3-Hydroxybenzaldehyde → 3-(2-{[tert-Butyl(dimethyl)silyl]oxy}ethoxy)benzaldehyde

HRID 591846Notes

Reaction equation

HRID 591846 reaction equation
[H-].[Na+].[OH:3][C:4]1[CH:5]=[C:6]([CH:9]=[CH:10][CH:11]=1)[CH:7]=[O:8].Br[CH2:13][CH2:14][O:15][Si:16]([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17]>CN(C=O)C.O>[C:19]([Si:16]([CH3:18])([CH3:17])[O:15][CH2:14][CH2:13][O:3][C:4]1[CH:5]=[C:6]([CH:9]=[CH:10][CH:11]=1)[CH:7]=[O:8])([CH3:22])([CH3:21])[CH3:20]

Participants

6

Reactant 3

HCID 1013-HydroxybenzaldehydeHCID 24758Sodium hydrideHCID 3608067(2-Bromoethoxy)-tert-butyldimethylsilane

Product 1

HCID 714171133-(2-{[tert-Butyl(dimethyl)silyl]oxy}ethoxy)benzaldehyde

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

To a suspension of sodium hydride (0.426 g, 10.7 mmol) in DMF (30 mL) at room temperature was added 3-hydroxybenzaldehyde (1.00 g, 8.20 mmol). The resulting suspension was stirred at room temperature for 1 hour and (2-bromo-ethoxy)-tert-butyl-dimethyl-silane (4.4 mL, 20.5 mmol), was then added. The resulting mixture was stirred at 60° C. under nitrogen for 14 hours, cooled to room temperature, diluted with water (100 mL), extracted with ethyl acetate (250 mL), and concentrated. The crude product was purified by column chromatography (SiO2, hexane/ethyl acetate=4:1) to afford 3-[2-(tert-butyl-dimethyl-silanyloxy)-ethoxy]-benzaldehyde. It was re-dissolved in THF (50 mL), mixed with 1 N tetra-n-butylammonium fluoride in THF (15 mL), and stirred at room temperature for 8 h. The reaction mixture was then concentrated and the residue was purified by column chromatography (SiO2, hexane/ethyl acetate=4:1) to afford 3-(2-hydroxy-ethoxy)-benzaldehyde as a colorless oil. Yield: 0.68 g (50% for two steps).

Workup

  1. stirringThe resulting mixture was stirred at 60° C. under nitrogen for 14 hours
  2. temperaturecooled to room temperature
  3. extractionextracted with ethyl acetate (250 mL)
  4. concentrationconcentrated
  5. customThe crude product was purified by column chromatography (SiO2, hexane/ethyl acetate=4:1)

Sources & evidence

ORD record
ord-2f1ad2f411ea4d62b26ddcb2a5585e5f
Source dataset
uspto-grants-2016_01
Patent number
US09238640B2

Reaction notes

Loading…