HCID 15871130, compound → HCID 15871131, compound

HRID 1861616Notes

Reaction equation

HRID 1861616 reaction equation
[CH3:1][Mg]I.[OH:4][C@H:5]1[CH2:10][C@H:9]2[CH2:11][C@@:8]32[C@H:12]2[C@H:22]([CH2:23][CH2:24][C@:6]13[CH3:7])[C@:20]1([CH3:21])[C:15](=[CH:16][C:17](=[O:25])[CH2:18][CH2:19]1)[CH:14]=[CH:13]2>C1COCC1.O.C([O-])(=O)C.[Cu+2].C([O-])(=O)C>[OH:4][C@H:5]1[CH2:10][C@H:9]2[CH2:11][C@@:8]32[C@H:12]2[C@H:22]([CH2:23][CH2:24][C@:6]13[CH3:7])[C@:20]1([CH3:21])[C:15](=[CH:16][C:17](=[O:25])[CH2:18][CH2:19]1)[CH2:14][C@H:13]2[CH3:1]

Participants

5

Reactant 2

HCID 15871130HCID 15871130, compoundHCID 178418373HCID 178418373, compound

Product 1

HCID 15871131HCID 15871131, compound

Reagents, catalysts & solvents 2

HCID 165397Cupric acetate monohydrateCatalystHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-5 °C

Procedure

80 ml of THF is added to a solution of methylmagnesium iodide (prepared from 2.5 g of magnesium and 6.4 ml of methyl iodide in 80 ml of diethyl ether), it is cooled to −5° C., and 1 g of copper acetate-monohydrate, dissolved in 50 ml of THF, is added. It is cooled to −20° C., and then a solution of 5 g of 17β-hydroxy-14β,15β-methylen-androsta-4,6-dien-3-one in 80 ml of THF is added in drops. After 2 hours, it is poured onto ice water/2N sulfuric acid and extracted with 3×80 ml of ethyl acetate. The organic extract is dried and concentrated by evaporation. The residue is chromatographed on silica gel (mobile solvent: dichloromethane/ethyl acetate 10:1). For further purification, it is recrystallized from ethyl acetate.

Workup

  1. additionis added
  2. temperatureIt is cooled to −20° C.
  3. additionit is poured onto ice water/2N sulfuric acid
  4. extractionextracted with 3×80 ml of ethyl acetate
  5. extractionThe organic extract
  6. customis dried
  7. concentrationconcentrated by evaporation
  8. customThe residue is chromatographed on silica gel (mobile solvent: dichloromethane/ethyl acetate 10:1)
  9. customFor further purification, it
  10. customis recrystallized from ethyl acetate

Sources & evidence

ORD record
ord-037ca663394b472084f9a981a26c8660
Source dataset
uspto-grants-2003_03
Patent number
US06534490B1

Reaction notes

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