Phosphorus oxychloride → 4-chloro-2-(2,6-dichlorophenyl)-2H-pyrazolo[4,3-c]pyridine

HRID 626659

Reaktionsgleichung

Reaktionsgleichung von HRID 626659
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Cl:8])[C:3]=1[N:9]1[CH:18]=[C:12]2[CH:13]=[N+:14]([O-])[CH:15]=[CH:16][C:11]2=[N:10]1.P(Cl)(Cl)([Cl:21])=O.C(=O)([O-])O.[Na+]>[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.C(OCC)(=O)C>[Cl:21][C:13]1[C:12]2=[CH:18][N:9]([C:3]3[C:2]([Cl:1])=[CH:7][CH:6]=[CH:5][C:4]=3[Cl:8])[N:10]=[C:11]2[CH:16]=[CH:15][N:14]=1

Komponenten

6

Edukt 3

HCID 24813Phosphorus oxychlorideHCID 516892Sodium BicarbonateHCID 677015532-(2,6-Dichlorophenyl)-2H-pyrazolo[4,3-c]pyridine 5-oxide

Produkt 1

HCID 866970364-chloro-2-(2,6-dichlorophenyl)-2H-pyrazolo[4,3-c]pyridineAusbeute 49 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 70681Tetrabutylammonium ChlorideKatalysatorHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

2-(2,6-Dichlorophenyl)-2H-pyrazolo[4,3-c]pyridine 5-oxide (1.12 g, 4 mmol) was slowly added to phosphorous oxychloride (8 mL). Tetrabutylammonium chloride (1.11 g, 4 mmol) was then added. The reaction mixture was heated at 80° C. for 5 hours and then cooled to room temperature. The reaction was poured into a mixture of ethyl acetate and sodium hydrogen carbonate (sat. aq.) and the layers were partitioned. The organic layer was washed with sodium hydrogen carbonate (sat. aq.) and brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resultant residue was purified by silica gel flash chromatography (20% ethyl acetate in cyclohexane) to afford the title compound as a white solid (590 mg, 49% yield). 1H NMR (400 MHz, DMSO-d6): δ 9.33 (d, J=1.0 Hz, 1H), 8.11 (d, J=6.0 Hz, 1H), 7.83 (d, J=1.3 Hz, 1H), 7.82-7.81 (m, 1H), 7.75-7.71 (m, 1H). LCMS (Method D): RT=3.42 min, m/z: 298 [M+H+].

Aufarbeitung

  1. temperaturecooled to room temperature
  2. customthe layers were partitioned
  3. washThe organic layer was washed with sodium hydrogen carbonate (sat. aq.) and brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe resultant residue was purified by silica gel flash chromatography (20% ethyl acetate in cyclohexane)

Quellen und Nachweise

ORD-Eintrag
ord-4dd650f0ed7046cb95d4f42a57c97827
Quelldatensatz
uspto-grants-2016_04
Patentnummer
US09309240B2

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