Imidazole → 1-Bromo-3-((((1,1-dimethylethyl)dimethylsilyl)oxy)methyl)benzene

HRID 1985298Notes

Reaction equation

HRID 1985298 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][CH:9]=1)[CH2:5][OH:6].[C:10]([Si:14](Cl)([CH3:16])[CH3:15])([CH3:13])([CH3:12])[CH3:11].N1C=CN=C1>CN(C)C=O.C(OCC)(=O)C>[Br:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][CH:9]=1)[CH2:5][O:6][Si:14]([C:10]([CH3:13])([CH3:12])[CH3:11])([CH3:16])[CH3:15]

Participants

6

Reactant 3

HCID 795ImidazoleHCID 28928tert-Butyldimethylsilyl chlorideHCID 851413-Bromobenzyl alcohol

Product 1

HCID 220331471-Bromo-3-((((1,1-dimethylethyl)dimethylsilyl)oxy)methyl)benzeneYield 93.1%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

14 g of 3-Bromobenzyl alcohol was dissolved in 200 ml of N,N-dimethylformamide, and 15 g of t-butylchlorodimethyl silane and 10 g of imidazole were added. After stirring was continued at room temperature overnight, the solution was diluted with ethyl acetate, and washed successively with 1N hydrochloric acid and saturated brine. After drying the organic layer over anhydrous magnesium sulfate, the solvent was evaporated. The residue was purified by silica gel column chromatography, and 21 g of [(3-bromobenzyl)oxy] (t-butyl)dimethylsilane was obtained in the 4:1 hexane-ethyl acetate fraction. Then, the obtained 21 g of [(3-bromobenzyl)oxy] (t-butyl)dimethylsilane was dissolved in 300 ml of tetrahydrofuran, and the mixture was cooled to −78° C. under nitrogen atmosphere. 55 ml of butyl lithium (1.52 M solution in hexane) was added thereto, and the mixture was stirred for 30 minutes. A solution of 11.5 g of 4-formylmorpholine solution in 20 ml of tetrahydrofuran was added. After stirring was continued at −78° C. for 1 hour, 1N-hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated. The residue was purified by silica gel column chromatography, to give 14.7 g of the title compound in the 4:1 hexane-ethyl acetate fraction.

Workup

  1. washwashed successively with 1N hydrochloric acid and saturated brine
  2. dry with materialAfter drying the organic layer over anhydrous magnesium sulfate
  3. customthe solvent was evaporated
  4. customThe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-80dcdd8f45a9408c89625a2b767ad208
Source dataset
uspto-grants-2009_06
Patent number
US07544835B2

Reaction notes

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