3-Bromo-4-fluoro-α,α-dimethylbenzeneacetaldehyde → 3-Bromo-4-fluoro-α,β,β-trimethylbenzeneethanol

HRID 83879Notes

Reaction equation

HRID 83879 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([C:9]([CH3:13])([CH3:12])[CH:10]=[O:11])[CH:5]=[CH:6][C:7]=1[F:8].[CH3:14][Mg+].[Br-]>C1COCC1>[Br:1][C:2]1[CH:3]=[C:4]([C:9]([CH3:13])([CH3:12])[CH:10]([OH:11])[CH3:14])[CH:5]=[CH:6][C:7]=1[F:8]

Participants

4

Reactant 2

HCID 866622533-Bromo-4-fluoro-α,α-dimethylbenzeneacetaldehydeHCID 178418689HCID 178418689, compound

Product 1

HCID 667406943-Bromo-4-fluoro-α,β,β-trimethylbenzeneethanolYield 66.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of 2-(3-bromo-4-fluorophenyl)-2-methylpropanal (27 g, 110 mmol) in anhyd THF (300 mL) at 0° C. was added MeMgBr (3M in ether, 73 mL, 220 mmol, 2 eq) dropwise over 2 h. After stirring 1 h, the reaction was allowed to warm to room temperature, quenched carefully with 1N HCl and extracted with EtOAc. The combined extracts were washed with brine, dried over MgSO4 and evaporated in vacuo. The residue was purified by column chromatography (Hex/EA=10:1) to give 3-(3-bromo-4-fluorophenyl)-3-methylbutan-2-ol (19 g, 66%). 1H NMR (400 MHz, CDCl3) δ 7.56-7.54 (m, 1H), 7.32-7.28 (m, 1H), 7.07 (t, J=8.4 Hz, 1H), 3.84-3.79 (m, 1H), 1.31 (d, J=6.4 Hz, 6H), 1.04 (d, J=6.4 Hz, 3H).

Workup

  1. customquenched carefully with 1N HCl
  2. extractionextracted with EtOAc
  3. washThe combined extracts were washed with brine
  4. dry with materialdried over MgSO4
  5. customevaporated in vacuo
  6. customThe residue was purified by column chromatography (Hex/EA=10:1)

Sources & evidence

ORD record
ord-b22d1495983047c09d7db351726284bb
Source dataset
uspto-grants-2014_09
Patent number
US08846739B2

Reaction notes

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