2001 Fiscal Year Annual Research Report

アルキル置換芳香族の100%選択的部分酸素化反応の開発

Research Project

Project/Area Number	13555247
Research Institution	Osaka University
Principal Investigator	福住俊一大阪大学, 大学院・工学研究科, 教授 (40144430)
Co-Investigator(Kenkyū-buntansha)	末延知義大阪大学, 大学院・工学研究科, 助手 (90271030) 今堀博大阪大学, 大学院・工学研究科, 助教授 (90243261)
Keywords	芳香族アルデヒド / 部分酸素化 / 光触媒 / 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
Research Abstract	アルキル置換芳香族を対応する芳香族アルデヒドに選択的に部分酸素化させる反応は、医薬品、染料、殺虫剤、香料などの種々の薬品の製造中間体として有用な芳香族アルデヒドを製造する上で、工業化学的に非常に重要な反応である。従来、アルキルベンゼンの部分酸素化には無機酸化剤が用いられて来たが、これらの酸化剤を用いてアルキルベンゼンの酸素化を行った場合には、生成する芳香族アルデヒドの収率が低く、選択性が悪いという欠点がある。また、化学量論量の無機酸化剤が必要となるため、環境汚染が深刻な問題となる。従って、酸化剤として酸素を用いる芳香族アルデヒドの触媒的製造法の開発が待ち望まれている。本研究は、光電子移動反応を利用して、酸化剤として無機酸化剤を使用せずに、酸素を用いてアルキル置換芳香族から芳香族アルデヒドを触媒的かつ高選択的に製造し得る方法を開発することを目的としている。一般に複数のアルキルで置換された芳香族の一つのアルキル基だけを選択的に酸素化して対応するアルデヒドにすることは至難の技である。しかし、光電子移動の反応性の差を利用すれば可能となる。アクリジニウムイオン誘導体の中で適当なものを選ぶことにより、複数のアルキルで置換された芳香族の一つのアルキル基だけを100%選択的に酸素化して対応するアルデヒドにする光触媒反応を開発した。また、α-メチルスチレンおよびアクリジニウムイオンの重アセトニトリル溶液に水銀ランプで300nm以上の光を照射すると、アセトフェノンとホルムアルデヒドが得られた。この光触媒酸素化反応はα-メチルスチレンから一重項励起状態のアクリジニウムイオンへの電子移動を経由して進行することがわかった。

Research Products

(29 results)

All Other

All Publications (29 results)

