Cesium carbonate → 4-Cyclopropyl-2-fluoro-1-nitrobenzene

HRID 79004

反応式

HRID 79004 の反応式
[F:1][C:2]1[CH:3]=[C:4](OS(C(F)(F)F)(=O)=O)[CH:5]=[CH:6][C:7]=1[N+:8]([O-:10])=[O:9].[CH:19]1(B(O)O)[CH2:21][CH2:20]1.C(=O)([O-])[O-].[Cs+].[Cs+]>C1(C)C=CC=CC=1>[CH:19]1([C:4]2[CH:5]=[CH:6][C:7]([N+:8]([O-:10])=[O:9])=[C:2]([F:1])[CH:3]=2)[CH2:21][CH2:20]1

参加物

5

反応物 3

HCID 10796Cesium carbonateHCID 2760897Cyclopropylboronic acidHCID 219987353-Fluoro-4-nitrophenyl trifluoromethanesulfonate

生成物 1

HCID 574239144-Cyclopropyl-2-fluoro-1-nitrobenzene収率 81.1%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
90 °C

実験手順

A stirred suspension of trifluoro-methanesulfonic acid 3-fluoro-4-nitro-phenyl ester (5.6 g, 19 mmol), cyclopropyl boronic acid (2.09 g, 23.3 mmol) Pd(dppf)Cl2 (1.24 g, 1.5 mmol) and 2M aqueous cesium carbonate (30 mL, 60 mmol) in toluene (20 mL) was degassed before being heated at 90° C. under an argon atmosphere for 2.5 hours. The reaction mixture was allowed to cool to room temperature before filtering through a pad of Celite®, washing with ethyl acetate. The filtrate was washed (water, brine), and then dried (MgSO4), filtered and concentrated in vacuo. The resultant residue was subjected to flash chromatography (Si—PPC, gradient 0-30% ethyl acetate in pentane) to give the title compound as a yellow solid (2.79 g, 81%). 1H NMR (DMSO-d6, 400 MHz) 8.03 (1 H, t, J=8.39 Hz), 7.28 (1 H, dd, J=13.19, 1.91 Hz), 7.16 (1 H, dd, J=8.61, 1.90 Hz), 2.14-2.05 (1 H, m), 1.21-1.05 (2 H, m), 0.92-0.82 (2 H, m).

後処理

  1. customwas degassed
  2. temperatureto cool to room temperature
  3. filtrationbefore filtering through a pad of Celite®
  4. washwashing with ethyl acetate
  5. washThe filtrate was washed (water, brine)
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-bcebc5a0d9714a5d9ad3123f096d0406
出典データセット
uspto-grants-2014_09
特許番号
US08841462B2

関連ノート

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