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

多氟烷基取代的四苯基硼酸络合物的高亲脂性和稳定有机阴离子的合成。

基本信息

批准号：
02650613
负责人：
KOBAYASHI Hiroshi
金额：
$ 1.28万
依托单位：
Kyushu University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1990
资助国家：
日本
起止时间：
1990 至 1991
项目状态：
已结题

项目摘要

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.

目前的研究项目是调查形成庞大的和亲脂性稳定的四芳基硼酸根离子取代许多多氟烷基，它们在一系列疏水溶剂中的溶解度，和在酸性条件下的化学稳定性。研究结果如下：1）建立了一种简便的合成全氟和多氟烷基取代碘代苯的方法，这些碘代苯可作为相应的四芳基硼酸酯的前体。2)发展了一种有效的Grigrlard反应方法，用于形成在每个苯基上被3-全氟烷基、3，5-双（多氟烷基）和3-三氟甲基-5-多氟烷基取代的四芳基硼酸酯。3)引入具有增加的末端三氟甲基数目的支链多氟烷基取代基增强了四芳基硼酸四甲基铵在多卤代甲烷溶剂中的溶解度，尤其是在多氟烃溶剂中有效。直链的全氟烷基取代基似乎会降低溶解度。4)在二氯甲烷/硫酸两相体系和硫酸甲醇溶液中的化学稳定性与取代基的吸电子效应一致，其中取代基的吸电子效应最大。三氟甲基基团是最有效的，正如所推测的。5)在较高温度和高真空下干燥的反锂离子在二氯甲烷中最亲电，从而加速Diels-Alder反应并影响加合物的exo/endo选择性。