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

研究了β碳上含3种氟取代基的乙烯脒盐与1，n-烷二胺的反应。β-氟代- [I]和β-三氟乙氧基乙烯脒盐[II]与乙二胺反应，以良好的产率得到相应的氟化七元环化合物二氮杂卓盐。相反，β-三氟甲基乙烯脒盐[III]容易与乙二胺反应，得到三氟甲基化的14-和21-元环化合物的混合物，而不产生7-元环化合物。当乙二胺用量较大且反应在高稀溶液中进行时，两种产物的比例约为1：1，并且观察到14元环化合物的选择性生成。通过各种波谱数据，特别是高分辨质谱数据，确定了这些大元环化合物的结构，最后通过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，仅以良好的产率得到相应的7元环化合物。通过分子轨道计算，讨论了乙烯脒盐III与乙二胺反应不生成7元环化合物的原因。探讨了大环化合物的形成机理，并研究了III与其它1，4-正二胺如1，3-丙二胺、1，4-丁二胺和1，6-己二胺的反应。总之，vinamidinium盐III与1，n-链烷二胺的反应顺利进行，产生不同环尺寸的三氟甲基化的大元环化合物。该反应为合成大环多胺提供了一种新的有效方法。

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.