Cesium carbonate → HCID 86689708, Verbindung

HRID 1396337

Reaktionsgleichung

Reaktionsgleichung von HRID 1396337
[CH2:1]([O:3][C:4]([C:6]1[N:7]=[N:8][C:9]([Cl:13])=[CH:10][C:11]=1Cl)=[O:5])[CH3:2].[N:14]1([C:19]2[N:24]=[C:23]([NH2:25])[CH:22]=[CH:21][CH:20]=2)[CH:18]=[CH:17][N:16]=[N:15]1.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.C(=O)(O)[O-].[Na+].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]>[CH2:1]([O:3][C:4]([C:6]1[N:7]=[N:8][C:9]([Cl:13])=[CH:10][C:11]=1[NH:25][C:23]1[CH:22]=[CH:21][CH:20]=[C:19]([N:14]2[CH:18]=[CH:17][N:16]=[N:15]2)[N:24]=1)=[O:5])[CH3:2]

Komponenten

8

Edukt 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 53428795Ethyl 4,6-dichloropyridazine-3-carboxylateHCID 84651201HCID 84651201, Verbindung

Produkt 1

HCID 86689708HCID 86689708, VerbindungAusbeute 15,3 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 312751,4-DioxaneLösungsmittelHCID 516892Sodium BicarbonateLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

4,6-Dichloro-pyridazine-3-carboxylic acid ethyl ester (200 mg, 0.905 mmol) and 6-[1,2,3]triazol-1-yl-pyridin-2-ylamine (147 mg, 0.914 mmol) were dissolved in 1,4-dioxane (6 mL) and the solution was purged with argon. Tris(dibenzylideneacetone)dipalladium (83 mg, 0.09 mmol), Xantphos (105 mg, 0.18 mmol), and cesium carbonate (884 mg, 2.7 mmol) were added and the reaction mixture was heated to 100° C. for 1 h. The reaction mixture was cooled, diluted with saturated aqueous sodium bicarbonate solution, then extracted with ethyl acetate. The combined organic extracts were washed with saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered and concentrated in vacuo. Purification by chromatography (silica, 25 to 100% ethyl acetate in hexanes) gave 6-chloro-4-(6-[1,2,3]triazol-1-yl-pyridin-2-ylamino)-pyridazine-3-carboxylic acid ethyl ester (48 mg, 15%) as a light yellow solid. 1H NMR (300 MHz, CHLOROFORM-d) δ ppm 9.34-9.43 (m, 1H) 8.54-8.57 (m, 1H) 8.43 (d, J=1.1 Hz, 1H) 7.87-7.97 (m, 3H) 7.60 (dd, J=7.4, 1.3 Hz, 1H) 4.55 (q, J=7.2 Hz, 2H) 1.50 (t, J=7.2 Hz, 3H); MS (EI/CI) m/z: 346 [M+H].

Aufarbeitung

  1. customthe solution was purged with argon
  2. temperatureThe reaction mixture was cooled
  3. extractionextracted with ethyl acetate
  4. washThe combined organic extracts were washed with saturated aqueous sodium chloride solution
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customPurification by chromatography (silica, 25 to 100% ethyl acetate in hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-290b4c712aa5453d864aad1405d213cb
Quelldatensatz
uspto-grants-2014_12
Patentnummer
US08901124B2

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