Activation of Dioxygen Mediated by Metal Ions, and Synthetic Application.
金属离子介导的分子氧的活化及其合成应用。
基本信息
- 批准号:61470081
- 负责人:
- 金额:$ 3.01万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for General Scientific Research (B)
- 财政年份:1986
- 资助国家:日本
- 起止时间:1986 至 1987
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
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.
本工作的主要目的是开发一种苯一步氧化制苯酚的合成方法。在早期的工作中,我们报道了Cu^+离子可以激活分子氧。当系统中存在苯时,产生苯酚和对苯二酚。初步估计反应步骤为方程式。(1)~(3),但机理尚不明确:iCu^+ + O_2 + 2 H ^+ -> 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)本文讨论了铜离子催化空气氧化苯的机理细节和合成的可行性。结论如下:1. [机制]。(1)动力学研究表明,活性物种为OH;(2)失活发生在OH或H_2O_2阶段;(3)H_2O_2的生成效率是定量的;(4)H_2O_2的生成速率远大于分解速率.(与其他系统比较)。氧<18>示踪实验表明,羟基环己二烯基及其过氧自由基是中间体。对苯二酚的生成是本体系的特征,这在其它体系如芬顿反应中是从未观察到的. [合成可行性]。苯酚与对苯二酚的相对比例强烈地取决于溶液pH。前者在较低pH(<3)时占主导地位,而后者在较高pH(>3)时占主导地位。在pH = 3的条件下,采用连续萃取和电解再生两种方法,可以在50%的电流效率下得到对苯醌,具有多种优点,因此具有很大的合成可行性。该反应无需过氧化氢,反应温和有效,选择性地得到苯酚或对苯二酚。
项目成果
期刊论文数量(20)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Atsutaka Kunai, Shintaro Hata, Sotaro Ito, and Kazuo Sasaki: "The Role of Oxygen in the Hydroxylation Reaction of Benzene with Fenton's Reagent. ^<18>O-Tracer Study." J. Amer. Chem. Soc.108(19). 6012-6016 (1986)
Atsutaka Kunai、Shintaro Hata、Sotaro Ito 和 Kazuo Sasaki:“氧气在芬顿试剂苯的羟基化反应中的作用。^<18>O-示踪剂研究。”
- DOI:
- 发表时间:
- 期刊:
- 影响因子:0
- 作者:
- 通讯作者:
丸内淳尭: J. Org. Chem.51(18). 3471-3474 (1986)
Juntaka Maruchi:J.Chem.51(18)3471-3474(1986)。
- DOI:
- 发表时间:
- 期刊:
- 影响因子:0
- 作者:
- 通讯作者:
九内淳堯: Journal of Organic Chemistry. 51. 3471-3474 (1986)
Atsushi Kunai:有机化学杂志 51. 3471-3474 (1986)
- DOI:
- 发表时间:
- 期刊:
- 影响因子:0
- 作者:
- 通讯作者:
Sotaro Ito, Atsutaka Kunai, Hiroshi Okada, and Kazuo Sasaki: "Direct Conversion of Benzene to Hydroquinone, Cooperative Action of Cu(I) Ion and Dioxygen." J. Org. Chem.53(2). 296-300 (1988)
Sotaro Ito、Atsutaka Kunai、Hiroshi Okada 和 Kazuo Sasaki:“苯直接转化为对苯二酚,Cu(I) 离子和分子氧的协同作用。”
- DOI:
- 发表时间:
- 期刊:
- 影响因子:0
- 作者:
- 通讯作者:
Sotaro Ito, Toshimichi Yamasaki, Hiroshi Okada, Susumu Okino, and Kazuo Sasaki: "Oxidation of Benzene to Phenols with Molecular Oxygen Promoted by Copper(I) Chloride." J. Chem. Soc., Perkin II. (1988)
Sotaro Ito、Toshimichi Yamasaki、Hiroshi Okada、Susumu Okino 和 Kazuo Sasaki:“氯化亚铜促进分子氧将苯氧化为苯酚。”
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- 发表时间:
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- 影响因子:0
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SASAKI Kazuo其他文献
SASAKI Kazuo的其他文献
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{{ truncateString('SASAKI Kazuo', 18)}}的其他基金
Unravelling fundamental interactions underlying the rotation mechanism of F1-ATPase
揭示 F1-ATPase 旋转机制背后的基本相互作用
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17K05562 - 财政年份:2017
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$ 3.01万 - 项目类别:
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Brain mechanisms underlying the anti-stress effects of green odor that is emanated from green leaves
绿叶散发的绿色气味具有抗应激作用的大脑机制
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20590227 - 财政年份:2008
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$ 3.01万 - 项目类别:
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Electrophysiological analysis of feeding-related network in the hypothalamus, based on the gluco-static and lipo-static theories
基于葡萄糖静态和脂肪静态理论的下丘脑摄食相关网络的电生理分析
- 批准号:
13670056 - 财政年份:2001
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$ 3.01万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Effects of acidic fibroblast growth factor released by feeding on learning and memory, endocrine and immune systems
进食释放的酸性成纤维细胞生长因子对学习记忆、内分泌和免疫系统的影响
- 批准号:
09470015 - 财政年份:1997
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$ 3.01万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Automatic measurement system of growth factor using bioassay of Hydra
利用Hydra生物测定的生长因子自动测定系统
- 批准号:
09555123 - 财政年份:1997
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$ 3.01万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
A study on the facilitation of learning and memory elicited by food intake.
一项关于食物摄入促进学习和记忆的研究。
- 批准号:
06454151 - 财政年份:1994
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$ 3.01万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Studies on Function and its Disorder of the Frontal Association Cortex
额叶联合皮层功能及其紊乱的研究
- 批准号:
62440024 - 财政年份:1987
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$ 3.01万 - 项目类别:
Grant-in-Aid for General Scientific Research (A)
Initiation of voluntary movement and cerebro-cerebellar neuronal circuit
自主运动和脑小脑神经元回路的启动
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59440023 - 财政年份:1984
- 资助金额:
$ 3.01万 - 项目类别:
Grant-in-Aid for General Scientific Research (A)
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