Methanol → Benzyl 4-formylbenzoate

HRID 1013480Notes

Reaction equation

HRID 1013480 reaction equation
[CH:1]([C:3]1[CH:11]=[CH:10][C:6]([C:7]([OH:9])=[O:8])=[CH:5][CH:4]=1)=[O:2].CO.C([O-])([O-])=O.[Cs+].[Cs+].[CH2:20](Br)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>CN(C=O)C.C(=O)(O)[O-].[Na+].O>[CH2:20]([O:8][C:7](=[O:9])[C:6]1[CH:10]=[CH:11][C:3]([CH:1]=[O:2])=[CH:4][CH:5]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

Participants

8

Reactant 4

HCID 887MethanolHCID 7498Benzyl BromideHCID 10796Cesium carbonateHCID 120884-Formylbenzoic acid

Product 1

HCID 11528845Benzyl 4-formylbenzoate

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 516892Sodium BicarbonateSolvent

Procedure

4-Formyl-benzoic acid (2.0 g, 13.3 mmol) was made 0.2 M in 10:1 MeOH:Water and stirred. The stirring slurry was adjusted to pH=8 with 20% aq Cs2CO3. The resulting homogenous solution was stirred at ambient temperature for 20 mins then concentrated to dryness in vacuo. The residue was dried under high vacuum then treated with benzyl bromide (3.4 g, 20.0 mmol) 0.5 M in DMF. The slurry was stirred under nitrogen at ambient temperature for 18 hours. The reaction mixture was diluted with ½ saturated aqueous sodium bicarbonate and extracted with EtOAc. The organic layer was separated and again washed with ½ saturated aqueous sodium bicarbonate, then washed with brine, dried (MgSO4) and concentrated in vacuo. The residue was purified by MPLC (5-45% EtOAc in Hexanes) to afford the title compound: MS: cal'd 241 (MH+), exp 241 (MH+)

Workup

  1. concentrationthen concentrated to dryness in vacuo
  2. customThe residue was dried under high vacuum
  3. stirringThe slurry was stirred under nitrogen at ambient temperature for 18 hours
  4. extractionextracted with EtOAc
  5. customThe organic layer was separated
  6. washagain washed with ½ saturated aqueous sodium bicarbonate
  7. washwashed with brine
  8. dry with materialdried (MgSO4)
  9. concentrationconcentrated in vacuo
  10. customThe residue was purified by MPLC (5-45% EtOAc in Hexanes)

Sources & evidence

ORD record
ord-2d4adefcd27840e393c904b2e3a4ee62
Source dataset
uspto-grants-2011_07
Patent number
US07981874B2

Reaction notes

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