二茂铁四唑和二茂铁甲醛缩3-取代丙二醇衍生物的合成

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.

Synthesis of Novel Ferrocenyl Tetrazole and 3-Substituted Acetal Derivatives

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.