1-Chloro-4-nitrobenzene → 4-Methoxy-4'-nitrobiphenyl

HRID 493511Notes

Reaction equation

HRID 493511 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6](B(O)O)=[CH:5][CH:4]=1.Cl[C:13]1[CH:18]=[CH:17][C:16]([N+:19]([O-:21])=[O:20])=[CH:15][CH:14]=1.[F-].[Cs+]>C(#N)C.O.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>[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:13]2[CH:18]=[CH:17][C:16]([N+:19]([O-:21])=[O:20])=[CH:15][CH:14]=2)=[CH:5][CH:4]=1

Participants

6

Reactant 3

HCID 74741-Chloro-4-nitrobenzeneHCID 25953Cesium fluorideHCID 201262(4-Methoxyphenyl)boronic acid

Product 1

HCID 111280794-Methoxy-4'-nitrobiphenylYield 81.7%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 18373917Acetonitrile--water (1/1)Solvent

Procedure

A mixture of 4-methoxyphenylboronic acid (3.70 g, 24.3 mmol), 1-chloro-4-nitrobenzene (3.84 g, 24.3 mmol) and cesium fluoride (7.40 g, 48.7 mmol) in 150 mL of 2:1 acetonitrile-water was degassed under vacuum for 20 minutes. Tetrakis(triphenylphosphine)palladium(0) (844.0 mg, 0.73 mmol) was added and the reaction refluxed for 3 h. The solvent was removed under reduced pressure and the residue partitioned between methylene chloride and water. The organic phase was separated, dried (Na2SO4) and the solvent removed under reduced pressure. Purification of the residue on silica gel using 5% ethyl acetate hexanes as the eluent gave 4′-methoxy-4-nitro-biphenyl (4.55 g, 81%).

Workup

  1. customwas degassed under vacuum for 20 minutes
  2. temperaturethe reaction refluxed for 3 h
  3. customThe solvent was removed under reduced pressure
  4. customthe residue partitioned between methylene chloride and water
  5. customThe organic phase was separated
  6. dry with materialdried (Na2SO4)
  7. customthe solvent removed under reduced pressure
  8. customPurification of the residue on silica gel using 5% ethyl acetate hexanes as the eluent

Sources & evidence

ORD record
ord-db7a25c0cd4c4212bc8f6abb303445a7
Source dataset
uspto-grants-2009_05
Patent number
US07534894B2

Reaction notes

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