A New Salen Analogue, [Co(babp)], as an Oxygenation Catalyst having Higher Catalytic Activity, Selectivity, and Durability

一种新的 Salen 类似物 [Co(babb)]，作为具有更高催化活性、选择性和耐久性的氧化催化剂

基本信息

批准号：
02453083
负责人：
SHIRAISH Shinsaku
金额：
$ 3.71万
依托单位：
University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1990
资助国家：
日本
起止时间：
1990 至 1991
项目状态：
已结题

项目摘要

1. The Co(II)complexes of a new salen analogue, 6, 6'-bis(acylamio)-2, 2'- bipyridine, [co(babp)], and its derivatives, whose N_2O_2 coordination sites were reconstructed by use of bipyridine and amide units, were demonstrated to be efficient catalysts with high durability, selectivity, and activity for oxygenation of 2, 6-dit-butylphenol to 2, 6-di-t-butylquinone. The high thermal stability of[Co(babp)]allow us to restore its catalytic activity by heating it to 200ﾟC under reduced pressure. Further, we studied activities of Ni(II)complexes of various N_2O_2-type ligands for epoxidation of olefins in two-phase systems consisting of dichloromethane and aqueous NaC10 solution at 25ﾟC using NaC10 as a terminal oxidant. Epoxidation reactions of styrene and cyclohexene catalyzed by[Ni(babp)], and its derivatives, [Ni(t-Bubabp)] and[Ni(Mebabp)], were not so much different from those catalyzed by[Ni(salen)], yielding 20-30% of corresponding epoxides.2. babp derivatives having various acyl moieties were newly designed, and their metal complexes were prepared.(1)Cu(II)complexes of babp derivatives having long-chain acyl groups were found to construct ordered mesophase structure.(2)Coordination behavior of babp derivatives having amino acid moieties were examined. The Cu(II)-catalyzed solvolysis of 6, 6'-(alpha-alanylamino or alpha-phenylalanylamino)-2, 2'-bipyridine in alcohol-borate buffer (pH 7.2) solutions at 20ﾟC was found to proceed with appreciable rate via formation of an amide-0-coordinated complex. The solvolysis of one of the aminoacyl groups was greatly accelerated as alcohol content increased, yielding amino acid esters even in the presence of appreciable amounts of water(0-40 v/v%).

1. The Co(II) complexes of a new sale analogue, 6, 6'-bis(acylamio)-2, 2'-bipyridine, [co(babp)], and its derivatives, whose N_2O_2 coordination sites were reconstructed by use of bipyridine and amide units, were demonstrated to be efficient catalysts with high durability, selectivity, and activity for oxygenation of 2, 6-二丁基苯酚至2，6-DI-T-T-叔丁基酮。 [CO（BABP）]的高热稳定性使我们能够通过在降压下将其加热到200 c来恢复其催化活性。此外，我们研究了各种N_2O_2型配体的Ni（II）复合物的活性，用于使用NAC10作为终末氧化剂的两阶段系统中的烯烃在两阶段系统中的氧化氧化。由[Ni（babp）]催化的苯乙烯和环己烯及其衍生物[Ni（t-bubabp）]和[ni（Mebabp）]的环氧反应与[Ni（mebabp）]的催化反应与[[Ni（salen）]催化的降低并没有太大不同，从而产生了相应的epoxides.2-30-30％。（1）发现具有长链酰基基团的BABP衍生物的CU（II）cu（ii）构建有序的中间相结构的BABP衍生物的复合物。（2）检查了具有氨基酸部分的BABP衍生物的协调行为。 6，6' - （α-烷基氨基氨基或α-苯基甲基氨基氨基氨基）的Cu（II）催化溶剂分解-2，2'-二吡啶在20°C时在20°C时在20°C下的溶液（pH 7.2）溶液中的溶液中，发现通过形成Amide-0-0-0-0-Coord-0-Coord-coord-cosord-Amide-0。随着酒精含量的增加，其中一个氨基酰基基团的溶解度大大加速，即使存在可欣赏的水（0-40 v/v％），也会产生氨基酸酯。

项目成果

期刊论文数量（18）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

M.Yamada,K.Araki,and S.Shiraishi: "Oxygenation of 2,6-Di-t-butylphenol Catalysed by a New Cabalt(II)Complex 〔Co(babp)〕:a salen Analogue having Higher Catalytic Activity,Selctivity,and Durability" J.Chem.Soc.,Perkin Trans.1. 2687-2690 (1990)

M.Yamada、K.Araki 和 S.Shiraishi：“新型 Cabalt(II) 络合物 [Co(bapp)] 催化的 2,6-二叔丁基苯酚的氧化：一种具有更高催化活性和选择性的 salen 类似物和耐久性”J.Chem.Soc.，Perkin Trans.1. 2687-2690 (1990)