Synthesis and Properties of Novel Non-planar Extended Quinonoid Molecules Having o-Quinonoid Structure

具有邻醌结构的新型非平面延伸醌类分子的合成及性能

• 批准号: 16550036
• 负责人: KURATA Hiroyuki
• 金额: $ 2.37万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16550036/
• 关键词: quinone; non-planar; spiro-compound; photo-responce; Suzuki-Miyaura coupling; thiophene; redox behavior; diradical; チオインジゴ; フェノキシラジカル; 光スイッチング; ESR

Our research results are summarized as follows.1.Synthesis and properties of the extended pyracyloquinone derivativeThe extended-quinone derivativeof cyclopenta[fg]acenaphthylene-1, 2-dione (pyracyloquinone) was first synthesized and characterized. The molecular structure determined by X-ray analysis and redox behavior reflect the antiaromatic characted of the pyracylene moiety.2.Synthesis and properties of novel redox system having dithieno snnelsted bis(spirodienone) skeletonIn the course of the synthetic study on thioindigo-extended quinones, we prepared bis(benzo[b]thiophene)-annelated dispiro[5.4.5.0]hexadeca-1,4,7,9,12,15-hexaene-3,14-dione, a new skeleton molecule. This compound showed a ring-opening trasformation by two-electron reduction, and a photo-responsive property detected by ESR spectroscopy. Furthermore, a novel quaterquinone derivative based on dithieno-annelated dispiro[5.4.5.0]hexadeca-1,4,7,9,12,15-hexaene-3,14-dione was synthesized, which is a dark-green crystalline substance with metallic luster, shows a srtong absorption at 675nm. The temperature dependency of the redox process was elucidated by cyclic voltammetry.3.Synthesis of dithieno annelated o-terphenoquinone derivativesNovel o-terphenoquinone derivatives having benzo[2,1-b : 3,4-b']dithiophene and benzo[1,2-b : 4,3-b']dithiophene skeletons were synthesized from the correspondig bisphenols, prepared by McMurry coupling of the diketone derivatives. These quinones exist as the equiblibium mixture of the quinone-form and the diradical-form. Further oxidation of them afforded another speaces having deep-red and deep-blue color respectively. Detailed study of these compouds are in progress.

我们的研究成果如下：1.吡酰醌延伸衍生物的合成及性质首次合成并表征了环戊[fg]苊二酮(吡酰醌)的延伸醌衍生物。通过X射线分析和氧化还原行为确定的分子结构反映了吡啶部分的反芳香特征。2.具有二噻吩并双(螺二烯酮)骨架的新型氧化还原体系的合成和性能在硫靛延伸醌的合成研究过程中，我们制备了双(苯并[b]噻吩)-稠化的氧化还原体系。 dispiro[5.4.5.0]hexadeca-1,4,7,9,12,15-hexaene-3,14-dione，一种新的骨架分子。该化合物通过双电子还原表现出开环转化，并通过 ESR 光谱检测到光响应特性。此外，还合成了一种基于二噻吩并合二螺[5.4.5.0]hexadeca-1,4,7,9,12,15-己烯-3,14-二酮的新型季醌衍生物，该衍生物是一种深绿色结晶物质，具有金属光泽，在675nm处有强吸收。通过循环伏安法阐明了氧化还原过程的温度依赖性。 3.二噻吩稠合邻三苯醌衍生物的合成以苯并[2,1-b : 3,4-b']二噻吩和苯并[1,2-b : 4,3-b']二噻吩骨架为原料合成了新型邻三苯醌衍生物。 双酚，通过二酮衍生物的 McMurry 偶联制备。这些醌以醌形式和双自由基形式的平衡混合物存在。它们的进一步氧化提供了另一种分别具有深红色和深蓝色的空间。对这些化合物的详细研究正在进行中。

项目成果

Stilbene‐Extended Trithienylmethanophanes: A Novel C3‐Symmetric Cage Molecule Capable of Accommodating an Organic Molecule as well as Three Silver(I) Ions.

二苯乙烯扩展三噻吩基甲烷烷：一种新型 C3 对称笼分子，能够容纳有机分子以及三个银 (I) 离子。

• DOI: 10.1002/chin.200536053
• 发表时间: 2005
• 期刊: ChemInform
• 作者: H. Kurata;Kenji Haruki;M. Oda
• 通讯作者: M. Oda

