Water → HCID 10993121, compound

HRID 1600589Notes

Reaction equation

HRID 1600589 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.[Si:22](Cl)([C:25]([CH3:28])([CH3:27])[CH3:26])([CH3:24])[CH3:23].C(N(CC)CC)C.O>CN(C)C=O.CN(C)C1C=CN=CC=1>[CH3:26][C:25]([Si:22]([CH3:24])([CH3:23])[O:20][C@H:18]1[CH2:17][CH2:16][C@@:15]2([CH3:21])[C:14](=[CH:13][CH2:12][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)([CH3:28])[CH3:27]

Participants

7

Reactant 4

HCID 962WaterHCID 5881DehydroepiandrosteroneHCID 8471TriethylamineHCID 28928tert-Butyldimethylsilyl chloride

Product 1

HCID 10993121HCID 10993121, compoundYield 90.3%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6228DimethylformamideSolvent

Procedure

Dissolve dehydroisoandrosterone (10.0 g, 34.67 mmol) in dimethylformamide (DMF, 150 mL) under an atmosphere of nitrogen. Add t-butyldimethylsilyl chloride (5.23 g, 34.67 mmol), triethylamine (5.32 mL, 38.14 mmol) and a catalytic amount of 4-dimethylaminopyridine (0.21 g, 1.73 mmol) with stirring at room temperature. After two days pour the reaction into rapidly stirring water (1.5 L). Filter the white solid and wash with water (2×50 mL). Dissolve the solid in ethyl acetate (350 mL) and wash with 0.5N hydrochloric acid (2×150 mL), half-saturated sodium bicarbonate (2×150 mL) and brine (100 mL). Dry the organic layer over anhydrous magnesium sulfate, filter and concentrate under vacuum. Purify the residue by flash chromatography (ethyl acetate/hexane, 15:85, silica gel) to provide (3β)-3-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-androst-5-en-17-one (12.60 g) as a white solid, Rf =0.78 (ethyl acetate/hexane, 1:1, silica gel), mp 146-148° C.

Workup

  1. additionAfter two days pour
  2. filtrationFilter the white solid
  3. washwash with water (2×50 mL)
  4. dissolutionDissolve the solid in ethyl acetate (350 mL)
  5. washwash with 0.5N hydrochloric acid (2×150 mL), half-saturated sodium bicarbonate (2×150 mL) and brine (100 mL)
  6. dry with materialDry the organic layer over anhydrous magnesium sulfate
  7. filtrationfilter
  8. concentrationconcentrate under vacuum
  9. customPurify the residue by flash chromatography (ethyl acetate/hexane, 15:85, silica gel)

Sources & evidence

ORD record
ord-d6899870f70e430ca6531f15150af95d
Source dataset
uspto-grants-1999_11
Patent number
US05977094

Reaction notes

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