Nitrogen → 2-[(2,5-Dichloro-4-pyridinyl)amino]benzonitrile

HRID 62492

Reaktionsgleichung

Reaktionsgleichung von HRID 62492
[Cl:1][C:2]1[CH:7]=[C:6](I)[C:5]([Cl:9])=[CH:4][N:3]=1.[NH2:10][C:11]1[CH:18]=[CH:17][CH:16]=[CH:15][C:12]=1[C:13]#[N:14].[O-]P(OP(OP([O-])([O-])=O)([O-])=O)(=O)[O-].[K+].[K+].[K+].[K+].[K+].N#N.C1C=CC(P(C2C(OC3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=CC=3)=CC=CC=2)C2C=CC=CC=2)=CC=1>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[Cl:1][C:2]1[CH:7]=[C:6]([NH:10][C:11]2[CH:18]=[CH:17][CH:16]=[CH:15][C:12]=2[C:13]#[N:14])[C:5]([Cl:9])=[CH:4][N:3]=1

Komponenten

8

Edukt 5

HCID 947NitrogenHCID 61695Pentapotassium TriphosphateHCID 729132-AminobenzonitrileHCID 4285986Bis[2-(diphenylphosphino)phenyl] etherHCID 534009652,5-Dichloro-4-iodopyridine

Produkt 1

HCID 575168982-[(2,5-Dichloro-4-pyridinyl)amino]benzonitrileAusbeute 79 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 167845palladium(II) acetateKatalysatorHCID 312751,4-DioxaneLösungsmittel

Versuchsvorschrift

The solution of 2,5-dichloro-4-iodopyridine (100 g, 365 mmol), 2-aminobenzonitrile (43.1 g, 365 mmol) and potassium triphosphate (233 g, 1095 mmol) in 1,4-dioxane (2.5 L) was degassed by N2 stream. To this solution was added DPEPhos (15.73 g, 29.2 mmol) and palladium acetate (3.28 g, 14.60 mmol). The reaction mixture was stirred at reflux for 18 hour. The solution was filtered through 0.5 in. celite and 0.2 inch of silica. The solution was evaporated. Solid was suspended in the diethyl ether and filtered. Diethyl ether was concentrated, and the resulting solid was filtered. 2-[(2,5-Dichloro-4-pyridinyl)amino]benzonitrile (80 g, 288 mmol, 79% yield) was isolated as an orange solid. 1H NMR (400 MHz, DMSO-d6) ppm 6.49 (s, 1 H) 7.50 (td, J=7.58, 1.01 Hz, 1 H) 7.56 (d, J=7.58 Hz, 1 H) 7.80 (td, J=7.83, 1.77 Hz, 1 H) 7.95 (dd, J=7.83, 1.52 Hz, 1 H) 8.26 (s, 1 H) 9.05 (brs, 1 H); HPLC Rt=2.88 min, MS (ESI): 263.9, 265.9 [M+H]+.

Aufarbeitung

  1. temperatureat reflux for 18 hour
  2. filtrationThe solution was filtered through 0.5 in
  3. customThe solution was evaporated
  4. filtrationfiltered
  5. concentrationDiethyl ether was concentrated
  6. filtrationthe resulting solid was filtered

Quellen und Nachweise

ORD-Eintrag
ord-3bf6d14b99cb4f94a474cd8d77000115
Quelldatensatz
uspto-grants-2016_09
Patentnummer
US09446034B2

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