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

• 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
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-02453083/
• 关键词: Oxyganation catalyst; Epoxidation; Cobalt complex; Nickel complex; Bipyridine; Alkyl long chain; Amino acids; Mesophase; ピリジン; ス-パ-オキシド錯体

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6，6 ′-双（酰胺基）-2，2 ′-联吡啶[co（babp）]及其衍生物的Co（II）配合物（其N_2O_2配位是由联吡啶和酰胺单元重构的）被证明是有效的催化剂，具有高的稳定性、选择性和活性，用于2，6-二丁基苯酚氧化为2，6-二叔丁基醌。[Co（babp）]的高热稳定性使我们能够通过在减压下将其加热到200 ° C来恢复其催化活性。在此基础上，我们研究了不同N_2O_2型配体的Ni（II）配合物在二氯甲烷和NaCl水溶液组成的两相体系中，以NaCl为末端氧化剂，在25 ℃下对烯烃环氧化反应的催化活性。[Ni（babp）]及其衍生物[Ni（t-Bubabp）]和[Ni（Mebabp）]催化苯乙烯和环己烯的环氧化反应与[Ni（salen）]催化的反应没有太大的区别，相应的环氧化物的产率为20-30%.新设计了具有各种酰基部分的BABP衍生物，并制备了它们的金属配合物。（1）具有长链酰基的babp衍生物的Cu（II）配合物具有有序的中间相结构。（2）研究了含氨基酸的babp衍生物的配位行为。在20 ℃时，6，6 ′-（α-丙氨酰氨基或α-苯丙氨酰氨基）-2，2 ′-联吡啶在乙醇-硼酸盐缓冲溶液（pH7.2）中的Cu（Ⅱ）催化溶剂分解反应，生成酰胺-O-配位络合物。随着醇含量的增加，其中一个氨基酰基的溶剂分解大大加速，即使在存在可观量的水（0-40 v/v%）的情况下也产生氨基酸酯。

项目成果

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)

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

M.Yamada、K.Araki、S.Shiraishi：“新型钴 (II) 络合物 [Co(bapp)] 催化的 2,6-二丁基苯酚氧化：一种具有更高催化活性、选择性和耐久性的 Salen 类似物J.Chem.Soc.，Perkin Trans.1.2687-2690 (1990)

K. Araki,T. Kuboki,M. Yamada,and S. Shiraishi: "Preferential Formation of Amino Acid esters in Aqueous Solutions:Amide Solvolysis of 6,6'ーDi(αーaminoacylamino)ー2,2'ーbipyridine by MetalーCoordination"

K. Araki、T. Kuboki、M. Yamada 和 S. Shiraishi：“在水溶液中优先形成氨基酸酯：6,6-二(α-氨基酰氨基)-2,2-联吡啶的酰胺溶剂分解金属配位”

K.Araki,T.Kuboki,M.Yamada,and S.Shiraishi: "Preferential Formation of Amino Acid Esters in Aqueous Solutions:Amide Solvolysis of 6,6'-Di(α-aminoacylamino)-2,2'-bipyridine by Metal-Coordination"

K. Araki、T. Kuboki、M. Yamada 和 S. Shiraishi：“在水溶液中优先形成氨基酸酯：6,6-二(α-氨基酰氨基)-2,2-联吡啶的酰胺溶剂分解金属配位”

K.Araki,T.Kuboki,M.Yamada,and S.Shiraishi: "A New Salen Analogue,〔Co(babp)〕,as an Oxygenation Catalyst:Effect of Substituent Groups on the Ligand Moiety"

K.Araki、T.Kuboki、M.Yamada 和 S.Shiraishi：“一种新的 Salen 类似物，〔Co(babb)〕，作为氧化催化剂：取代基对配体部分的影响”