Activation of Dioxygen Mediated by Metal Ions, and Synthetic Application.
| Project/Area Number |
61470081
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
工業物理化学
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| Research Institution | HIROSHIMA UNIVERSITY |
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Principal Investigator |
SASAKI Kazuo Professor, Faculty of Engineering, Hiroshima University, 工学部, 教授 (00034322)
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| Co-Investigator(Kenkyū-buntansha) |
KUNAI Atsutaka Research Assistant, Faculty of Engineering, Hiroshima Univ., 工学部, 助手 (90029190)
ITO Sotaro Assistant Professor, Faculty of Engineering, Hiroshima Univ., 工学部, 助教授 (90034404)
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| Project Period (FY) |
1986 – 1987
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| Project Status |
Completed (Fiscal Year 1987)
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| Budget Amount *help |
¥4,700,000 (Direct Cost: ¥4,700,000)
Fiscal Year 1987: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1986: ¥4,200,000 (Direct Cost: ¥4,200,000)
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| Keywords | Activation of Dioxygen / Hydroxyl Radical / Copper(I) Ion / Mediator / One-Step Synthesis of Phenols / ベンゼンの酸化 / 金属イオンの効果 |
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| Research Abstract |
The main object of this work is placed on developing a synthetic method for one-step oxidation of benzene to phenols. In earlier works, we reported that Cu^+ ions can activate molecular xoygen. When benzene is present in the system, both phenol and hydroquinone are produced. The primary steps are estimated to be the reactions expressed by eqs. (1)-(3), but most of mechanistic details were left ambiguous.
iCu^+ + O_2 + 2H^+ -> 2Cu^<2+> + H_2O_2 (1) ; Cu^+ + H_2O_2 + H^+ -> Cu^<2+> + OH + H_2O (2) ;
OH + C_6H_6 -----> C_6H_5OH (3)
In this work, mechanistic detail and synthetic feasibility of air oxidation of benzene catalyzed by Copper(1) ions were discussed. Conclusions are as follows.
1. [Mechanism]. (1) By kinetic study, it is confirmed that active species is OH; (2) Deactivation occurs at the stage of OH or H_2O_2; (3) Efficiency for H_2O_2 production is quantitative; (4) The formation rate of H_2O_2 is much gaster than the decomposition rate.
2. [Comparison with Other Systems]. ^<18>O-Tracer experiment indicates that hydroxy- cyclohexadienyl and its peroxy radicals are the intermediates. The formation of hydroquinone is characteristic feature of the present system, which is never observed in the other systems, such as the Fenton's reaction.
3. [Synthetic Feasibility]. The relative ratio of phenol to hydroquinone strongly depends on solution pH. The former dominates at lower pHs (<3), and the latter at higher pHs (>3). When both continuous extraction and electrolytic regeneration of Cu^+ were applied to the system at pH 3, p-benzoquinone was obtained in a 50% current efficiency.
The present system has several merits and, therefore, provides much synthetic feasibility. Namely, (1) Hydrogen peroxide is unnecessary; (2) The reaction is effective and mild; (3) Either phenol or hydroquinone is obtained selectively.
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Report
(2 results)
Research Products
(10 results)
