Development of Novel Qumoid Compounds by Taking Advantage of the Molccular Cavities as a Steric Protection Environment

利用分子腔作为空间保护环境开发新型 Qumoid 化合物

• 批准号: 12440204
• 负责人: GOTO Kei
• 金额: $ 6.91万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12440204/
• 关键词: kinetic stabilization; quinoid compounds; calixarene; benzoquinone; quinoneimine; thioquinone; X-ray crystallographic analysis; 立体保護; 電子移動

Novel bowl-type molecular cavities have been applied to synthesis of a variety of quinoid compounds including highly reactive ones. A bridged calix[6]arene, where a 1,4-benzoquinone moiety is covalently anchored in the cavity of the calix[6]arene macrocycle with a rigid cone conformation, was synthesized and its structure was determined by X-ray analysis. The cyclic voltammogram showed 'that :its reduction potential is negatively shifted in comparison with the reference compounds without the calixarene macrocode. A stable N- unsubstituted quinoneimine was successfully synthesized by thermolysis of the corresponding p-azidophenol under basic conditions. Its crystal structure was established by X-ray analysis, presenting the first example of the crystallographic analysis of an N-unsubstituted quinoneimine. It was revealed that the imine moiety is effectively protected by the calix[6]arene macrocycle. The cyclic voltammogram indicated that the quinoneimine is subject to two-electron reduction in one step in contrast to the corresponding quinone, which is reduced by two steps. Stabilization of other reactive quinoid species such as thioquinones was also investigated.

新型碗型分子腔已应用于合成各种醌型化合物，包括高反应性化合物。合成了桥联的杯[6]芳烃，其中1,4-苯醌部分以刚性锥体构象共价锚定在杯[6]芳烃大环的空腔中，并通过X射线分析确定了其结构。循环伏安图显示：与不含杯芳烃宏代码的参考化合物相比，其还原电位发生负移。通过在碱性条件下热解相应的对叠氮苯酚，成功合成了稳定的N-未取代醌亚胺。通过 X 射线分析确定了其晶体结构，这是 N-未取代醌亚胺晶体学分析的第一个例子。结果表明，亚胺部分受到杯[6]芳烃大环的有效保护。循环伏安图表明，醌亚胺一步发生双电子还原，而相应的醌则发生两步还原。还研究了其他反应性醌类物质（例如硫醌）的稳定性。

项目成果

K.Goto: "Synthesis, Structure, and Reactions of the First Stable Aromatic S-Nitrosothiol Bearing a Novel Dendrimer-type Steric Protection Group"Chem. Lett.. 2001・12. 1204-1205 (2001)

K.Goto：“带有新型树枝状立体保护基团的第一个稳定芳香族 S-亚硝基硫醇的合成、结构和反应”Chem. 2001・1205 (2001)

K. Goto: "Synthesisk, Structure, and Reactions of the First Stable Atomatic S-Nitrosothiol Bearing a Novel Dendrimer-Type Steric Protection Group"Chem. Lett.. 2001. 1204-1205 (2001)

K. Goto：“带有新型树枝状聚合物型空间保护基团的第一个稳定原子 S-亚硝基硫醇的合成、结构和反应”Chem。

K.Goto: "A Novel Dendrimer-Type m-Terphenyl Substituent for the Kinetic Stabilization of Highly Reactive Species"Tetrahedron Lett.. 42・29. 4875-4877 (2001)

K.Goto：“用于高反应性物质动力学稳定的新型树枝状聚合物型间三联苯取代基”Tetrahedron Lett.. 42・29（2001）。

Kei Goto: "Synthesis and Reactions of Conformational Isomers of a Stable Selenenic Acid Bearing a Bridged Calix[6]arene Framework"Heteroatom Chemistry. 12. 195-197 (2002)

Kei Goto：“带有桥联杯[6]芳烃框架的稳定硒酸的构象异构体的合成和反应”杂原子化学。

K. Goto: "Synthesis and Reactions of Conformational Isomers of a Stable Selenenic Acid Bearing a Bridged Calix[6] arene Framework"Heteroatom Chem.. 12. 195-197 (2001)

K. Goto：“带有桥接杯[6]芳烃框架的稳定硒酸的构象异构体的合成和反应”Heteroatom Chem.. 12. 195-197 (2001)