3,4-dihydro-2H-pyran → HCID 86733141, compound

HRID 267627Notes

Reaction equation

HRID 267627 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[C:21]#[N:22])[CH2:4][C@@H:3]1[OH:23].O1C=CCCC1.C(=O)([O-])[O-].[Ca+2].[Br-].[Li+]>C1C=CC=CC=1.CC(N(C)C)=O.C(Cl)(Cl)Cl.C1(C)C=CC(S(O)(=O)=O)=CC=1>[C: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@H:3]([OH:23])[CH:2]=[CH:19]1)[CH2:6][CH2:7]3)#[N:22]

Participants

9

Reactant 4

HCID 80803,4-dihydro-2H-pyranHCID 10112Calcium CarbonateHCID 82050Lithium BromideHCID 86733142HCID 86733142, compound

Product 1

HCID 86733141HCID 86733141, compoundYield 11%

Reagents, catalysts & solvents 4

HCID 6101p-Toluenesulfonic acidCatalystHCID 241BenzeneSolventHCID 6212ChloroformSolventHCID 31374DimethylacetamideSolvent

Procedure

p-Toluenesulphonic acid (10 mg.) was added to a stirred solution of 2β-bromo-17β-cyano-3α-hydroxy-5α-androstane (2.65 g.,) and dihydropyran (10 ml.) in dry benzene (200 ml.). After 45 minutes at room temperature the solution was washed with aqueous 10% sodium bicarbonate (25 ml.) and water prior to being dried (MgSO4), filtered and evaporated to give crude 2β-bromo-17β-cyano-3α-(tetrahydropyran-2'ξ-yloxy)-5α-androstane. A mixture of calcium carbonate (15 g.), anhydrous lithium bromide (22.5 g.) and the tetrahydropyranyl derivative in dimethylacetamide (100 ml.) was stirred and heated on an oil bath (110°) for 6 hours. After cooling, the reaction mixture was diluted with chloroform and washed with water before drying (MgSO4) filtration and evaporation to a residue which was dissolved in methanol (100 ml.) and aqueous 2N hydrochloric acid (2 ml.). After 21/2 hours at room temperature and methanol was removed by evaporation and the residue dissolved in chloroform (25 ml.). This solution was washed with aqueous 10% sodium bicarbonate (25 ml.) and water (25 ml.) before drying (MgSO4), filtration and evaporation to a gum (2.55 g.). A sample (1.0 g.), after preparative TLC eluting with acetone/petrol (1:2,), afforded title compound (230 mg.,) as a white froth; [α]D 0°, (c 0.3). A sample was recrystallised from ether/petrol (x2); m.p. 129°-133°; [α]P 4°, c 0.5.

Workup

  1. washAfter 45 minutes at room temperature the solution was washed with aqueous 10% sodium bicarbonate (25 ml.) and water
  2. dry with materialto being dried (MgSO4)
  3. filtrationfiltered
  4. customevaporated
  5. customto give crude 2β-bromo-17β-cyano-3α-(tetrahydropyran-2'ξ-yloxy)-5α-androstane
  6. temperatureheated on an oil bath (110°) for 6 hours
  7. temperatureAfter cooling
  8. washwashed with water
  9. custombefore drying
  10. filtration(MgSO4) filtration and evaporation to a residue which
  11. dissolutionwas dissolved in methanol (100 ml.)
  12. customAfter 21/2 hours at room temperature and methanol was removed by evaporation
  13. dissolutionthe residue dissolved in chloroform (25 ml.)
  14. washThis solution was washed with aqueous 10% sodium bicarbonate (25 ml.) and water (25 ml.)
  15. custombefore drying
  16. filtration(MgSO4), filtration and evaporation to a gum (2.55 g.)
  17. washA sample (1.0 g.), after preparative TLC eluting with acetone/petrol (1:2,)

Sources & evidence

ORD record
ord-669aaf69c05e432a9753a00ed01058d9
Source dataset
uspto-grants-1976_03
Patent number
US03943124

Reaction notes

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