Allyl iodide → 2-allyl-2-butyl-6-methoxy-3,4-dihydro-1(2H)-naphthalenone

HRID 2113659

Reaction equation

HRID 2113659 reaction equation
[H-].[Na+].[CH2:3]([CH:7]1[CH2:16][CH2:15][C:14]2[C:9](=[CH:10][CH:11]=[C:12]([O:17][CH3:18])[CH:13]=2)[C:8]1=[O:19])[CH2:4][CH2:5][CH3:6].[CH2:20](I)[CH:21]=[CH2:22]>CN(C=O)C>[CH2:22]([C:7]1([CH2:3][CH2:4][CH2:5][CH3:6])[CH2:16][CH2:15][C:14]2[C:9](=[CH:10][CH:11]=[C:12]([O:17][CH3:18])[CH:13]=2)[C:8]1=[O:19])[CH:21]=[CH2:20]

Participants

5

Reactant 3

HCID 11166Allyl iodide2×HCID 24758Sodium hydrideHCID 586040732-butyl-6-methoxy-3,4-dihydro-1(2H)-naphthalenone

Product 1

HCID 586040462-allyl-2-butyl-6-methoxy-3,4-dihydro-1(2H)-naphthalenone

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
2.5 °C

Procedure

NaH (0.32 g of a 60% dispersion in mineral oil, 8.0 mmol) was added to an ice-cold solution of 2-butyl-6-methoxy-3,4-dihydro-1(2H)-naphthalenone (1.55 g, 6.7 mmol) in anhydrous DMF (30 mL). The mixture was purged with N2 and stirred at 0-5° C. for 45 minutes. Allyl iodide (0.91 mL, 10.0 mmol) was added and, after a few minutes, the cooling bath was removed and the mixture was stirred overnight at room temperature. Additional NaH (0.16 g of a 61.1% dispersion in mineral oil, 4.1 mmol) was added and the mixture was stirred at room temperature for 15 minutes. Allyl iodide (0.46 mL, 5.0 mmol) was added and the mixture was stirred at room temperature for 24 hours. The mixture was partitioned between EtOAc and water, and the aqueous phase was back-extracted with several portions of EtOAc. The combined organics were washed with brine, dried over MgSO4, filtered, and concentrated under vacuum. The residue was purified by Biotage™ (Charlottesville, Va.) flash chromatography on a 40M (4×15 cm) silica gel column, eluting with 1% to 4% EtOAc in hexane, to afford 2-allyl-2-butyl-6-methoxy-3,4-dihydro-1(2H)-naphthalenone as an oil.

Workup

  1. customThe mixture was purged with N2
  2. customthe cooling bath was removed
  3. stirringthe mixture was stirred overnight at room temperature
  4. additionAdditional NaH (0.16 g of a 61.1% dispersion in mineral oil, 4.1 mmol) was added
  5. stirringthe mixture was stirred at room temperature for 15 minutes
  6. stirringthe mixture was stirred at room temperature for 24 hours
  7. customThe mixture was partitioned between EtOAc and water
  8. extractionthe aqueous phase was back-extracted with several portions of EtOAc
  9. washThe combined organics were washed with brine
  10. dry with materialdried over MgSO4
  11. filtrationfiltered
  12. concentrationconcentrated under vacuum
  13. customThe residue was purified by Biotage™ (Charlottesville, Va.) flash chromatography on a 40M (4×15 cm) silica gel column
  14. washeluting with 1% to 4% EtOAc in hexane

Sources & evidence

ORD record
ord-4ffa97b3f8e743c692bc0288aacb38db
Source dataset
uspto-grants-2008_10
Patent number
US07432284B2

Linked notes

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