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Exploitation of Superstructure Porphyrin and Other Functional Complexes : Structure-Function Relationship.

超结构卟啉和其他功能复合物的开发：结构-功能关系。

基本信息

批准号：
01470046
负责人：
MIYAMOTO Takeshi
金额：
$ 3.84万
依托单位：
The 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：
1989
资助国家：
日本
起止时间：
1989 至 1990
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-01470046/
关键词：
Superstructure Porphyrin Complexes Structure-Function Platinum

项目摘要

1. Syntheses of Superstructure Porphyrin and Oxygenation Reaction.A new bulky porphyrin, meso-tetrakis (2-methoxy-5, 5, 8, 8-tetramethyl-6, 6, 7, 7-tetrahydro-1-anthryl) porphyrin (abbr. AP) was synthesized. Four atropisomers (alphabetaalphabeta, alphaalphabetabeta, alphaalphaalphabeta, alphaalphaalpha) were separated and purified by column chromatography. The isomers all showed remarkable high thermal stability toward atropisomerization. Under a high temperature (ca. 190^OC) in 2- (2-methoxyethoxy) ethanol, ruthenium (II) ion was incorporated into each isomer with the retention of the ligand conformation. The stereoselectivity of the isomeric ruthenium (II) porphyrins to incoming ligands (py or CO) was examined by ^1H-NMR spectroscopy.Another ruthenium porphyrin, tetrakis (2,6-difluorophenyl) porphinato ruthenium (II) (CO) (N-Melm), was prepared. It catalyzed oxidation of hydrocarbons (styrene, alpha-methylstyrene, cyclooctene or cyclohexane) by use of t-BuOOH or hypochlorite as oxidant.2. Syntheses and Structure of Antineoplastic Platinum Complexes.A 1R, 2R-diaminocyclohexaneplatinum (II) complex of B_2O_5H_2^<2->, (C_6H_<14>N_2)Pt(B_2O_5H_2)・H_2O, is synthesized by reacting (C_6H_<14>N_2)Pt(OH)_2 with boric acid in the presence of dipotassium tetraborate tetrahydrate in aqueous solution. X-ray structural analysis revealed that the B_2O_5H_2^<2-> anion and the platinum (II) cation from a six-membered chelate.A series of new dinuclear platinum (II) complexes, [PtL_2(slac)]_2・H_2O where slac = sulfoacetate dianion ; L_2 = 1,2-diaminocyclohexane (1a-1c) or 1,2-diaminoethane (2), L = isopropylamine (3) or ammine (4), have been prepared from the reaction of [PtL_2(OH)_2] with sulfoacetic acid. They have di-mu-carboxylato bridged dinuclear zwitterionic structures in crystals. Among them, complexes (1a-1c) show significant antitumor activities against mice leukemia L1210.

1.超结构卟啉的合成及氧化反应研究一种新的大体积卟啉meso-四（2-甲氧基-5，5，8，8-四甲基-6，6，7，7-四氢-1-蒽基）卟啉（简称meso-tetra-tetrahydro-1-anthryl）。AP）。通过柱层析分离和纯化了四种阻转异构体（α-alphabeta、alphaalphabeta、alphaalphabeta、alphaalphaalpha）。异构体都表现出显着的高阻转异构化的热稳定性。在高温下（约190 ^OC）在2-（2-甲氧基乙氧基）乙醇中，钌（II）离子掺入到每个异构体中，保留配体构象。用~ 1H-NMR研究了钌（II）卟啉的异构体对引入配体（py或CO）的立体选择性，并合成了一种钌卟啉--四（2，6-二氟苯基）卟啉合钌（II）（CO）（N-Melm）。以t-BuOOH或次氯酸盐为氧化剂，催化氧化烃类（苯乙烯、α-甲基苯乙烯、环辛烯或环己烷）.反式铂配合物的合成与结构研究在四水合硼酸二钾存在下，（C_6H_ N_2）Pt（OH）_2与硼酸反应，合成了1 R，2 R-二氨基环己烷合铂（II）B_2O_5H_2^配合<2->物<14>（C_6H_N_2）Pt（B_2O_5H_2）·H_2O<14>。X-射线衍射分析表明，B_2O_5H_2^2阴离子与铂（II）阳离子形成六元螯合物，并合成了一系列新的双核铂（II）配合物[PtL_2（slac）]_2·H_2O，其中slac =磺酸乙酸根阴离子<2->; L_2 = 1，2-二氨基环己烷（1a-1c）或1，2-二氨基乙烷（2），L =异丙胺（3）或氨（4），由[PtL_2（OH）_2]与磺基乙酸反应制得。它们在晶体中具有二-μ-羧基桥联的双核两性离子结构。其中，配合物（1a-1c）对小鼠白血病L1210具有明显的抗肿瘤活性。