Triethylamine → 2-(2-Nitrophenyl)-4-fluoroanisole

HRID 1824318Notes

Reaction equation

HRID 1824318 reaction equation
[F:1][C:2]1[CH:3]=[C:4](B(O)O)[C:5]([O:8][CH3:9])=[CH:6][CH:7]=1.[N+:13]([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1Br)([O-:15])=[O:14].C(N(CC)CC)C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CN(C)C=O>[N+:13]([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1[C:4]1[CH:3]=[C:2]([F:1])[CH:7]=[CH:6][C:5]=1[O:8][CH3:9])([O-:15])=[O:14]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 113411-Bromo-2-nitrobenzeneHCID 27826735-Fluoro-2-methoxyphenylboronic acid

Product 1

HCID 221477232-(2-Nitrophenyl)-4-fluoroanisoleYield 172.4%

Reagents, catalysts & solvents 3

HCID 11776TriphenylphosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 4-fluoroanisole-2-boronic acid (3.3 g, 19.4 mmol), 2-nitrobromobenzene (3.56 g, 17.6 mmol), triphenylphosphine (367 mg, 1.4 mmol), triethylamine (4.6 g, 45.8 mmol), and 40 mL of dimethylformamide was sparged with nitrogen for 5 minutes before adding palladium acetate (160 mg, 0.7 mmol) and heating the mixture to 100° C. for 5 hours. The reaction was cooled and concentrated in vacuo. The residue was partitioned between ethyl acetate and water. The organic layer was shaken with 0.1N sodium hydroxide, dried over magnesium sulfate, filtered, and concentrated in vacuo. The crude product was purified via flash silica gel chromatography eluting with 2% ethyl acetate/hexanes followed by 4% ethyl acetate/hexanes to give 7.5 g of the title compound. Yield: 86%. EA. MS(FD).

Workup

  1. customwas sparged with nitrogen for 5 minutes
  2. temperatureThe reaction was cooled
  3. concentrationconcentrated in vacuo
  4. customThe residue was partitioned between ethyl acetate and water
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe crude product was purified via flash silica gel chromatography
  9. washeluting with 2% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-631a43120c29464a97e372d48c34562d
Source dataset
uspto-grants-2006_05
Patent number
US07041684B2

Reaction notes

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