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

HRID 1012609

반응식

HRID 1012609 반응식
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]

참가 물질

9

반응물 4

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

생성물 1

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

시약·촉매·용매 4

HCID 167845palladium(II) acetate촉매HCID 962Water용매HCID 8857Ethyl Acetate용매HCID 312751,4-Dioxane용매

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온도
100 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-769df04fde574f98aa7bded2a81404cd
출처 데이터셋
uspto-grants-2011_07
특허 번호
US07977387B2

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