Pentafluoroiodobenzene → 2,3,4,5,6-Pentafluoro-2'-methoxy-5'-methyl-1,1'-biphenyl

HRID 1847102

Reaction equation

HRID 1847102 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([CH3:9])=[CH:5][C:4]=1B1OC(C)(C)C(C)(C)O1.I[C:20]1[C:25]([F:26])=[C:24]([F:27])[C:23]([F:28])=[C:22]([F:29])[C:21]=1[F:30]>C1(C)C=CC=CC=1.C(=O)([O-])[O-].[K+].[K+].[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.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:26][C:25]1[C:24]([F:27])=[C:23]([F:28])[C:22]([F:29])=[C:21]([F:30])[C:20]=1[C:4]1[CH:5]=[C:6]([CH3:9])[CH:7]=[CH:8][C:3]=1[O:2][CH3:1]

Participants

7

Reactant 2

HCID 70008PentafluoroiodobenzeneHCID 796621212-(2-Methoxy-5-methylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Product 1

HCID 573278032,3,4,5,6-Pentafluoro-2'-methoxy-5'-methyl-1,1'-biphenylYield 93%

Reagents, catalysts & solvents 4

HCID 74236Tetrabutylammonium BromideCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolventHCID 11430Potassium CarbonateSolvent

Procedure

Compound 5 (11.3 g, 45.54 mmol, 1 equiv) and iodopentafluorobenzene (10.6 g, 36.2 mmol, 1 equiv) were dissolved in toluene (200 mL) and 1.0M potassium carbonate solution (200 mL). Tetrabutylammonium bromide (1.6 g, 5 mmol, 0.11 equiv) was added and the solution sparged with nitrogen for 10 minutes. Tetrakis(triphenylphosphine)palladium(0) (2.63 g, 2.28 mmol, 0.05 equiv) was added and the reaction was refluxed for one day. The reaction was cooled to room temperature, then the layers were separated. The aqueous phase was back extracted with ethyl acetate (2×200 mL). Combined organic phases were combined, dried over sodium sulfate and concentrated under reduced pressure. The residue was purified over silica gel (200 g), eluting with heptanes to give 2,3,4,5,6-pentafluoro-2′-methoxy-5′-methyl-1,1′-biphenyl (6) (9.7 g, 74% yield) as a pale-yellow oil. This material contained a small amount of unreacted iodopentafluorobenzene which was identified by 19F NMR. The material was used subsequently.

Workup

  1. customthe solution sparged with nitrogen for 10 minutes
  2. temperaturethe reaction was refluxed for one day
  3. customthe layers were separated
  4. extractionThe aqueous phase was back extracted with ethyl acetate (2×200 mL)
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified over silica gel (200 g)
  8. washeluting with heptanes

Sources & evidence

ORD record
ord-e95ef93340a349c391c502c27ec4471d
Source dataset
uspto-grants-2015_02
Patent number
US08952114B2

Linked notes

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