Allyl bromide → N-Allyl-4-acetamido-3-bromo-2,6-dimethylanisole

HRID 1488453Notes

Reaction equation

HRID 1488453 reaction equation
[H-].[Na+].[C:3]([NH:6][C:7]1[CH:12]=[C:11]([CH3:13])[C:10]([O:14][CH3:15])=[C:9]([CH3:16])[C:8]=1[Br:17])(=[O:5])[CH3:4].[CH2:18](Br)[CH:19]=[CH2:20]>O1CCCC1>[CH2:20]([N:6]([C:7]1[CH:12]=[C:11]([CH3:13])[C:10]([O:14][CH3:15])=[C:9]([CH3:16])[C:8]=1[Br:17])[C:3](=[O:5])[CH3:4])[CH:19]=[CH2:18]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 229056464-Acetamido-3-bromo-2,6-dimethylanisole

Product 1

HCID 22905637N-Allyl-4-acetamido-3-bromo-2,6-dimethylanisoleYield 85%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

Sodium hydride (1.1 g, 27 mmol, 60% dispersion in oil) contained in a round-bottom flask fitted with a reflux condenser was washed using dry hexanes, tetrahydrofuran (50 mL) was added, and the suspension was stirred at 0° C. under a nitrogen atmosphere. A solution of 4-acetamido-3-bromo-2,6-dimethylanisole (7.3 g, 27 mmol) dissolved in tetrahydrofuran (50 mL) was added dropwise using a canulla over about 0.5 h. Allyl bromide (4.85 mL, 84.8 mmoI) was added to the cold solution in one portion, and the mixture was warmed to 60° C. and held there for 17 h. The reaction mixture was quenched with saturated aq. ammonium chloride and extracted with diethyl ether. The combined extracts were washed with brine and dried (MgSO4). Removal of solvents and purification of the resulting viscous liquid by flash column chromatography using 1:3 ethyl acetate:hexanes as eluent gave N-allyl-4-acetamido-3-bromo-2,6-dimethylanisole (8, 8.7 g, 85% yield) as a viscous liquid. Spectral data: 13C NMR: δ 15.2, 16.3, 21.5, 50.1, 59.3, 117.1, 123.3, 129.2, 130.2, 132.37, 132.4, 136.5, 156.2, 169.1; HRMS: calcd. for C14H19BrNO2 (M+H+) 312.0599, fnd. 312.0586.

Workup

  1. customfitted with a reflux condenser
  2. washwas washed
  3. additionwas added
  4. additionwas added dropwise
  5. customover about 0.5 h
  6. temperaturethe mixture was warmed to 60° C.
  7. customThe reaction mixture was quenched with saturated aq. ammonium chloride
  8. extractionextracted with diethyl ether
  9. washThe combined extracts were washed with brine
  10. dry with materialdried (MgSO4)
  11. customRemoval of solvents and purification of the resulting viscous liquid by flash column chromatography

Sources & evidence

ORD record
ord-0b7f611c54bb4ee9bf76b0984e536c2a
Source dataset
uspto-grants-1997_10
Patent number
US05674876

Reaction notes

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