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3,4-Dimethylaniline → Methyl 4-[(3,4-dimethylphenyl)amino]-2-methyl-1-oxo-1,2-dihydro-3-isoquinolinecarboxylate

HRID 572515
ノート
印刷プレビュー

反応式

HRID 572515 の反応式
[CH3:1][N:2]1[C:11]([C:12]([O:14][CH3:15])=[O:13])=[C:10](OS(C(F)(F)F)(=O)=O)[C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[C:3]1=[O:24].[CH3:25][C:26]1[CH:27]=[C:28]([NH2:33])[CH:29]=[CH:30][C:31]=1[CH3:32].C(=O)([O-])[O-].[Cs+].[Cs+].CC1C2OC3C(=CC=CC=3)CC=2C(P(C2C=CC=CC=2)C2C=CC=CC=2)=C(P(C2C=CC=CC=2)C2C=CC=CC=2)C=1C>O1CCOCC1.C(OCC)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:25][C:26]1[CH:27]=[C:28]([NH:33][C:10]2[C:9]3[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=3)[C:3](=[O:24])[N:2]([CH3:1])[C:11]=2[C:12]([O:14][CH3:15])=[O:13])[CH:29]=[CH:30][C:31]=1[CH3:32]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

8

反応物 4

HCID 72483,4-DimethylanilineHCID 10796Cesium carbonateHCID 57370308Dimethyl bis diphenylphosphino xantheneHCID 86700721Methyl 2-methyl-1-oxo-4-{[(trifluoromethyl)sulfonyl]oxy}-1,2-dihydro-3-isoquinolinecarboxylate

生成物 1

HCID 68295443Methyl 4-[(3,4-dimethylphenyl)amino]-2-methyl-1-oxo-1,2-dihydro-3-isoquinolinecarboxylate収率 76.3%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 3283Diethyl Ether溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
100 °C

実験手順

To a solution of methyl 2-methyl-1-oxo-4-{[(trifluoromethyl)sulfonyl]oxy}-1,2-dihydro-3-isoquinolinecarboxylate (0.84 g, 2.3 mmol) and (3,4-dimethylphenyl)amine (0.362 g, 2.99 mmol) in 1,4-dioxane (25 mL) under nitrogen was added cesium carbonate (1.124 g, 3.45 mmol), dimethylbisdiphenylphosphinoxanthene (0.103 g, 0.172 mmol) and Pd(OAc)2 (0.026 g, 0.115 mmol) and the mixture was stirred at 100° C. for 16 hours. The mixture was diluted with diethyl ether, filtered through Celite and the filter cake was washed with diethyl ether. The crude product was purified on silica using EtOAc/hexanes 10-30% to provide the title compound as a yellow solid (0.59 g, 74%). 1H NMR (400 MHz, CDCl3) δ ppm 8.48 (dd, J=1.2, 5.9 Hz, 1 H), 7.69-7.52 (m, 3 H), 6.89 (d, J=8.2 Hz, 1 H), 6.55-6.29 (m, 2 H), 5.66 (s, 1 H), 3.86 (s, 3 H), 3.62-3.51 (m, 3 H), 3.57 (s, 4 H), 2.14 (s, 9 H), 2.24-2.07 (m, 6 H), 1.56 (s, 3 H);); ES-LCMS: 337.3 (M+1).

後処理

  1. filtrationfiltered through Celite
  2. washthe filter cake was washed with diethyl ether
  3. customThe crude product was purified on silica

出典と根拠

ORDレコード
ord-605ae13b083044e0b0ec092ea85d7b58
出典データセット
uspto-grants-2015_05
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09029391B2

反応ノート

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