucleus is reported. Androstenolone acetate (>1) reacted with carbon disulfide, iodomethane and sodium hydride to furnish 3β-acetoxy-16-[bis(methylthio)methylene]-5-androst-5-en-17-one (>2). The reactions of >2 with hydrazine hydrate and methylhydrazine afforded the 5’-methylthio- pyrazolo[4’,3’:16,17]androst-5-en-3β-ols >3a and >3b, respectively. Treatment of >2 with amidinium, guanidinium, and isothiuronium salts in the presence of sodium methoxide yielded the 6’-methoxy- pyrimido[5’,4’:16,17]androst-5-en-3β-ols (>4a->4e).