Sulfuric Acid → 17-Hydroxypregna-4,9(11)-diene-3,20-dione

HRID 1380494Notes

Reaction equation

HRID 1380494 reaction equation
S(=O)(=O)(O)[OH:2].[C:6]([C@@:8]1([OH:28])[CH2:13][CH2:12][C@H:11]2[C@H:14]3[C:24](=[CH:25][CH2:26][C@:9]12[CH3:10])[C@:22]1([CH3:23])[C:17](=[CH:18][C:19](=[O:27])[CH2:20][CH2:21]1)[CH2:16][CH2:15]3)#[CH:7]>O.C1COCC1.CO>[OH:28][C@:8]1([C@:9]2([CH3:10])[C@H:11]([C@H:14]3[C:24](=[CH:25][CH2:26]2)[C@:22]2([CH3:23])[C:17](=[CH:18][C:19](=[O:27])[CH2:20][CH2:21]2)[CH2:16][CH2:15]3)[CH2:12][CH2:13]1)[C:6](=[O:2])[CH3:7]

Participants

6

Reactant 2

HCID 1118Sulfuric AcidHCID 14779271HCID 14779271, compound

Product 1

HCID 11813817-Hydroxypregna-4,9(11)-diene-3,20-dione

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

Mercuric oxide red (0.064 g) and concentrated sulfuric acid (0.086 ml) are stirred in water (1 ml) for 75 minutes at 67°. This mercuric oxide mixture is added to a mixture of 17β-ethynyl-17α-hydroxyandrosta-4,9(11)-dien-3-one (II A, Example 2, 0.84 g) in THF (5 ml) and methanol (24 ml) at 38°. This mixture is stirred for 3 hours and then cooled to 20°-25°. The mixture is quenched with phosphate buffer (pH=7, 10 ml) and then filtered to remove the insoluble mercury salts. The phases are separated and the aqueous layer is back-extracted with methylene chloride (3 times). The organic phases are combined and washed with saline, dried over sodium sulfate and concentrated under reduced pressure to give the title compound. NMR (CDCl3) 0.70, 1.42, 2.33, 5.60 and 5.80δ.

Workup

  1. temperaturecooled to 20°-25°
  2. customThe mixture is quenched with phosphate buffer (pH=7, 10 ml)
  3. filtrationfiltered
  4. customto remove the insoluble mercury salts
  5. customThe phases are separated
  6. extractionthe aqueous layer is back-extracted with methylene chloride (3 times)
  7. washwashed with saline
  8. dry with materialdried over sodium sulfate
  9. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-211c90ec380d4b2caef5dcdf728fe2e3
Source dataset
uspto-grants-1986_04
Patent number
US04582644

Reaction notes

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