3-Chloro-4-fluoroaniline → tert-Butyl 4-[(3-chloro-4-fluorophenyl)amino]-3-cyano-5,8-dihydrothieno[2,3-b:5,4-c']dipyridine-7(6H)-carboxylate

HRID 38541

Reaktionsgleichung

Cl[C:2]1[C:7]([C:8]#[N:9])=[CH:6][N:5]=[C:4]2[S:10][C:11]3[CH2:12][N:13]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:14][CH2:15][C:16]=3[C:3]=12.[Cl:24][C:25]1[CH:26]=[C:27]([CH:29]=[CH:30][C:31]=1[F:32])[NH2:28].CC(C1C=C(C(C)C)C(C2C=CC=CC=2P(C2CCCCC2)C2CCCCC2)=C(C(C)C)C=1)C.C(=O)([O-])[O-].[Cs+].[Cs+]>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].C1COCC1.CN(C=O)C>[Cl:24][C:25]1[CH:26]=[C:27]([NH:28][C:2]2[C:7]([C:8]#[N:9])=[CH:6][N:5]=[C:4]3[S:10][C:11]4[CH2:12][N:13]([C:17]([O:19][C:20]([CH3:21])([CH3:23])[CH3:22])=[O:18])[CH2:14][CH2:15][C:16]=4[C:3]=23)[CH:29]=[CH:30][C:31]=1[F:32]

Komponenten

Reaktionsbedingungen

Temperatur: 90 °C

Versuchsvorschrift

To a solution of tert-butyl 4-chloro-3-cyano-5,8-dihydrothieno[2,3-b:5,4-c′]dipyridine-7(6H)-carboxylate from Example 53A (150 mg, 0.43 mmol) in a degassed mixture of DMF (1.5 mL) and THF (1.5 mL) were added 3-chloro-4-fluoroaniline (62 mg, 0.43 mmol), XPHOS (4.1 mg, 0.009 mmol), caesium carbonate (196 mg, 0.60 mmol) and tris(dibenzylideneacetone)dipalladium(0) (24 mg, 0.026 mmol). The mixture was heated to 90° C. for 1 h. The solvent was removed in vacuo, and the residue was purified by column chromatography on silica gel (eluent: DCM/MeOH 50:1) to yield 190 mg (70% purity, 68% yield) of the title compound, which was used in the next step without further purification.

Aufarbeitung

customThe solvent was removed in vacuo
customthe residue was purified by column chromatography on silica gel (eluent: DCM/MeOH 50:1)

Quellen und Nachweise

ORD-Eintrag: ord-86ef515523bc4511902653c08c8cb36c
Quelldatensatz: uspto-grants-2013_09
DOI: 10.6084/m9.figshare.5104873.v1
Patentnummer: US08524722B2

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