Prednisone → 21-Hydroxypregna-1,4-diene-3,11,20-trione

HRID 982532Notes

Reaction equation

HRID 982532 reaction equation
C[Si](I)(C)C.O[C@:7]1([C@:28]2([CH3:29])[C@H:14]([C@H:15]3[C@H:25]([C:26](=[O:30])[CH2:27]2)[C@:23]2([CH3:24])[C:18](=[CH:19][C:20](=[O:31])[CH:21]=[CH:22]2)[CH2:17][CH2:16]3)[CH2:13][CH2:12]1)[C:8](=[O:11])[CH2:9][OH:10].S([O-])([O-])=O.[Na+].[Na+]>C(#N)C>[OH:10][CH2:9][C:8](=[O:11])[C@@H:7]1[C@:28]2([CH3:29])[C@H:14]([C@H:15]3[C@H:25]([C:26](=[O:30])[CH2:27]2)[C@:23]2([CH3:24])[C:18](=[CH:19][C:20](=[O:31])[CH:21]=[CH:22]2)[CH2:17][CH2:16]3)[CH2:13][CH2:12]1

Participants

5

Reactant 3

HCID 5865PrednisoneHCID 24437Sodium SulfiteHCID 85247Trimethylsilyl iodide

Product 1

HCID 19183721-Hydroxypregna-1,4-diene-3,11,20-trione

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

Trimethylsilyl iodide (5.12 ml, 7.20 g, 36.0 mmol) is added dropwise to a solution of 17α,21-dihydroxypregna-1,4-diene-3,11,20-trione (3.23 g) in freshly distilled acetonitrile. After 30 min, sodium sulfite solution (5%, 150 ml) is added to the reaction mixture. The mixture is partitioned with chloroform (400 ml). The phases are separated, and the aqueous phases is extracted twice with chloroform. The organic layers are combined, washed with sodium bicarbonate (5%), saline, dried over sodium sulfate and concentrated. The concentrate is flash chromatographed eluting with ethyl acetate/hexane (2.3/1). The appropriate fractions are pooled to give 21-hydroxypregna-1,4-diene-3,11,20-trione as an oil and 17-epi-21-hydroxypregna-1,4-diene-3,11,20-trione as a solid, mp 203-206°.

Workup

  1. customThe mixture is partitioned with chloroform (400 ml)
  2. customThe phases are separated
  3. extractionthe aqueous phases is extracted twice with chloroform
  4. washwashed with sodium bicarbonate (5%), saline
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated
  7. customchromatographed
  8. washeluting with ethyl acetate/hexane (2.3/1)

Sources & evidence

ORD record
ord-31802dc1b3444ae58c4fe595a52864dc
Source dataset
uspto-grants-1991_02
Patent number
US04996318

Reaction notes

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