CREATION AND CHARACTERIZATION OF CARBENES HAVING UNUSUAL STRUCTURE

具有不寻常结构的卡宾的产生和表征

• 批准号: 13640531
• 负责人: TAKAHASHI Yasutake
• 金额: $ 2.24万
• 依托单位: Mie University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13640531/
• 关键词: Endoperoxides; Dioxetane; Photoreaction; Sensitizer; Electron Transfer; Benzocyclobutenylidene

Single-electron oxidation and reduction of endoperoxides and dioxetanes result in their decomposition via chain process to generate singlet oxygen and chemiluminescence. In this study, synthesis of oligomeric endoperoxides and dioxetanes is examined in order to constitute electron-relay reaction systems. Also studied is the photoreaction and control of the systemsSynthesis of polymethylnaphthelenes and diaryldoxetanes are performed. Triiodobenzene, ethynylbenzene, and phthalic acids are used to synthesize the above mentioned oligomers of linear, side-chained, and dendrimer typesPhotoinduced decomposition of the oligomeric peroxides results in extrusion of dioxygen. Product analysis suggests efficient generation of singlet oxygen. The yield of singlet oxygen was tentatively determined to be about 70% by using fluorescence spectrophotometry. However, the value lacks reproducibility. Quite recently, it is found that the spectrophotometer has poor optical design and unexpectedly diminished sensitivity of the detector. The spectrophotometer with modified optical design and new detector is used to investigate the effect of sensitizer and solvent on the yield of singlet oxygen production

内过氧化物和二氧杂环丁烷的单电子氧化还原反应导致它们通过链式过程分解产生单线态氧和化学发光。在这项研究中，低聚内过氧化物和二氧杂环丁烷的合成进行了检查，以构成电子中继反应系统。研究了体系的光反应和控制，合成了多甲基萘和二芳基氧杂环丁烷。用三碘苯、乙炔苯和邻苯二甲酸合成了上述线型、侧链和树枝状低聚物。低聚过氧化物的光诱导分解导致分子氧的挤出。产物分析表明有效产生单线态氧。用荧光分光光度法初步测定了单线态氧的产率约为70%。然而，该值缺乏可重复性。最近，人们发现分光光度计的光学设计很差，检测器的灵敏度意外降低。采用改进的光学设计和新的检测器的分光光度计，考察了敏化剂和溶剂对单线态氧产率的影响

项目成果

Y.Takahashi: "Geometrically Strained Carbenes : Interdependence among Geometry, Spin Multiplicity, and Reactivity"J.Synth.Org.Chem., Jpn.. 59. 1070-1077 (2001)

Y.Takahashi：“几何应变卡宾：几何形状、自旋多重性和反应性之间的相互依赖性”J.Synth.Org.Chem., Jpn.. 59. 1070-1077 (2001)

Y Takahashi, Athanassios Nicolaides, Hideo Tomioka: "Geometrically Strained Carbenes : Interdependence among Geometry, Spin Multiplicity, and Reactivity"J.Synth.Org.Chem.Jpn.. 59. 1070-1077 (2001)

Y Takahashi、Athanassios Nicolaides、Hideo Tomioka：“几何应变卡宾：几何、自旋多重性和反应性之间的相互依赖性”J.Synth.Org.Chem.Jpn.. 59. 1070-1077 (2001)

T.Niwa, K.Kikuchi, Y.Takahashi, H.Ikeda, T.Miyashi: "Electron Transfer (ET) Fluorescence Quenching in Benzonitrile. Evidence of an Intermolecular ET with ΔG < -0.5 eV being a Diffusion-Controlled Process"J.Phys.Chem.A. 106. 4345-4349 (2002)

T.Niwa、K.Kikuchi、Y.Takahashi、H.Ikeda、T.Miyashi：“苯甲腈中的电子转移 (ET) 荧光淬灭。ΔG < -0.5 eV 的分子间 ET 是扩散控制过程的证据”J物理化学A 106。4345-4349 (2002)

T.Niwa: "Electron Transfer (ET) Fluorescence Quenching in Benzonitrile. Evidence of an Intermolecular ET with ΔG < -0.5 eV being a Diffusion-Controlled Process"J.Phys.Chem.A. 106. 4345-4349 (2002)

T. Niwa：“苯甲腈中的电子转移 (ET) 荧光淬灭。ΔG < -0.5 eV 的分子间 ET 是扩散控制过程的证据”J.Phys.Chem.A. 106. 4345-4349 (2002)