CHEMISTRY OF 3-(N-ACETYLUREIDO)-4,5-OXIDOANDROSTAN-17BETA-OL ACETATES

Epoxidation of 3-ureido-∆4-androsten-17β-ol derivatives 1a and 6a afforded exclusively the cis-4,5-oxido derivatives 2a and 7a, whereas the unsaturated N-acetylureido compounds yielded a mixture of oxides with predominant formation of the cis oxides. The trans-ureido oxides 3 and 8 were prepared from the cis-3-hydroxy 4,5-oxides 4 and 10. The hydroxyl group was epimerized through the mesylates to the trans-azido oxides S and 11. Reduction of the azides with hydrazine hydrate gave the amines which were converted into the ureides with nitrourea. Dilute acid-catalyzed treatment of the cw-3-(N-acetylureido) oxides 2b and 7b proceeded slowly to the trans-diaxial opened products 12 and 13. Neighboring-group participation of the N-acetylureido group was realized in the acid treatment of the trans oxides 3 and 8. © 1969, American Chemical Society. All rights reserved.