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

HRID 2184010노트

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HRID 2184010 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>O1CCCC1.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

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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 tetrahydrofuran (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 0.2M 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 brine (200 ml), dried over anhydrous sodium sulphate, filtered and evaporated. Purification by chromatography on silica gel eluting with isohexane on a gradient of ethyl acetate (5-10%) gave 2-fluoro-2′-methylthio-5-nitrobiphenyl as a pale yellow solid (6.95 g, 99%): δH (360 MHz, CDCl3) 2.42 (3H, s), 7.21-7.32 (3H, m), 7.37 (1H, d, J 7), 7.44 (1H, td, J 8 and 2), 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 brine (200 ml)
  6. dry with materialdried over anhydrous sodium sulphate
  7. filtrationfiltered
  8. customevaporated
  9. customPurification by chromatography on silica gel eluting with isohexane on a gradient of ethyl acetate (5-10%)

출처 및 근거

ORD 기록
ord-470160545f924e8b899f18ebf57b2570
출처 데이터셋
uspto-grants-2005_05
특허 번호
US06900215B2

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