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

HRID 242772

반응식

HRID 242772 반응식
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

참가 물질

7

반응물 3

HCID 6115AnilineHCID 10796Cesium carbonateHCID 142929Benzene, 1-bromo-3-methyl-2-nitro-

생성물 1

HCID 10704534(3-Methyl-2-nitrophenyl)phenylamine수율 88.1%

시약·촉매·용매 3

HCID 167845palladium(II) acetate촉매HCID 634876Binap, (A+-)-촉매HCID 1140Toluene용매

반응 조건

온도
110 °C

실험 절차

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.

후처리

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

출처 및 근거

ORD 기록
ord-6970c8b8c212497992ab4d54a1cb1d73
출처 데이터셋
uspto-grants-2014_02
특허 번호
US08653089B2

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