Methyl iodide → (4-Bromo-2-chlorophenyl)methanol

HRID 2076617Notes

Reaction equation

HRID 2076617 reaction equation
C(=O)([O-])[O-].[K+].[K+].CI.[Br:9][C:10]1[CH:18]=[CH:17][C:13]([C:14](O)=[O:15])=[C:12]([Cl:19])[CH:11]=1.[H-].C([Al+]CC(C)C)C(C)C.O.O.O.O.O.O.O.O.O.O.S([O-])([O-])(=O)=O.[Na+].[Na+].S([O-])([O-])(=O)=O.[Mg+2]>CN(C)C=O.C1(C)C=CC=CC=1.O>[Br:9][C:10]1[CH:18]=[CH:17][C:13]([CH2:14][OH:15])=[C:12]([Cl:19])[CH:11]=1

Participants

10

Reactant 6

HCID 6328Methyl iodideHCID 11430Potassium CarbonateHCID 24083Sulfuric acid magnesium salt (1:1)HCID 62649Sodium sulfate decahydrateHCID 1088294-Bromo-2-chlorobenzoic acidHCID 21225700Diisobutylaluminumhydride

Product 1

HCID 43805739(4-Bromo-2-chlorophenyl)methanol

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 6228DimethylformamideSolvent

Procedure

Potassium carbonate (1.38 g, 10 mmol) and methyl iodide (0.623 ml, 10 mmol) were added to a solution of 4-bromo-2-chlorobenzoic acid (2.0 g, 8.5 mmol) in N,N-dimethylformamide (8 ml) under ice-cooling, and the mixture was stirred at room temperature for 3 hours. After the reaction mixture was poured into water and the mixture was extracted with ethyl acetate, the organic layer was successively washed with water and a saturated aqueous NaCl solution and dried with anhydrous sodium sulfate. The solvent was removed under reduced pressure to give an oily residue. After diisobutyl aluminum hydride-11.0M toluene solution (24 ml, 24 mmol) was added dropwise to a solution of the obtained residue in toluene (30 ml) at −78° C., the temperature of the mixture was raised to room temperature over 3 hours. After sodium sulfate decahydrate (12 g) was added to the reaction mixture and the mixture was stirred at room temperature for 30 minutes, Celite (12 g) and anhydrous magnesium sulfate (12 g) were added thereto and the mixture was stirred at room temperature for 30 minutes. After the insolubles were removed by filtration, the solvent was removed from the obtained filtrate under reduced pressure to give crudely purified (4-bromo-2-chlorophenyl)methanol as a solid. According to a method similar to Example (17-1), from crude (4-bromo-2-chlorophenyl)methanol obtained in the above, (4-bromo-2-chlorophenyl)acetonitrile was obtained as a pale yellow solid (1.4 g, yield: 71%).

Workup

  1. temperaturecooling
  2. extractionthe mixture was extracted with ethyl acetate
  3. washthe organic layer was successively washed with water
  4. dry with materiala saturated aqueous NaCl solution and dried with anhydrous sodium sulfate
  5. customThe solvent was removed under reduced pressure
  6. customto give an oily residue
  7. temperaturethe temperature of the mixture was raised to room temperature over 3 hours
  8. stirringthe mixture was stirred at room temperature for 30 minutes
  9. stirringthe mixture was stirred at room temperature for 30 minutes
  10. customAfter the insolubles were removed by filtration
  11. customthe solvent was removed from the obtained filtrate under reduced pressure

Sources & evidence

ORD record
ord-0d6f273ec93c4ebd9c478fd9d33fafb7
Source dataset
uspto-grants-2011_04
Patent number
US07923573B2

Reaction notes

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