Water → 1-Bromo-4-[(2-ethoxyethoxy)methyl]benzene

HRID 1978697Notes

Reaction equation

HRID 1978697 reaction equation
[Br:1][C:2]1[CH:9]=[CH:8][C:5]([CH2:6][OH:7])=[CH:4][CH:3]=1.[H-].[Na+].Br[CH2:13][CH2:14][O:15][CH2:16][CH3:17].O>CN(C=O)C>[Br:1][C:2]1[CH:9]=[CH:8][C:5]([CH2:6][O:7][CH2:13][CH2:14][O:15][CH2:16][CH3:17])=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 611412-Bromoethyl ethyl etherHCID 701194-Bromobenzyl alcohol

Product 1

HCID 219956581-Bromo-4-[(2-ethoxyethoxy)methyl]benzeneYield 46.6%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

In DMF (120 ml) was dissolved 4-bromobenzyl alcohol (15 g). To the mixture was added under ice-cooling 65% sodium hydride (3.0 g), and the mixture was stirred at room temperature for 3 hours. To the mixture was added dropwise at room temperature 2-bromoethylethyl ether (11.4 g), and the mixture was stirred at room temperature for 3 hours. The reaction mixture was added to water, and the mixture was extracted with ethyl acetate, washed with saturated brine and dried with magnesium sulfate. Under reduced pressure, the solvent was evaporated, and the residue was purified with silica gel column chromatography (hexane/ethyl acetate=10/1) to give 1-bromo-4-[(2-ethoxyethoxy)methyl]benzene (9.0 g). In THF (104 ml) was dissolved 1-bromo-4-[2-ethoxyethoxy)methyl)]benzene (8.7 g). To the mixture was added dropwise at −78° C. 1.6M n-butyllithium/hexane (23 ml), and the mixture was stirred for 1 hour. To the mixture was added dropwise trimethyl borate (8.7 g), and the mixture was stirred for 30 minutes and warmed to room temperature. To the mixture was added 5% sulfuric acid (35 ml), and the mixture was stirred for 15 minutes. The reaction mixture was extracted with ethyl acetate, washed with saturated brine and dried with magnesium sulfate. Under reduced pressure, the solvent was evaporated, and the residue was purified with silica gel column chromatography (hexane/ethyl acetate=1/2) to give 4-[(2-ethoxyethoxy)methyl]phenyl borate (2.1 g).

Workup

  1. additionTo the mixture was added under ice-
  2. stirringthe mixture was stirred at room temperature for 3 hours
  3. extractionthe mixture was extracted with ethyl acetate
  4. washwashed with saturated brine
  5. dry with materialdried with magnesium sulfate
  6. customUnder reduced pressure, the solvent was evaporated
  7. customthe residue was purified with silica gel column chromatography (hexane/ethyl acetate=10/1)

Sources & evidence

ORD record
ord-5db3526a04294684955c83fc4f8aa6c8
Source dataset
uspto-grants-2001_05
Patent number
US06235771B1

Reaction notes

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