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

HRID 1776164

반응식

HRID 1776164 반응식
Cl[C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].[C:12]1(B(O)O)[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=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].CCOCC>[F:8][C:5]1[CH:6]=[CH:7][C:2]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[C:3]([N+:9]([O-:11])=[O:10])[CH:4]=1

참가 물질

9

반응물 4

HCID 10340Sodium CarbonateHCID 14798Sodium HydroxideHCID 66827Phenylboronic AcidHCID 676591-Chloro-4-fluoro-2-nitrobenzene

생성물 1

HCID 113789504-Fluoro-2-nitro-1,1'-biphenyl수율 82.4%

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 (0.175 g, 1 mmol), phenylboronic acid (0.134 g, 1.1 mmol), sodium carbonate (0.317 g, 3 mmol), palladium diacetate (0.009 g, 0.04 mmol), tetrabutylammonium bromide (0.322 g, 1 mmol) in water (2 mL). The mixture was heated to 165° C. in a microwave reactor for 7.5 minutes. The reaction was cooled and poured into ether and 0.1N aqueous sodium hydroxide. The ether layer was washed with saturated aqueous sodium chloride, dried (anhydrous sodium sulfate), filtered, and concentrated. The crude product was purified by silica gel column chromatography (5-30% methylene chloride in hexanes) to give the desired product as a pale yellow oil (0.179 g, 82%). 1H NMR (CDCl3, 300 MHz) δ 7.62-7.58 (dd, 1H, J=2.7, 8.1 Hz), 7.46-7.40 (m, 4H), 7.38-7.34 (m, 1H), 7.31-7.26 (m, 2H). HPLC analysis (C18, 5-95% acetonitrile in H2O+0.1% trifluoroacetic acid over 20 min: retention time, % area at 254 nm): 9.95 min, 96.3%.

후처리

  1. customA microwave reaction vessel
  2. temperatureThe reaction was cooled
  3. washThe ether layer was washed with saturated aqueous sodium chloride
  4. dry with materialdried (anhydrous sodium sulfate)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude product was purified by silica gel column chromatography (5-30% methylene chloride in hexanes)

출처 및 근거

ORD 기록
ord-44c15b57a1cb4f52be96b51a20434241
출처 데이터셋
uspto-grants-2016_02
특허 번호
US09265772B2

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