Sodium Sulfite → 3beta-Hydroxy-5alpha,6alpha-epoxyandrostane-17-one

HRID 42081Notes

Reaction equation

HRID 42081 reaction equation
[OH:1][C@H:2]1[CH2:19][CH2:18][C@@:17]2([CH3:20])[C:4]([CH2:5][CH2:6][C@@H:7]3[C@@H:16]2[CH2:15][CH2:14][C@@:12]2([CH3:13])[C@H:8]3[CH2:9][CH2:10][C:11]2=[O:21])=[CH:3]1.C1C=C(Cl)C=C(C(OO)=[O:30])C=1.[O-]S([O-])=O.[Na+].[Na+].C([O-])(O)=O.[Na+]>C(Cl)Cl>[OH:1][C@H:2]1[CH2:19][CH2:18][C@@:17]2([CH3:20])[C@:4]3([O:30][C@H:5]3[CH2:6][C@@H:7]3[C@@H:16]2[CH2:15][CH2:14][C@@:12]2([CH3:13])[C@H:8]3[CH2:9][CH2:10][C:11]2=[O:21])[CH2:3]1

Participants

6

Reactant 4

HCID 24437Sodium SulfiteHCID 70297m-Chloroperbenzoic acidHCID 516892Sodium BicarbonateHCID 99478893beta-Hydroxyandrost-4-en-17-one

Product 1

HCID 70751553beta-Hydroxy-5alpha,6alpha-epoxyandrostane-17-oneYield 47,115.699%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a stirred solution of 3β-hydroxyandrost-4-en-17-one (0.81 g) in CH2Cl2 (7.4 mL) cooled at 0° C., a solution of mCPBA (0.77 mg) in CH2Cl2 (13.6 mL) was added dropwise. After 0.5 h at 0° C. and 0.5 h at room temperature, a 10% aqueous solution of Na2SO3 was added. The mixture was neutralized by addition of 5% NaHCO3 solution and extracted with CH2Cl2 (3×100 mL). The combined organic extracts were washed with H2O, dried over Na2SO4, and evaporated to dryness. The residue was purified by flash chromatography (SiO2, n-hexane/CH2Cl2/acetone 60/20/20) to give 3β-hydroxy-5α,6α-epoxyandrostane-17-one (0.64 g, 75%). 1H-NMR (300 MHz, DMSO-d6, ppm from TMS): δ 4.62 (1H, d), 3.52 (1H, m), 2.87 (1H, d), 2.44-0.56 (19H, m), 1.00 (3H, s), 0.72 (3H, s).

Workup

  1. extractionextracted with CH2Cl2 (3×100 mL)
  2. washThe combined organic extracts were washed with H2O
  3. dry with materialdried over Na2SO4
  4. customevaporated to dryness
  5. customThe residue was purified by flash chromatography (SiO2, n-hexane/CH2Cl2/acetone 60/20/20)

Sources & evidence

ORD record
ord-44cac69729b64d39b789eb43a8e19262
Source dataset
uspto-grants-2013_09
Patent number
US08536160B2

Reaction notes

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