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有机化学
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有机化学 ›› 2008, Vol. 28 ›› Issue (04): 741-745. 上一篇    下一篇

研究简报

二茂铁四唑和二茂铁甲醛缩3-取代丙二醇衍生物的合成

张慧卿a,b，周智明*,a，方敏a   

  1. (a北京理工大学化工与环境学院 北京 100081)
    (b北京化工大学理学院 北京 100029)
  • 收稿日期:2006-12-25 修回日期:2007-11-07 发布日期:2008-04-17
  • 通讯作者: 周智明

Synthesis of Novel Ferrocenyl Tetrazole and 3-Substituted Acetal Derivatives

ZHANG Hui-Qinga,b,ZHOU Zhi-Ming*,a,FANG Mina   

  1. (a School of Chemical Engineering and the Environment, Beijing Institute of Techology, Beijing 100081)
    (b School of Science, Beijing University of Chemical Technology, Beijing 100029)
  • Received:2006-12-25 Revised:2007-11-07 Published:2008-04-17
  • Contact: ZHOU Zhi-Ming

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被引次数

6

以甲酰基二茂铁6为原料, 通过与NH4OH•HCl的缩合反应得到二茂铁肟7, 再经脱水剂脱水得到二茂铁腈8, 最后在(n-C4H9)3SnCl的作用下与NaN3反应生成新化合物二茂铁四唑(9). 以甲酰基二茂铁为原料, 在对甲苯磺酸(PTSA)的催化作用下与原甲酸三甲酯反应生成二甲基二茂铁缩醛(10), 然后与(R)-(－)-3-氯-1,2-丙二醇反应得到新的二茂铁缩醛衍生物12, 12再与NaN3发生取代反应得到新的二茂铁缩醛衍生物13. 而新的二茂铁缩醛衍生物15的合成则是先由(R)-(－)-3-氯-1,2-丙二醇与CH3OH在NaOH的作用下生成(R)-(－)-1-甲氧基-2,3-丙二醇(14), 再由14与二甲基二茂铁缩醛(10)反应得到的. 所合成的新化合物都用MS, 1H NMR和IR谱确证了它们的结构.

关键词: 二茂铁, 四唑, 缩醛, 合成

Condensation of the prepared formyl ferrocene 6 with hydroxylammonium chloride gave ferrocenyl oxime 7, which was dehydrated to produce ferrocenyl nitrile 8. This nitrile was converted to new ferrocenyl tetrazol (9) using (n-C4H9)3SnCl and NaN3. In the presence of toluene-4-sulfonic acid (PTSA) the reaction between formyl ferrocene 6 and trimethyl orthoformate gave dimethyl acetal 10. Transacetalization of acetal 10 with (R)-(－)-3-chloro-1,2-propanediol furnished new ferrocenyl acetal 12, which was converted to ferrocenyl acetal 13 by a reaction with NaN3. The new ferrocenyl acetal 15 was obtained by a reaction of acetal 10 with (R)-(－)-1-methoxy-2,3-propanediol (14), which was obtained by a reaction of (R)-(－)-3- chloro-1,2-propanediol with CH3OH in the presence of NaOH. All of these new compounds were characterized by MS, 1H NMR and IR spectra.

Key words: tetrazole, ferrocene, acetal, synthesis