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.

新型碗状分子腔已被应用于合成包括高活性醌类化合物在内的多种醌类化合物。合成了一种桥联杯[6]芳烃，其中1，4-苯醌部分共价锚定在具有刚性锥形构象的杯[6]芳烃大环的空腔中，并通过X射线分析确定了其结构。循环伏安曲线表明：与不含杯芳烃宏码的参比化合物相比，其还原电位负移。在碱性条件下，通过对叠氮苯酚的缩合反应，成功地合成了稳定的N-未取代醌亚胺。它的晶体结构是通过X射线分析确定的，这是N-未取代的醌亚胺的晶体学分析的第一个例子。结果表明，亚胺部分被杯[6]芳烃大环有效地保护。循环伏安图表明，醌亚胺是在一个步骤中进行双电子还原，而相应的醌，这是由两个步骤。还研究了其他反应性醌类物质如硫代醌的稳定化。

项目成果

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: "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: "Synthesis, Structure, and Reactions of a Novel Triarylsilanol with a Bowl-type Framework : A Silanol Extremely Resistant to Self-Condensation"Chem. Lett.. 2001. 1258-1259 (2001)

K.Goto：“具有碗型骨架的新型三芳基硅烷醇的合成、结构和反应：一种极耐自缩合的硅烷醇”Chem。

Toshiyuki Saiki: "Structural Elucidation of 1, 3-Phenylenebis(methylene)-Bridged Calix[6]arenes with Four Uncapped Hydroxy Groups"Bulletin of the Chemical Society of Japan. 73. 1893-1902 (2000)

Toshiyuki Saiki：“具有四个未封端羟基的 1, 3-亚苯基双（亚甲基）-桥联杯[6]芳烃的结构阐明”日本化学会通报。

Kei Goto: "Synthesis and Crystal Structure of a Stable S-Nitrosothiol Bearing a Novel Steric Protection Group and of the Corresponding S-Nitrothiol"Tetrahedron Letters. 41. 8479-8483 (2000)

Kei Goto：“带有新型空间保护基团的稳定 S-亚硝基硫醇和相应 S-硝基硫醇的合成和晶体结构”四面体字母。