2,4-Difluoroaniline → [2-Chloro-4-(2,4-difluoro-phenylamino)-phenyl]-(2-methyl-5-nitro-phenyl)-methanone

HRID 1012609

反応式

HRID 1012609 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:10]2[CH:15]=[C:14]([N+:16]([O-:18])=[O:17])[CH:13]=[CH:12][C:11]=2[CH3:19])=[O:9])=[C:4]([Cl:20])[CH:3]=1.[F:21][C:22]1[CH:28]=[C:27]([F:29])[CH:26]=[CH:25][C:23]=1[NH2:24].C([O-])([O-])=O.[Cs+].[Cs+].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>O1CCOCC1.CC([O-])=O.CC([O-])=O.[Pd+2].CCOC(C)=O.O>[Cl:20][C:4]1[CH:3]=[C:2]([NH:24][C:23]2[CH:25]=[CH:26][C:27]([F:29])=[CH:28][C:22]=2[F:21])[CH:7]=[CH:6][C:5]=1[C:8]([C:10]1[CH:15]=[C:14]([N+:16]([O-:18])=[O:17])[CH:13]=[CH:12][C:11]=1[CH3:19])=[O:9]

参加物

9

反応物 4

HCID 97092,4-DifluoroanilineHCID 10796Cesium carbonateHCID 634876Binap, (A+-)-HCID 11494123(4-Bromo-2-chloro-phenyl)-(2-methyl-5-nitro-phenyl)-methanone

生成物 1

HCID 11618303[2-Chloro-4-(2,4-difluoro-phenylamino)-phenyl]-(2-methyl-5-nitro-phenyl)-methanone

試薬・触媒・溶媒 4

HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
100 °C

実験手順

Compound 492 (5.4 g, 15.2 mmol) was dissolved in dry 1,4-dioxan (150 mL) in a 200 mL screw cap vessel. 2,4-Difluoroaniline (1.7 mL, 16.7 mmol) was added and argon was blown over the mixture. Cs2CO3 (14.9 g, 45.7 mmol), BINAP (0.38 g, 0.6 mmol) and Pd(OAc)2 (0.14 g, 0.6 mmol) were added and argon was blown through the mixture and the screw cap vessel was closed. The mixture was stirred at 100° C. for 7 h. The reaction mixture was poured into H2O (100 mL) and EtOAc (200 mL). The water phase was extracted with EtOAc (×3) and the combined organic phases were washed with brine, dried (MgSO4), filtered and concentrated in vacuo. The crude product was purified by flash chromatography using CH2Cl2/petroleum ether (40-60) 2:3→1:1→1:0 followed by EtOAc as the eluent to afford the title compound as a yellow crystalline compound.

後処理

  1. customscrew cap vessel
  2. customthe screw cap vessel
  3. customwas closed
  4. extractionThe water phase was extracted with EtOAc (×3)
  5. washthe combined organic phases were washed with brine
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe crude product was purified by flash chromatography

出典と根拠

ORDレコード
ord-769df04fde574f98aa7bded2a81404cd
出典データセット
uspto-grants-2011_07
特許番号
US07977387B2

関連ノート

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