Water → 7beta-Ethyl-estra-1,3,5(10)-trien-17-one

HRID 1266011Notes

Reaction equation

HRID 1266011 reaction equation
[CH2:1]([C@H:3]1[CH2:20][C:19]2[C@H:14]([CH2:15][CH2:16][C:17](=O)[CH:18]=2)[C@@H:13]2[C@@H:4]1[C@H:5]1[C@@:9]([CH2:11][CH2:12]2)([CH3:10])[C:8](=[O:22])[CH2:7][CH2:6]1)[CH3:2].O.CCOC(C)=O.CCCCCC>C(#N)C>[CH2:1]([C@H:3]1[CH2:20][C:19]2[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=2[C@@H:13]2[C@@H:4]1[C@H:5]1[C@@:9]([CH2:11][CH2:12]2)([CH3:10])[C:8](=[O:22])[CH2:7][CH2:6]1)[CH3:2]

Participants

5

Reactant 3

HCID 962WaterHCID 154550417beta-Ethyl-estr-4-ene-3,17-dioneHCID 21226206Ethyl acetate hexane

Product 1

HCID 571798617beta-Ethyl-estra-1,3,5(10)-trien-17-oneYield 84.7%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of enone 55 (0.35 g, 1.17 mmol) in acetonitrile (10 mL) was added a CuBr2 (0.31 g, 1.4 mmol) and stirred overnight at room temperature. Water was added until disappearance of the green color, and the acetonitrile was removed under reduced pressure. The residue was extracted with EtOAc. The combined organic layers were dried over anhydrous MgSO4, filtered, and the combined organic layers were washed with water; brine, dried over anhydrous MgSO4, filtered, and concentrated to afford a gum. Chromatography (20% EtOAc/hexane) yielded estrone 56 as a yellow solid (0.28 g, 80%): The major 7α-ethyl isomer of 56: 1H NMR (300 MHz, CDCl3) δ0.91 (s, 3, CH3), 0.95 (t, J=7.3 Hz, 3, CH2CH3), 6.59 (d, J=2.5 Hz, 1, ArH), 6.65 (dd, J=2.5, 8.4 Hz, 1, ArH), 7.13(d, J=8.4 Hz, 1, ArH).

Workup

  1. customthe acetonitrile was removed under reduced pressure
  2. extractionThe residue was extracted with EtOAc
  3. dry with materialThe combined organic layers were dried over anhydrous MgSO4
  4. filtrationfiltered
  5. washthe combined organic layers were washed with water
  6. dry with materialbrine, dried over anhydrous MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto afford a gum

Sources & evidence

ORD record
ord-5971124618e948f8aa8ab07d6c6cbf50
Source dataset
uspto-grants-2003_04
Patent number
US06548491B2

Reaction notes

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