Potassium Carbonate → tert-Butyl 4-(3,3,3-trifluoroprop-1-en-2-yl)phenylcarbamate

HRID 2197598Notes

Reaction equation

HRID 2197598 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[CH:4][CH:3]=1.C(=O)([O-])[O-].[K+].[K+].CC1(C)CC(C)OB([C:30]([C:32]([F:35])([F:34])[F:33])=[CH2:31])O1>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[F:33][C:32]([F:35])([F:34])[C:30]([C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[CH:4][CH:3]=1)=[CH2:31]

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 27736084-Bromoaniline, N-BOC protectedHCID 164142704,4,6-Trimethyl-2-(3,3,3-trifluoroprop-1-en-2-yl)-1,3,2-dioxaborinane2×

Product 1

HCID 86630282tert-Butyl 4-(3,3,3-trifluoroprop-1-en-2-yl)phenylcarbamateYield 69.4%

Reagents, catalysts & solvents 1

HCID 178418397HCID 178418397, compoundCatalyst

Procedure

To a mixture of tert-butyl 4-bromophenylcarbamate (1.67 g, 6.14 mmol), potassium carbonate (3.38 g, 24.46 mmol), and tetrakis(triphenylphosphine)palladium (365 mg, 0.316 mmol), was added 4,4,6-trimethyl-2-(3,3,3-trifluoroprop-1-en-2-yl)-1,3,2-dioxaborinane (1.64 g, 7.39 mmol), and degassed 1,2-dimethoxyethane (40 mL) and water (20 mL). The mixture for refluxed for 2 hours, cooled to ambient temperature, added more of 4,4,6-trimethyl-2-(3,3,3-trifluoroprop-1-en-2-yl)-1,3,2-dioxaborinane (475 mg, 2.14 mmol) and tetrakis(triphenylphosphine)palladium-(189 mg, 0.164 mmol), and refluxed for 5 hours. The reaction mixture was cooled to room temperature, filtered, diluted with water (200 mL), extracted twice with ethyl acetate (200 mL), washed with brine, dried (Na2SO4) and concentrated to an orange oil. The residue was purified by silica gel chromatography (AnaLogix® SF25-40G; 50 micron silica; eluted with 0-15% ethyl acetate in hexane at 30 mL/min) to provide the title compound (1.223 g, 4.26 mmol, 69.4% yield) as a yellow solid. 1H NMR (300 MHz, DMSO-d6) δ ppm 9.53 (s, 1H), 7.52 (d, J=8.8, 2H), 7.40 (d, J=8.4, 2H), 6.03-5.99 (m, 1H), 5.97-5.94 (m, 1H), 1.48 (s, 9H); MS (DCI/NH3) m/e 305 (M+NH4)+.

Workup

  1. customdegassed 1,2-dimethoxyethane (40 mL) and water (20 mL)
  2. temperatureThe mixture for refluxed for 2 hours
  3. temperaturerefluxed for 5 hours
  4. temperatureThe reaction mixture was cooled to room temperature
  5. filtrationfiltered
  6. additiondiluted with water (200 mL)
  7. extractionextracted twice with ethyl acetate (200 mL)
  8. washwashed with brine
  9. dry with materialdried (Na2SO4)
  10. concentrationconcentrated to an orange oil
  11. customThe residue was purified by silica gel chromatography (AnaLogix® SF25-40G; 50 micron silica; eluted with 0-15% ethyl acetate in hexane at 30 mL/min)

Sources & evidence

ORD record
ord-f3209763d32641529df0eaa50ca3ca31
Source dataset
uspto-grants-2012_12
Patent number
US08338603B2

Reaction notes

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