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。新的Salen类似物的复合物，6，6'bis（Acylamio）-2，2'-二吡啶，是衍生物，其N_2O_2配位ITE是通过使用Bipyride和Amide单位重建的，被证明是有效性，是耐用性，对2，6-D IT叔丁醇的氧合的选择性至2，6-Di-T-T-叔丁基酮。在25°C Cy NAC10的两阶段系统中的环氧化烯烃配体的配体，由[Ni（babp）] atives催化为Asatyrene和Cyclohexene，[Ni（t-bubabp）]和[Ni（t-Bubabp）]和[Ni（Mebababp）（Mebababp）（mebababp）和[ni（t-bubabp）]和环己烯催化]与ES催化的那些是新设计的，并制备了其金属配合物（1）CU（II）具有长链酰基的衍生物的络合物。 Cu（II） - 6' - （α-）α--）α--苯甲酸或α-苯基苯基氨基氨基的溶解度 - 2' - 2'-二吡质酯在20°C TE的醇 - 硫化溶液（pH 7.2）溶液中酰胺-0协调的复合物。

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)