Synthesis of novel redox systems having thiophenes highly integrated with quinone methides structure

具有与醌甲基化物结构高度集成的噻吩的新型氧化还原体系的合成

• 批准号: 23550053
• 负责人: KURATA Hiroyuki
• 金额: $ 3.41万
• 依托单位: Fukui University of Technology (2013)Osaka University (2011-2012)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2011
• 资助国家: 日本
• 起止时间: 2011 至 2013
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-23550053/
• 关键词: キノメチド; チオフェン; フェノール; キノン; 酸化還元; 立体障害; ターチオフェン; ラジカル; 酸化反応; オリゴチオフェン; 酸化還元系; エレクトロクロミズム

We have been interested in conjugated thiophene systems whose all hydrogen atoms are substituted by 2,6-di-tert-butyl-4-methylenecyclohexa-2,5-dienone (quinone-methide) structure. We have prepared thiophene and bithiophene derivatives (we named them "tetraquinothiophene"(1) and "hexaquinobithiohene"(2), respectively). These attract attention in term of dynamic multi-stage redox system as well as cross conjugated system adopting sulfur atom. Compounds 1 and 2 were synthesized from bromothiophene derivatives via Suzuki-Miyaura coupling. The structure of 1 was determined by X-ray analysis. There were little torsion of pinch-bonds and central five membered ring formed twist boat like conformation. The electrochemical properties of 1 and 2 were examined by cyclic voltammetry and the first reduction waves of them were observed irreversibly. It indicates conformational changes occur with one-electron reduction about both 1 and 2.

我们对所有氢原子都被2，6-二叔丁基-4-亚甲基环己-2，5-二烯酮（醌甲基）结构取代的共轭噻吩体系很感兴趣。我们已经制备了噻吩和联噻吩衍生物（我们分别命名为“四喹啉噻吩”（1）和“六喹啉二噻吩”（2））。其中动态多级氧化还原体系和硫原子交叉共轭体系引起了人们的关注。以溴噻吩衍生物为原料，通过Suzuki-Miyaura偶联反应合成了化合物1和2。通过X射线衍射分析确定了化合物1的结构。该化合物的中心五元环形成了扭曲的船形构象。用循环伏安法研究了化合物1和2的电化学性质，发现化合物1和2的第一个还原波是不可逆的。这表明构象变化发生在1和2附近的单电子还原。

项目成果

Triarylamines on [3]Radialene Scaffold : Novel [3]Radialene-based, Multi-step, Wide-range Redox Systems with Remarkably Low Oxidation Potentials

[3]Radialene 支架上的三芳基胺：新型基于 [3]Radialene 的多步骤、宽范围氧化还原系统，具有极低的氧化电位

• DOI: 10.1246/cl.2011.1033
• 发表时间: 2011
• 期刊: Chem.Lett.
• 作者: 松本幸三

Synthesis of p-Chloroazacalix[5]arene Pentamethyl Ether: Ring Size-Dependent Desorption of N-Benzyl Groups

对氯氮杂萼[5]芳烃五甲醚的合成：N-苄基的环尺寸依赖性解吸

• DOI: 10.3987/com-12-s
• 发表时间: 2012
• 期刊: Heterocycles
• 影响因子: 0.6
• 作者: T. Kushida;C. Camacho;A. Shuto;S. Irle;M. Muramatsu;T. Katayama;S. Ito;Y. Nagasawa;H. Miyasaka;E. Sakuda;N. Kitamura;Z. Zhou;A. Wakamiya;S. Yamaguchi;Hirohito Tsue
• 通讯作者: Hirohito Tsue

Aromaticity and π-bond covalency: prominent intermolecular covalent bonding interaction of a Kekule hydrocarbon with very significant singlet biradical character

• DOI: 10.1039/c2cc31955a
• 发表时间: 2012-01-01
• 期刊: CHEMICAL COMMUNICATIONS
• 影响因子: 4.9
• 作者: Shimizu, Akihiro;Hirao, Yasukazu;Yakushi, Kyuya
• 通讯作者: Yakushi, Kyuya

Bicyclo[6.3.0]undecapentaenyl Anion: The Next Higher Homolog of Indenyl Anion with Exceptionally Large Ion-Pairing Effects on its Tropicity

双环[6.3.0]十一五烯基阴离子：茚基阴离子的下一个更高同系物，对其热带性具有异常大的离子对影响

• DOI: 10.1002/asia.201301307
• 发表时间: 2014
• 期刊: Chemistry-An Asian Journal
• 影响因子: 4.1
• 作者: Hiroaki Ozoe;Yasutaka Uno;Chitoshi Kitamura;Hiroyuki Kurata;Masaji Oda;John W. Jones;Jr.;Lawrence T. Scott;Takeshi Kawase
• 通讯作者: Takeshi Kawase

キノメチド構造が高度に集積化されたオリゴチオフェン類の合成と性質

具有高度集成的Chinommethide结构的低聚噻吩的合成与性能

• 发表时间: 2013
• 作者: I. Tanaka;H. Kikuchi;H. Ohta;Y. Watanabe;M. Hayashi;鈴木 健志・蔵田 浩之・平尾 泰一・西内智彦・久保 孝史
• 通讯作者: 鈴木 健志・蔵田 浩之・平尾 泰一・西内智彦・久保 孝史