Generation and Application of Radicals and Polyradicals

自由基和多自由基的产生和应用

基本信息

  • 批准号:
    05453031
  • 负责人:
  • 金额:
    $ 4.1万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for General Scientific Research (B)
  • 财政年份:
    1993
  • 资助国家:
    日本
  • 起止时间:
    1993 至 1994
  • 项目状态:
    已结题

项目摘要

This project established 1) a new and efficient radical generation method which is applicable to organic synthesis (investigation A), 2) a new route to trimethylenemethane diradical from [3] dendralene (investigation B), and 3) a methodology utilizing pyridinyl radicals as spin building blocks for high spin organic compounds (investigation C).In the investigation A,a very efficient and mild radical generation method was realized by utilizing Nacyloxyphthalimides which can be readily prepared from various carboxylic acid in high yields. The reaction proceeds in the presence of colored radical scavenger in aqueous solvent with visible light excitation at room temperature and the reaction is readily applied to reductive decarboxylation, decarboxylative phenylselenenylation, and decarboxylative phenyltellurenylation. The quantum yields of theses reactions are usually over unity and readily available right sources such as projector lamp, halogen lamp, and sunlight can be used. Since phenylselenenyl group is known to be converted to various functional groups, this method clearly widens the scope of synthetic methods starting from carboxylic acids.In the investigation B,a novel photochemical reaction of [3] dendralene derivative leading to trimethylenemethane diradical intermediate was found. The intermediate was successfully trapped by molecular oxygen or in the flash photolysis experiment.4,4'-(m-Phenylene) bis (1-menthyl-2,6-diphenylpyridinyl) diradical and its analogues were prepared and their spin-multiplicities in the ground states were investigated by means of ESR in the investigation C.
本课题建立了1)一种新的、高效的适用于有机合成的自由基生成方法(研究A); 2)从[3] dendralene得到三亚甲基甲烷双自由基的新途径(研究B),和3)利用吡啶基自由基作为高自旋有机化合物的自旋结构单元的方法在研究A中,通过利用N酰氧基邻苯二甲酰亚胺实现了非常有效和温和的自由基产生方法,所述N酰氧基邻苯二甲酰亚胺可以容易地由各种羧酸以高产率制备。该反应在有色自由基清除剂存在下在水溶剂中在室温下用可见光激发进行,并且该反应容易地应用于还原脱羧、脱羧苯基硒化和脱羧苯基碲化。这些反应的量子产率通常超过1,并且可以使用容易获得的合适光源,如投影灯、卤素灯和太阳光。由于已知苯基硒基可转化为各种官能团,因此该方法明显拓宽了从羧酸开始的合成方法的范围。在研究B中,发现了[3] dendralene衍生物导致三亚甲基甲烷双自由基中间体的新型光化学反应。该中间体被分子氧或闪光光解实验成功捕获。4,本文合成了4 ′-(间苯撑)双(1-薄荷基-2,6-二苯基吡啶基)自由基及其类似物,用ESR研究了它们的基态自旋多重性。

项目成果

期刊论文数量(11)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Keiji Okada: "Redox-Mediated Decarboxylative Photo-Phenylselenenylation of N-Acyloxyphthalimides" Chem.Lett. 2021-2024 (1993)
Keiji Okada:“N-酰氧基邻苯二甲酰亚胺的氧化还原介导的脱羧光苯基硒化”Chem.Lett。
  • DOI:
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    0
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  • 通讯作者:
K.Kawamata: "Photoisomerization of (alpha-Anthryl)-ethyl spiro [cyclopropane-1,9'-fluorene]-2-carboxylates Studied by Stepwaise Two-color Two-photon Flash Photolysis" J.Phy.Chem.98. 2090-2094 (1994)
K.Kawamata:“通过 Stepwaise 双色双光子闪光光解研究的 (α-蒽基)-乙基螺环 [环丙烷-1,9-芴]-2-羧酸酯的光异构化”J.Phy.Chem.98。
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    0
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Koya Kawamata: "Photoisomerization of(α-Anthryl)ethyl spiro〔cyclopropane-1,9'-fluorene〕-2-carboxylates Stepwise Two-color Two-photon Flash Photolysis" J.Phy.Chem.98. 2090-2094 (1994)
Koya Kawamata:“(α-蒽基)乙基螺[环丙烷-1,9-芴]-2-羧酸酯的光异构化逐步双色双光子闪光光解”J.Phy.Chem.98 2090-2094 (1994)。 )
  • DOI:
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    0
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Keiji Okada: "Redox-Mediated Decarboxylative Photo-Phenylselenenylation of N-Acyloxyphthalimides" Chemistry Letters. 2021-2024 (1993)
Keiji Okada:“氧化还原介导的 N-酰氧基邻苯二甲酰亚胺的脱羧光苯基硒化”化学快报。
  • DOI:
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  • 影响因子:
    0
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Keiji Okada: "Novel Photochemical Reaction of〔3〕Dendralene Derivatives" Tetrahedron Lett.35. 5251-5252 (1994)
Keiji Okada:“新型光化学反应〔3〕Dendralene衍生物”Tetrahedron Lett.35(1994)。
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    0
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OKADA Keiji其他文献

