Acymmetric oxidation using non-enzymatically oxidant

本研究从高转化率、高转化率、高选择性和活性氧物种的研究出发，在多相固体体系下，利用多相非酶催化剂对苯的羟基化和几种烯烃的氧化反应进行了研究。与Fe^2+或Cu^+离子的离子交换或螯合树脂以及使用L-抗坏血酸。在这些体系中，苯的羟基化反应均采用固-液两相体系，在相当清洁的溶液中进行，无沉积物生成，回收的多相催化剂外观与原始催化剂基本相同。本反应易于进行，以良好的产率得到苯酚，并且苯酚产率随着循环次数而稳定增加。非均相催化体系的研究结果显然是一种简便而有效的方法， ...更多信息 进行连续的芳族羟基化。在固液两相体系中进行了烯丙基化合物、环己烯和苯乙烯等烯烃的氧化反应。烯丙基氯和苯乙烯体系容易生成环氧氯丙烷，苯乙烯体系容易生成苯甲醛> 2，5-二氧代-5-苯基戊烷>苯乙醛> 1-苯基-1，2-乙烷等氧化产物，但不生成其它化合物。以甲苯和苯甲醚为原料，采用非均相非酶催化剂，在非均相固相体系中，对甲苯和苯甲醚羟基化反应中的活性氧物种进行了O-、M-、P-取向研究。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机理的支持结果。在此基础上，建立了考虑电性和几何性元素的配体非对称非酶氧化剂模型，并开发了以Fe^（2+）和Cu^+为中心金属离子的络合催化剂。少

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