Phosphorus oxychloride → 7-Bromo-4-[(2,4-dichloro-5-methoxyphenyl)amino]-6-methoxy-3-quinolinecarbonitrile

HRID 1593778Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1593778
[Br:1][C:2]1[CH:3]=[C:4]([CH:23]=[CH:24][C:25]=1[O:26][CH3:27])[NH:5][CH:6]=[C:7]([C:21]#[N:22])[C:8]([NH:10][C:11]1[CH:16]=[C:15]([O:17][CH3:18])[C:14]([Cl:19])=[CH:13][C:12]=1[Cl:20])=O.P(Cl)(Cl)(Cl)=O>C(#N)C>[Br:1][C:2]1[CH:3]=[C:4]2[C:23]([C:8]([NH:10][C:11]3[CH:16]=[C:15]([O:17][CH3:18])[C:14]([Cl:19])=[CH:13][C:12]=3[Cl:20])=[C:7]([C:21]#[N:22])[CH:6]=[N:5]2)=[CH:24][C:25]=1[O:26][CH3:27]

Komponenten

4

Edukt 2

HCID 24813Phosphorus oxychlorideHCID 693135643-bromo-4-methoxyanilino-N-(2,4-dichloro-5-methoxyphenyl)-2-cyano-2-propenamide

Produkt 1

HCID 115181097-Bromo-4-[(2,4-dichloro-5-methoxyphenyl)amino]-6-methoxy-3-quinolinecarbonitrileAusbeute 44,9 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

A suspension of 3-bromo-4-methoxyanilino-N-(2,4-dichloro-5-methoxyphenyl)-2-cyano-2-propenamide (4.00 g, 8.50 mmol) in 200 mL of acetonitrile was heated to reflux and phosphorous oxychloride (5.0 mL) was added dropwise, via syringe. The reaction mixture was heated at reflux overnight, then cooled to room temperature and concentrated in vacuo. The residue was cooled to 0° C. and saturated aqueous sodium bicarbonate was added. The mixture was stirred for 1 hour and then extracted with a large volume of ethyl acetate. The organic layer was washed with saturated aqueous sodium bicarbonate, dried over magnesium sulfate and filtered. The filtrate was reduced in volume until solids appeared. The solids were collected by filtration, washed with diethyl ether and hexanes to provide 1.73 g of 7-bromo-4-[(2,4-dichloro-5-methoxyphenyl)amino]-6-methoxy-3-quinolinecarbonitrile as a light tan solid, mp >250° C. 1H NMR (400 MHz, DMSO-d6) δ 3.87 (s, 3H), 4.04 (s, 3H), 7.41 (s, 1H), 7.78 (s, 1H), 7.99(s, 1H), 8.22 (s, 1H), 8.48 (s, 1H), 9.93 (s, 1H); MS (ES) m/z449.9, 451.9, 453.9 (M−H)−

Aufarbeitung

  1. temperaturewas heated
  2. temperatureto reflux
  3. temperatureThe reaction mixture was heated
  4. temperatureat reflux overnight
  5. concentrationconcentrated in vacuo
  6. temperatureThe residue was cooled to 0° C.
  7. additionsaturated aqueous sodium bicarbonate was added
  8. extractionextracted with a large volume of ethyl acetate
  9. washThe organic layer was washed with saturated aqueous sodium bicarbonate
  10. dry with materialdried over magnesium sulfate
  11. filtrationfiltered
  12. filtrationThe solids were collected by filtration
  13. washwashed with diethyl ether and hexanes

Quellen und Nachweise

ORD-Eintrag
ord-e16ac575d24c48099f9add2f638c906c
Quelldatensatz
uspto-grants-2007_11
Patentnummer
US07297795B2

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