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

使用反应性氟化氨盐合成氟化大元环化合物

• 批准号: 10650833
• 负责人: YAMANAKA Hiroki
• 金额: $ 1.66万
• 依托单位: KYOTO INSTITUTE OF TECHNOLOGY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10650833/
• 关键词: Fluorinated vinamidinium salt; Diazepinium salt; Fluorinated heterocycles; large membered heterocycles; Ring polyamine; 大環状含フッ素複素環化合物; ペンタジエニウム塩

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.

研究了具有3种含氟取代基的乙酰胺盐在β碳上与1，N-烷二胺的反应。β-氟-[I]和β-三氟乙氧基乙胺盐[II]与乙二胺反应，以较高的产率得到相应的含氟七元环化合物地西平盐。相反，β-三氟甲基乙二胺盐[III]很容易与乙二胺反应生成14元和21元的三氟甲基化环状化合物的混合物，而不生成7元环化合物。当乙二胺用量较大时，反应在高稀溶液中进行，两种产物的比例约为1：1，有选择性地生成14元环化合物。这些大分子环化合物的结构通过各种光谱数据，特别是高分辨质谱学数据进行了确定，并通过X射线结构分析进行了确证。然而，有趣的是，N-甲基和N，N‘-二甲基乙二胺与III反应只得到相应的7元环化合物，产率很高。借助于分子轨道计算，讨论了乙二胺与乙胺盐III反应不生成7元环化合物的原因。讨论了大元环化合物的形成机理，并研究了III与1，3-丙二胺、1，4-丁二胺、1，6-己二胺等1，N-烷二胺的反应。在上述条件下，两种底物以2：2和3：3的比例反应得到了大分子环化合物的混合物。综上所述，乙二胺盐III与1，N-烷二胺反应顺利地生成了不同环大小的三氟甲基化大分子环化合物。该反应为合成大分子环多胺提供了一种新的有效方法。