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

HRID 1200168

Reaction equation

HRID 1200168 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 solvent 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 (ε 13.750).

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 solvent removed under vacuum
  8. customThe crude product was chromatographed on silica gel

Sources & evidence

ORD record
ord-c34074fb0580423a8bdc707ed881cde9
Source dataset
uspto-grants-1990_02
Patent number
US04904650

Linked notes

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