P-Anisidine → 4-methoxy-N-(4-nitrophenyl)aniline

HRID 1879546Notes

Reaction equation

HRID 1879546 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1.[CH3:11][O:12][C:13]1[CH:19]=[CH:18][C:16]([NH2:17])=[CH:15][CH:14]=1>O1CCOCC1.CCOCC.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>[CH3:11][O:12][C:13]1[CH:19]=[CH:18][C:16]([NH:17][C:2]2[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=2)=[CH:15][CH:14]=1

Participants

7

Reactant 2

HCID 7732P-AnisidineHCID 114661-Bromo-4-nitrobenzene

Product 1

HCID 27480234-methoxy-N-(4-nitrophenyl)anilineYield 58.5%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 634876Binap, (A+-)-CatalystHCID 3283Diethyl EtherSolventHCID 312751,4-DioxaneSolvent2×

Procedure

A mixture of palladium acetate (37 mg, 0.165 mmol) and BINAP (154 mg, 0.248 mmol) in 5 mL dioxane was stirred for 10 min under Ar atmosphere. To this mixture was added 1-bromo-4-nitrobenzene (1.11 g, 5.5 mmol), 4-methoxyaniline (745 mg, 6.07 mmol), CsCO3 (2.5 g, 7.73 mmol), and 10 mL of dioxane. The mixture was heated at reflux for 15 h and cooled and diluted with ether (80 mL). The solid was removed through filtration and the filtrate was concentrated. The residue was chromatographed (hexane/EtOAc) to afford 4-methoxy-N-(4-nitrophenyl)aniline as a yellow solid (786 mg, 58%). MS (ESI) m/z 245 (M+H+).

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 15 h
  3. temperaturecooled
  4. customThe solid was removed through filtration
  5. concentrationthe filtrate was concentrated
  6. customThe residue was chromatographed (hexane/EtOAc)

Sources & evidence

ORD record
ord-2c2d9dc39d0d474a85061a120a39d396
Source dataset
uspto-grants-2012_11
Patent number
US08318132B2

Reaction notes

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