Synthesis and Applications of Organotin Clusters with Multi-Layered Structure

合成了新型氟二苯醚[XR^F_2SnOSnR^F_2Y]_2（R^F=C_6F_<13>C_2H_4;C_4F_9C_2H_4，X，Y=Cl,Br，NCS）。正如预期的那样，这些化合物是高度亲氟的，因此当溶解在二元氟/有机溶剂混合物中时，对氟溶剂表现出高的分配系数。使用这些催化剂进行的含氟双相（反式）酯化反应使催化剂的定量回收成为可能，从而允许循环使用超过20次。更重要的是，即使使用严格1:1的反应物，反应也能达到100%的转化率和产率。这意味着氟双相技术实现了平衡反应的完美转化，这是以前已经实现的。接下来，用C_8F_<17>SO_3和（C_8F_<17>SO_2）_2N取代上述化合物中的氯原子，希望进一步提高亲氟性。所需要的化合物以水合物的形式得到，但它们并非完全不溶于含氟溶剂，这与我们的预期相反。另一方面，它们可溶于极性有机溶剂，令我们惊讶的是，当暴露于氟和极性有机溶剂的二元混合物中时，它们优先溶于氟溶剂。这种异常现象可以用极性有机溶剂代替水合水来解释。基于这一特性，氟二氨基诺烷被证明可以作为含氟表面活性剂。

Novel fluorodistannoxanes [XR^F_2SnOSnR^F_2Y]_2(R^F=C_6F_<13>C_2H_4;C_4F_9C_2H_4,X,Y=Cl,Br,NCS) were synthesized. As expected, these compounds were highly fluorophilic and thus exhibited high partition coefficients for the fluorous solvents when dissolved in a binary flurous/organic solvent mixture. The fluorous biphasic (trans)esterification by use of these catalysts enabled quantitative recovery of the catalysts, hence allowing the recycled use more than 20 times. More importantly, the reaction proceeded in 100% conversion and yield even by use of reactants in a strict 1:1 ratio. This means that the fluorous biphasic technology enabled the perfect conversion of the equilibrium reactions, which had be been realized before.Next, the chlorine atoms in the above compounds were replaced by C_8F_<17>SO_3 and (C_8F_<17>SO_2)_2N with the hope to further increase the fluorophilicity. The desired compounds were obtained as hydrates, but they were not completely insoluble in fluorous solvents in contrary to our expectation. On the hand, they were soluble in polar organic solvents and, to our surprise, they preferentially dissolved in fluorous solvents when exposed to a binary mixture of fluorous and polar organic solvents. This anomaly was explained by replacement of hydrated water with polar organic solvents. Based on this character, fluorous distannoxanes proved to work as fluorous surfactants.