100% Selective Oxygenation of Alkyl Substituted Benzenes

100%%20选择性%20氧化%20的%20烷基%20取代%20苯

• 批准号: 13555247
• 负责人: FUKUZUMI Shunichi
• 金额: $ 8.32万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 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/en/grant/KAKENHI-PROJECT-13555247/
• 关键词: Photoinduced Electron Transfer; Photocatalysis; Molecular Oxygen; Oxygenation; NAD^+ Analog; Aromatic Hydrocarbon; Aldehyde; Olefin; 芳香族アルデヒド; 部分酸素化; 電子移動; アクリジニウムイオン; アルキルベンゼン; 酸素; α-メチルスチレン

A ring-substituted toluene with an electron-withdrawing substituent, p-tolunitrile, is oxygenated with molecular oxygen to yield the corresponding aldehyde using tetrafluoro-p-dicyanobenzene as a photosensitizer under photoirradiation with an Hg lamp (λ > 300 nm). The 100 % selective oxygenation of p-xylene to p-tolualdehyde is achieved using 10-methyl-9-phenylacridinium ion as a photosensitizer under visible light irradiation, leading to yield p-tolualdehyde exclusively as the final oxygenated product. Both oxygenation reactions are initiated by photoinduced electron transfer from the ring-substituted toluene to the singlet excited state of the photosensitizer. The reason for the high selectivity in the photocatalytic oxygenation of various toluene derivatives is discussed based on the photoinduced electron transfer mechanism.

带有电子带图的甲苯甲苯的甲苯p-二氟硝基列以分子氧氧合为氧气，以使用Tetrafluoro-pictyanonobenbenene作为光敏剂在光敏度下使用HG Lamp（HG Lamp（hg lame），使用Tetrafluoro-pictyanonobenenzene来产生相应的醛。在可见光光照射下，P-二甲苯至P-二醛的100％选择性氧合作为光（可见光的光传感器）实现，从而使P-Tolulauldeyde仅作为最终的氧合产物。两种氧合反应都是通过光诱导的电子从环取代的甲苯转移到光敏态的单个激发态的。根据光诱导的电子转移机制，讨论了各种甲苯衍生物的光催化氧合的高选择性的原因。

项目成果

Shunichi Fukuzumi et al.: "Fullerenes 2002--Volume 12. (Proceedings of the 201^<st> Meeting of the Electrochemical Society)"The Electrochemical Society, INC. 37 (2002)

Shunichi Fukuzumi 等人：“Fullerenes 2002--Volume 12.（电化学学会 201^<st> 会议记录）”The Electrochemical Society, INC. 37 (2002)

Shunichi Fukuzumi et al.: "C-H Bond Activation of External Substrates with a Bis(m-oxo)dicopper(III) Complex"J. Am. Chem. Soc.. 123・25. 6203-6204 (2001)

Shunichi Fukuzumi 等人：“使用 Bis(m-oxo)dicoper(III) 络合物活化外部基质” J. Am. Soc. 123・25 (2001)

Shunichi Fukuzumi et al.: "Porphyrin Monolayer-Modified Gold Clusters as Photoactive Materials"Adv. Mater. 13・15. 1197-1199 (2001)

Shunichi Fukuzumi 等人：“作为光活性材料的卟啉单层修饰金簇”Adv. 13・1199 (2001)。

Shunichi Fukuzumi et al.: "Formation, Charcterization, and Reactivity of Bis(μ-oxo)dinickel(III) Complexes Supported by A Series of Bis[2-(2-pyridyl)ethyl]amine Ligands"J. Am. Chem. Soc.. 123・45. 11168-11178 (2001)

Shunichi Fukuzumi 等人：“一系列双[2-(2-吡啶基)乙基]胺配体支持的双(μ-氧代)二镍(III)络合物的形成、表征和反应性”J. Am.社会.. 123・45. 11168-11178 (2001)

Fukuzumi, S. et al.: "Electron Transfer Properties of Bisphenol Derivatives in Relation with the Developing Properties in Silver Salt Photothermographic Systems"J. Imag. Sci. Tech.. 47(in press). (2003)

Fukuzumi, S. 等人：“双酚衍生物的电子转移特性与银盐光热成像系统中显影特性的关系”J。