Diiodomethane → 1beta,2beta-Methylene-19-tetrahydropyranyloxy-5-androstene-3beta,17beta-diol

HRID 1390738Notes

Reaction equation

HRID 1390738 reaction equation
[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][CH2:8][C@@:9]12[C@@H:26]3[C@H:17]([C@H:18]4[C@@:22]([CH2:24][CH2:25]3)([CH3:23])[C@@H:21]([OH:27])[CH2:20][CH2:19]4)[CH2:16][CH:15]=[C:14]1[CH2:13][C@@H:12]([OH:28])[CH:11]=[CH:10]2.[CH2:29](COC)OC.C(I)I>CCOCC.[Cu].[Zn]>[CH2:29]1[C@@H:11]2[C@H:12]([OH:28])[CH2:13][C:14]3[C@:9]([CH2:8][O:7][CH:2]4[CH2:3][CH2:4][CH2:5][CH2:6][O:1]4)([C@H:10]12)[C@@H:26]1[C@H:17]([C@H:18]2[C@@:22]([CH2:24][CH2:25]1)([CH3:23])[C@@H:21]([OH:27])[CH2:20][CH2:19]2)[CH2:16][CH:15]=3

Participants

6

Reactant 3

HCID 6346DiiodomethaneHCID 80711,2-DimethoxyethaneHCID 2280690319-Tetrahydropyranyloxy-1,5-androstadiene-3beta,17beta-diol

Product 1

HCID 706050941beta,2beta-Methylene-19-tetrahydropyranyloxy-5-androstene-3beta,17beta-diol

Reagents, catalysts & solvents 2

HCID 10290809Zinc copper coupleCatalystHCID 3283Diethyl EtherSolvent2×

Procedure

To a stirred solution of 19-tetrahydropyranyloxy-1,5-androstadiene-3β,17β-diol in a mixture of dry ether and glyme is added zinc-copper couple and methylene iodide. This reaction mixture is refluxed for four hours, cooled to room temperature, diluted with ether and filtered. The ether filtrate is washed with an aqueous sodium chloride solution, washed with water, and dried over anhydrous magnesium sulfate. The ether is removed under reduced pressure and the residue which remains is crystallized from an acetone-hexane solution to yield 1β,2β-methylene-19-tetrahydropyranyloxy-5-androstene-3β,17β-diol.

Workup

  1. temperatureThis reaction mixture is refluxed for four hours
  2. filtrationfiltered
  3. washThe ether filtrate is washed with an aqueous sodium chloride solution
  4. washwashed with water
  5. dry with materialdried over anhydrous magnesium sulfate
  6. customThe ether is removed under reduced pressure
  7. customthe residue which remains is crystallized from an acetone-hexane solution

Sources & evidence

ORD record
ord-9e0834e2f38844af8b01ab1d04fa277c
Source dataset
uspto-grants-1979_02
Patent number
US04139617

Reaction notes

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