Sodium Bicarbonate → Methyl 2-fluoro-3-formylbenzoate

HRID 2369933Notes

Reaction equation

HRID 2369933 reaction equation
Br[CH2:2][C:3]1[C:4]([F:13])=[C:5]([CH:10]=[CH:11][CH:12]=1)[C:6]([O:8][CH3:9])=[O:7].C(=O)(O)[O-:15].[Na+]>CS(C)=O>[F:13][C:4]1[C:3]([CH:2]=[O:15])=[CH:12][CH:11]=[CH:10][C:5]=1[C:6]([O:8][CH3:9])=[O:7]

Participants

4

Reactant 2

HCID 516892Sodium BicarbonateHCID 22050044Methyl 3-(bromomethyl)-2-fluorobenzoate

Product 1

HCID 57423810Methyl 2-fluoro-3-formylbenzoateYield 64.4%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

A mixture of methyl 3-(bromomethyl)-2-fluorobenzoate (11.5 g, 46.4 mmol) from Step B above and solid sodium bicarbonate (33.0 g, 398.7 mmol) in DMSO (150 mL) was refluxed until the reaction was complete by TLC (2-3 h). The mixture was cooled in an ice bath immediately and then partitioned between brine and ethyl acetate. The combined organics were concentrated and purified by column chromatography (silica gel, 9:1 hexanes/ethyl acetate) to afford methyl 2-fluoro-3-formylbenzoate as a white solid (5.44 g, 64%): 1H NMR (300 MHz, CDCl3) δ 10.43 (s, 1H), 8.21 (t, J=7.8 Hz, 1H), 8.07 (t, J=6.0 Hz, 1H), 7.35 (t, J=7.8 Hz, 1H), 3.93 (s, 3H).

Workup

  1. temperaturewas refluxed until the reaction
  2. customwas complete by TLC (2-3 h)
  3. temperatureThe mixture was cooled in an ice bath immediately
  4. custompartitioned between brine and ethyl acetate
  5. concentrationThe combined organics were concentrated
  6. custompurified by column chromatography (silica gel, 9:1 hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-a7a900b85f02427fbead353c58ac650e
Source dataset
uspto-grants-2014_04
Patent number
US08710046B2

Reaction notes

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