[Publications] Shunichi Fukuzurni et al.: "Fine Tuning of the Interaction between the Copper(I) and Disulfide Bond Formation of a Bis(m-thiolato)dicopper(II) Complex by Reductive Cleavage of the Disulfide Bond with Copper(I)"J. Am. Chem. Soc.. 123・17. 4087-4088 (2001)
[Publications] 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)
[Publications] Shunichi Fukuzumi et al.: "Charge Separation in a Novel Artificial Photosynthetic Reaction Center Lives 380ms"J. Am. Chem. Soc.. 123・27. 6617-6628 (2001)
[Publications] Shunichi Fukuzumi et al.: "Oxygenation of Phenols to Catechols by A (μ-η^2:η^2-peroxo)dicopper(II) Complex : Mechanistic Insight into the Phenolase Activity of Tyrosinase"J. Am. Chem. Soc.. 123・27. 6708-6709 (2001)
[Publications] Shunichi Fukuzumi et al.: "Change in Spin State and Enhancement of Redox Reactivity of Photoexcited States of Aromatic Carbonyl Compounds by Complexation with Metal Ion Salts Acting as Lewis Acids. Lewis Acid-Catalyzed Photoaddition of Benzyltrimethylsilane and Tetramethyltin via Photoinduced Electron Transfer"J. Am. Chem. Soc.. 123・32. 7756-7766 (2001)
[Publications] Shunichi Fukuzumi et al.: "Photoalkylation of 10-Alkylacridinium Ion via a Charge-Shift Type of Photoinduced Electron Transfer Controlled by Solvent Polarity"J. Am. Chem. Soc.. 123・35. 8459-8467 (2001)
[Publications] Shunichi Fukuzumi et al.: "Metal Ion-Catalyzed Cycloaddition vs hydride Transfer Reactions of NADH Analogues with ρ-Benzoquinones"J. Am. Chem. Soc.. 123・42. 10191-10199 (2001)
[Publications] Shunichi Fukuzumi et al.: "Photochemical and Electrochemical Properties of Zinc Chlorin-C_<60>, Dyad as Compared to Corresponding Free-Base Chlorin-C_<60>, Free-Base Porphyrin-C_<60> and Zinc Porphyrin-C_<60> Dyads."J. Am. Chem. Soc.. 123・43. 10676-10683 (2001)
[Publications] 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)
[Publications] Shunichi Fukuzumi et al.: "Extremely Slow Long-Range Electron Transfer Reactions across Zeolite-Solution Interface"J. Am. Chem. Soc.. 123・45. 11331-11332 (2001)
[Publications] Shunichi Fukuzumi et al.: "Scandium Ion-Promoted Photoinduced Electron-Transfer Oxidation of Fullerences and Derivatives by p-Chloranil and p-Benzoquinone"J. Am. Chem. Soc.. 123・50. 12458-12465 (2001)
[Publications] Shunichi Fukuzumi et al.: "Large Photocurrent Generation of Gold Eelectrodes Modified with [60]Fullerene-Linked Oligothiophenes Bearing a Tripodal Rigid Anchor"J. Am. Chem. Soc.. 124・4. 532-533 (2002)
[Publications] Shunichi Fukuzumi et al.: "Oxo-transfer Reaction from A Bis(μ-oxo)dicopper(III) Complex"J. Am. Chem. Soc.. 124・6. 998-1002 (2002)
[Publications] Shunichi Fukuzumi et al.: "Efficient Catalysis of Rare-Earth Metal Ions in Photoinduced Electron-Transfer Oxidation of Benzyl Alcohols by a Flavin Analogue"J. Phys. Chem. A. 105・46. 10501-10510 (2001)
[Publications] Shunichi Fukuzumi et al.: "Electron Transfer Properties of Singlet Oxygen and Promoting Effects of Scandium Ion"J. Phys. Chem. A. 106・7. 1241-1247 (2002)
[Publications] Shunichi Fukuzumi et al.: "Dehydrogenation vs Oxygenation in Photosensitized Oxidation of 9-Substituted 1O-Methyl-9, 1O-dihydroacridine in the Presence of Scandium Ion"J. Phys. Chem. A. 106・7. 1465-1472 (2002)
[Publications] Shunichi Fukuzumi et al.: "Characterization of Imidazolate-Bridged Dinuclear and Mononuclear Hydroperoxo Complexes"Inorg. Chem. 40・13. 3200-3207 (2001)
[Publications] Shunichi Fukuzumi et al.: "Modulation of Coordination Chemistry in Copper(I) Complexes Supported by Bis[2-(2-pyridyl)ethyl]amine-Based Tridentate Ligands"Inorg. Chem. 40・26. 6604-6609 (2001)
[Publications] Shunichi Fukuzumi et al.: "Spectroscopy and Photocurrent Generation in Nanostructured Thin FiIms of Porphyrin-Fullerene Dyad Clusters"Chem. Lett. 784-785 (2001)
[Publications] Shunichi Fukuzumi et al.: "Quantitative Evaluation of Lewis Acidity of Zinc Ion with Tetradentate Tripodal Ligands in Formation of the Superoxide Complexes"Chem. Lett. 920-921 (2001)
[Publications] Shunichi Fukuzumi et al.: "Evaluation of Lewis Acidity of Organotin Compounds and the Catalytic Reactivity in Electron Transfer"Chem. Lett. 978-979 (2001)
[Publications] Shunichi Fukuzumi et al.: "Superoxide Anion Generation via Electron-Transfer Oxidation of Catechin Dianion by Molecular Oxygen in an Aprotic Medium"Chem. Lett. 1152-1153 (2001)
[Publications] Shunichi Fukuzumi et al.: "Coordination of Semiquinone and Superoxide Radical Anions to the Zinc Ion in SOD Model Complexes that Act as the Key Step in Disproportionation of the Radical Anions"Chem. Eur. J.. 7・22. 4947-4953 (2001)
[Publications] Shunichi Fukuzumi et al.: "Concentration Effects of Porphyrin Monolayers on the Structure and Photoelectrochemical Properties of Mixed Self-Assembled Monolayers of Porphyrin and Alkanethiol on Gold Electrodes"Langmuir. 17・16. 4925-4931 (2001)
[Publications] Shunichi Fukuzumi et al.: "Porphyrin Monolayer-Modified Gold Clusters as Photoactive Materials"Adv. Mater. 13・15. 1197-1199 (2001)
[Publications] Shunichi Fukuzumi et al.: "Charge-transfer emission of compact porphyrin-fullerene dyad analyzed by Marcus theory of electron-transfer"Spectrochim. Acta Part A. 57. 2229-2244 (2001)
[Publications] Shunichi Fukuzumi 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"Chem. Commun.. 356-357 (2002)
[Publications] Shunichi Fukuzumi et al.: "Thermal Intramolecular Electron Transfer in a Ferrocene-Naphthoquinone Linked Dyad Promoted by Metal Ion"Angew. Chem. Int. Ed.. 41・4. 620-622 (2002)
[Publications] Shunichi Fukuzumi et al.: "Fullerenes 2001--Volume 11. (Proceedings of the Eighth International Symposium of the 197th Meeting of The Electrochemical Society)"The Electrochemical Society, INC.. 69 (2001)

