Water → 4-Cyclopropyl-2-fluoro-1-nitrobenzene

HRID 1185256노트

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HRID 1185256 반응식
FC(F)(F)S(O[C:7]1[CH:12]=[CH:11][C:10]([N+:13]([O-:15])=[O:14])=[C:9]([F:16])[CH:8]=1)(=O)=O.[CH:19]1(B(O)O)[CH2:21][CH2:20]1.ClCCl.C(=O)([O-])[O-].[Cs+].[Cs+].O>C1(C)C=CC=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH:19]1([C:7]2[CH:12]=[CH:11][C:10]([N+:13]([O-:15])=[O:14])=[C:9]([F:16])[CH:8]=2)[CH2:21][CH2:20]1

참가 물질

8

반응물 5

HCID 962WaterHCID 6344DichloromethaneHCID 10796Cesium carbonateHCID 2760897Cyclopropylboronic acidHCID 219987353-Fluoro-4-nitrophenyl trifluoromethanesulfonate

생성물 1

HCID 574239144-Cyclopropyl-2-fluoro-1-nitrobenzene수율 91.7%

시약·촉매·용매 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)촉매HCID 1140Toluene용매

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온도
90 °C

실험 절차

A mixture of 3-fluoro-4-nitrophenyl trifluoromethanesulfonate (7.15 g, 24.73 mmol), cyclopropylboronic acid (2.55 g, 29.67 mmol), [1,1′-bis(diphenylphosphino)-ferrocene]dichloropalladium(II), complexed with dichloromethane (1:1) (1.62 g, 1.98 mmol), and 2M cesium carbonate in water (19.8 mL, 39.56 mmol) in toluene (39.5 mL) was degassed for 20 min. The reaction mixture was stirred at 90° C. under N2 for 2.5 h. The reaction was cooled to RT, diluted with ethyl acetate (200 mL), and filtered through a pad of Celite. The filtrate was washed with brine, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude residue was purified via flash column chromatography eluted with 0 to 75% DCM/hexane to give 4.11 g (91.7%) of 4-cyclopropyl-2-fluoro-1-nitrobenzene as an oil. 1H NMR (400 MHz, MeOD) δ 7.98 (dd, J=10.2, 6.6 Hz, 1H), 7.12-7.02 (m, 2H), 2.11-1.97 (m, 1H), 1.20-1.11 (m, 2H), 0.89-0.82 (m, 2H).

후처리

  1. customwas degassed for 20 min
  2. temperatureThe reaction was cooled to RT
  3. additiondiluted with ethyl acetate (200 mL)
  4. filtrationfiltered through a pad of Celite
  5. washThe filtrate was washed with brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe crude residue was purified via flash column chromatography
  10. washeluted with 0 to 75% DCM/hexane

출처 및 근거

ORD 기록
ord-a1635af6c8074d88a7f52fb8601296ec
출처 데이터셋
uspto-grants-2014_03
특허 번호
US08669361B2

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