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

HRID 433876Notes

Reaction equation

HRID 433876 reaction equation
[CH3:1][C@@:2]12[C@H:12]3[C:13]([CH2:15][C@:16]4([CH3:22])[C:20](=[O:21])[CH2:19][CH2:18][C@H:17]4[C@@H:11]3[CH2:10][CH2:9][C:8]1=[CH:7][C:5](=[O:6])[CH2:4][CH2:3]2)=[O:14]>O1CCOCC1.Cl>[CH3:22][C@:16]12[CH2:15][C:13](=[O:14])[C@H:12]3[C@@H:11]([CH:10]=[CH:9][C:8]4[C@:2]3([CH3:1])[CH2:3][CH2:4][C:5](=[O:6])[CH:7]=4)[C@@H:17]1[CH2:18][CH2:19][C:20]2=[O:21]

Participants

4

Reactant 1

HCID 223997Adrenosterone

Product 1

HCID 15549867Androsta-4,6-diene-3,11,17-trione

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolvent2×HCID 312751,4-DioxaneSolvent

Procedure

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+).

Workup

  1. customSolid dihydro-DDQ rapidly separated from the solution
  2. filtrationthe mixture was filtered through a sintered glass funnel, most of the dioxane
  3. customwas evaporated under reduced pressure
  4. customthe residue was chromatographed over silica gel (1000 g)
  5. customThe light-yellowish material from evaporation of the eluate

Sources & evidence

ORD record
ord-78172b695d294060978671dcfd080908
Source dataset
uspto-grants-2003_12
Patent number
US06670352B2

Reaction notes

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