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

HRID 900703ノート

反応式

HRID 900703 の反応式
[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]

参加物

4

反応物 2

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

実験手順

A mixture of 3-isopropoxy4-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-isoquinolin4-yl]-acetic acid using the general procedure for Intermediate 20. Characterised as the ethyl ester, [MH]+ 496.

後処理

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

出典と根拠

ORDレコード
ord-3faf7742997541479f70605b321f797b
出典データセット
uspto-grants-2008_04
特許番号
US07361661B2

反応ノート

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