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

HRID 521822

反応式

HRID 521822 の反応式
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

参加物

8

反応物 5

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

生成物 1

HCID 574239144-Cyclopropyl-2-fluoro-1-nitrobenzene収率 91.7%

試薬・触媒・溶媒 2

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

反応条件

温度
90 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-70c988a1222b4ebaa89d61ae43e69663
出典データセット
uspto-grants-2016_05
特許番号
US09328106B2

関連ノート

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