Photochemical Reactivities of Polar Molecules

极性分子的光化学反应性

• 批准号: 08650979
• 负责人: ISHIDA Akito
• 金额: $ 0.38万
• 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: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08650979/
• 关键词: photochemistry; benzalaniline; charge transfer; electron density; molecular orbital; reactive intermediate; polarization; nucleophilic addition; ベンザルアニリン; 光化学反応; 励起三重項状態; ラジカルイオン; 電子移動; 置換基効果; 分子軌道法; 1,3-双極子

The photochemilcal reactivity of benzalaniline apd its derivatives has been studied. Photoirradiation of a benzalaniline derivative .in tetrahydrofuran (THE) afforded a 1 : 1 THF adduct. The effective excitation band was the absorption around 260 nm named band II giving the singlet second photoexcited state. In the series, the reactivity highly depended upon the electron donating-withdrawing property as well as the position of the substituent. The reactive derivatives have been classified into three categories ; the derivative with an electron donating group at the 4-position, with an electron withdrawing group at the 4'-position, and with a halogen at the 4-position. The individual key-steps for the three categories, namely, hydrogen abstraction at the singlet second photoexcited state, successive electron and proton transfer at the singlet second photoexcited state, and hydrogen abstraction at the triplet second photoexcited state, have been proposed, respectively, on the basis of a mechanistic study using the electrolyte effect, observation of transient intermediates, quenching experiments, and the deuterium isotope effect. The characteristic positional dependence of the substituent effect on the reactivity has been discussed using semi-empirical MO calculation.

研究了亚苄基苯胺及其衍生物的光化学反应性。亚苄基苯胺衍生物在四氢呋喃（THF）中的光辐射提供1：1的THF加合物。有效激发带是260 nm附近的吸收，称为带II，给出单重第二光激发态。在该系列中，反应活性高度依赖于给-吸电子性质以及取代基的位置。反应性衍生物分为三类：在4-位具有给电子基团的衍生物、在4 '-位具有吸电子基团的衍生物和在4-位具有卤素的衍生物。在电解质效应机理研究、瞬态中间体观察、猝灭实验、电子转移和质子转移的基础上，分别提出了单重态第二光激发态夺氢、单重态第二光激发态连续电子和质子转移以及三重态第二光激发态夺氢这三类反应的关键步骤。和氘同位素效应。用半经验分子轨道计算讨论了取代基效应对反应活性的位置依赖性。

项目成果

Suzuki, Masanori ; Ikeno, Taketo ; Osoda Kazuhiko ; Narasaka, Koichi ; Suenobu, Tomoyoshi ; Fukuzumi, Shunichi ; Ishida, Akito: "Substituent effect by 1,4-benzenedicarbonitriles as sensitizers on the photoinduced electron transfer reactions in alcohols."

铃木正德；

Kojima,Masanobu: "Dimerization of 1-Phenylcycloalkcne Cation Radicals Dependent on their Structure." J.Am.Chem.Soc.118. 2612-2617 (1996)

Kojima,Masanobu：“1-苯基环烷阳离子自由基的二聚取决于其结构。”

Mikami,Koichi: "Addition reaction of allylic stannanes to the triplet excited state of C60 via photoinduced electron-transfer process" Synlett.85-87 (1997)

Mikami, Koichi：“通过光致电子转移过程将烯丙基锡与 C60 的三重激发态进行加成反应”Synlett.85-87 (1997)

Yanagida, Shozo ; Ogata, Tomoyuki, Kuwana, Yasuhiro ; Wada, Yuji ; Murakoshi, Kei ; Ishida, Akito ; Takamuku, Setsuo ; Kusaba, Mitsuhiro ; Nakashima, Nobuaki: "Synthesis of 2,2' : 5,2''-terpyridine and 2,2' : 5'2'' : 5'', 2'''-quaterpyridine and their pho

柳田翔三；

Itoh, Shinobu ; Komori, Takashi ; Chiba, Yutaka ; Ishida, Akito ; Takamuku, Setsuo ; Fukuzimi, Shunichi: "The photochemical oxidation of benzyl alcohols by the triplet excited state of coenzyme pyrroloquinolinequinone" Chem.Commun.465-466 (1996)

伊藤忍；