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

HRID 572515
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HRID 572515 반응식
[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]
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참가 물질

8

반응물 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

생성물 1

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

시약·촉매·용매 3

HCID 167845palladium(II) acetate촉매HCID 3283Diethyl Ether용매HCID 312751,4-Dioxane용매

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온도
100 °C

실험 절차

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).

후처리

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

출처 및 근거

ORD 기록
ord-605ae13b083044e0b0ec092ea85d7b58
출처 데이터셋
uspto-grants-2015_05
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US09029391B2

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