p-Toluenesulfonic acid → 3alpha-Hydroxy-17beta-methoxycarbonyl-5alpha-androst-1-en-11-one

HRID 1606493Notes

Reaction equation

HRID 1606493 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[C:16](=[O:21])[CH2:15][C@@:13]2([CH3:14])[C@H:9]3[CH2:10][CH2:11][C@@H:12]2[C:22]([O:24][CH3:25])=[O:23])[CH2:4][C@@H:3]1[OH:26].O1C=CCCC1.C1(C)C=CC(S(O)(=O)=O)=CC=1.[Br-].[Li+].C(=O)([O-])[O-].[Ca+2]>C1C=CC=CC=1.CC(N(C)C)=O>[OH:26][C@@H:3]1[CH:2]=[CH:19][C@@:18]2([CH3:20])[C@@H:5]([CH2:6][CH2:7][C@@H:8]3[C@@H:17]2[C:16](=[O:21])[CH2:15][C@@:13]2([CH3:14])[C@H:9]3[CH2:10][CH2:11][C@@H:12]2[C:22]([O:24][CH3:25])=[O:23])[CH2:4]1

Participants

8

Reactant 5

HCID 6101p-Toluenesulfonic acidHCID 80803,4-dihydro-2H-pyranHCID 10112Calcium CarbonateHCID 82050Lithium BromideHCID 867331322beta-Bromo-3alpha-hydroxy-17beta-methoxycarbonyl-5alpha-androstan-11-one

Product 1

HCID 867331393alpha-Hydroxy-17beta-methoxycarbonyl-5alpha-androst-1-en-11-one

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 31374DimethylacetamideSolvent

Procedure

A solution of 2β-bromo-3α-hydroxy-17β-methoxycarbonyl-5α-androstan-11-one. (3.48 g.,), dihydropyran (8 ml.) and p-toluenesulphonic acid (60 mg.) in benzene (150 ml.) was stirred at room temperature for 15 minutes before being washed with aqueous 10% sodium bicarbonate and water. The benzene solution was dried and evaporated to give a gum which was dissolved in dimethylacetamide (120 ml.). After the addition of anhydrous lithium bromide (14.4 g.) and calcium carbonate (11.2 g.) the mixture was heated (100°) for 6 hr. Cooling, dilution with chloroform and filtration gave a solution which was washed with water, dried, filtered and evaporated. The residue was dissolved in methanol (200 ml.) containing aqueous 2N hydrochloric acid (1 ml.). After 4 hr. the methanol was removed by evaporation and chloroform added. This solution, after being washed with aqueous 10% sodium bicarbonate and water, was dried, filtered and evaporated to an oil. The addition of ether resulted in crystallisation of the title compound (1.125 g.); m.p. 172°-175°; [α]D + 40°, (c 0.7).

Workup

  1. washbefore being washed with aqueous 10% sodium bicarbonate and water
  2. dry with materialThe benzene solution was dried
  3. customevaporated
  4. customto give a gum which
  5. temperaturewas heated (100°) for 6 hr
  6. temperatureCooling
  7. filtrationdilution with chloroform and filtration
  8. customgave a solution which
  9. washwas washed with water
  10. customdried
  11. filtrationfiltered
  12. customevaporated
  13. dissolutionThe residue was dissolved in methanol (200 ml.)
  14. additioncontaining aqueous 2N hydrochloric acid (1 ml.)
  15. customthe methanol was removed by evaporation and chloroform
  16. additionadded
  17. washThis solution, after being washed with aqueous 10% sodium bicarbonate and water
  18. customwas dried
  19. filtrationfiltered
  20. customevaporated to an oil
  21. additionThe addition of ether

Sources & evidence

ORD record
ord-ab036369a2f2444594abc10ce98f0e6d
Source dataset
uspto-grants-1976_04
Patent number
US03953429

Reaction notes

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