Photoinduced Electron-Transfer Reactions of Polyenes and Small Ring Compounds

多烯和小环化合物的光致电子转移反应

• 批准号: 03403005
• 负责人: MIYASHI Tsutomu
• 金额: $ 16.64万
• 依托单位: TOHOKU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (A)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03403005/
• 关键词: the Cope Rearrangement; Dimethylenefuran Derivative; Dimethylenepyrrole Derivative; Photoinduced Electron Transfer; Solid-State Photochemistry; ラジカルカチオンコーピ転位; テトラメチレンエタンビラジカル; ラジカルカチオンコ-プ転位; ミクロヘキサン1,4ージイル; テトラメチレンエタンラジカルカチオン

The photoinduced CR Cope rearrangements of 2,5-diaryl-1,5-hexadiene derivatives were investigated in terms of the energy surface. Combining chemical evidences with results on Ea for cyclization of diene cation radicals and the energy level of the cyclohexa-1,4-cation radical ion-pair obtained by pulse-radiolysis and photoacoustic calorimetric analysis, a cation radical cyclization-diradical cleavage mechanism was established for the photoinduced CR Cope rearrangement. The PET reaction of 1,4-diaryl-2,3-dimethylbicyclo[2.2.0]hexanes which is related to the CR Cope rearrangement provided the sensitizer and solvent polarity-dependent dual reactivity of 1,4-diaryl-2,3-dimethylbicyclo[2.2.0]hexane cation radicals. The intramolecular [2+2]cycloadditions of 2,6-diaryl-1,6-heptadiene cation radicals to form bicyclo[3.2.0]hexanes occurred efficiently, but the efficiency markedly decreased with an increase in the number of the methylene group between two stirene units for the PET reactions of 2, … More 7-diaryl-1,7-octadienes and 2,8-diaryl-1,8-nonadienes.The PET reactions of the 3,4-bis(styryl)-substituted furan and pyrrole derivatives were investigated by laser flash photolysis, which proved the generation of fused dimethylenefuran and dimethylenepyrrole derivatives and provided rate constants of chemical capture with electron-deficient diylophiles. By combination of these results with stereochemistry of chemical capture and MO calcultations, the ground state singlet states of fused dimethylenefuran and dimethylenepyrrole derivatives was determined. Experimental verification of the inversion of the spin multiplicity of dimethylenepyrroles is currently investigated for pyrrole derivatives with an electron-withdrawing group.Photoexciation reactions of solid state molecular complexes of BTDA and three divinyl benzenes provided intersting [2+2]cycloaddition reactions via electron-transfer. The probable absolute asymmetric synthesis via the single crystal-to-single crystal transformation is currently investigated for the solid state PET reaction of the molecular complex of BTDA and omicron-divinylbenzene. Less

用能面方法研究了2，5-二芳基-1，5-己二烯衍生物的光致CR-Cope重排反应。结合化学证据和二烯基阳离子自由基环化的电子能谱结果以及脉冲辐解和光声量热分析得到的环己-1，4-阳离子自由基离子对的能级，建立了光致CR-Cope重排反应的阳离子自由基环化-双自由基裂解机理.与CR Cope重排相关的1，4-二芳基-2，3-二甲基双环[2.2.0]己烷的PET反应为1，4-二芳基-2，3-二甲基双环[2.2.0]己烷阳离子自由基提供了敏化剂和溶剂极性相关的双重反应性。2，6-二芳基-1，6-庚二烯阳离子自由基在分子内[2+2]环加成生成双环[3.2.0]己烷，但在2，…的聚酯反应中，其效率随着两个苯乙烯单元之间亚甲基数目的增加而显著降低用激光闪光光解研究了3，4-二(苯乙烯基)取代呋喃和吡咯衍生物的PET反应，证明了聚二甲基呋喃和二甲基吡咯衍生物的生成，并提供了与缺乏电子的二亲电子分子的化学捕获速率常数。将这些结果与化学俘获立体化学和分子轨道计算相结合，确定了聚二甲基呋喃和二甲基吡咯衍生物的基态单重态。目前对含吸电子基团的吡咯衍生物的自旋多重数反转进行了实验验证。BTDA与三种二乙烯基苯的固体分子络合物的光激发反应通过电子转移提供了有趣的[2+2]环加成反应。目前，对于BTDA与欧米克-二乙烯基苯分子络合物的固态PET反应，可能的绝对不对称合成是通过单晶到单晶的转变来进行的。较少

项目成果

K.Kikuchi,C.Sato,M.Watabe,H.Ikeda,Y.Takahashi,T.Miyashi: "New Aspects on Fluorescence Quenching by Molecular Oxygen" J.Am.Chem.Soc.115. 5180-5184 (1993)

K.Kikuchi、C.Sato、M.Watabe、H.Ikeda、Y.Takahashi、T.Miyashi：“分子氧荧光猝灭的新方面”J.Am.Chem.Soc.115。

K.Kikuchi, N.Matsushita, M.Hayashi, T.Katagiri, Y.Takahashi, T.Miyashi: "Solvent Effects on Photoinduced Electron-Transfer Reactions" J.Phys.Chem.97. 11960-11940 (1993)

K.Kikuchi、N.Matsushita、M.Hayashi、T.Katagiri、Y.Takahashi、T.Miyashi：“溶剂对光诱导电子转移反应的影响”J.Phys.Chem.97。

Y.Takahashi: "Cycloreversion of Arene Endoperoxides induced by Electron Transfer" J.Chem.Soc.,Chem.Commun.,. (in press).

Y.Takahashi：“电子转移诱导的芳烃内过氧化物的环化”J.Chem.Soc.，Chem.Commun.，。

T.Hirano,T.Kumagai,T.Miyashi,K.Akiyama,Y.Ikegami: "Inversion of the Ground State Spin Multiplicity by ElectronーWithdrawing Groups in Trimethylenemethane Derivatives Generated Photochemically from Methylenezuadricyclane Derivatives" J.Org.Chem.,. 57. 876-8

T. Hirano、T. Kumagai、T. Miyashi、K. Akiyama、Y. Ikegami：“由亚甲基三环烷衍生物光化学生成的三亚甲基甲烷衍生物中吸电子基团对基态自旋多重性的反转”J.Org.Chem.,。 57.876-8

K.Kikuchi,M.Hoshi,T.Niwa,Y.Takahashi,T.Miyashi: "Heavyーatom Effects on the Excited Singletーstate Electron Transfer Reaction" J.Phys.Chem.,. 95. 38-42 (1991)

K. Kikuchi、M. Hoshi、T. Niwa、Y. Takahashi、T. Miyashi：“重原子对激发单态电子转移反应的影响”J.Phys.Chem., 95. 38-42 (1991) ）