Dichloromethane → 2-((4-amino-3-(3-aminophenyl)-1H-pyrazolo[3,4-d]pyrimidin-1-yl)methyl)-3-phenyl-4H-chromen-4-one

HRID 239675

Reaktionsgleichung

Reaktionsgleichung von HRID 239675
[NH2:1][C:2]1[N:7]=[CH:6][N:5]=[C:4]2[N:8]([CH2:12][C:13]3[O:14][C:15]4[C:20]([C:21](=[O:29])[C:22]=3[C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)=[CH:19][CH:18]=[CH:17][CH:16]=4)[N:9]=[C:10](I)[C:3]=12.C([NH:33][C:34]1[CH:35]=[C:36](B(O)O)[CH:37]=[CH:38][CH:39]=1)(=O)C.C(=O)([O-])[O-].[Na+].[Na+].ClCCl>CN(C=O)C.C(O)C.O>[NH2:1][C:2]1[N:7]=[CH:6][N:5]=[C:4]2[N:8]([CH2:12][C:13]3[O:14][C:15]4[C:20]([C:21](=[O:29])[C:22]=3[C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)=[CH:19][CH:18]=[CH:17][CH:16]=4)[N:9]=[C:10]([C:38]3[CH:37]=[CH:36][CH:35]=[C:34]([NH2:33])[CH:39]=3)[C:3]=12

Komponenten

8

Edukt 4

HCID 6344DichloromethaneHCID 10340Sodium CarbonateHCID 157274(3-Acetamidophenyl)boronic acidHCID 582691472-((4-Amino-3-iodo-1H-pyrazolo[3,4-d]pyrimidin-1-yl)methyl)-3-phenyl-4H-chromen-4-one

Produkt 1

HCID 582693132-((4-amino-3-(3-aminophenyl)-1H-pyrazolo[3,4-d]pyrimidin-1-yl)methyl)-3-phenyl-4H-chromen-4-oneAusbeute 38 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 702EthanolLösungsmittelHCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

To a solution of Example 57a (0.400 g, 0.804 mmoles) in DMF (10 ml), ethanol (5 ml) and water (5 ml), 3-Acetamidophenyl boronic acid (0.187 g, 1.045 mmoles) and sodium carbonate (0.426 g, 4.02 mmoles) were added and the system is degassed for 30 min. Palladium tetrakis triphenylphosphine (0.183 g, 0.158 mmoles) was added under nitrogen atmosphere and heated to 80° C. After 12 h, the reaction mixture was celite filtered, concentrated and extracted with ethyl acetate. The organic layer was dried over sodium sulphate and concentrated under reduced pressure. To the concentrate ethanol (5 ml) and Con.HCl (0.5 ml) were added and refluxed for 2 h. The reaction mixture was basified with sodium carbonate solution and extracted with ethyl acetate. The organic layer was dried over sodium sulphate and concentrated under reduced pressure. The crude product was purified by column chromatography with methanol: dichloromethane to afford the title compound as yellow solid (0.140 g, 38% yield). MP: 157-159° C. 1H-NMR (δ ppm, DMSO-d6, 400 MHz): δ 8.21(s,1H), 8.06(dd, J=7.8,1.3 Hz, 1H),7.77(dt, J=8.6,1.5 Hz, 1H),7.49(t, J=7.4 Hz, 1H),7.37-7.29(m,5H), 7.17(t, J=7.7 Hz, 1H), 6.84(s,1H), 6.71(d, J=7.5 Hz, 1H),6.65(d, J=7.9 Hz, 1H), 5.51(s,2H), 5.34(s, 2H). Mass: 460.84(M+).

Aufarbeitung

  1. customthe system is degassed for 30 min
  2. concentrationconcentrated
  3. extractionextracted with ethyl acetate
  4. dry with materialThe organic layer was dried over sodium sulphate
  5. concentrationconcentrated under reduced pressure
  6. additionHCl (0.5 ml) were added
  7. temperaturerefluxed for 2 h
  8. extractionextracted with ethyl acetate
  9. dry with materialThe organic layer was dried over sodium sulphate
  10. concentrationconcentrated under reduced pressure
  11. customThe crude product was purified by column chromatography with methanol

Quellen und Nachweise

ORD-Eintrag
ord-9a503c44c3654cd8993c57a9aa1beaf8
Quelldatensatz
uspto-grants-2014_02
Patentnummer
US08642607B2

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