2001 Fiscal Year Annual Research Report

アルキル置換芳香族の100%選択的部分酸素化反応の開発

Principal Investigator

福住 俊一 大阪大学, 大学院・工学研究科, 教授 (40144430)

Research Products

[Publications] Shunichi Fukuzurni et al.: "Fine Tuning of the Interaction between the Copper(I) and Disulfide Bond Formation of a Bis(m-thiolato)dicopper(II) Complex by Reductive Cleavage of the Disulfide Bond with Copper(I)"J. Am. Chem. Soc.. 123・17. 4087-4088 (2001)

[Publications] 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)

[Publications] Shunichi Fukuzumi et al.: "Charge Separation in a Novel Artificial Photosynthetic Reaction Center Lives 380ms"J. Am. Chem. Soc.. 123・27. 6617-6628 (2001)

[Publications] Shunichi Fukuzumi et al.: "Oxygenation of Phenols to Catechols by A (μ-η^2:η^2-peroxo)dicopper(II) Complex : Mechanistic Insight into the Phenolase Activity of Tyrosinase"J. Am. Chem. Soc.. 123・27. 6708-6709 (2001)

[Publications] Shunichi Fukuzumi et al.: "Photoalkylation of 10-Alkylacridinium Ion via a Charge-Shift Type of Photoinduced Electron Transfer Controlled by Solvent Polarity"J. Am. Chem. Soc.. 123・35. 8459-8467 (2001)

[Publications] Shunichi Fukuzumi et al.: "Metal Ion-Catalyzed Cycloaddition vs hydride Transfer Reactions of NADH Analogues with ρ-Benzoquinones"J. Am. Chem. Soc.. 123・42. 10191-10199 (2001)

[Publications] Shunichi Fukuzumi et al.: "Photochemical and Electrochemical Properties of Zinc Chlorin-C_<60>, Dyad as Compared to Corresponding Free-Base Chlorin-C_<60>, Free-Base Porphyrin-C_<60> and Zinc Porphyrin-C_<60> Dyads."J. Am. Chem. Soc.. 123・43. 10676-10683 (2001)

[Publications] 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)

[Publications] Shunichi Fukuzumi et al.: "Extremely Slow Long-Range Electron Transfer Reactions across Zeolite-Solution Interface"J. Am. Chem. Soc.. 123・45. 11331-11332 (2001)

[Publications] Shunichi Fukuzumi et al.: "Scandium Ion-Promoted Photoinduced Electron-Transfer Oxidation of Fullerences and Derivatives by p-Chloranil and p-Benzoquinone"J. Am. Chem. Soc.. 123・50. 12458-12465 (2001)

[Publications] Shunichi Fukuzumi et al.: "Large Photocurrent Generation of Gold Eelectrodes Modified with [60]Fullerene-Linked Oligothiophenes Bearing a Tripodal Rigid Anchor"J. Am. Chem. Soc.. 124・4. 532-533 (2002)

