Creation, Properties, and Chemical Behavior of Saturn-Type C_<60> Complexes.

在近年来的研究中<60>，<60>几乎都是以C_2与几种反应物的直接转化反应为研究对象。我们对C_2的研究<60>主要有以下几个方面：1）C_2<60>与超大环冠醚形成Saturn型配合物; 2）在所形成的Saturn型配合物的顶端位置区域选择性地引入官能团。我们设计了两种冠醚（36-冠-4和由四个1，4-亚苯基和醚单元组成的冠醚（1））作为主体分子，合成了C_3的土星型配合物<60>。我们已经发现36-冠-4是铵盐的潜在主体分子，并报道了（Syn.通信：30，849-858（2000））。但我们<60>在几种条件下进行了包结实验，但对于C_3与36-冠-4和由四个1，4-亚苯基和醚单元组成的冠醚（1）的包结，还没有得到明显的结果。我们认为 ...更多信息 由于两种冠醚的柔性使包结实验失败，因此我们设计并合成了一种由四个1，3-二乙炔基苯和醚单元组成的新型冠醚（2）。在2的合成路线中，我们选择了苯环单元和三键单元在Pd催化剂下的偶联反应作为最后一步，以较高的收率得到所需的冠醚。用<60>电子吸收光谱法研究了在甲苯中回流1h的条件下，C_2对合成冠醚的包结行为。此外，C6-和宿主2之间的Job图和xxxnm处的等吸光点。提供了溶液中存在1：1络合物的证据。用Rose和Drago法测定了包合物在430-440 nm波长范围内的吸光度差，并计算了包合物的缔合常数。我们将把结果以“超大环化合物及其含C_的土星型超分子实体的合成”为题向美国化学会报告<60>。少

In the recent studies on C_<60>, the direct conversion reactions of C_<60> with several reactants are almost. Our researches on C_<60> are characterized by the following points ; 1) the creation of Saturn-type complexes of C_<60> with the supermacrocyclic crown ethers, 2) the regioselective introduction of functional groups at the apical positions of the created Saturn-type complexes. We have designed two crown crown ethers (36-crown-4 and crown ether consisting of four 1,4-phenylene and ether units (1)) as the host molecules for the creation of Saturn-type complexes of C_<60> and accomplished their syntheses. We have found that 36-crown-4 is a potential host molecule for ammonium salts and reported (Syn. Commun., 30, 849-858 (2000)). But we have not yet obtained the obvious results about the inclusion of C_<60> with 36-crown-4 and crown ether consisting of four 1,4-phenylene and ether units (1) although we have tried the inclusion experiment under the several conditions. We have thoug … More ht the inclusion experiment fails by reason of the flexibility of two crown ethers, so we have designed a novel crown ether consisting of four 1,3-diethynylbenzene and ether units (2) and achieved its synthesis. In the synthetic route of 2, we have chosen the coupling reaction between benzene ring unit and triple bond unit with Pd catalyst as a final step to obtain the desired crown ether in higher yield. The inclusion behavior of C_<60> into the synthesized crown ether under the reflux for 1 hour in toluene has been observed by the measurement of electronic absorption spectrum. Furthermore, Job's plot and isosbestic point at xxxnm between C6-and host 2. provided evidence for 1 : 1 complex in solution. The association constant of the inclusion complexes was determined from the difference of absorbance at 430-440 nm region using Rose and Drago method. We will report the results to J.Am.Chem.Soc. as the article titled "Synthesis of Supermacrocycles and its Saturn type Supramolecular Entity with C_<60>". Less