Sodium Iodide → Methyl 5-chloro-3-formyl-2-(2-methoxy-2-oxoethoxy)benzoate

HRID 1749921Notes

Reaction equation

HRID 1749921 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:13]=[O:14])[C:5]([OH:12])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].C(=O)([O-])[O-].[K+].[K+].[I-].[Na+].Br[CH2:24][C:25]([O:27][CH3:28])=[O:26]>CC(C)=O.CCCCCC.C(OCC)(=O)C>[Cl:1][C:2]1[CH:3]=[C:4]([CH:13]=[O:14])[C:5]([O:12][CH2:24][C:25]([O:27][CH3:28])=[O:26])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8]

Participants

7

Reactant 4

HCID 5238Sodium IodideHCID 11430Potassium CarbonateHCID 60984Methyl bromoacetateHCID 13146779Methyl 5-chloro-3-formyl-2-hydroxybenzoate

Product 1

HCID 86682046Methyl 5-chloro-3-formyl-2-(2-methoxy-2-oxoethoxy)benzoateYield 75.6%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolvent2×HCID 21226206Ethyl acetate hexaneSolvent

Procedure

A solution of methyl 5-chloro-3-formyl-2-hydroxybenzoate (6.4 g, 30 mmol) in acetone (50 mL) was added with potassium carbonate (7.4 g, 54 mmol), the mixture was successively added with sodium iodide (0.60 g, 3.0 mmol) and methyl bromoacetate (6.9 g, 45 mmol), and the mixture was stirred at room temperature for 10 hours, and then refluxed for 5 hours by heating. The reaction mixture was cooled to room temperature, and then added with acetone, and the mixture was filtered through Celite. The solvent was evaporated from the filtrate under reduced pressure, the solid formed was suspended in hexane/ethyl acetate (9:1), thereby washed, and then collected by filtration to obtain the objective substance. The filtrate was concentrated under reduced pressure, and the residue was subjected to by silica gel column chromatography (eluted with hexane/ethyl acetate (9:1→1:1)) to further obtain the objective substance. Two portions of the objective substance were combined to obtain 6.5 g (75%) of methyl 5-chloro-3-formyl-2-(2-methoxy-2-oxoethoxy)benzoate.

Workup

  1. temperaturerefluxed for 5 hours
  2. temperatureby heating
  3. temperatureThe reaction mixture was cooled to room temperature
  4. filtrationthe mixture was filtered through Celite
  5. customThe solvent was evaporated from the filtrate under reduced pressure
  6. customthe solid formed
  7. washwashed
  8. filtrationcollected by filtration
  9. customto obtain the objective substance
  10. concentrationThe filtrate was concentrated under reduced pressure
  11. washthe residue was subjected to by silica gel column chromatography (eluted with hexane/ethyl acetate (9:1→1:1))
  12. customto further obtain the objective substance

Sources & evidence

ORD record
ord-53505c0ff927415cb4eff33a8b8ca5b9
Source dataset
uspto-grants-2015_10
Patent number
US09156827B2

Reaction notes

Loading…