Ethanol → 4-Methyl-2-(4-nitro-3-trifluoromethyl-phenyl)-pentanoic acid ethyl ester

HRID 1512395ノート

反応式

HRID 1512395 の反応式
[CH3:1][CH:2]([CH3:21])[CH2:3][CH:4]([C:8]1[CH:13]=[CH:12][C:11]([N+:14]([O-:16])=[O:15])=[C:10]([C:17]([F:20])([F:19])[F:18])[CH:9]=1)[C:5]([OH:7])=[O:6].S(=O)(=O)(O)O.[CH2:27](O)[CH3:28]>>[CH2:27]([O:6][C:5](=[O:7])[CH:4]([C:8]1[CH:13]=[CH:12][C:11]([N+:14]([O-:16])=[O:15])=[C:10]([C:17]([F:18])([F:19])[F:20])[CH:9]=1)[CH2:3][CH:2]([CH3:21])[CH3:1])[CH3:28]

参加物

4

反応物 3

HCID 702EthanolHCID 1118Sulfuric AcidHCID 579956164-Methyl-2-(4-nitro-3-trifluoromethyl-phenyl)-pentanoic acid

生成物 1

HCID 579955184-Methyl-2-(4-nitro-3-trifluoromethyl-phenyl)-pentanoic acid ethyl ester収率 83%

実験手順

To a solution of 4-methyl-2-(4-nitro-3-trifluoromethyl-phenyl)-pentanoic acid (42.3 g, 139 mmol) in absolute ethanol (300 mL) was added concentrated sulfuric acid (95-98%, 9.0 mL) and the solution was heated at reflux overnight. The reaction mixture was concentrated under reduced pressure; the residue was treated with a solution of sodium carbonate (5%, 300 mL) and the mixture was extracted with ethyl acetate (300 mL). The organic layer was washed with brine (300 mL), dried over sodium sulfate, and concentrated under reduced pressure. Purification by silica-gel flash chromatography eluting with heptane/EtOAc (10:1) gave 4-methyl-2-(4-nitro-3-trifluoromethyl-phenyl)-pentanoic acid ethyl ester (38.4 g, 83%) as a yellowish oil: 1H NMR (300 MHz, CDCl3): δ 7.90 (d, 1H, J=8.4 Hz), 7.82 (s, 1 H), 7.74 (dd, 1 H, J=8.4, 1.5 Hz), 4.18 (m, 2 H), 3.83 (t, 1 H, J=7.5 Hz), 2.06 (m, 1 H), 1.70 (m, 1 H), 1.50 (m, 1 H), 1.27 (t, 3H, J=7.2 Hz), 0.97 (d, 3 H, J=6.6 Hz), 0.96 (d, 3 H, J=6.3 Hz); 13C NMR (75 MHz, CDCl3): δ 172.24, 146.83, 145.04, 132.40, 127.51 (q, J=5 Hz), 125.28, 123.80 (q, J=32 Hz), 121.78 (q, J=272 Hz), 61.45, 49.45, 42.65, 26.03, 22.41, 22.17, 14.10.

後処理

  1. temperaturethe solution was heated
  2. temperatureat reflux overnight
  3. concentrationThe reaction mixture was concentrated under reduced pressure
  4. additionthe residue was treated with a solution of sodium carbonate (5%, 300 mL)
  5. extractionthe mixture was extracted with ethyl acetate (300 mL)
  6. washThe organic layer was washed with brine (300 mL)
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customPurification by silica-gel flash chromatography
  10. washeluting with heptane/EtOAc (10:1)

出典と根拠

ORDレコード
ord-161e0581efbd48af9311379324909299
出典データセット
uspto-grants-2012_07
特許番号
US08217064B2

反応ノート

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