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

HRID 2410483Notes

Reaction equation

HRID 2410483 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]OC.FC1C(C)=C(C2C=CC(C(O)=O)=CC=2COC)C=CC=1.[C:35]([O-:38])(=[O:37])[CH3:36].[Na+]>CC(O)=O>[C:35]([O:38][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:37])[CH3:36]

Participants

5

Reactant 3

HCID 517045Sodium AcetateHCID 580663983'-Fluoro-2-(methoxymethyl)-2'-methylbiphenyl-4-carboxylic acidHCID 58554220Methyl 4-bromo-3-(methoxymethyl)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 (Intermediate 1 Step 1, 6.5 g, 21 mmol) in AcOH (32.5 mL) was added sodium acetate (3.46 g, 42 mmol) and the reaction mixture was stirred at 100° C. for 15 hours. After concentration in vacuo, the residue was partitioned between EtOAc and water. The organic layer was washed with a 5% aqueous solution of NaHCO3 and brine, dried over MgSO4 and concentrated in vacuo. Purification by chromatography (silica, chex/EtOAc) afforded the title compound as a white solid (4.78 g, 79%). 1H NMR (DMSO-d6) δ 8.03 (m, 1H), 7.85 (m, 2H), 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 a 5% aqueous solution of NaHCO3 and brine
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated in vacuo
  6. customPurification by chromatography (silica, chex/EtOAc)

Sources & evidence

ORD record
ord-ab0ce231757747db94b0b136732e410f
Source dataset
uspto-grants-2014_08
Patent number
US08815919B2

Reaction notes

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