2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → Exemestane

HRID 1383021

Reaction equation

HRID 1383021 reaction equation
[CH2:1]=[C:2]1[C:19]2[C@:14]([CH3:21])([CH2:15][CH2:16][C:17](=[O:20])[CH:18]=2)[C@@H:13]2[C@H:4]([C@H:5]3[C@@:9]([CH2:11][CH2:12]2)([CH3:10])[C:8](=[O:22])[CH2:7][CH2:6]3)[CH2:3]1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>O1CCOCC1>[CH2:1]=[C:2]1[C:19]2[C@:14]([CH3:21])([CH:15]=[CH:16][C:17](=[O:20])[CH:18]=2)[C@@H:13]2[C@H:4]([C@H:5]3[C@@:9]([CH2:11][CH2:12]2)([CH3:10])[C:8](=[O:22])[CH2:7][CH2:6]3)[CH2:3]1

Participants

4

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 129518006-Methylideneandrost-4-ene-3,17-dione

Product 1

HCID 60198ExemestaneYield 50.3%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

0.50 g of 6-methylenandrost-4-ene-3,17-dione and 0.57 g of dichlorodicyanobenzoquinone were refluxed in 20 ml of anhydrous dioxane for about 15 hours. To remove the DDQ the suspension was filtered through alumina. After evaporation of the solvent the residue was dissolved in ethyl acetate, the organic layer washed with water, dried over sodium sulfate and the solent removed under vacuum. The crude product was chromatographed on silica gel using hexane/ethyl acetate 40% to yield 0.25 g of pure 6-methylenandrosta-1,4-diene-3,17-dione, m.p. 188°-191° C., λmax 247 mμ (ε13.750). Found: C 81.01, H 8.05. C20H24O2 requires: C 81.04, H 8.16.

Workup

  1. customTo remove the DDQ the suspension
  2. filtrationwas filtered through alumina
  3. customAfter evaporation of the solvent the residue
  4. dissolutionwas dissolved in ethyl acetate
  5. washthe organic layer washed with water
  6. dry with materialdried over sodium sulfate
  7. customthe solent removed under vacuum
  8. customThe crude product was chromatographed on silica gel

Sources & evidence

ORD record
ord-4e238f561f2d4149b3487001592a2348
Source dataset
uspto-grants-1989_02
Patent number
US04808616

Linked notes

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