Borane → 3-Bromo-5-chlorophenol

HRID 1044702

Reaction equation

HRID 1044702 reaction equation
CP(C)CCP(C)C.[Br:9][C:10]1[CH:11]=[C:12]([Cl:16])[CH:13]=[CH:14][CH:15]=1.[B]1OC(C)(C)C(C)(C)[O:18]1.B.OOS([O-])=O.[K+]>CC(C)=O.O.C1CC=CCCC=C1.C1C=C[C]2[CH][CH][CH][C]2C=1.[Ir]>[Br:9][C:10]1[CH:15]=[C:14]([OH:18])[CH:13]=[C:12]([Cl:16])[CH:11]=1

Participants

9

Reactant 5

HCID 6331BoraneHCID 79281-Bromo-3-chlorobenzeneHCID 1410591,2-Bis(dimethylphosphino)ethaneHCID 6364989PinacolboraneHCID 23707502Potassium hydroxy sulfite

Product 1

HCID 226301803-Bromo-5-chlorophenolYield 62%

Reagents, catalysts & solvents 3

HCID 178420247(1,5-cyclooctadiene)-eta5-indenyl)iridium(I)CatalystHCID 180AcetoneSolventHCID 962WaterSolvent

Conditions

Temperature
150 °C

Procedure

Under an atmosphere of dry nitrogen, 103 mg 1,5-cyclooctadiene(H5-indenyl)iridium (I) was put in a 25 mL Pyrex bottle. Subsequently were added 0.04 mL 1,2-bis(dimethylphosphino)ethane, 0.61 mL 3-bromochlorobenzene and 1.52 mL pinacolborane. The mixture was stirred at 150° C. for 3.5 h. After cooling to room temperature, the borane adduct was taken up in 17 mL acetone to give a clear solution. This solution was added slowly to 17.41 mL of a 0.30 M solution of oxone in water cooled in an ice bath. The mixture was stirred vigorously for 15 min. at room temperature and extracted three times with DCM. The combined organic phases were dried over Na2SO4 and evaporated to dryness. The residue was purified by flash chromatography (DCM) to yield 750 mg (62%) of a beige solid. 1H NMR complies with known data (compound (I), Maleczka, 2003).

Workup

  1. temperatureAfter cooling to room temperature
  2. customto give a clear solution
  3. temperaturecooled in an ice bath
  4. stirringThe mixture was stirred vigorously for 15 min. at room temperature
  5. extractionextracted three times with DCM
  6. dry with materialThe combined organic phases were dried over Na2SO4
  7. customevaporated to dryness
  8. customThe residue was purified by flash chromatography (DCM)

Sources & evidence

ORD record
ord-2b79712341fa47a1a049f74f73b13afe
Source dataset
uspto-grants-2013_10
Patent number
US08563723B2

Linked notes

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