Acetic Acid → 19-Acetoxy-delta(sup 1)-testosterone

HRID 839591Notes

Reaction equation

HRID 839591 reaction equation
[C:1]([O:4][CH2:5][C@@:6]12[C@@H:23]3[C@H:14]([C@H:15]4[C@@:19]([CH2:21][CH2:22]3)([CH3:20])[C:18](=[O:24])[CH2:17][CH2:16]4)[CH2:13][CH2:12][C:11]1=[CH:10][C:9](=[O:25])[CH2:8][CH2:7]2)(=[O:3])[CH3:2].[BH4-].[Na+].C(O)(=O)C>CO>[C:1]([O:4][CH2:5][C@@:6]12[C@@H:23]3[C@H:14]([C@H:15]4[C@@:19]([CH2:21][CH2:22]3)([CH3:20])[C@@H:18]([OH:24])[CH2:17][CH2:16]4)[CH2:13][CH2:12][C:11]1=[CH:10][C:9](=[O:25])[CH2:8][CH2:7]2)(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 4311764Sodium borohydrideHCID 1294241219-Acetoxyandrost-4-en-3,17-dione

Product 1

HCID 2483372119-Acetoxy-delta(sup 1)-testosterone

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of 25.6 g of 19-acetoxyandrost-4-ene- 3,17 -dione in 4 liters of methanol cooled to 0° C is added 3.1 g of sodium borohydride, and the mixture is stirred at 0° C for 1 hour after which 30 ml of acetic acid is added and the methanol removed under reduced pressure. The resulting residue is taken up in ethyl acetate and washed with water. The organic layer is dried over magnesium sulfate, filtered and the solvent removed. The solid residue is dissolved in 2 liters of chloroform treated with 125 g of manganese dioxide and stirred for 2 hours. The reaction mixture is filtered, and the solvent removed under reduced pressure. The residue is chromatographed on alumina using benzene-ether (1:1) as the eluant. The product is recrystallized from acetone-hexane to give 19-acetoxy-17β-hydroxyandrost-4-en-3-one, M.P. 125°-127° C.

Workup

  1. additionis added
  2. customthe methanol removed under reduced pressure
  3. washwashed with water
  4. dry with materialThe organic layer is dried over magnesium sulfate
  5. filtrationfiltered
  6. customthe solvent removed
  7. dissolutionThe solid residue is dissolved in 2 liters of chloroform
  8. additiontreated with 125 g of manganese dioxide
  9. filtrationThe reaction mixture is filtered
  10. customthe solvent removed under reduced pressure
  11. customThe residue is chromatographed on alumina
  12. customThe product is recrystallized from acetone-hexane

Sources & evidence

ORD record
ord-44a176eaaaed4db6b69fffe0ac50c67c
Source dataset
uspto-grants-1978_06
Patent number
US04096254

Reaction notes

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