Acetic Acid → 3beta-Acetoxy-14beta-hydroxy-17beta-methyl-5beta-androstane

HRID 618867Notes

Reaction equation

HRID 618867 reaction equation
O[C@H:2]1[CH2:19][CH2:18][C@@:17]2([CH3:20])[C@H:4]([CH2:5][CH2:6][C@@H:7]3[C@@H:16]2[CH2:15][CH2:14][C@@:12]2([CH3:13])[C@:8]3([OH:23])[CH2:9][CH2:10][C@@H:11]2[CH:21]=O)[CH2:3]1.P([O-])([O-])(O)=O.[Na+].[Na+].[CH3:31][C:32]([OH:34])=[O:33]>>[C:32]([O:34][C@H:2]1[CH2:19][CH2:18][C@@:17]2([CH3:20])[C@H:4]([CH2:5][CH2:6][C@@H:7]3[C@@H:16]2[CH2:15][CH2:14][C@@:12]2([CH3:13])[C@:8]3([OH:23])[CH2:9][CH2:10][C@@H:11]2[CH3:21])[CH2:3]1)(=[O:33])[CH3:31]

Participants

4

Reactant 3

HCID 176Acetic AcidHCID 24203Sodium Phosphate, DibasicHCID 109033043beta,14beta-Dihydroxy-5beta-androstane-17beta-carboxaldehyde

Product 1

HCID 111108583beta-Acetoxy-14beta-hydroxy-17beta-methyl-5beta-androstane

Procedure

A solution of 9.1 g of 3β,14β-dihydroxy-5β-androstane-17β-carboxaldehyde (Boutagy J. and Thomas R., Aust. J. Chem., 1971, 24, 2723), and p-toluensulphonyl hydrazide (5.6 g) in AcOH (60 mL) was stirred at room temp. for 3 hrs and then poured in a saturated aqueous solution of di-sodium hydrogen phosphate. The mixture was extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate and evaporated to dryness under reduced pressure. The residue was dissolved in MeOH (200 mL) and zinc iodide (1.2 g) was added. To this solution sodium cyanoborohydride (2.6 g) was added portionwise and the temperature was raised to the boiling point of the reaction mixture. After 3 hrs the solvent was evaporated to dryness under reduced pressure, the crude product was dissolved in ethyl acetate and neutralised with 0.1 N NaOH, the organic layer was dried over anhydrous sodium sulfate and evaporated to dryness under reduced pressure. The residue was purified by chromatography (SiO2) using n-hexane/ethyl ether 75/25 as eluant to give 5.7 g of 3β-acetoxy-14β-hydroxy-17β-methyl-5β-androstane (VIII-a) as a white solid.

Workup

  1. extractionThe mixture was extracted with ethyl acetate
  2. dry with materialthe organic layer was dried over anhydrous sodium sulfate
  3. customevaporated to dryness under reduced pressure
  4. dissolutionThe residue was dissolved in MeOH (200 mL)
  5. additionzinc iodide (1.2 g) was added
  6. additionTo this solution sodium cyanoborohydride (2.6 g) was added portionwise
  7. temperaturethe temperature was raised to the boiling point of the reaction mixture
  8. customAfter 3 hrs the solvent was evaporated to dryness under reduced pressure
  9. dissolutionthe crude product was dissolved in ethyl acetate and neutralised with 0.1 N NaOH
  10. dry with materialthe organic layer was dried over anhydrous sodium sulfate
  11. customevaporated to dryness under reduced pressure
  12. customThe residue was purified by chromatography (SiO2)

Sources & evidence

ORD record
ord-4447919a3bfd42c3b2a05e08ee9d5672
Source dataset
uspto-grants-1999_09
Patent number
US05955632

Reaction notes

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