2-Bromo-1-fluoro-4-nitrobenzene → 2-Fluoro-2'-methylthio-5-nitrobiphenyl

HRID 586271

반응식

HRID 586271 반응식
Br[C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[F:11].[CH3:12][S:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=1B(O)O.[F-].[K+].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>C1COCC1.O1CCOCC1.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]>[F:11][C:3]1[CH:4]=[CH:5][C:6]([N+:8]([O-:10])=[O:9])=[CH:7][C:2]=1[C:15]1[CH:16]=[CH:17][CH:18]=[CH:19][C:14]=1[S:13][CH3:12]

참가 물질

8

반응물 4

HCID 696992-Bromo-1-fluoro-4-nitrobenzeneHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 522689Potassium FluorideHCID 27735432-(Methylthio)benzeneboronic acid

생성물 1

HCID 222852772-Fluoro-2'-methylthio-5-nitrobiphenyl수율 99%

시약·촉매·용매 3

HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 8028Tetrahydrofuran용매HCID 312751,4-Dioxane용매

반응 조건

온도
50 °C

실험 절차

A mixture of 2-bromo-1-fluoro-4-nitrobenzene (5.89 g, 26.8 mmol), 2-(methylthio)benzeneboronic acid (5.62 g, 33.5 mmol) and potassium fluoride (5.13 g, 88.3 mmol) in THF (70 ml) was degassed with nitrogen for 30 min. This mixture was then treated with tris(dibenzylideneacetone)dipalladium(0) (496 mg, 0.541 mmol) followed by tri-tert-butylphosphine (5.35 ml of a 0.2 M solution in 1,4-dioxane, 1.07 mmol) and the reaction was degassed for a further 10 min. The resulting slurry was then heated at 50° C. for 16 h under nitrogen. After cooling, the reaction mixture was partitioned between ethyl acetate (300 ml) and water (300 ml). The organic layer was washed with saturated aqueous NaCl (200 ml), dried (Na2SO4), and evaporated. Purification by chromatography (silica gel, 5-10% EtOAc/isohexane) gave 6.95 g (99%) of the title compound as a pale yellow solid: 1H NMR (360 MHz, CDCl3) δ 2.42 (3H, s), 7.21-7.32 (3H, m), 7.37 (1H, d, J 7.4 Hz), 7.44 (1H, td, J 7.7, 1.6 Hz), 8.27-8.31 (2H, m).

후처리

  1. customwas degassed with nitrogen for 30 min
  2. customwas degassed for a further 10 min
  3. temperatureAfter cooling
  4. customthe reaction mixture was partitioned between ethyl acetate (300 ml) and water (300 ml)
  5. washThe organic layer was washed with saturated aqueous NaCl (200 ml)
  6. dry with materialdried (Na2SO4)
  7. customevaporated
  8. customPurification by chromatography (silica gel, 5-10% EtOAc/isohexane)

출처 및 근거

ORD 기록
ord-6e1be896244947258f62a193cfeb7f7a
출처 데이터셋
uspto-grants-2005_08
특허 번호
US06936608B2

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