Dehydroepiandrosterone → 7-Oxodehydroepiandrosterone 3-acetate

HRID 650700

Reaction equation

HRID 650700 reaction equation
[CH3:1][C@@:2]12[C:10](=[O:11])[CH2:9][CH2:8][C@H:7]1[C@@H:6]1[CH2:12][CH:13]=[C:14]3[CH2:19][C@@H:18]([OH:20])[CH2:17][CH2:16][C@:15]3([CH3:21])[C@H:5]1[CH2:4][CH2:3]2.[C:22]([O:26]O)(C)(C)[CH3:23].Cl[O-:29].[Ca+2].Cl[O-]>ClCCCl>[C:22]([O:20][C@H:18]1[CH2:17][CH2:16][C@@:15]2([CH3:21])[C:14](=[CH:13][C:12](=[O:29])[C@@H:6]3[C@@H:5]2[CH2:4][CH2:3][C@@:2]2([CH3:1])[C@H:7]3[CH2:8][CH2:9][C:10]2=[O:11])[CH2:19]1)(=[O:26])[CH3:23]

Participants

5

Reactant 3

HCID 5881DehydroepiandrosteroneHCID 6410tert-Butyl hydroperoxideHCID 24504Calcium hypochlorite

Product 1

HCID 97982297-Oxodehydroepiandrosterone 3-acetate

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

DHEA-Ac (2, 1.1 gm., 0.0033 mol.) was dissolved in a mixture of 1,2-dichloroethane (10 ml) and tert-butyl hydroperoxide (70% aqueous solution from Aldrich, 3.0 ml, 0.023 mol). The mixture was stirred at room temperature and solid calcium hypochlorite (0.65 gm.) was added in very small portions over a period of seven hours. The aqueous layer was then separated and the organic layer was stirred with sodium sulfite solution (3.0 gm in 10 ml of water) for 3 hours at 40-45° C. and filtered over a small bed of celite. The aqueous yellow layer was removed and the organic layer was washed with half saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated on a rotary evaporator. The crude product was crystallized from methanol, afforded 3β-acetoxyandrost-5-en-7,17-dione (3) as a white solid, weight 0.38 gm.

Workup

  1. customThe aqueous layer was then separated
  2. stirringthe organic layer was stirred with sodium sulfite solution (3.0 gm in 10 ml of water) for 3 hours at 40-45° C.
  3. filtrationfiltered over a small bed of celite
  4. customThe aqueous yellow layer was removed
  5. washthe organic layer was washed with half saturated brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. customthe solvent was evaporated on a rotary evaporator
  8. customThe crude product was crystallized from methanol

Sources & evidence

ORD record
ord-2a5b23e9dda54fa49da026455cc3fcf7
Source dataset
uspto-grants-2001_08
Patent number
US06274746B1

Linked notes

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