Aniline → (3-Methyl-2-nitrophenyl)phenylamine

HRID 242772Notes

Reaction equation

Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([CH3:8])[C:3]=1[N+:9]([O-:11])=[O:10].[C:12]1([NH2:18])[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C([O-])([O-])=O.[Cs+].[Cs+]>C1(C)C=CC=CC=1.CC([O-])=O.CC([O-])=O.[Pd+2].C1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:8][C:4]1[C:3]([N+:9]([O-:11])=[O:10])=[C:2]([NH:18][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH:7]=[CH:6][CH:5]=1

Participants

Conditions

Temperature: 110 °C

Procedure

A mixture of 1-bromo-3-methyl-2-nitrobenzene (1 g, 4.63 mmol), phenylamine (422 μL, 4.63 mmol), Cs2CO3 (2.11 g, 6.48 mmol) and (R)-BINAP (5 mol %, 143 mg, 0.23 mmol) in toluene (20 mL) was degassed with a stream of nitrogen prior to addition of Pd(OAc)2 (25 mg, 0.11 mmol) and was stirred at 110° C. under a nitrogen atmosphere for 18 h. After cooling to RT, the mixture was partitioned between EtOAc and water. The organic layer was washed with brine, then dried (Na2SO4) and concentrated in vacuo. The resulting residue was purified by column chromatography (Si—PCC, gradient 0-35% DCM in cyclohexane) affording (3-Methyl-2-nitrophenyl)phenylamine as a red oil (931 mg, 88%). LCMS: RT 3.97 min [M+H]+ 229.1.

Workup

customwas degassed with a stream of nitrogen
temperatureAfter cooling to RT
customthe mixture was partitioned between EtOAc and water
washThe organic layer was washed with brine
dry with materialdried (Na2SO4)
concentrationconcentrated in vacuo
customThe resulting residue was purified by column chromatography (Si—PCC, gradient 0-35% DCM in cyclohexane)

Sources & evidence

ORD record: ord-6970c8b8c212497992ab4d54a1cb1d73
Source dataset: uspto-grants-2014_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08653089B2

Reaction notes

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