[Publications] Shunichi Fukuzumi et al.: "Oxo-transfer Reaction from A Bis(μ-oxo)dicopper(III) Complex"J. Am. Chem. Soc.. 124・6. 998-1002 (2002)

[Publications] Shunichi Fukuzumi et al.: "Efficient Catalysis of Rare-Earth Metal Ions in Photoinduced Electron-Transfer Oxidation of Benzyl Alcohols by a Flavin Analogue"J. Phys. Chem. A. 105・46. 10501-10510 (2001)

[Publications] Shunichi Fukuzumi et al.: "Electron Transfer Properties of Singlet Oxygen and Promoting Effects of Scandium Ion"J. Phys. Chem. A. 106・7. 1241-1247 (2002)

[Publications] Shunichi Fukuzumi et al.: "Dehydrogenation vs Oxygenation in Photosensitized Oxidation of 9-Substituted 1O-Methyl-9, 1O-dihydroacridine in the Presence of Scandium Ion"J. Phys. Chem. A. 106・7. 1465-1472 (2002)

[Publications] Shunichi Fukuzumi et al.: "Characterization of Imidazolate-Bridged Dinuclear and Mononuclear Hydroperoxo Complexes"Inorg. Chem. 40・13. 3200-3207 (2001)

[Publications] Shunichi Fukuzumi et al.: "Modulation of Coordination Chemistry in Copper(I) Complexes Supported by Bis[2-(2-pyridyl)ethyl]amine-Based Tridentate Ligands"Inorg. Chem. 40・26. 6604-6609 (2001)

[Publications] Shunichi Fukuzumi et al.: "Spectroscopy and Photocurrent Generation in Nanostructured Thin FiIms of Porphyrin-Fullerene Dyad Clusters"Chem. Lett. 784-785 (2001)

[Publications] Shunichi Fukuzumi et al.: "Quantitative Evaluation of Lewis Acidity of Zinc Ion with Tetradentate Tripodal Ligands in Formation of the Superoxide Complexes"Chem. Lett. 920-921 (2001)

[Publications] Shunichi Fukuzumi et al.: "Evaluation of Lewis Acidity of Organotin Compounds and the Catalytic Reactivity in Electron Transfer"Chem. Lett. 978-979 (2001)

[Publications] Shunichi Fukuzumi et al.: "Superoxide Anion Generation via Electron-Transfer Oxidation of Catechin Dianion by Molecular Oxygen in an Aprotic Medium"Chem. Lett. 1152-1153 (2001)

[Publications] Shunichi Fukuzumi et al.: "Coordination of Semiquinone and Superoxide Radical Anions to the Zinc Ion in SOD Model Complexes that Act as the Key Step in Disproportionation of the Radical Anions"Chem. Eur. J.. 7・22. 4947-4953 (2001)

[Publications] Shunichi Fukuzumi et al.: "Concentration Effects of Porphyrin Monolayers on the Structure and Photoelectrochemical Properties of Mixed Self-Assembled Monolayers of Porphyrin and Alkanethiol on Gold Electrodes"Langmuir. 17・16. 4925-4931 (2001)

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

[Publications] Shunichi Fukuzumi et al.: "Charge-transfer emission of compact porphyrin-fullerene dyad analyzed by Marcus theory of electron-transfer"Spectrochim. Acta Part A. 57. 2229-2244 (2001)

[Publications] Shunichi Fukuzumi 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"Chem. Commun.. 356-357 (2002)

[Publications] Shunichi Fukuzumi et al.: "Thermal Intramolecular Electron Transfer in a Ferrocene-Naphthoquinone Linked Dyad Promoted by Metal Ion"Angew. Chem. Int. Ed.. 41・4. 620-622 (2002)

[Publications] Shunichi Fukuzumi et al.: "Fullerenes 2001--Volume 11. (Proceedings of the Eighth International Symposium of the 197th Meeting of The Electrochemical Society)"The Electrochemical Society, INC.. 69 (2001)

福住俊一大阪大学, 大学院・工学研究科, 教授 (40144430)