Acymmetric oxidation using non-enzymatically oxidant

研究了非均相非酶催化剂在非均相固体体系下苯的羟基化反应和几种烯烃的氧化反应，其转化率高，循环利用率高，并对活性氧进行了研究。采用具有螯合官能团的硅胶、Fe <2+>或Cu^+离子的离子交换或螯合树脂和l -抗坏血酸进行螯合制备非酶非均相催化剂。在固液两相体系中，苯的羟基化反应在非常干净的溶液中进行，没有形成沉积物，回收的多相催化剂的外观与原催化剂基本保持一致。该反应易于进行，苯酚收率高，且随着循环次数的增加，苯酚收率稳步提高。结果表明，非均相催化体系是实现连续芳羟基化反应的一种简便有效的方法。用固液两相体系对烯丙基化合物、环己烯和苯乙烯等几种烯烃进行了氧化反应。烯丙基氯和苯乙烯体系很容易生成环氧氯丙烷，苯乙烯体系则容易生成苯甲醛> - 2,5-二氧基-5-苯基戊烷> -苯乙醛> -1 -苯基-1,2-乙二醇等氧化产物。采用非均相非酶催化剂，在非均相固体体系下对甲苯和茴香醇的羟基化反应进行了o-、m-、p-取向的活性氧研究。这些o-、m-、p-取向的结果表明，这些非酶催化的非均相氧化反应给出了类氧机制的支持结果。在此基础上，制备了考虑电元素和几何元素的配体不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