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

HRID 901147Notes

Reaction equation

HRID 901147 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([OH:10])=[C:6]([Cl:11])[CH:5]=1.[CH2:13](Br)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.C(=O)([O-])[O-].[K+].[K+]>CN(C)C=O>[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([O:10][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[C:6]([Cl:11])[CH:5]=1

Participants

5

Reactant 3

HCID 7498Benzyl BromideHCID 11430Potassium CarbonateHCID 77580Methyl 3-chloro-4-hydroxybenzoate

Product 1

HCID 21044521Methyl 4-(benzyloxy)-3-chlorobenzoate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A mixture of 3-chloro-4-hydroxy benzoic acid methyl ester (4.665 g, 25 mmol), benzyl bromide (5.13 g, 30 mmol) and potassium carbonate (6.91 g, 50 mmol) in N,N-dimethylformamide (50 mL) was stirred overnight at room temperature. The reaction mixture was poured onto crushed ice (ca. 300 g) and the product was extracted with ethyl acetate (2×100 mL). The combined organic layers were dried over sodium sulphate and concentrated under reduced pressure. The residue was dissolved in dichloromethane and precipitated by addition of hexane. Yield: 6.47 g (94%) white powder. 1H-NMR (400 MHz, CDCl3) δ=3.90 (s, 3H, —OCH3), 5.23 (s, 2H, —CH2Ar), 6.99 (d, J=9.0 Hz, 1H), 7.31-7.48 (m, 5H), 7.89 (dd, J=9.0, 2.3 Hz, 1H), 8.08 (d, J=2.3 Hz, 1H).

Workup

  1. additionThe reaction mixture was poured
  2. extractionthe product was extracted with ethyl acetate (2×100 mL)
  3. dry with materialThe combined organic layers were dried over sodium sulphate
  4. concentrationconcentrated under reduced pressure
  5. dissolutionThe residue was dissolved in dichloromethane
  6. customprecipitated by addition of hexane

Sources & evidence

ORD record
ord-4e1d2acf05344a46990642be6cab0252
Source dataset
uspto-grants-2008_04
Patent number
US07361677B2

Reaction notes

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