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Acymmetric oxidation using non-enzymatically oxidant

使用非酶促氧化剂的不对称氧化

基本信息

批准号：
63550634
负责人：
MATSUBARA Yoshio
金额：
$ 1.02万
依托单位：
Kinki University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1988
资助国家：
日本
起止时间：
1988 至 1989
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-63550634/
关键词：
Non-enzymatically oxidation Oxigenase mode Heterogeneous oxidation Hydroxylation of benzene Epoxydation NIH shift oxygen active species Acymmetric oxidation モノオキシゲナーゼモデル

项目摘要

This study was investigated on the hydroxylation of benzene and oxidative reaction of several olefins by use of heterogeneous non-enzymatically catalysts under heterogeneous solid systems in terms of excellent conversion with high turn over- and recycle-abilities, and study of active oxygen species.Preparation of heterogeneous non-enzymatically catalysts were carried out by the chelation of silica gel having chelate function group, ion-exchange- or chelate- resins with Fe^<2+> or Cu^+ ion and using of L-ascorbic acid. Hydroxylation of benzene in these system were carried out with the solid-liquid two-phase system in a quite clean solution without formation of deposits, and the appearance of recovered heterogeneous catalysts remained almost the same as that of original. The present reaction proceeded easily to give phenol in good yield and the phenol yield increases steadily with the recycling times. Results of the heterogeneous catalyst system are obviously the easy and potent way to c … More arry out successive aromatic hydroxylations. Oxidative reaction of several olefins such as allyl compounds, cyclohexene and styrene in these system were carried out with the solid-liquid two-phase system. The allyl chloride and styrene systems proceeded easily to give epichlorohydrine for allyl chloride system and oxidative products such as benzaldehyde > 2,5-dioxo-5-phenylpentane > phenylacetoaldehyde > 1-phenyl-1,2-ethanediol for styrene system, however, other compounds did not take place. Study of active oxygen species was carried out by the o-, m-, p- orientation on hydroxylation of toluene and anisol using heterogeneous non-enzymatically catalysts under heterogeneous solid systems. Result of these o-, m-, p- orientation indicate that these oxidative reactions using heterogeneous non-enzymatically catalyst give the supporting result of oxenoid mechanism. From these results, the acymmetric non-enzymaticalry oxidant model was prepared in terms of ligand which considered element of electric and geometric, and development of complex catalyst contains Fe^<2+> and Cu^+ as a center metallic ions. Less

本研究采用多相非酶催化剂在非均相固体体系下进行苯的羟基化反应和多种烯烃的氧化反应，研究其优异的转化率、高转化率和循环能力，以及活性氧物种的研究。通过硅胶螯合制备多相非酶催化剂。具有螯合官能团、具有Fe 2+ 或Cu 2+ 离子的离子交换树脂或螯合树脂以及使用L-抗坏血酸。该体系中苯的羟基化是在非常干净的溶液中以固液两相体系进行的，没有形成沉积物，回收的非均相催化剂的外观几乎与原始催化剂相同。本反应很容易进行，以良好的收率得到苯酚，并且苯酚收率随着循环次数的增加而稳定增加。多相催化剂体系的结果显然是进行连续芳香族羟基化的简单而有效的方法。烯丙基化合物、环己烯、苯乙烯等多种烯烃在该体系中的氧化反应是在固液两相体系中进行的。烯丙基氯和苯乙烯体系很容易生成环氧氯丙烷，对于苯乙烯体系，氧化产物为苯甲醛>2,5-二氧代-5-苯基戊烷>苯乙醛>1-苯基-1,2-乙二醇，但没有发生其他化合物。通过在非均相固体体系下使用非均相非酶催化剂对甲苯和苯甲醚的羟基化进行邻、间、对位取向的活性氧物种的研究。这些o-、m-、p-取向的结果表明这些使用非均相非酶催化剂的氧化反应给出了oxenoid机制的支持结果。根据这些结果，从配体角度建立了考虑电学和几何元素的非酶氧化剂模型，并开发了以Fe^2+和Cu^+为中心金属离子的络合物催化剂。较少的