Estra-1,3,5(10),16-tetraen-6-one-3-yl acetate → Estra-1,3,5(10),16-tetraen-3,6-diol

HRID 1585851Notes

Reaction equation

HRID 1585851 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].C([O:10][C:11]1[CH:28]=[CH:27][C:26]2[C@@H:25]3[C@H:16]([C@H:17]4[C@@:21]([CH2:23][CH2:24]3)([CH3:22])[CH:20]=[CH:19][CH2:18]4)[CH2:15][C:14](=[O:29])[C:13]=2[CH:12]=1)(=O)C>C1COCC1>[CH3:22][C@:21]12[CH2:23][CH2:24][C@H:25]3[C@@H:16]([CH2:15][CH:14]([OH:29])[C:13]4[CH:12]=[C:11]([OH:10])[CH:28]=[CH:27][C:26]=43)[C@@H:17]1[CH2:18][CH:19]=[CH:20]2

Participants

4

Reactant 2

HCID 15870994Estra-1,3,5(10),16-tetraen-6-one-3-yl acetateHCID 21226445Aluminium lithium hydride2×

Product 1

HCID 15870995Estra-1,3,5(10),16-tetraen-3,6-diolYield 10%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a suspension of lithium aluminum hydride (LAH, 95%, 46.9 mg, 1.17 mmol) in 5 mL of anhydrous THF was added estra-1,3,5(10),16-tetraen-6-one-3-yl acetate, 6 (422.9 mg, 1.360 mmol) in 5 mL of anhydrous THF dropwise, with stirring. See FIG. 13. The reaction was stirred 50 min., after which further LAH (46.5 mg, 1.16 mmol) was added and the reaction stirred 22 h. After refluxing 4 h TLC still showed starting material. The reaction was quenched with 0.5 mL of water+0.5 mL of 20% (w/w) sulfuric acid and concentrated under reduced pressure. The residue was extracted four times with 10 mL portions of hot ethyl acetate and filtered through Celite. The combined filtrates were concentrated and purified twice by flash chromatography to give solid product (0.05 g, 0.2 mmol, 10%), m.p. 150-157° C. (NA-1993B-29, 32B)

Workup

  1. stirringThe reaction was stirred 50 min.
  2. stirringthe reaction stirred 22 h
  3. temperatureAfter refluxing 4 h TLC
  4. customThe reaction was quenched with 0.5 mL of water+0.5 mL of 20% (w/w) sulfuric acid
  5. concentrationconcentrated under reduced pressure
  6. extractionThe residue was extracted four times with 10 mL portions of hot ethyl acetate
  7. filtrationfiltered through Celite
  8. concentrationThe combined filtrates were concentrated
  9. custompurified twice by flash chromatography

Sources & evidence

ORD record
ord-ee80970f3b1943debc5018a6462d29e8
Source dataset
uspto-grants-1999_08
Patent number
US05939570

Reaction notes

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