SYNTHESIS OF FLUORINATED LARGE MEMBERED RING COMPOUNDS USING REACTIVE FLUORINATED VINAMIDINIUM SALTS

研究了在β碳上具有3种氟取代基的vinamidinium盐与1，n -烷二胺的反应。β-氟- [I]和β-三氟乙氧基氨基盐[II]与乙二胺反应得到相应的氟化7元环化合物重氮鎓盐，收率较高。相反，β-三氟甲基vinamidinium salt [III]很容易与乙二胺反应，生成三氟甲基化的14和21元环化合物混合物，而不生成7元环化合物。当加入大量的乙二胺，在高稀溶液中进行反应时，两种产物的比例约为1:1，可选择性生成14元环化合物。利用各种光谱数据，特别是HRMS，确定了这些大成员环化合物的结构，最后用x射线结构分析证实了它们的结构。然而，有趣的是，N-甲基和N， N'-二甲基乙二胺与III反应后，只生成相应的7元环化合物。用MO计算方法分析了丙二胺盐与乙二胺反应不生成七元环化合物的原因。讨论了大元环化合物的形成机理。还研究了III与1,3 -丙二胺、1,4 -丁二胺、1,6 -己二胺等其它1，n -烷二胺的反应。在所有情况下，两种底物以2:2和3:3的比例反应的大成员环化合物的混合物都获得了良好的产量。综上所述，vinamidinium salt III与1，n -烷二胺的反应顺利进行，生成了不同环尺寸的三氟甲基化大成员环化合物。该反应可能是合成大分子环多胺的一种新方法。

The reactions of the vinamidinium salts having 3 kinds of fluoro substituents at β carbon with 1, n-alkanediamines were investigated. The reaction β-fluoro- [I] and β-trifluoroethoxy vinamidinium salt [II] with ethylenediamine gave the corresponding fluorinated 7-membered ring compounds, diazepinium salts, in good yields. On the contrary, β-trifluoromethyl vinamidinium salt [III] reacted easily with ethylenediamine to afford a mixture of trifluoromethylated 14- and 21-membered ring compounds without giving of 7-membered ring compound. The ratio of both products was about 1:1 and selective formation of 14-membered ring compound was observed when large amounts of ethylenediamine was employed and the reaction was conducted in high dilute solution. The structures of these large membered ring compounds were determined by various spectra data, especially HRMS, and finally confirmed by X-ray structural analysis. However, interestingly, N-methyl- and N, N'-dimethylethlenediamine reacted with III to give only the corresponding 7-membered ring compounds in good yields. The reason why the reaction of vinamidinium salt III with ethylenediamine did not produce the 7-membered ring compound was considered by aid of MO calculations. The mechanism of the formation of large membered ring compound was discussed.The reactions of III with other 1, n-alkanediamine such as 1, 3-propanediamine, 1, 4-butanediamine and 1, 6-hexanediamine were also studied. In all cases, mixtures of the large membered ring compounds, which both substrates reacted in ratio of 2:2 and 3:3, were obtained in good yields.In summary, the reaction of vinamidinium salt III with 1, n-alkanediamine smoothly proceeded to produce trifluoromethylated large membered ring compounds of different ring size. This reaction could be a new useful method to synthesize large membered ring polyamines.