Chloromethyl Methyl Ether → 3-Bromo-5-ethoxy-4-(methoxymethoxy)benzaldehyde

HRID 401167Notes

Reaction equation

HRID 401167 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([O:11][CH2:12][CH3:13])[C:9]=1[OH:10])[CH:5]=[O:6].[H-].[Na+].[CH2:16](Cl)[O:17][CH3:18].CCOC(C)=O>CN(C=O)C>[Br:1][C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([O:11][CH2:12][CH3:13])[C:9]=1[O:10][CH2:16][O:17][CH3:18])[CH:5]=[O:6]

Participants

6

Reactant 4

HCID 7864Chloromethyl Methyl EtherHCID 8857Ethyl AcetateHCID 24758Sodium hydrideHCID 6124963-Bromo-5-ethoxy-4-hydroxybenzaldehyde

Product 1

HCID 653644473-Bromo-5-ethoxy-4-(methoxymethoxy)benzaldehydeYield 59.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of 3-bromo-5-ethoxy-4-hydroxybenzaldehyde (1.0 g, 4.1 mmol) in DMF (10 mL) was cooled at 0° C., NaH (180 mg, 4.5 mmol) was added, and the mixture was stirred for 15 minutes. MOM-Cl (360 mg, 4.5 mmol) was added, and the mixture was warmed to room temperature in two hours. TLC (PE:EtOAc=5:1) indicated that the starting material was consumed. Ice water was added to quench the reaction, and aqueous layer was extracted with EtOAc (30 mL×3). The combined organic layer was washed with brine (20 mL), dried over Na2SO4, filtered, concentrated, and purified by column chromatograph to give 3-bromo-5-ethoxy-4-(methoxymethoxy)benzaldehyde (0.7 g, yield: 59.3%).

Workup

  1. customwas consumed
  2. additionIce water was added
  3. customto quench
  4. customthe reaction, and aqueous layer
  5. extractionwas extracted with EtOAc (30 mL×3)
  6. washThe combined organic layer was washed with brine (20 mL)
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. custompurified by column chromatograph

Sources & evidence

ORD record
ord-a274b6558d5c43efba76761dd0cc26cb
Source dataset
uspto-grants-2014_06
Patent number
US08741915B2

Reaction notes

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