Diisopropyl Ether → 1,2-Dichloro-3-(trifluoromethyl)-5-[1-(trifluoromethyl)ethenyl]benzene

HRID 885823Notes

Reaction equation

HRID 885823 reaction equation
Br[C:2]1[CH:3]=[C:4]([Cl:13])[C:5]([Cl:12])=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:7]=1.C(OC(C)C)(C)C.C([Li])CCC.COB(OC)OC.Br[C:34]([C:36]([F:39])([F:38])[F:37])=[CH2:35].C(=O)([O-])[O-].[K+].[K+]>CCCCCC.O1CCCC1.CC(C1C=CC=C(C(C)C)C=1N1C(=[Pd])N(C2C(C(C)C)=CC=CC=2C(C)C)C=C1)C.CC(C1C=CC=C(C(C)C)C=1N1C(=[Pd])N(C2C(C(C)C)=CC=CC=2C(C)C)C=C1)C.C1C=C2C(C(C=CC2=O)=O)=CC=1.C1C=C2C(C(C=CC2=O)=O)=CC=1.C(OCC)(=O)C.O>[Cl:13][C:4]1[CH:3]=[C:2]([C:34]([C:36]([F:39])([F:38])[F:37])=[CH2:35])[CH:7]=[C:6]([C:8]([F:11])([F:10])[F:9])[C:5]=1[Cl:12]

Participants

12

Reactant 6

HCID 7914Diisopropyl EtherHCID 8470Trimethyl borateHCID 11430Potassium CarbonateHCID 2726961-Propene, 2-bromo-3,3,3-trifluoro-HCID 250672915-Bromo-1,2-dichloro-3-(trifluoromethyl)benzeneHCID 178418339Butyllithium

Product 1

HCID 866433841,2-Dichloro-3-(trifluoromethyl)-5-[1-(trifluoromethyl)ethenyl]benzeneYield 79.1%

Reagents, catalysts & solvents 5

HCID 111824871,3-Bis(2,6-diisopropylphenyl)imidazol-2-ylidene(1,4-naphthoquinone)palladium(0) dimerCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a stirred solution of 5-bromo-2,3-dichlorobenzotrifluoride (26.2 g) and diisopropyl ether (9.1 g) in hexane (250 mL) at −10° C. was added dropwise 1.55M n-butyllithium in hexane (57.5 mL). After stirring at same temperature for 0.5 hour, trimethoxyborane (9.26 g) in tetrahydrofuran (30 mL) was added dropwise. After a further 10 minutes, water (150 mL), 2-bromo-3,3,3-trifluoropropene (23.4 g), potassium carbonate (36.9 g) and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene(1,4-naphthoquinone)palladium(0) dimer (0.131 g) were added to the reaction mixture, which was stirred at 60° C. for 4 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, poured into ice-water (50 mL) and ethyl acetate (75 mL) and filtered. The filtrate was separated, and the organic layer was washed with water and brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure to provide a residue. The residue was purified by column chromatography on silica gel eluted with hexane to afford the title compound as a colorless oil (21.8 g).

Workup

  1. waitAfter a further 10 minutes
  2. stirringwas stirred at 60° C. for 4 hours
  3. customAfter the completion of the reaction
  4. filtrationfiltered
  5. customThe filtrate was separated
  6. washthe organic layer was washed with water and brine
  7. dry with materialdried over anhydrous sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customto provide a residue
  10. customThe residue was purified by column chromatography on silica gel
  11. washeluted with hexane

Sources & evidence

ORD record
ord-908b124911474cbf91b3c2baae6d9605
Source dataset
uspto-grants-2012_08
Patent number
US08242283B2

Reaction notes

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