Benzyl Bromide → Methyl 4-(benzyloxy)-3-bromobenzoate

HRID 424043Notes

Reaction equation

HRID 424043 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:9]=[CH:10][C:11]=1[OH:12])[C:5]([O:7][CH3:8])=[O:6].C(=O)([O-])[O-].[K+].[K+].[CH2:19](Br)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1>C(#N)C>[CH2:19]([O:12][C:11]1[CH:10]=[CH:9][C:4]([C:5]([O:7][CH3:8])=[O:6])=[CH:3][C:2]=1[Br:1])[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1

Participants

5

Reactant 3

HCID 7498Benzyl BromideHCID 11430Potassium CarbonateHCID 4778958Methyl 3-bromo-4-hydroxybenzoate

Product 1

HCID 23111814Methyl 4-(benzyloxy)-3-bromobenzoateYield 75%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

Methyl 3-bromo-4-hydroxybenzoate [prepared as per Tetrahedron, 2003, 59, 9173] (3.47 g, 15.0 mmol) was dissolved in acetonitrile (50 ml), anhydrous potassium carbonate (3.11 g, 22.5 mmol) was added and the stirred mixture was treated with benzyl bromide (3.08 g, 18.0 mmol) and held at reflux for 5 hours. Upon cooling the solvent was removed in vacuo and the mixture partitioned between water and dichloromethane. The organic layer was separated, the solvent removed in vacuo and the residue subjected to column chromatography on silica. Elution with 10% ethyl acetate in petroleum ether afforded methyl 4-benzyloxy-3-bromobenzoate (3.6 g, 75%) as a colourless solid. 1H NMR (DMSO-d6) 8.12 (1H, d), 7.96 (1H, dd), 7.51 (2H, m), 7.43 (2H, t), 7.35 (2H, m), 5.32 (2H, s), 3.84 (3H, s).

Workup

  1. temperatureat reflux for 5 hours
  2. temperatureUpon cooling the solvent
  3. customwas removed in vacuo
  4. customthe mixture partitioned between water and dichloromethane
  5. customThe organic layer was separated
  6. customthe solvent removed in vacuo
  7. washElution with 10% ethyl acetate in petroleum ether

Sources & evidence

ORD record
ord-6a94995b92d24cd0b3a501fb47c77796
Source dataset
uspto-grants-2012_01
Patent number
US08101648B2

Reaction notes

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