Tris(dimethylamino)borane → 1-Dimethylamino-4-(trifluoromethoxy)benzene

HRID 1420843Notes

Reaction equation

HRID 1420843 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][C:9]([F:12])([F:11])[F:10])=[CH:4][CH:3]=1.[CH3:13][N:14](B(N(C)C)N(C)C)[CH3:15].CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.O.C1(C)C=CC=CC=1P>[CH3:13][N:14]([CH3:15])[C:2]1[CH:7]=[CH:6][C:5]([O:8][C:9]([F:12])([F:11])[F:10])=[CH:4][CH:3]=1

Participants

7

Reactant 3

HCID 78081Tris(dimethylamino)boraneHCID 5210081-Bromo-4-(trifluoromethoxy)benzeneHCID 23676156Sodium t-butoxide

Product 1

HCID 187825851-Dimethylamino-4-(trifluoromethoxy)benzeneYield 29.3%

Reagents, catalysts & solvents 3

HCID 15049146(2-Methylphenyl)phosphaneCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

A mixture of 1-bromo-4-(trifluoromethoxy)benzene (2.41 g), tris(dimethylamino)borane (1.43 g), sodium t-butoxide (1.34 g), tris(dibenzylideneacetone)dipallidium (18 mg), and o-tolylphosphine (12 mg) in toluene (30 ml) was heated under reflux for 4 h. The mixture was cooled, diluted with water (30 mL) and extracted with ethyl acetate (3×10 mL). The combined organic fractions were washed with brine, dried (MgSO4) and the solvent was evaporated under reduced pressure. The residue was purified by chromatography on silica gel, eluting with hexane/EtOAc (99:1 increasing to (95:5) to give the title compound as an oil (600 mg). 1H NMR (360 MHz, CDCl3) δ2.95 (6 H, s), 6.66 (2 H, d, J 9 Hz), and 7.08 (2 H, d, J 8.5 Hz). m/z (ES+) m/z 206 (M+1).

Workup

  1. temperaturewas heated
  2. temperatureunder reflux for 4 h
  3. temperatureThe mixture was cooled
  4. extractionextracted with ethyl acetate (3×10 mL)
  5. washThe combined organic fractions were washed with brine
  6. dry with materialdried (MgSO4)
  7. customthe solvent was evaporated under reduced pressure
  8. customThe residue was purified by chromatography on silica gel
  9. washeluting with hexane/EtOAc (99:1 increasing to (95:5)

Sources & evidence

ORD record
ord-93bbbba332ef4812bb4992a04fb3d4fc
Source dataset
uspto-grants-2000_06
Patent number
US06071927

Reaction notes

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