1987 Fiscal Year Final Research Report Summary
Shape-selective Oxidation Catalyzed by Sterically Controlled Metalloporphyrins
| Project/Area Number |
61470041
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
無機・錯塩・放射化学
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| Research Institution | The university of Tokyo |
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Principal Investigator |
MIYAMOTO Takeshi Department of Chemistry, Faculty of Science, The University of Tokyo, 理学部化学科, 助教授 (30011604)
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| Project Period (FY) |
1986 – 1987
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| Keywords | Synthetic Porphyrins / Hypochlorite / Epoxidation / Enzymatic Process / Porphyrin Catalyst / 触媒耐久性 |
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| Research Abstract |
New types of synthetic metalloporphyrin catalyzed epoxidation of olefins. The reaction was carried out in dichloromethane-water system by use of hypochlorite as an oxygen source. In the oxygenation of styrene catalyzed by an atropisomeric manganese porphyrin(<alpha><alpha> <alpha><alpha> isomer), the reaction took place in the preference for open site to the crowded one. Several orthosubstituted tetraphenylporphyrins were prepared:The ortho positions were substituted by nitro, fluoro or chloro groups. Their complexes showed high stability to the decomposition of catalyst. By use of these iron(III) complexes, we developed the iron porphyrin-hypochlorite system to efficient catalyst. The initial rate of the epoxidation exhibited the substrate saturation kinetics similar to the enzymatic process. From the systematic survey of epoxidation catalyzed by these metalloporphyrins, it is evident that Michaelis-Menten's parameters and and product selectivity are influenced by shape of catalysts. In addition it was indicated that the epoxidation mechanism is different between manganese and iron catalysts.
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[Publications] T. K,Miyamoto, S,Takagi, T,Hasegawa, S,Tsuzuki, E,Takahashi, K,Okude, I,Banno, Y,Sasaki: "Synthesis and Properties of 5,10,15,20-tetrakis(3,5-di-t-buty1-2-nitropheny1)- Porphyrin: Conformational Stabilities of the Respective Atropisomers and Oxygenation Capabilities of the Iron(III) and Manganese(III) Complexes." Bull. Chem. Soc. Jpn.,. 60. 1649-1659 (1987)
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[Publications] E,Takahashi, H,Amatsu, T. K.Miyamoto,Y,Sasaki: "Development of the Porphyrin Complexes as the Robust.Homogeneous Catalyst and the Catalytic Epoxidation Reactions Similar to the Enzymatic Process of Crtochrome P450 --Fe(III) and Mn(III) Complexes of 5,10,15,20-Tetrakis(2,6- difluqrophenyl)porphyrin---" Nippon Kagaku Kaishi.
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