Water → ethyl (Z)-2-ethoxy-3-[4-(6-methylaminopyrid-2-yl)phenyl]acrylate

HRID 390587노트

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HRID 390587 반응식
[CH2:1]([O:3]/[C:4](=[CH:10]\[C:11]1[CH:16]=[CH:15][C:14](B2OC(C)(C)C(C)(C)O2)=[CH:13][CH:12]=1)/[C:5]([O:7][CH2:8][CH3:9])=[O:6])[CH3:2].[CH3:26][NH:27][C:28]1[N:33]=[C:32](Br)[CH:31]=[CH:30][CH:29]=1.[F-].[Cs+].O>COCCOCCOC.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(OCC)(=O)C>[CH2:1]([O:3]/[C:4](=[CH:10]\[C:11]1[CH:12]=[CH:13][C:14]([C:32]2[CH:31]=[CH:30][CH:29]=[C:28]([NH:27][CH3:26])[N:33]=2)=[CH:15][CH:16]=1)/[C:5]([O:7][CH2:8][CH3:9])=[O:6])[CH3:2]

참가 물질

8

반응물 4

HCID 962WaterHCID 25953Cesium fluorideHCID 134703156-bromo-N-methylpyridin-2-amineHCID 86626073ethyl (Z)-2-ethoxy-3-[4-(4,4,5,5-tetramethyl[1.3]dioxaborolan-2-yl)phenyl]acrylate

생성물 1

HCID 86626072ethyl (Z)-2-ethoxy-3-[4-(6-methylaminopyrid-2-yl)phenyl]acrylate수율 76.6%

시약·촉매·용매 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)촉매HCID 8150Diglyme용매HCID 8857Ethyl Acetate용매

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온도
80 °C

실험 절차

1.0 g (2.9 mmol) of ethyl (Z)-2-ethoxy-3-[4-(4,4,5,5-tetramethyl[1.3]dioxaborolan-2-yl)phenyl]acrylate, 0.4 g (2.4 mmol) of 6-methylamino-2-bromopyridine and 1.1 g (7.2 mmol) of caesium fluoride are dissolved in 60 mL of diethylene glycol dimethyl ether. After bubbling nitrogen through the reaction mixture for 20 minutes, 0.1 g (0.15 mmol) of dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium is added. The reaction mixture is heated at 80° C. for 18 hours with vigorous stirring. After cooling, the reaction is worked up by addition of 60 mL of water and extraction with ethyl acetate. The organic phases are combined, washed with saturated aqueous sodium chloride solution and then dried over magnesium sulfate. After filtration, the solvents are evaporated off. The crude product obtained is purified by chromatography on a column of silica eluted with a 90/10 heptane/ethyl acetate mixture to give 0.6 g (76%) of ethyl (Z)-2-ethoxy-3-[4-(6-methylaminopyrid-2-yl)phenyl]acrylate.

후처리

  1. customAfter bubbling nitrogen through the reaction mixture for 20 minutes
  2. temperatureAfter cooling
  3. washwashed with saturated aqueous sodium chloride solution
  4. dry with materialdried over magnesium sulfate
  5. filtrationAfter filtration
  6. customthe solvents are evaporated off
  7. customThe crude product obtained
  8. customis purified by chromatography on a column of silica
  9. washeluted with a 90/10 heptane/ethyl acetate mixture

출처 및 근거

ORD 기록
ord-5c44d422ad654f2d83632f33b4849ee6
출처 데이터셋
uspto-grants-2013_02
특허 번호
US08383652B2

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