2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → 16alpha-Fluoro-1,6alpha-dimethyl-7-methylenandrosta-1,4-diene-3,17-dione

HRID 621623Notes

Reaction equation

HRID 621623 reaction equation
[F:1][C@@H:2]1[CH2:7][C@H:6]2[C@H:8]3[C@H:18]([CH2:19][CH2:20][C@:4]2([CH3:5])[C:3]1=[O:25])[C@:16]1([CH3:17])[C:11](=[CH:12][C:13](=[O:22])[CH2:14][C@H:15]1[CH3:21])[C@@H:10]([CH3:23])[C:9]3=[CH2:24].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>O1CCOCC1>[F:1][C@@H:2]1[CH2:7][C@H:6]2[C@H:8]3[C@H:18]([CH2:19][CH2:20][C@:4]2([CH3:5])[C:3]1=[O:25])[C@:16]1([CH3:17])[C:11](=[CH:12][C:13](=[O:22])[CH:14]=[C:15]1[CH3:21])[C@@H:10]([CH3:23])[C:9]3=[CH2:24]

Participants

4

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 1863203216alpha-Fluoro-1beta,6alpha-dimethyl-7-methylenandrost-4-ene-3,17-dione

Product 1

HCID 1863203116alpha-Fluoro-1,6alpha-dimethyl-7-methylenandrosta-1,4-diene-3,17-dioneYield 64.9%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

A mixture of 16α-fluoro-1β,6α-dimethyl-7-methylenandrost-4-ene-3,17-dione (344 mg) and dichlorodicyanobenzoquinone (363 mg) in dioxane (20 ml) is refluxed for about 15 hours. Then the resulting suspension is cooled, the precipitate filtered off and the filtrate evaporated in vacuo. The residue is dissolved in ethyl acetate, the organic layer washed with water, dried over sodium sulfate and the solvent removed under vacuum. The crude product is chromatographed on silica gel using hexane/ethyl acetate as eluant to yield 16α-fluoro-1,6α-dimethyl-7-methylenandrosta-1,4-diene-3,17-dione (222 mg).

Workup

  1. temperatureis refluxed for about 15 hours
  2. temperatureThen the resulting suspension is cooled
  3. filtrationthe precipitate filtered off
  4. customthe filtrate evaporated in vacuo
  5. dissolutionThe residue is dissolved in ethyl acetate
  6. washthe organic layer washed with water
  7. dry with materialdried over sodium sulfate
  8. customthe solvent removed under vacuum
  9. customThe crude product is chromatographed on silica gel

Sources & evidence

ORD record
ord-0c2009cd927e49e295afc8433c522396
Source dataset
uspto-grants-1989_04
Patent number
US04824830

Reaction notes

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