2004 Fiscal Year Final Research Report Summary
Functionalization of Mesoporous Silica Surface by Anchoring of Chemically-active Groups and Applications to Precise Organic Synthesis
| Project/Area Number |
14350426
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
触媒・化学プロセス
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| Research Institution | Toyohashi University of Technology |
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Principal Investigator |
TSUTSUMI Kazuo Toyohashi University of Technology, International Cooperation Center for Engineering Education Development, Professor, 工学教育国際協力研究センター, 教授 (00013178)
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| Co-Investigator(Kenkyū-buntansha) |
MATSUMOTO Akihiko Toyohashi University of Technology, Faculty of Engineering, Associate Professor, 工学部, 助教授 (90239088)
IWASA Seiji Toyohashi University of Technology, Faculty of Engineering, Associate Professor, 工学部, 助教授 (30303712)
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| Project Period (FY) |
2002 – 2004
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| Keywords | mesoporous silica / silica / adsorption heats / adsorption / calorimetry / zeolite / 不斉合成 / 環境融和型触媒 |
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| Research Abstract |
Mesoporous silicas(MS) with uniform pore structure were successfully prepared. Chemical active groups such as aminopropyl, octyl, and epoxycyclohexyl groups were anchored on MS surfaces, designated as MS-NH2,MS-C8 and MS-ep, respectively. Mesoporous organosilicas including ethytene chains, aminopropyl, thiol and pyridinium groups in the framework structures were also obtained (abbreviated as MOS-Ey,MOS-NH2,MOS-SH and MOS-Py, respectively). The following researches were performed by use of these samples.
1.Acetaldehyde adsorption on MS-NH2 : The sorptivity of acetaldehyde was drastically improved by the anchoring of aminopropyl groups. Especially, the sorptivity at low concentration increased in MS-NH2 with narrower pore sizes of ca. 1 nm.
2.Surface stability and hydrophobe/hydrophile control : MS-C8 exhibited hydrophobic character. MS-Ep showed more hydrophilic character than MS, while the pore structure stably retained after water sorption. MOS-Ey was rather hydrophobic and exhibited go
… More
od sorptivity for alkane vapor.
3.Acid sites formation by oxidation of MOS-SH : Thiol groups on MOS-SH surface were converted to sulfonic acid ones (-SO_3H) by an oxidation treatment. Solid acidity of the MOS-SO_3H characterized by ammonia adsorption microcalorimetry was comparable to that of aluminosilicate zeolites.
4.Application to organic synthesis : We found that asymmetric 2,6-bis(oxazolinyl)pyridine(pybox)/ruthenium catalyst was adsorbed on silica such as MS and MS-NH2 and acted as solid-supported catalyst for a catalytic asymmetric cyclopropanation reaction. In the case of catalytic asymmetric cyclopropanation reactions of diazoester and alkenes, the reaction was successfully proceeded with pybox/Ru(II) catalyst in both water phase and two phases to give the corresponding cyclopropylesters along with over 95% enantioselectivities. Furthermore, monooxazolinylphenyl (phemox)/palladium complexes supported on MOS-Py catalyzed Sonogashira coupling reactions of iodonitrobenzene and ethynybenzene derivatives at 333K without any other co-catalysts such as CuI. The efficiency of phemox/Pd catalyst supported on MOS-Py was almost same as the non-supported catalyst. Less
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Research Products
(20 results)
