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

土星型 C_<60> 配合物的形成、性质和化学行为。

• 批准号: 11640551
• 负责人: YAMAGUCHI Yoshihiro
• 金额: $ 1.86万
• 依托单位: Kinki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640551/
• 关键词: Macrocyclic crown ether; Synthesis; Fullerene (C_<60>); Saturn-type C_<60> complex; 土星型抱接C_<60>

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

在近年来对C_<60>的研究中，C_<60>与几种反应物的直接转化反应几乎是相同的。我们对C_<60>的研究有以下几个特点：1)用超大环冠醚生成C_<60>的土星型配合物；2)在所生成的土星型配合物的顶端位置选择性地引入官能团。我们设计了两种冠冠醚（36-冠-4和由4个1,4-苯基和醚组成的冠醚(1)）作为宿主分子，用于生成C_<60>的土星型配合物，并完成了它们的合成。我们发现36-冠-4是一个潜在的铵盐寄主分子，并报道了（Syn. comm .）。中国科学，30,849-858(2000))。但我们虽在几种条件下进行了包合实验，但仍未得到由四个1,4-苯基和醚组成的36-冠-4和冠醚(1)包合C_<60>的明显结果。由于两个冠醚的柔韧性导致包合实验失败，我们设计了一个由四个1,3-二乙基苯和醚单元(2)组成的新型冠醚，并实现了它的合成。在2的合成路线中，我们选择了苯环单元与三键单元在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。通过电子吸收光谱测量，观察了C_<60>在甲苯中回流1小时后在合成冠醚中的包合行为。此外，约伯的情节和等吸点在c6和主机2之间的xxxnm。为溶液中1:1配合物的存在提供了证据。采用Rose和Drago法测定包合物在430 ~ 440nm区域的吸光度差，从而确定包合物的缔合常数。我们会把结果报告给j.a.m chem。soc。如《C_<60>的超巨环及其土星型超分子实体的合成》一文。少

项目成果

Y.Yamaguchi,S.Kobayashi,T.Wakamiya,Y.Matsubara,Z.Yoshida: "A Simple Hybrid Cyclyne Consisting of 1,3-Diethynylbenzen-and Ether Units : Synthesis and Novel Ag^+-Induced Cyclization Leading to the Perylene Skeleton Formation"Journal of the American Chemical

Y.Yamaguchi，S.Kobayashi，T.Wakamiya，Y.Matsubara，Z.Yoshida：“一种由 1,3-二乙炔基苯和醚单元组成的简单杂化环炔：合成和新型 Ag^ 诱导环化形成苝骨架

Yoshihiro Yamaguchi,Shigeya Kobayashi,Tateaki Wakamiya,Yoshio Matsubara,and Zen-ichi Yoshida: "SYNTHESIS OF HYDROPHOBIC SUPERMACROCYCLIC POLYETHERS"Synthetic Communications. 30巻5号. 849-858 (2000)

Yoshihiro Yamaguchi、Shigeya Kobayashi、Tateaki Wakamiya、Yoshio Matsubara 和 Zen-ichi Yoshida：“疏水性超大环聚醚的合成”Synthetic Communications 第 30 卷，第 5 期。849-858 (2000)。

Y.Yamaguchi,S.Kobayashi,T.Wakamiya Y.Matsubara,Z.Yoshida: "Synthesis of Hydrophobic Supermacrocyclic Polyethers"Synthetic Communication. 30. 849-858 (2000)

Y.Yamaguchi，S.Kobayashi，T.Wakamiya Y.Matsubara，Z.Yoshida：“疏水性超大环聚醚的合成”合成通讯。

Y.Yamaguchi, S.Kobayashi, T.Wakamiya, Y.Matsubara, Z.Yoshida: "Synthesis of Hydrophobic Supermacrocyclic Polyethers."Syn.Commun.. 30. 849-858 (2000)

Y.Yamaguchi、S.Kobayashi、T.Wakamiya、Y.Matsubara、Z.Yoshida：“疏水性超大环聚醚的合成”。Syn.Commun.. 30. 849-858 (2000)

Y.Yamaguchi, Y.Matsubara, Z.Yoshida: "Synthesis of Supermacrocyclic Crown Ethers and Creation of their Saturn-type C_<60> Complexes."Japan Society for the Promotiom of Science 116 Committee Report. 51. 203-216 (1999)

Y.Yamaguchi、Y.Matsubara、Z.Yoshida：“超大环冠醚的合成及其土星型 C_<60> 配合物的创建”。日本学术振兴会 116 委员会报告。