[3+3] -PHOTOCYCLOADDITION OF ARENEDICARBOXYLIC ACID DERIVATIVES AND ALKYLBENZENES

[3 3] -芳二羧酸衍生物和烷基苯的光环加成

• 批准号: 09640708
• 负责人: KUBO Yasuo
• 金额: $ 2.05万
• 依托单位: SHIMANE UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640708/
• 关键词: ACID DERIVATIVES; ACID ANHYDRIDES; IMIDES; ALKYLBENZENES; PHOTOCHEMICAL REACTIONS; CYCLOADDITIONS; SINGLET EXCITED STATE; ELECTRON TRANSFER; 励起一重項状態

The purpose of this investigation is to clarify the mechanism and applicability of [3+3]-photocycloaddition of arenedicarboxylic acid derivatives and alkylbenzenes. The results obtained are as follows :1. From the investigations of the photoreactions of naphthalene derivatives, having acid anhydride, imide, diester, and dicyano groups at the 1,2-, 1,3- 1,4-, 2,3-, or, 1, 8-positions of the naphthalene ring, with alkylbenzenes, such as toluene, xylenes, and so on, [3+3]-photocycloaddition was found to be general in the reactions of naphthalene derivatives, having acid anhydride and imide group at the 1,8-positions of the naphthalene ring.2. No [3+3]-photocycloadditions were observed in the reactions of arenedicarboxylic acid derivatives, having arene structure other that naphthalene, such as benzene, anthracene, or phenanthrene.3. The quenching rate constants of the fluorescence of 1 , 8-naphthalenedicarboxylic anhydride and 1,8-naphthalenedicarboximide by alkylbenzenes were found to correlate well to the occurrence of the [3+3]-photoaddition.4. The free energy change AG associated with one-electron transfer from alkylbenzenes to the singlet excited states of arenedicarboxylic acid derivatives were revealed to play an important role to determine the type of the observed photoreactions. A large negative AG value seems to be essential for the occurrence of the reaction.5. From these results, possible reaction mechanism for the [3+3]-photocycloaddition, involving electron transfer from alkylbenzenes to the singlet excited states of arenedicarboxylic acid derivatives, proton transfer within the formed radical ion pair, electron transfer within the producedradical pair, and final thermal cycloaddition between the resulted anion and cation, was proposed. Applicability of the reaction and solvent effect on the reaction were reasonably explained by the reaction mechanism.

本研究的目的是阐明芳烃二羧酸衍生物与烷基苯的[3+3]-光环加成反应的机理和适用性。主要研究结果如下：1.通过对萘环1，2-、1，3-、1，4-、2，3-或1，8-位上具有酸酐、酰亚胺、二酯和二氰基基团的萘衍生物与甲苯、二甲苯等烷基苯的光反应的研究，发现[3+3]-光环加成反应在萘衍生物的反应中是普遍的，在萘环的1，8-位上具有酸酐和酰亚胺基团。在具有非萘芳烃结构的芳烃二羧酸衍生物如苯、蒽、菲的反应中没有观察到[3+3]-光环加成反应.烷基苯对1，8-萘二甲酸酐和1，8-萘二甲酰亚胺的荧光猝灭速率常数与[3+3]-光加成反应的发生有很好的相关性.与单电子转移从烷基苯芳烃二羧酸衍生物的单重激发态的自由能变化AG被揭示发挥重要作用，以确定所观察到的光反应的类型。大的负AG值似乎是反应发生的必要条件。根据这些结果，提出了[3+3]-光环加成反应可能的反应机理，包括电子从烷基苯转移到芳烃二羧酸衍生物的单重激发态，质子在所形成的自由基离子对内转移，电子在所产生的自由基对内转移，以及最终阴离子和阳离子之间的热环加成反应.通过反应机理合理地解释了反应的适用性和溶剂效应。

项目成果

Yasuo Kubo(久保恭男): "Photoreactions of N-Merhyl-1,8-naphthalimide with Methylbenzenes : [3+3]-Additions and Water-Incorporated Additions" Chemistry Letters. 1999.2. 175-176 (1999)

Yasuo Kubo：“N-甲基-1,8-萘酰亚胺与甲基苯的光反应：[3+3]-加成和水掺入加成”《化学快报》1999.2（1999）。

Yasuo Kubo(久保恭男): "Photoreactions of N-Methyl-1,8-naphthalimide with Methylbenzenes : 〔3+3〕-Additions and Water-Incorporated Additions" Chemistry Letters. 1999・2. 175-176 (1999)

Yasuo Kubo：“N-甲基-1,8-萘二甲酰亚胺与甲苯的光反应：[3+3]-加成和水掺入加成”化学快报1999・2（1999）。

Y.KUBO,N.FUSEYA,AND S.NAKAJIMA: "Photoreactions of N-Methyl-1,8-naphthalimide with Methylbenzenes : [3+3] -Additions and Water-Incorporated Additions." Chem.Lett.1999-2. 175-176 (1999)

Y.KUBO、N.FUSEYA 和 S.NAKAJIMA：“N-甲基-1,8-萘二甲酰亚胺与甲苯的光反应：[3 3]-加成和水掺入加成。”