Sodium Carbonate → 4,4'-Difluoro-2-nitro-1,1'-biphenyl

HRID 1776195

반응식

HRID 1776195 반응식
Cl[C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].[F:12][C:13]1[CH:18]=[CH:17][C:16](B(O)O)=[CH:15][CH:14]=1.C(=O)([O-])[O-].[Na+].[Na+].[OH-].[Na+]>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.O.C([O-])(=O)C.C([O-])(=O)C.[Pd+2].C(OCC)C>[F:8][C:5]1[CH:6]=[CH:7][C:2]([C:16]2[CH:17]=[CH:18][C:13]([F:12])=[CH:14][CH:15]=2)=[C:3]([N+:9]([O-:11])=[O:10])[CH:4]=1

참가 물질

9

반응물 4

HCID 10340Sodium CarbonateHCID 14798Sodium HydroxideHCID 676591-Chloro-4-fluoro-2-nitrobenzeneHCID 2856454-Fluorophenylboronic acid

생성물 1

HCID 3454114,4'-Difluoro-2-nitro-1,1'-biphenyl수율 52%

시약·촉매·용매 4

HCID 74236Tetrabutylammonium Bromide촉매HCID 167845palladium(II) acetate촉매HCID 962Water용매HCID 3283Diethyl Ether용매

반응 조건

온도
165 °C

실험 절차

A microwave reaction vessel was charged with 2-chloro-5-fluoronitrobenzene (0.878 g, 5.0 mmol), 4-fluorophenylboronic acid (0.770 g, 5.5 mmol), sodium carbonate (1.590 g, 15.0 mmol), palladium diacetate (0.045 g, 0.2 mmol), tetrabutylammonium bromide (1.612 g, 5.0 mmol) in water (10 mL). The mixture was heated to 165° C. in a microwave reactor for 10 mins. The reaction was cooled to room temperature and poured into diethyl ether and 0.1N aqueous sodium hydroxide. The organic layer was washed with saturated aqueous sodium chloride, dried (anhydrous sodium sulfate), filtered, and concentrated in vacuo. The residue was purified by silica gel chromatography (10-30% methylene chloride/hexanes) to give the desired product as a yellow solid (0.61 g, 52%). 1H NMR (CDCl3, 300 MHz) δ 7.61 (dd, 1H, J=8.1, 2.7 Hz), 7.44-7.30 (m, 2H), 7.30-7.21 (m, 2H), 7.16-7.07 (m, 2H).

후처리

  1. customA microwave reaction vessel
  2. temperatureThe reaction was cooled to room temperature
  3. washThe organic layer was washed with saturated aqueous sodium chloride
  4. dry with materialdried (anhydrous sodium sulfate)
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by silica gel chromatography (10-30% methylene chloride/hexanes)

출처 및 근거

ORD 기록
ord-fbf307eac0ea4eb5975156187f04bf2a
출처 데이터셋
uspto-grants-2016_02
특허 번호
US09265772B2

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