OKADA Keiji的其他文献

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{{ truncateString('OKADA Keiji', 18)}}的其他基金

Synthesis and development of functional materials using organic- and metal-based electronic spins
利用有机和金属电子自旋合成和开发功能材料
  • 批准号:
    26288041
  • 财政年份:
    2014
  • 资助金额:
    $ 4.1万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Abomasal curd formation of colostrum and gamma globlin(IgG) absorption in the newborn calves.
初乳皱胃凝乳的形成和新生犊牛丙种球蛋白(IgG)的吸收。
  • 批准号:
    23580418
  • 财政年份:
    2011
  • 资助金额:
    $ 4.1万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Spin-Controlled Approach toward Development of Molecular Functions and Properties for Open-Shell Materials
用于开发开壳材料分子功能和性能的自旋控制方法
  • 批准号:
    22350066
  • 财政年份:
    2010
  • 资助金额:
    $ 4.1万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Development and Application of (Stable Radical)-substituted Radical Ions
(稳定自由基)取代自由基离子的开发与应用
  • 批准号:
    17350072
  • 财政年份:
    2005
  • 资助金额:
    $ 4.1万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Introduction an dinspection of immune profile test into metabolic profile test of cow heads.
将免疫谱检测引入牛头代谢谱检测中。
  • 批准号:
    14360184
  • 财政年份:
    2002
  • 资助金额:
    $ 4.1万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
A STUDY OF WHITE DIARRHEA CAUSED BY DAM'S MILK IN JAPANESE BLACK CALVES.
对日本黑犊牛母乳引起的白色腹泻的研究。
  • 批准号:
    10839002
  • 财政年份:
    1998
  • 资助金额:
    $ 4.1万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)

相似海外基金

Interplay Between Antiaromaticity and Diradical Character: New Structures and New Directions
反芳香性和双自由基特征之间的相互作用:新结构和新方向
  • 批准号:
    2246964
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    2023
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    $ 4.1万
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Tuning Antiaromaticity and Diradical Properties in Diarenoindacenes, Diindenoacenes, and Related Quinoidal Scaffolds
调节二茚并苯、二茚并苯和相关醌基支架的反芳香性和双自由基性质
  • 批准号:
    1954389
  • 财政年份:
    2020
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    $ 4.1万
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Development of multi-signaling cation sensor based on diradical metal complex
基于双自由基金属配合物的多信号阳离子传感器的研制
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    25810081
  • 财政年份:
    2013
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    $ 4.1万
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Metal-Catalyzed Diradical Reactivity: From Fundamental Thermal- and Photo-Chemistry to Novel Nanomaterials
金属催化的双自由基反应:从基础热化学和光化学到新型纳米材料
  • 批准号:
    1265703
  • 财政年份:
    2013
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Syntheses of compounds with ultralong C-C bond and investigation of their diradical character
超长C-C键化合物的合成及其双自由基性质的研究
  • 批准号:
    24750032
  • 财政年份:
    2012
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    $ 4.1万
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Metal-Catalyzed Diradical Reactivity: From Fundamental Thermal- and Photo-Chemistry to Novel Nanomaterials
金属催化的双自由基反应:从基础热化学和光化学到新型纳米材料
  • 批准号:
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  • 财政年份:
    2010
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RUI: A Theoretical Investigation of Multireference Diradical Molecules
RUI:多参考双自由基分子的理论研究
  • 批准号:
    0809462
  • 财政年份:
    2008
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The Singlet Diradical Character of Multiple Bonded Compounds of the Heavier Group 13 and 14 Elements
重13族和14族元素多重键合化合物的单线态双自由基特征
  • 批准号:
    0641020
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    2007
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    $ 4.1万
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CAREER: Towards Space- and Time- resolved Generation of p-Benzyne Diradical: Development of Photoswitchable Analogs of Natural Enediyne Antibiotics
职业:实现对苯炔双自由基的空间和时间分辨生成:天然烯二炔抗生素的光开关类似物的开发
  • 批准号:
    0449478
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    $ 4.1万
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    Continuing Grant
CAREER: Towards Space- and Time- resolved Generation of p-Benzyne Diradical: Development of Photoswitchable Analogs of Natural Enediyne Antibiotics
职业:实现对苯炔双自由基的空间和时间分辨生成:天然烯二炔抗生素的光开关类似物的开发
  • 批准号:
    0631210
  • 财政年份:
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  • 资助金额:
    $ 4.1万
  • 项目类别:
    Continuing Grant
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