Chemistry of Azacalixarenes and Their Analogs

氮杂杯芳烃及其类似物的化学

• 批准号: 09440219
• 负责人: INAZU Takahiko
• 金额: $ 9.02万
• 依托单位: Kyushu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09440219/
• 关键词: azacalixarene; betaine; inclusion compound; macro rings; calixarene; host-guest chemistry; ベタリン; ホストーゲスト化学

In order to investigate the inclusion abilities of the multi- functionalized azacalixarenes, in which the cation sites and the anion sites exist in one molecule, so-called betaine-type host molecules, we started to synthesize the calixarenes, in which several nitrogen atoms are at the side chains in the macro rings. At first, couplingreactions between the para-substituted 2,6-bis(hydroxymethyl)phenols and benzylamine were carried out and the targeted molecule, [3.3.3]- azacalixarene, were obtained. The quartenarization of the nitrogen atoms at the side chains gave the unexpected step-shaped molecule, according to the steric interactions between the aromatic rings and the bulky benzyl groups at the side chains.In case of diaza[3.1.3.1]calixarene derivative, the quarternarization of the two nitrogen atoms at the side-chains, followed by the deprotection at the phenolic hydroxyl groups, gave the expected target molecule, the betaine-type macrocyclic host molecule. The investigations of the inclusion phenomena between the obtained betaine-type azacalixarene as the host molecule and the betaine-type guest molecule, such as the amino adds, are now under way.

为了研究多官能团化氮杂杯芳烃分子的包结能力，我们开始合成具有多个氮原子的杯[芳烃]芳烃化合物。首先，对位取代的2，6-二羟甲基苯酚与苯甲胺发生偶联反应，得到目标分子[3.3.3]-氮杂杯芳烃。在二氮杂[3.1.3.1]杯芳烃类化合物中，侧链上的氮原子季节化，然后在酚羟基上脱保护，得到了预期的目标分子甜菜碱型大环宿主分子。作为主体分子的甜菜碱型氮杂杯芳烃与甜菜碱型客体分子如氨基加合物之间的包合现象的研究目前正在进行中。

项目成果

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H.Takemura：“含氟大环笼化合物的钾配合物：氟原子和金属离子之间的相互作用”Angew.Chem.（印刷中）。

M.Suenaga: "Synthesis of the Trinaphthophenalenium Cation" Angew.Chem.Int.Ed.37・1/2. 90-91 (1998)

M.Suenaga：“三萘酚阳离子的合成”Angew.Chem.Int.Ed.37・1/2（1998）。

H.Takemura: "Facile Syntheses of Highly Symmetrical Cage Type Cryptands Consist of Pyridine Rings:Properties as Host Molecules" J.Syn.Org.Chem.Jpn.,. 56・7. 209-215 (1998)

H.Takemura：“由吡啶环组成的高度对称笼型穴状化合物的简易合成：作为主体分子的性质”J.Syn.Org.Chem.Jpn.，209-215。

T.Inazu: "Synthesis and Properties of A New Series of Trogerophanes" J.Heterocyclic Chem.(in press.). (1998)

T.Inazu：“新系列 Trogerophanes 的合成和性能”J.Heterocycl Chem.（出版中）。