Cesium carbonate → HCID 90410005, Verbindung

HRID 626599Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 626599
Cl[C:2]1[CH:7]=[C:6]([O:8][C:9]2[CH:10]=[N:11][C:12]([N+:15]([O-:17])=[O:16])=[CH:13][CH:14]=2)[CH:5]=[CH:4][N:3]=1.[CH2:18]([N:25]1[CH2:30][CH2:29][N:28]([C:31]([NH2:33])=[O:32])[CH2:27][CH2:26]1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.CCOC(C)=O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CC(C1C=C(C(C)C)C(C2C=CC=CC=2P(C2CCCCC2)C2CCCCC2)=C(C(C)C)C=1)C>[CH2:18]([N:25]1[CH2:26][CH2:27][N:28]([C:31]([NH:33][C:2]2[CH:7]=[C:6]([O:8][C:9]3[CH:10]=[N:11][C:12]([N+:15]([O-:17])=[O:16])=[CH:13][CH:14]=3)[CH:5]=[CH:4][N:3]=2)=[O:32])[CH2:29][CH2:30]1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

Komponenten

8

Edukt 3

HCID 10796Cesium carbonateHCID 8518614-benzylpiperazine-1-carboxamideHCID 593227792-Chloro-4-((6-nitropyridin-3-yl)oxy)pyridine

Produkt 1

HCID 90410005HCID 90410005, VerbindungAusbeute 66,5 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylKatalysatorHCID 8857Ethyl AcetateLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
120 °C

Versuchsvorschrift

A suspension of Example A1 (0.5 g, 1.987 mmol), 4-benzylpiperazine-1-carboxamide (0.741 g, 3.38 mmol), cesium carbonate (0.971 g, 2.98 mmol) and X-Phos (0.047 g, 0.099 mmol) in dioxane (20 mL) was purged 5 min with Ar. To the reaction mixture was added Pd2 dba3 (0.055 g, 0.060 mmol) and it was then heated to 120° C. After 16 h, the reaction was cooled to RT, diluted with EtOAc (100 mL) and filtered through diatomaceous earth. The filter cake was washed with additional EtOAc and the combined filtrates concentrated to afford crude product. This was purified by silica gel chromatography (0-8% MeOH/DCM) to afford 4-benzyl-N-(4-((6-nitropyridin-3-yl)oxy)pyridin-2-yl)piperazine-1-carboxamide (0.574 g, 66%). 1H NMR (400 MHz, DMSO-d6): δ 9.41 (s, 1H), 8.56 (d, J=2.8 Hz, 1H), 8.40 (d, J=8.9 Hz, 1H), 8.23 (d, J=5.7 Hz, 1H), 7.94 (dd, J=8.9, 2.8 Hz, 1H), 7.55 (d, J=2.3 Hz, 1H), 7.30-7.29 (m, 5H), 6.79 (dd, J=5.7, 2.4 Hz, 1H), 3.47 (s, 2H), 3.43 (t, J=4.7 Hz, 4H), 2.32 (t, J=4.7 Hz, 4H); MS (ESI) m/z: 435.2 (M+H+).

Aufarbeitung

  1. temperaturethe reaction was cooled to RT
  2. filtrationfiltered through diatomaceous earth
  3. washThe filter cake was washed with additional EtOAc
  4. concentrationthe combined filtrates concentrated
  5. customto afford crude product
  6. customThis was purified by silica gel chromatography (0-8% MeOH/DCM)

Quellen und Nachweise

ORD-Eintrag
ord-bba4116e947240ffa3b5e64c92c2d326
Quelldatensatz
uspto-grants-2016_04
Patentnummer
US09309224B2

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