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.

以四氟对二氰基苯为光敏剂，在汞灯(λ&GT；300 nm)的照射下，用分子氧氧化具有吸电子取代基的环取代甲苯，生成相应的醛。以10-甲基-9-苯基吖啶离子为光敏剂，在可见光照射下实现了对二甲苯100%选择性氧化制对甲苯甲醛，最终氧化产物为对甲苯甲醛。这两种氧化反应都是通过光致电子从环取代甲苯转移到光敏剂的单重态激发态来引发的。从光诱导电子转移机理出发，讨论了各种甲苯衍生物光催化氧化选择性高的原因。

项目成果

Fukuzumi, S.et al.: "Stepwise charge separation and charge recombination in ferrocene-meso, meso-linked porphyrin dimer-fullerene triad"Journal of the American Chemical Society. 124・18. 5165-5174 (2002)

Fukuzumi, S. 等人：“二茂铁-内消旋、内消旋卟啉二聚体-富勒烯三联体中的逐步电荷分离和电荷重组”美国化学会杂志 124・18 (2002)。

Fukuzumi, S.et al.: "Oxo-Transfer Reaction from a Bis(μ-oxo) dicopper(III) Complex to Sulfides"Journal of the American Chemical Society. 124・6. 998-1002 (2002)

Fukuzumi, S. 等人：“从双（μ-氧）二铜（III）络合物到硫化物的氧化转移反应”美国化学会杂志 124・6（2002 年）。

Fukuzumi, S.et al.: "Mechanisms of Electron Transfer Oxidation of NADH Analogs and the Chemiluminescence. Detection of the Keto and Enol Radical Cations"Journal of the American Chemical Society. 125・16. 4808-4816 (2003)

Fukuzumi, S. 等人：“NADH 类似物的电子转移氧化机制和化学发光。酮和烯醇自由基阳离子的检测”美国化学会杂志 125・16 (2003)。

Fukuzumi, S.et al.: "Evidence that gold(III) porphyrins are not electrochemically inert : facile generation of gold (II) 5,10,15,20-tetrakis(3,5-di-tert-butylphenyl) porphyrin"Chemical Communications (Cambridge, United Kingdom). 4. 356-357 (2002)

Fukuzumi, S.et al.：“金 (III) 卟啉不是电化学惰性的证据：轻松生成金 (II) 5,10,15,20-四(3,5-二叔丁基苯基)卟啉”

Fukuzumi, S.et al.: "Photophysical and Electrochemical Properties of New Bacteriochlorins and Characterization of Radical Cation and Radical Anion Species"Journal of Physical Chemistry A. 106・20. 5105-5113 (2002)

Fukuzumi, S. 等：“新菌绿素的光物理和电化学性质以及自由基阳离子和自由基阴离子种类的表征”《物理化学杂志》A. 106・20 (2002)。