Sulfuric Acid → 4,17beta-Dihydroxy-14alpha,15alpha-methylene-androst-4-ene-3-one

HRID 49758Notes

Reaction equation

HRID 49758 reaction equation
[OH:1][C@H:2]1[CH2:7][C@@H:6]2[CH2:8][C@:5]32[C@H:9]2[C@H:19]([CH2:20][CH2:21][C@:3]13[CH3:4])[C@:17]1([CH3:18])[C:12]3([O:23][CH:13]3[C:14](=[O:22])[CH2:15][CH2:16]1)[CH2:11][CH2:10]2.S(=O)(=O)(O)O.C(OCC)(=O)C.C(=O)([O-])[O-].[Na+].[Na+]>C(O)(=O)C>[OH:23][C:13]1[C:14](=[O:22])[CH2:15][CH2:16][C@@:17]2([CH3:18])[C:12]=1[CH2:11][CH2:10][C@@H:9]1[C@@H:19]2[CH2:20][CH2:21][C@@:3]2([CH3:4])[C@@:5]31[CH2:8][C@H:6]3[CH2:7][C@@H:2]2[OH:1]

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 8857Ethyl AcetateHCID 10340Sodium CarbonateHCID 8782849617beta-Hydroxy-4,5-epoxy-14alpha,15alpha-methylene-androstan-3-one

Product 1

HCID 155133384,17beta-Dihydroxy-14alpha,15alpha-methylene-androst-4-ene-3-one

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

An epoxide mixture (3.5 g), 17β-hydroxy-4,5-epoxy-14α,15α-methylene-androstan-3-one, (step 1) is dissolved in 50 mL of acetic acid, which contains 2% by volume of concentrated sulfuric acid. The solution is allowed to stand for 3 days at 10° C. After that, it is treated with 200 mL ethyl acetate and neutralized with sodium carbonate solution. The organic phase is dried and concentrated. The residue is dissolved in 100 mL of methanol, treated with 4 g of potassium hydroxide, refluxed for 1 hour and then cooled. After neutralization with 50% acetic acid, it is poured into 1 L of water and the crystals are filtered off with suction, 4,17β-Dihydroxy-14α,15α-methylene-androst-4-ene-3-one being obtained.

Workup

  1. customThe organic phase is dried
  2. concentrationconcentrated
  3. dissolutionThe residue is dissolved in 100 mL of methanol
  4. additiontreated with 4 g of potassium hydroxide
  5. temperaturerefluxed for 1 hour
  6. temperaturecooled
  7. additionAfter neutralization with 50% acetic acid, it is poured into 1 L of water
  8. filtrationthe crystals are filtered off with suction, 4,17β-Dihydroxy-14α,15α-methylene-androst-4-ene-3-one being
  9. customobtained

Sources & evidence

ORD record
ord-c8a352c0a05e41e0b43ed42a8dd9ad40
Source dataset
uspto-grants-2004_03
Patent number
US06710039B1

Reaction notes

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