Chemistry of Cyclophane-type Multi-bridged Compounds Containing Bridgehead Nitrogen Atom

含桥头氮原子的环芳型多桥化合物的化学

• 批准号: 06453040
• 负责人: INAZU Takahiko
• 金额: $ 4.61万
• 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 (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06453040/
• 关键词: n-pi interaction; ring contraction; inclusion phenomena; cyclophane; azacyclophane; カゴ型化合物; プロトン包接体; 電荷移動錯体

In order to investigate the n-pi interaction within a cyclophane-type multi-brigded compound, in which non-bonded electron pairs on the bridge-head nitrogen atom and the pi electron cloud on aromatic ring exist, we started to synthesize multi-bridged cyclophanes containing nitrogen atom at the bridgehead position. At first, coupling reactions between 1,3,5- tris (halomethyl) benzene and tris (N-tosylalkyl) amine were carried out, and the targeted compounds were obtained. But, the existence of the three nitrogen atoms at benzylic positions prevented to give the clear-cut evidence of the intramolecular n-pi interaction within the caged compound.Then, the elimination of three nitrogen atoms at benzylic positions was tried by the extrusion of nitrogens via N-nitroso derivative, but unfortunately failed. Further, in order to eliminate the influence of the another hetero atoms at benzylic positions, ring contraction reactions of the obtained dithia cage compound as a model compound were carried out and the extrusion of the two sulfur atoms successfully succeeded. Hitherto, the targeted tribridged cage compound containing three sulfur atomsat the benzylic positions was obtained. The extrusion of the sulfur atoms is under investigation.

为了研究桥头氮原子上存在非键电子对和芳环上存在pi电子云的环芳型多桥化合物中的n-pi相互作用，我们开始合成桥头位置含氮原子的多桥环番化合物。首先，将1，3，5-三(卤甲基)苯与三(N-甲苯磺酰基烷基)胺进行偶联反应，得到目标化合物。但是，由于苯位上三个氮原子的存在，无法给出笼状化合物中分子内n-pi相互作用的明确证据。然后，人们试图通过N-亚硝基衍生物挤出氮来消除分子中的三个氮原子，但不幸的是失败了。此外，为了消除苄基上另一个杂原子的影响，将得到的二硫杂环化合物作为模型化合物进行了缩环反应，成功地实现了两个硫原子的挤出反应。到目前为止，目标三桥笼化合物中的三个硫原子位于苄基位置。硫原子的挤压正在调查中。

项目成果

H.Takemura: "Synthesis and Inclusion Properties of Pyridinophane-Linked Macrocycles" J.Chem.Soc., Perkin Trans. 1. 277-280 (1996)

H.Takemura：“吡啶并芬连接的大环化合物的合成和包合特性”J.Chem.Soc.，Perkin Trans。

F. Inokuchi: "“Cation-π Interactions" Detected by Mass Spectrometry : Selective Recognition of Alkali Metal Cations by a π-Basic Molecular Cavity" Angew. Chem. Int. Ed. Engl.34. 1364-1366 (1995)

F. Inokuchi：“通过质谱检测的“阳离子-π 相互作用”：通过 π 碱性分子腔选择性识别”Angew，Ed 1364-1366。

T.Inazu,: "Nucleophilicity of Water and Alcohols toward Solvolytic Displacement at Silicon" Mem.Fac.Sci.Kyushu Univ.Ser.C,. 19(2). 129-138 (1994)

T.Inazu，：“水和醇的亲核性对硅的溶剂分解置换”Mem.Fac.Sci.Kyushu Univ.Ser.C，。

H. Takemura: "Synthsis and Properties of N-Substituted Azacalix[n]arenes" J. Incl. Phenom. Mol. Recog.18. 1-14 (1995)

H. Takemura：“N-取代的 Azacalix[n] 芳烃的合成和性质”J. Incl。

S. Osada: "Transannular Interactions in Fluorine-substituted [3.3] Metacyclophanes" Chem. Lett.1103-1104 (1995)

S. Osada：“氟取代的[3.3] Metacyclophanes 中的跨环相互作用”Chem。