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

反応式

HRID 38541 の反応式
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]

参加物

8

反応物 4

HCID 97083-Chloro-4-fluoroanilineHCID 10796Cesium carbonateHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylHCID 58116935tert-Butyl 4-chloro-3-cyano-5,8-dihydrothieno[2,3-b:5,4-c']dipyridine-7(6H)-carboxylate

生成物 1

HCID 58116801tert-Butyl 4-[(3-chloro-4-fluorophenyl)amino]-3-cyano-5,8-dihydrothieno[2,3-b:5,4-c']dipyridine-7(6H)-carboxylate収率 68%

試薬・触媒・溶媒 3

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 6228Dimethylformamide溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
90 °C

実験手順

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.

後処理

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

出典と根拠

ORDレコード
ord-86ef515523bc4511902653c08c8cb36c
出典データセット
uspto-grants-2013_09
特許番号
US08524722B2

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