【作者】 易文斌；

【导师】 蔡春；

【作者基本信息】 南京理工大学 ， 应用化学， 2006， 博士

【摘要】 研究了全氟萘烷／甲苯(C₁₀F₁₈／CH₃C₆H₅)，全氟萘烷／氟苯(C₁₀F₁₈／C₆H₅F)，全氟萘烷／苯甲醚(C₁₀F₁₈／C₆H₅OCH₃)，全氟甲基环己烷／甲苯(CF₃C₆F₁₁／CH₃C₆H₅)，全氟甲基环己烷／苯(CF₃C₆F₁₁／C₆H₆)，全氟甲基环己烷／正己烷(CF₃C₆F₁₁／C₆H₁₄)，1-溴代全氟辛烷／甲苯(C₈F₁₇Br／CH₃C₆H₅)氟两相体系（FBS）的相行为。 用相应的稀土氯化物或氧化物和全氟辛基磺酸反应来制备RE（OPf）₃（RE=Sc，Y，La～Lu）。并以DSC、ICP、IR和元素分析等手段对其进行了表征。 以RE（OPf）₃为催化剂，并选取全氟己烷(C₆F₁₄)、全氟甲苯（C₇F₈）、全氟甲基环己烷(C₇F₁₄)、全氟辛烷(C₈F₁₈)、1-溴代全氟辛烷(C₈F₁₇Br)和全氟萘烷(C₁₀F₁₈)为全氟溶剂，对硝化反应、酯化反应、Friedel-Crafts酰化反应、Friedel-Crafts烷基化反应、缩醛合成反应、Aldol缩合（醛和酮）反应、醇胺缩合反应、Mannich反应、氧化反应等有机反应进行了研究。考察了温度、时间、催化剂种类和用量、氟溶剂的种类和氟相与有机相相比等工艺条件对上述反应的影响。研究表明Yb（OPf）₃和全氟萘烷(C₁₀F₁₈)分别是最好的催化剂和全氟溶剂。含有催化剂的氟相通过简单的相分离，就可回收利用，氟相重复使用5次，其催化活性无明显降低。合成了部分过渡金属相应的全氟辛基磺酸盐（M（OPf）_x，M=Ti～Zn，x=2，3，4，5），并将它们用于催化烷基化、缩合和氧化反应，结果表明Co（OPf）₂是其中最有效的催化剂。 发现了一种新的催化体系：稀土盐-全氟磺酸-氟溶剂（RE（OPf）₃-PfOH-PFC），在该体系中能有效进行Friedel-Crafts酰化反应、Friedel-Crafts烷基化反应和二硝化反应。更多还原

【Abstract】 The behavior of fluorous biphasic systems （FBS） as followed were studied: perfluorodecalin/toluene (C₁₀F₁₈/CH₃C₆H₅), perfluorodecalin/fluorobenzene (C₁₀F₁₈/ C₆H₅F), perfluorodecalin/anisole (C₁₀F₁₈/C₆H₅OCH₃), perfluoromethylcyclohexane /toluene (CF₃C₆F₁₁/CH₃C₆H₅), perfluoromethylcyclohexane/benzene (CF₃C₆F₁₁/C₆H₆), perfluoromethylcyclohexane/hexane (CF₃C₆F₁₁/C₆H₁₄), perfluorooctyl bromide/toluene (C₈F₁₇Br/CH₃C₆H5).The catalyst of rare earth（III） perfluorooctanesulfonates （RE（OPf）₃, RE=Sc,Y, La～ Lu） were prepared from either rare earth chlorides（III） or oxides and perfluorooctane-sulfonic acid. The perflates obtained were characterized by DSC, ICP, IR, and Elemental Analysis. The perflates thus acted as novel catalysts for nitration, esterification, Friedel-Crafts acylation and alkylation, synthesis of acetal, aldol-condensation, condensation of alcohol with amine, Mannich reaction, and oxidation in fluorous biphasic system. Perfluorohexane (C₆F₁₄), perfluoromethylcyclohexane （C7F14）, perfluorotoluene （C₇F₈）, perfluorooctane (C₈F₁₈), perfluorooctyl bromide (C₈F₁₇Br) and perfluorodecalin (C₁₀F₁₈ , cis and /ram-mixture) can be used as fluorous solvents for these reactions. Effects of reaction temperature, reaction time, amount and species of catalyst, species of fluorous solvent, and the ratio of fluorous phase/organic phase on these reactions were investigated. Yb（OPf）₃ and C₁₀F₁₈ were the best catalyst and fluorous solvent respectively. By simple phase separation the fluorous phase containing catalyst could be re-utilized up to five times only with a little decrease in activity.The perfluorinated metal catalysts （M（OPf）_x, M = Ti～Zn, x = 2,3,4,5） were also prepared for Friedel-Crafts alkylation, aldol-condensation, and oxidation. It was found that Co（OPf）₂ was the most active catalyst.A novel catalytic system named ’RE（OPf）₃-PfOH-PFC’ has been found highly effective for Friedel-Crafts reaction and dinitration.更多还原