Hexane → alpha-(4-Bromophenyl)-3-(tert-butyldimethylsilyloxy)benzyl alcohol

HRID 2036159Notes

Reaction equation

HRID 2036159 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:13]=[CH:14][CH:15]=1)[O:5][Si:6]([C:9]([CH3:12])([CH3:11])[CH3:10])([CH3:8])[CH3:7].C([Li])CCC.CCCCCC.[Br:27][C:28]1[CH:35]=[CH:34][C:31]([CH:32]=[O:33])=[CH:30][CH:29]=1>O1CCCC1>[Br:27][C:28]1[CH:35]=[CH:34][C:31]([CH:32]([OH:33])[C:2]2[CH:15]=[CH:14][CH:13]=[C:4]([O:5][Si:6]([C:9]([CH3:12])([CH3:11])[CH3:10])([CH3:8])[CH3:7])[CH:3]=2)=[CH:30][CH:29]=1

Participants

6

Reactant 4

HCID 8058HexaneHCID 707414-BromobenzaldehydeHCID 11254705(3-Bromophenoxy)(tert-butyl)dimethylsilaneHCID 178418339Butyllithium

Product 1

HCID 53744634alpha-(4-Bromophenyl)-3-(tert-butyldimethylsilyloxy)benzyl alcoholYield 98.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

3-Bromophenoxy-tert-butyldimethylsilane (146 g, 0.51 mol, Example 1, infra) was dissolved in dry tetrahydrofuran under nitrogen and cooled to −78° C. A solution of 1.6 M n-butyllithium in hexane (318 mL, 0.51 mol) was added dropwise at a rate to maintain temperature below −70° C. The reaction was stirred for 30 minutes after the addition was complete, and the cold solution was transferred to another vessel containing a cold (−78° C.) solution of 4-bromobenzaldehyde (94.3 g, 0.51 mol) in 1000 mL of dry tetrahydrofuran under nitrogen. The transfer rate was monitored to maintain reaction temperature below −70° C. The reaction mixture was stirred for another 45 minutes at −78° C. and then quenched with 100 mL of saturated aqueous ammonium chloride. After warming to room temperature, the mixture was diluted with 2000 mL of diethyl ether and washed with 2000 mL of water followed by 500 mL of saturated sodium chloride. The ethereal solution was dried over sodium sulfate and the solvent removed to give 197.2 g of crude α-(4-bromophenyl)-3-(tert-butyldimethylsilyloxy)benzyl alcohol as a yellow oil.

Workup

  1. temperatureto maintain temperature below −70° C
  2. additionafter the addition
  3. customthe cold solution was transferred to another vessel
  4. temperatureto maintain
  5. customreaction temperature below −70° C
  6. stirringThe reaction mixture was stirred for another 45 minutes at −78° C.
  7. customquenched with 100 mL of saturated aqueous ammonium chloride
  8. temperatureAfter warming to room temperature
  9. additionthe mixture was diluted with 2000 mL of diethyl ether
  10. washwashed with 2000 mL of water
  11. dry with materialThe ethereal solution was dried over sodium sulfate
  12. customthe solvent removed

Sources & evidence

ORD record
ord-7e2a685d31ca4900a47418044f13da9d
Source dataset
uspto-grants-2013_11
Patent number
US08575169B2

Reaction notes

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