高等学校化学学报

高等学校化学学报 ›› 2003, Vol. 24 ›› Issue (4): 632.

• 论文 • 上一篇    下一篇

(Z)-2-苯氧(硫)基甲基-2-戊烯-γ-内酯和(Z)-2-苯氧(硫)亚甲基-γ-戊内酯的简便合成

刘利军1, 罗芬台2   

  1. 1. 宁夏大学化学化工学院, 银川 750021;
    2. 台湾中央研究院化学研究所, 台北 11529
  • 收稿日期:2002-02-27 出版日期:2003-04-24 发布日期:2003-04-24
  • 通讯作者: 刘利军(1958年出生),女,教授,从事有机合成研究.E-mail:ljliu@163.com E-mail:ljliu@163.com
  • 基金资助:

    科技部医药技术创新博士基金(批准号:96-901-06-70);台湾科学基金;台湾中央研究院自然科学基金资助

A Facile Syntheses of (Z)-2-Phenoxy(THIO)methylene-γ-pentanolide and (Z)-2-Phenoxy(THIO)methyl-2-penten-γ- lactone

LIU Li Jun1, LUO Fen Tair2   

  1. 1. College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750001, China;
    2. Institute of Chemistry, Academia Sinica, Taipei 11529, China
  • Received:2002-02-27 Online:2003-04-24 Published:2003-04-24

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摘要： 以3-苯氧(硫)基丙炔(1)为原料,经5步反应合成(Z)-2-苯氧(硫)基甲基-2-戊烯-γ-内酯(8)和(Z)-2-苯硫亚甲基-γ-戊内酯(9).合成关键步骤为TMSCl/NaI/H2O/CH3CN体系中化合物(3)的碘氢化和去共轭.

关键词: 碘氢化反应, &gamma, -戊内酯, 合成, 去共轭

Abstract: Starting from 3 phenoxy(thio) 1 propyne 1a(1b), 5 phenoxy(thio)3 pentyn 2 ol 2a(2b) were obtained by Grignard reaction. After treating 2a(2b) with Jones reagent, hydroiodination of 3a(3b) with a reagent system of TMSCl/NaI/H2O in CH 3CN, the conjugated product (Z) 5 phenoxy(thio) 4 iodo 3 pentene 2 one 4a(4b) and de conjugated product (Z) 5 phenoxy(thio) 4 iodo 3 pentene 2 one 5a(5b) were generated. In the presence of Pd(PPh3)4, Et 3N, and CO in toluene, the intramolecular cyclization of reducing products of 4a(4b) and 5a(5b) afforded the target compounds (Z)2 phenoxy(thio) methylene γ pentanolide 9a(9b) and (Z)2 phenoxy(thio) methyl 2 penten γ lactone 8a(8b) respectively in good yields. All compounds have been fully characterized by 1H and 13CNMR, IR and MS spectroscopy. The one pot deconjugation and hydroiodination of 3a(3b) with a reagent system of TMSCl/NaI/H2O in CH3CN was the key step.

Key words: Hydroiodination, &gamma, Pentenolide, Synthesis, Deconjugation

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