Sodium Acetate → Methyl 3-(acetoxymethyl)-4-bromobenzoate

HRID 219814Notes

Reaction equation

HRID 219814 reaction equation
[Br:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[CH2:12]Br.[C:14]([O-:17])(=[O:16])[CH3:15].[Na+]>CC(O)=O>[C:14]([O:17][CH2:12][C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][C:2]=1[Br:1])[C:6]([O:8][CH3:9])=[O:7])(=[O:16])[CH3:15]

Participants

4

Reactant 2

HCID 517045Sodium AcetateHCID 11460987Methyl 4-Bromo-3-(bromomethyl)benzoate

Product 1

HCID 22574808Methyl 3-(acetoxymethyl)-4-bromobenzoateYield 79.3%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of methyl 4-bromo-3-(bromomethyl)benzoate (6.5 g; 21 mmol; 1 eq.) in AcOH (32.5 mL) was added sodium acetate (3.46 g; 42 mmol; 2 eq.) and the reaction mixture was stirred at 100° C. for 12 hours. After concentration in vacuo, the residue was partitioned between EtOAc and water. The organic layer was washed with 5% aq. NaHCO3 then brine, dried over MgSO4 and concentrated in vacuo. Purification by column chromatography (c-hexane/EtOAc, 5/1) afforded the title compound as a white solid (4.78 g, 79%). 1H NMR (DMSO-d6, 300 MHz) δ 8.03 (m, 1H), 7.85-7.84 (d, J=1.3 Hz, 1H), 5.18 (s, 2H), 3.87 (s, 3H), 2.11 (s, 3H). HPLC (Method A) Rt 4.37 min (purity 98.1%).

Workup

  1. concentrationAfter concentration in vacuo
  2. customthe residue was partitioned between EtOAc and water
  3. washThe organic layer was washed with 5% aq. NaHCO3
  4. dry with materialbrine, dried over MgSO4
  5. concentrationconcentrated in vacuo
  6. customPurification by column chromatography (c-hexane/EtOAc, 5/1)

Sources & evidence

ORD record
ord-9f03246824ac4dd996f9ffe485399bcf
Source dataset
uspto-grants-2012_06
Patent number
US08202865B2

Reaction notes

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