Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl ester → (E)-3-(3-isopropoxy-4-methoxy-phenyl)-acrylic acid ethyl ester

HRID 1745803

반응식

HRID 1745803 반응식
[CH:1]([O:4][C:5]1[CH:6]=[C:7]([CH:10]=[CH:11][C:12]=1[O:13][CH3:14])[CH:8]=O)([CH3:3])[CH3:2].[CH2:15]([O:17][C:18]([CH:20]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)=[O:19])[CH3:16]>C1(C)C=CC=CC=1>[CH2:15]([O:17][C:18](=[O:19])/[CH:20]=[CH:8]/[C:7]1[CH:10]=[CH:11][C:12]([O:13][CH3:14])=[C:5]([O:4][CH:1]([CH3:3])[CH3:2])[CH:6]=1)[CH3:16]

참가 물질

4

반응물 2

HCID 70670Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl esterHCID 5920923-Isopropoxy-4-methoxybenzaldehyde

생성물 1

HCID 69201427(E)-3-(3-isopropoxy-4-methoxy-phenyl)-acrylic acid ethyl ester

시약·촉매·용매 1

HCID 1140Toluene용매

실험 절차

A mixture of 3-isopropoxy-4-methoxy-benzaldehyde (3.9 g, 20 mmol) and (ethoxycarbonylmethylene)triphenylphosphorane (6.96 g. 20 mmol) in toluene (100 ml) is heated at reflux for 2 hours, cooled to ambient temperature and evaporated. The crude product is taken in to dichloromethane and eluted through a pad of silica to afford (E)-3-(3-isopropoxy-4-methoxy-phenyl)-acrylic acid ethyl ester, TLC Rf 0.70 (1:1 hexane-ethyl acetate). This intermediate is dissolved in nitromethane (10 ml), 1,1,3,3-tetramethylguanidine (0.5 ml) is added and the reaction heated at 70° C. for 36 hours. The solvent is evaporated, the residue is taken into ethyl acetate and washed with 2N aqueous HCl, water and brine. After drying over sodium sulfate and evaporation, the crude product is purified by flash column chromatography (4:1 hexane-ethyl acetate elution) to afford 3-(3-isopropoxy-4-methoxy-phenyl)-4-nitro-butyric acid ethyl ester, 1H NMR (400 MHz, CDCl3) δ 1.20 (t J 7 3H), 1.38 (d J 7 6H), 2.75 (d J 6 2H), 3.90 (m 1H), 4.10 (m 2H), 4.48-4.78 (m 3H), 6.75-6.86 (m 3H). This intermediate is converted into [1-(3,5-diisopropoxy-phenyl)-6-isopropoxy-7-methoxy-isoquinolin-4-yl]-acetic acid using the general procedure for Intermediate 20. Characterised as the ethyl ester, [MH]+ 496.

후처리

  1. temperatureis heated
  2. temperatureat reflux for 2 hours
  3. customevaporated
  4. washeluted through a pad of silica

출처 및 근거

ORD 기록
ord-6bbbdf1a70474599b35fd172282b5fb4
출처 데이터셋
uspto-grants-2006_03
특허 번호
US07019136B2

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