Synthesis of Tetrakis(2-furyl)methane

四(2-呋喃基)甲烷的合成

• 发表时间: 2005
• 期刊: Chemistry Lett. 34・7
• 作者: Takeshi Kawase;Hiroyuki Kurata;Hiroyuki Kurata;Hiroyuki Kurata;Takeshi Kawase;Hiroyuki Kurata;Hiroyuki Kurata;Hiroyuki Kurata;Hiroyuki Kurata;Yusuke Kasai;Hiroyuki Kurata;Nobuyuki Harada;Hiroyuki Kurata;Nobuyuki Harada;Hiroyuki Kurata;Nobuyuki Harada;Krisztina Gyimesi-Forras;Junpei Naito;Shunsuke Kuwahara;Kouzou Matsumoto;Masashi Kosaka;Takeshi Kawase;Kouzou Matsumoto;Kazuaki Akasaka;Takeshi Kawase;Takuma Fujita;Kouzou Matsumoto;Shunsuke Kuwahara;Takeshi Kawase;Kouzou Matsumoto;Shunji Ito;Krisztina Gyimesi-Forras;Takeshi Kawase;Junpei Naito;Kouzou Matsumoto;Takeshi Kawase;Shunsuke Kuwahara;Masashi Kosaka;Kouzou Matsumoto;Nobuyuki Harada;Kazuaki Akasaka;Takeshi Kawase;Takeshi Kawase;Takuma Fujita;Shunsuke Kuwahara;Shunji Ito;Junpei Naito;Kazuaki Akasaka;Takuma Fujita;Hiroyuki Kurata
• 通讯作者: Hiroyuki Kurata

7,7-Dipyridyl-2,6-di-tert-butyl-p-quinone Methides : Synthesis, Complexation with Silver(I) Ion, and Oxidation to their Pyridine N-Oxide

7,7-联吡啶-2,6-二叔丁基-对醌甲基化物：合成、与银(I)离子络合以及氧化成吡啶N-氧化物

• 发表时间: 2006
• 期刊: Chemistry Lett. 35・1
• 作者: Takeshi Kawase;Hiroyuki Kurata;Hiroyuki Kurata;Hiroyuki Kurata;Takeshi Kawase;Hiroyuki Kurata;Hiroyuki Kurata;Hiroyuki Kurata;Hiroyuki Kurata;Yusuke Kasai;Hiroyuki Kurata;Nobuyuki Harada;Hiroyuki Kurata;Nobuyuki Harada;Hiroyuki Kurata;Nobuyuki Harada;Krisztina Gyimesi-Forras;Junpei Naito;Shunsuke Kuwahara;Kouzou Matsumoto
• 通讯作者: Kouzou Matsumoto

Synthesis, Structure and Properties of a Cyclopent[fg]acenaphthylene-l,2-bis(p-quinone methide)s Derivative. An Extended Pyracyloquinone

环戊二烯-1,2-双(对醌甲基化物)衍生物的合成、结构和性能。

• 发表时间: 2005
• 期刊: Chemistry Letters 34,12
• 作者: H.Takemura;K.Sako;S.Onaka;Kouzou Matsumoto;Hiroyuki Kurata
• 通讯作者: Hiroyuki Kurata

Synthesis, Structure and Properties of a Cyclopent[fg]acenaphthylene-1,2-bis(p-quinone methide)s Derivative. An Extended Pyracyloquinone

环戊二烯-1,2-双(对醌甲基化物)衍生物的合成、结构和性能。

• 发表时间: 2005
• 期刊: Chemistry Lett. 34・12
• 作者: Takeshi Kawase;Hiroyuki Kurata;Hiroyuki Kurata;Hiroyuki Kurata;Takeshi Kawase;Hiroyuki Kurata;Hiroyuki Kurata;Hiroyuki Kurata;Hiroyuki Kurata;Yusuke Kasai;Hiroyuki Kurata;Nobuyuki Harada;Hiroyuki Kurata;Nobuyuki Harada;Hiroyuki Kurata;Nobuyuki Harada;Krisztina Gyimesi-Forras;Junpei Naito;Shunsuke Kuwahara;Kouzou Matsumoto;Masashi Kosaka;Takeshi Kawase;Kouzou Matsumoto;Kazuaki Akasaka;Takeshi Kawase;Takuma Fujita;Kouzou Matsumoto;Shunsuke Kuwahara;Takeshi Kawase;Kouzou Matsumoto;Shunji Ito;Krisztina Gyimesi-Forras;Takeshi Kawase;Junpei Naito;Kouzou Matsumoto;Takeshi Kawase;Shunsuke Kuwahara;Masashi Kosaka;Kouzou Matsumoto;Nobuyuki Harada;Kazuaki Akasaka;Takeshi Kawase;Takeshi Kawase;Takuma Fujita;Shunsuke Kuwahara;Shunji Ito;Junpei Naito;Kazuaki Akasaka;Takuma Fujita;Hiroyuki Kurata;Shunsuke Kuwahara;Takeshi Kawase;Shunji Ito;Hiroyuki Kurata
• 通讯作者: Hiroyuki Kurata