Cesium fluoride → Methyl 4-amino-3-chloro-6-(3,4-dimethylphenyl)pyridine-2-carboxylate

HRID 1837453Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1837453
[CH3:1][C:2]1[CH:3]=[C:4](B(O)O)[CH:5]=[CH:6][C:7]=1[CH3:8].[F-].[Cs+].C1(P(C2C=CC=CC=2)CCCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[NH2:44][C:45]1[CH:50]=[C:49](Cl)[N:48]=[C:47]([C:52]([O:54][CH3:55])=[O:53])[C:46]=1[Cl:56]>C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O.C(N(CC)CC)C>[NH2:44][C:45]1[CH:50]=[C:49]([C:4]2[CH:5]=[CH:6][C:7]([CH3:8])=[C:2]([CH3:1])[CH:3]=2)[N:48]=[C:47]([C:52]([O:54][CH3:55])=[O:53])[C:46]=1[Cl:56]

Komponenten

9

Edukt 4

HCID 25953Cesium fluorideHCID 821241,4-Bis(diphenylphosphino)butaneHCID 27343483,4-Dimethylphenylboronic acidHCID 22677331Methyl 4-amino-3,6-dichloropyridine-2-carboxylate

Produkt 1

HCID 22677522Methyl 4-amino-3-chloro-6-(3,4-dimethylphenyl)pyridine-2-carboxylateAusbeute 50 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 167845palladium(II) acetateKatalysatorHCID 962WaterLösungsmittelHCID 6342AcetonitrileLösungsmittelHCID 8471TriethylamineLösungsmittel

Versuchsvorschrift

A solution of 3,4-dimethylphenylboronic acid (2.1 g, 14.0 mmol), cesium fluoride (6.3 g, 41.5 mmol), 1,4-bis(diphenylphosphino)butane (0.5 g, 1.2 mmol), methyl 4-amino-3,6-dichloropyridine-2-carboxylate (2.5 g, 10.0 mmol) and triethylamine (5 mL) in acetonitrile (100 mL) was sparged for thirty minutes with nitrogen. Palladium acetate (0.3 g, 1.2 mmol) was added and the reaction mixture heated under reflux for three hours. After cooling water (200 mL) was added and the mixture extracted with ethyl acetate (2×100 mL). The organic layer was washed with brine (100 mL), dried (NaSO4), and concentrated. The residue was purified by column chromatography (33 percent ethyl acetate in hexane) to give methyl 4-amino-3-chloro-6-(3,4-dimethylphenyl)pyridine-2-carboxylate (1.4 g, 5.0 mmol), mp 154-156° C.

Aufarbeitung

  1. temperaturethe reaction mixture heated
  2. temperatureunder reflux for three hours
  3. additionwas added
  4. extractionthe mixture extracted with ethyl acetate (2×100 mL)
  5. washThe organic layer was washed with brine (100 mL)
  6. dry with materialdried (NaSO4)
  7. concentrationconcentrated
  8. customThe residue was purified by column chromatography (33 percent ethyl acetate in hexane)

Quellen und Nachweise

ORD-Eintrag
ord-009b1d8a67404275b1c35f58e9a27735
Quelldatensatz
uspto-grants-2004_08
Patentnummer
US06784137B2

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