Tri-tert-butylphosphine tetrafluoroborate → HCID 57541263, Verbindung

HRID 1514626Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1514626
CC(C)([O-])C.[Na+].[CH3:7][N:8]([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[S:9]([CH2:12][C:13]([O:15][CH3:16])=[O:14])(=[O:11])=[O:10].Br[C:24]1[CH:25]=[CH:26][C:27]2[CH:38]=[CH:37][C:31]3=[N:32][CH:33]=[C:34]([Cl:36])[CH:35]=[C:30]3[C:29](=[O:39])[C:28]=2[CH:40]=1.F[B-](F)(F)F.C([PH+](C(C)(C)C)C(C)(C)C)(C)(C)C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O1CCOCC1>[Cl:36][C:34]1[CH:35]=[C:30]2[C:29](=[O:39])[C:28]3[CH:40]=[C:24]([CH:12]([S:9]([N:8]([CH3:7])[C:17]4[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=4)(=[O:10])=[O:11])[C:13]([O:15][CH3:16])=[O:14])[CH:25]=[CH:26][C:27]=3[CH:38]=[CH:37][C:31]2=[N:32][CH:33]=1

Komponenten

7

Edukt 4

HCID 2734635Tri-tert-butylphosphine tetrafluoroborateHCID 14002850methyl 2-(N-methyl-N-phenylsulfamoyl)acetateHCID 159808187-Bromo-3-chloro-5H-benzo[4,5]cyclohepta[1,2-B]pyridin-5-oneHCID 23676156Sodium t-butoxide

Produkt 1

HCID 57541263HCID 57541263, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 167845palladium(II) acetateKatalysatorHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
90 °C

Versuchsvorschrift

Sodium tert-butoxide (8.99 g, 94 mmol) was added in one portion to a 250 mL flask containing methyl {[methyl(phenyl)amino]sulfonyl}acetate (7.59 g, 31.2 mmol) and dioxane (125 ml) at room temperature. After 15 min., 7-bromo-3-chloro-5H-benzo[4,5]cyclohepta[1,2-b]pyridin-5-one (10.00 g, 31.2 mmol) was added followed by palladium(II) acetate (0.350 g, 1.560 mmol) and tri-t-butylphosphonium tetrafluoroborate (1.358 g, 4.68 mmol). The resulting suspension was degassed by sparging with nitrogen for 30 min. Then, the mixture was heated to 90° C. in a pre-warmed bath and left to stir for 1 h. Then, the reaction mixture was cooled to room temperature, acidified with 1N HCl (100 mL), basified with saturated aqueous sodium hydrogen carbonate (460 mL) and extracted with dichloromethane (3×250 mL). The combined organics were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (EtOAc/Hexanes gradient) to afford the title compound as a yellow foam. 1H NMR (600 MHz, DMSO-D6) δ 8.99 (d, 1H); 8.46 (d, 1H); 8.42 (d, 1H); 8.03 (dd, 1H); 7.81 (d, 1H); 7.44 (d, 1H); 7.33 (d, 1H); 7.22 (m, 2H); 7.17 (m, 2H); 7.11 (m, 1H); 6.10 (s, 1H); 3.71 (s, 3H); 3.20 (s, 3H). LRMS (APCI) calculated for C24H20ClN2O5S [M+H]+, 483.1. found 483.0.

Aufarbeitung

  1. customThe resulting suspension was degassed
  2. customby sparging with nitrogen for 30 min
  3. waitleft
  4. temperatureThen, the reaction mixture was cooled to room temperature
  5. extractionextracted with dichloromethane (3×250 mL)
  6. dry with materialThe combined organics were dried over anhydrous Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by column chromatography on silica gel (EtOAc/Hexanes gradient)

Quellen und Nachweise

ORD-Eintrag
ord-edc734fd3a4b431788e67e3831049b1f
Quelldatensatz
uspto-grants-2012_07
Patentnummer
US08222269B2

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