Adrenosterone → Androsta-4,6-diene-3,11,17-trione

Participants

Reaction Steps

Adrenosterone (androst-4-ene-3,11,17-trione, A-1, 50 g, 166.7 mmol) was dissolved in dioxane (1200 mL, dry), which had been saturated with HCl gas at 10° C. under argon, and a chilled solution of 2,3-dichloro-5,6-dicyanoquionone (DDQ, 50 g, 220 mmol) in hydrogen chloride saturated dioxane (450 mL) was added slowly to the stirred solution. Solid dihydro-DDQ rapidly separated from the solution. After 1.5 h, the mixture was filtered through a sintered glass funnel, most of the dioxane was evaporated under reduced pressure and the residue was chromatographed over silica gel (1000 g) using chloroform as the eluting solvent. The light-yellowish material from evaporation of the eluate was 48.7 g of the dienone compound A-2: mp 237° C.; UV (MeOH) λmax 278 nm (ε24,600); IR (CHCl3) 1745 (17-C=0), 1705 (11-C=0) and 1650 (3-conjugated C=0) cm−1; 1H NMR (CDCl3) δ0.92 (s, 3, 18-CH3), 1.32 (s, 3, 19-CH3), 5.63 (s, 1, 4-H) and 6.13 (s, 2, 6- and 7-H); m/z 298 (M+).

Provenance & Evidence