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

HRID 242772

反応式

HRID 242772 の反応式
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

参加物

7

反応物 3

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

生成物 1

HCID 10704534(3-Methyl-2-nitrophenyl)phenylamine収率 88.1%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 634876Binap, (A+-)-触媒HCID 1140Toluene溶媒

反応条件

温度
110 °C

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-6970c8b8c212497992ab4d54a1cb1d73
出典データセット
uspto-grants-2014_02
特許番号
US08653089B2

関連ノート

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