Reaktion #70379

ord-2e784977854e4c5fa8c99135fb7e0db7

Reaktionsgleichung

O=S([O-])[O-].[Na+].[Na+]
Na2SO3
O=C(OO)c1cccc(Cl)c1
mCPBA
C[C@]12CC[C@H](O)CC1=CC[C@@H]1[C@@H]2CC[C@]2(C)C(=O)CC[C@@H]12
3β-hydroxyandrost-5-en-17-one
O=C([O-])O.[Na+]
NaHCO3
→
C[C@]12CC[C@H]3[C@@H](C[C@@H]4O[C@@]45CCCC[C@]35C)[C@@H]1CCC2=O
5α,6α-epoxyandrostan-17-one
C[C@]12CC[C@H]3[C@@H](C[C@H]4O[C@]45CCCC[C@]35C)[C@@H]1CCC2=O
5β,6β-epoxyandrostan-17-one

Edukte

O=S([O-])[O-].[Na+].[Na+]
Na2SO3
O=C(OO)c1cccc(Cl)c1
mCPBA
C[C@]12CC[C@H](O)CC1=CC[C@@H]1[C@@H]2CC[C@]2(C)C(=O)CC[C@@H]12
3β-hydroxyandrost-5-en-17-one
O=C([O-])O.[Na+]
NaHCO3

Reagenzien

Keine

Lösungsmittel

ClCCl
CH2Cl2
ClCCl
CH2Cl2

Reaktionsbedingungen

Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    Extraktionextracted with CH2Cl2 (3×100 mL)
  2. 2
    WaschenThe combined organic extracts were washed with H2O
  3. 3
    Trocknendried over Na2SO4
  4. 4
    Sonstigeevaporated to dryness

Vorschrift

To a stirred solution of 3β-hydroxyandrost-5-en-17-one (0.81 g) in CH2Cl2 (7.4 mL) cooled at 0° C., a solution of mCPBA (0.77 mg) in CH2Cl2 (14 mL) was added dropwise. After 0.5 h at 0° C. and 0.5 h at room temperature, a 10% Na2SO3 aqueous solution was added. The mixture was neutralized by addition of 5% aqueous NaHCO3 solution and extracted with CH2Cl2 (3×100 mL). The combined organic extracts were washed with H2O, dried over Na2SO4, and evaporated to dryness to give 5α,6α-epoxyandrostan-17-one and 5β,6β-epoxyandrostan-17-one as a white foam (1/1 mixture; 1.24 g, 97%). 1H-NMR (300 MHz, acetone-d6, ppm from TMS): 3β-hydroxy-5α,6α-epoxyandrostan-17-one δ 3.26 (1H, d), 2.96 (1H, d), 2.70-1.12 (18H, m), 1.36 (3H, s), 0.83 (3H, s); 3β-hydroxy-5α,6β-epoxyandrostan-17-one: δ 2.98 (1H, d), 2.93 (1H, d), 2.71-1.13 (18H, m), 1.06 (3H, s), 0.84 (3H, s).

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US08536160B2uspto-grants-2013_09