YASHIRO Morio University of Tokyo, Institute of Industrial Science, Assistant, 生産技術研究所・第四部, 助手 (30192785)
ARAKI Koji University of Tokyo, Institute of Industrial Science, Associated Professor, 生産技術研究所・第四部, 助教授 (40134639)
|Budget Amount *help
¥5,800,000 (Direct Cost : ¥5,800,000)
Fiscal Year 1991 : ¥1,400,000 (Direct Cost : ¥1,400,000)
Fiscal Year 1990 : ¥4,400,000 (Direct Cost : ¥4,400,000)
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%).