Allyl bromide → HCID 10421382, compound

HRID 2270502Notes

Reaction equation

HRID 2270502 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[CH:5][CH:6]=[C:7]2[C:12]=1[CH2:11][C:10](=[O:13])[CH2:9][CH2:8]2.[Li+].CC([N-][CH:19]([CH3:21])[CH3:20])C.[CH2:22](Br)C=C>C1COCC1>[CH3:1][O:2][C:3]1[CH:4]=[CH:5][CH:6]=[C:7]2[C:12]=1[CH:11]([CH2:22][CH:19]1[CH2:20][CH2:21]1)[C:10](=[O:13])[CH2:9][CH2:8]2

Participants

5

Reactant 3

HCID 7841Allyl bromide2×HCID 2724682Lithium diisopropylamideHCID 41360218-Methoxy-2-tetralone

Product 1

HCID 10421382HCID 10421382, compoundYield 97.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 3.52 g (20 mmol) 8-methoxy-2-tetralone in 50 mL THF in a three-neck round-bottomed flask, equipped with a gas inlet and septum, was added 14.3 mL LDA (22 mmol, 1.5 M in cyclohexane) at −30° C. under a nitrogen atmosphere. The solution was allowed to warm to 0° C. over a thirty-minute period and 2.4 mL (24 mmol) allyl bromide was added. TLC analysis was used to monitor the reaction. After stirring for two hours, the TLC analysis appeared to show little progress. The reaction mixture was therefore treated with 1.1 mL (12 mmol) allylbromide and the mixture was heated to reflux for 72 hours. The reaction mixture was quenched with 10% sodium bisulfate to pH 2-3. After removal of THF under reduced pressure, the mixture was extracted with ethyl acetate (2×1 L) and the combined organic layers were washed with brine, dried (MgSO4), filtered and concentrated in vacuo. The resulting oil was purified by liquid chromatography on 400 g of silica gel 60 (230-400 m), eluting with hexane/acetone (9:1) and collecting 40 mL fractions. Fractions homogeneous by TLC were combined and concentrated in vacuo to give 4.5 g (97.8%) of pure title compound as a near colorless oil.

Workup

  1. additionwas added
  2. customthe reaction
  3. temperaturethe mixture was heated
  4. temperatureto reflux for 72 hours
  5. customThe reaction mixture was quenched with 10% sodium bisulfate to pH 2-3
  6. customAfter removal of THF under reduced pressure
  7. extractionthe mixture was extracted with ethyl acetate (2×1 L)
  8. washthe combined organic layers were washed with brine
  9. dry with materialdried (MgSO4)
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customThe resulting oil was purified by liquid chromatography on 400 g of silica gel 60 (230-400 m)
  13. washeluting with hexane/acetone (9:1)
  14. customcollecting 40 mL fractions
  15. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-028a6656129b4396ac65984f3d0c1dfa
Source dataset
uspto-grants-2001_12
Patent number
US06331636B1

Reaction notes

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