Syntheses of highly lipophilic and stable organic anions of poly-fluoroalkyl-substituted tetraphenylboron ate-complex tipe.

目前的研究项目是研究由许多多氟烷基取代的体积大和亲脂稳定的四芳基硼酸盐离子的形成，它们在一系列疏水溶剂中的溶解度，以及在酸条件下的化学稳定性。研究结果如下：1)开发了制备全氟和多氟烷基取代碘苯的简便方法，可作为四芳基硼酸盐的前驱体。2)建立了高效的grgrlard反应方法，在每个苯基上生成3-全氟烷基取代的四芳基硼酸-5、3,5 -二（多氟烷基）和3-三氟甲基-5-多氟烷基。3)引入末端三氟甲基数量增加的支化多氟烷基取代基，提高了四芳基硼酸四甲基铵在聚卤甲烷溶剂中的溶解度，在聚氟碳溶剂中尤其有效。直链全氟烷基取代基似乎降低了溶解度。4)在二氯甲烷/硫酸两相和甲醇硫酸溶液中测定的化学稳定性与取代基的吸电子作用一致，其中。据推测，三氟甲基是最有效的。5)在高真空条件下高温干燥的反锂离子在二氯甲烷中亲电性最强，加速了Diels-Alder反应，影响了加合物的外/内选择性。

The present research project is to investigate the formation of bulky and lipophilic stable tetraarylborate ions substituted by many polyfluoroalkyl groups, their solubilities in a range of hydrophobic solvents, and chemical stabilities under acid conditions. Research results are as follows : 1) Convenient methods were developed for the preparation of perfluoro- and polyfluoro-alkyl-substituted iodobenzenes which were useful as precursors for the corresponding tetraarylborates. 2) Efficient Grigrlard reaction methods were developed for the formation of tetraarylborate-s substituted by 3-perfluoroalkyl, 3, 5-bis (polyfluoroalkyl), and 3-trifluoromethyl-5-polyfluoroalkyl on each phenyl group. 3) Introduction of branched polyfluoroalkyl substituents with an increased number of terminal trifluoromethyl groups enhanced the solubilities of tetramethylammonium tetraarylborates in polyhalomethane solvents, especially effective in polyfluorocarbon solvents. Straight-chained perfluoroalkyl substituents seemed to depress the solubility. 4) Chemical stabilities measured in dichloromethane/sulfuric acid two-phases and in methanolic sulfuric acid solutions were in accordance with the electron-withdrawing effect of substituents, among which. trifluoromethyl groups was most effective as presumed. 5) Counter lithium ion, which was dried at higher temperature under high vacuum, was most electrophilic in dichloromethane to accelerate the Diels-Alder reaction and to affect the exo/endo selectivity of the adducts.