Lithium Carbonate → HCID 12836876, compound

HRID 848781Notes

Reaction equation

HRID 848781 reaction equation
Br[C@@H:2]1[CH2:19][C@@:18]2([CH3:20])[C@@H:5]([CH2:6][CH2:7][C@@H:8]3[C@@H:17]2[CH2:16][CH2:15][C@@:13]2([CH3:14])[C@H:9]3[CH2:10][CH2:11][C@@H:12]2[O:21][CH3:22])[CH2:4][C:3]1=[O:23].C(=O)([O-])[O-].[Li+].[Li+].[Cl-].[Li+]>CN(C=O)C>[CH3:22][O:21][C@H:12]1[CH2:11][CH2:10][C@H:9]2[C@H:8]3[C@H:17]([CH2:16][CH2:15][C@:13]12[CH3:14])[C@:18]1([CH3:20])[C@H:5]([CH2:4][C:3](=[O:23])[CH:2]=[CH:19]1)[CH2:6][CH2:7]3

Participants

5

Reactant 3

HCID 11125Lithium CarbonateHCID 433294Lithium ChlorideHCID 70565089HCID 70565089, compound

Product 1

HCID 12836876HCID 12836876, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A mixture of 2α-bromo-17β-methoxy-5α-androstan-3-one (U.S. Pat. No. 3,301,850, Example 15, 3.0 g.), lithium carbonate (1.5 g.) and lithium chloride (0.5 g.) in DMF (30 ml.) are heated at reflux under nitrogen for 1.5 hours. The mixture is cooled, filtered and the solids washed with DMF. The filtrate and washings are combined and diluted with water (10 ml.) to give a precipitate. The precipitate is collected, washed, dried and column chromatographed over silica gel (200 g.) eluting by gradient between SSB (5 l.) and SSB:ethyl acetate (70:30, 5 l.). The appropriate fractions (TLC) are pooled and concentrated to give a solid which after recrystallization from hexane gives the title compound, m.p. 115°-117°, UV (ethanol) λ=229 nm (ε=10,350); MS (m/e) 302, 287 and 260; NMR (CDCl3) 0.79, 1.01, 3.20, 3.34, 5.84 and 7.13 δ.

Workup

  1. temperatureat reflux under nitrogen for 1.5 hours
  2. temperatureThe mixture is cooled
  3. filtrationfiltered
  4. washthe solids washed with DMF
  5. additiondiluted with water (10 ml.)
  6. customto give a precipitate
  7. customThe precipitate is collected
  8. washwashed
  9. customdried
  10. customcolumn chromatographed over silica gel (200 g.)
  11. washeluting by gradient between SSB (5 l.) and SSB
  12. concentrationconcentrated
  13. customto give a solid which
  14. customafter recrystallization from hexane

Sources & evidence

ORD record
ord-9afdb9fd3f0a4dbfb81a2048fe5f3900
Source dataset
uspto-grants-1981_10
Patent number
US04297350

Reaction notes

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