Dimethylformamide → 3alpha-Hydroxy-5alpha-pregn-16-ene-11,20-dione

HRID 1606383Notes

Reaction equation

HRID 1606383 reaction equation
C1(C)C=CC(S([O:10][C@H:11]2[CH2:30][CH2:29][C@@:28]3([CH3:31])[C@@H:13]([CH2:14][CH2:15][C@@H:16]4[C@@H:27]3[C:26](=[O:32])[CH2:25][C@@:24]3([CH3:33])[C@H:17]4[CH2:18][CH:19]=[C:20]3[C:21](=[O:23])[CH3:22])[CH2:12]2)(=O)=O)=CC=1.C([O-])(=O)C.[K+].CN(C)C=O>O>[OH:10][C@@H:11]1[CH2:30][CH2:29][C@@:28]2([CH3:31])[C@@H:13]([CH2:14][CH2:15][C@@H:16]3[C@@H:27]2[C:26](=[O:32])[CH2:25][C@@:24]2([CH3:33])[C@H:17]3[CH2:18][CH:19]=[C:20]2[C:21](=[O:23])[CH3:22])[CH2:12]1

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 517044Potassium AcetateHCID 867333133beta-Toluene-p-sulphonyloxy-5alpha-pregn-16-ene-11,20-dione

Product 1

HCID 566733253alpha-Hydroxy-5alpha-pregn-16-ene-11,20-dioneYield 50.3%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A stirred mixture of 3β-toluene-p-sulphonyloxy-5α-pregn-16-ene-11,20-dione (627 g.), potassium acetate (918 g.), dimethylformamide (4.25 l.) and water (425 ml.) was heated on the steam bath for 4 hr. Most of the dimethylformamide was removed under reduced pressure and water was added to the residue with stirring. The solid (420 g.) was collected, washed and dried at 40° in vacuo. This material in peroxide free dioxan (7 l.) was flushed with nitrogen and a solution of potassium hydroxide (200 g.) in water (2 l.) was added. The mixture was stirred and heated at 50°-60° for 7 hr. and then left at room temperature overnight. Acetic acid (50 ml.) was added and the precipitated solid was filtered off, washed with water and dried. The dry solid was heated under reflux with benzene (2 l.) for 2 hr. the mixture cooled and filtered to give 3α-hydroxy-5α-pregn-16-ene-11,20-dione (215 g.).

Workup

  1. temperaturewas heated on the steam bath for 4 hr
  2. customMost of the dimethylformamide was removed under reduced pressure and water
  3. additionwas added to the residue
  4. customThe solid (420 g.) was collected
  5. washwashed
  6. customdried at 40° in vacuo
  7. customThis material in peroxide free dioxan (7 l.) was flushed with nitrogen
  8. additiona solution of potassium hydroxide (200 g.) in water (2 l.) was added
  9. stirringThe mixture was stirred
  10. temperatureheated at 50°-60° for 7 hr
  11. additionAcetic acid (50 ml.) was added
  12. filtrationthe precipitated solid was filtered off
  13. washwashed with water
  14. customdried
  15. temperatureThe dry solid was heated
  16. temperatureunder reflux with benzene (2 l.) for 2 hr
  17. temperaturethe mixture cooled
  18. filtrationfiltered

Sources & evidence

ORD record
ord-fa3c22caebc443b8aa1263b07616067d
Source dataset
uspto-grants-1976_04
Patent number
US03952031

Reaction notes

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