Water → 2-(4-Amino-3-trifluoromethyl-phenyl)-4-methyl-pentanoic acid ethyl ester

HRID 1512396노트

반응식

HRID 1512396 반응식
[CH2:1]([O:3][C:4](=[O:23])[CH:5]([C:10]1[CH:15]=[CH:14][C:13]([N+:16]([O-])=O)=[C:12]([C:19]([F:22])([F:21])[F:20])[CH:11]=1)[CH2:6][CH:7]([CH3:9])[CH3:8])[CH3:2].[Sn](Cl)Cl.O>C(O)C>[CH2:1]([O:3][C:4](=[O:23])[CH:5]([C:10]1[CH:15]=[CH:14][C:13]([NH2:16])=[C:12]([C:19]([F:21])([F:20])[F:22])[CH:11]=1)[CH2:6][CH:7]([CH3:9])[CH3:8])[CH3:2]

참가 물질

5

반응물 3

HCID 962WaterHCID 24479Stannous ChlorideHCID 579955184-Methyl-2-(4-nitro-3-trifluoromethyl-phenyl)-pentanoic acid ethyl ester

생성물 1

HCID 579955332-(4-Amino-3-trifluoromethyl-phenyl)-4-methyl-pentanoic acid ethyl ester수율 89.2%

시약·촉매·용매 1

HCID 702Ethanol용매

실험 절차

A suspension of 4-methyl-2-(4-nitro-3-trifluoromethyl-phenyl)-pentanoic acid ethyl ester (38.3 g, 115 mmol), tin (II) chloride (87.2 g, 460 mmol) and water (16.6 g, 920 mmol) in ethanol (500 mL) was heated at reflux for four hours. The reaction mixture was concentrated under reduced pressure; the residue was treated with ethyl acetate (300 mL) and aqueous NaOH solution (1 N, 2.5 L). The aqueous layer was extracted with ethyl acetate (3×600 mL). The combined organic layers were washed with brine (1 L), dried over Na2SO4, and concentrated under reduced pressure. The residue was purified by silica-gel flash chromatography eluting with heptane/ethyl acetate (10:1) to give 2-(4-amino-3-trifluoromethyl-phenyl)-4-methyl-pentanoic acid ethyl ester (31.1 g, 89%) as a yellow oil: 1H NMR (300 MHz, CDCl3): δ 7.35 (d, 1H, J=2.1 Hz), 7.27 (dd, 1H, J=8.4, 2.1 Hz), 6.69 (d, 1 H, J=8.4 Hz), 4.10 (m, 4 H), 3.54 (t, 1 H, J=7.8 Hz), 1.91 (m, 1H), 1.58 (m, 1 H), 1.44 (m, 1 H), 1.21 (t, 3 H, J=6.9 Hz), 0.90 (d, 3 H, J=6.6 Hz), 0.89 (d, 3 H, J=6.6 Hz); 13C NMR (75 MHz, CDCl3): δ 174.14, 143.45, 132.22, 128.58, 125.91 (q, J=4 Hz), 124.80 (q, J=271 Hz), 117.35, 113.60 (q, J=29 Hz), 60.60, 48.54, 42.35, 25.77, 22.46, 22.18, 14.04.

후처리

  1. temperaturewas heated
  2. temperatureat reflux for four hours
  3. concentrationThe reaction mixture was concentrated under reduced pressure
  4. additionthe residue was treated with ethyl acetate (300 mL) and aqueous NaOH solution (1 N, 2.5 L)
  5. extractionThe aqueous layer was extracted with ethyl acetate (3×600 mL)
  6. washThe combined organic layers were washed with brine (1 L)
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by silica-gel flash chromatography
  10. washeluting with heptane/ethyl acetate (10:1)

출처 및 근거

ORD 기록
ord-f877fe0ee6bb4f39bbd3990ab44b6763
출처 데이터셋
uspto-grants-2012_07
특허 번호
US08217064B2

반응 노트

불러오는 중…