| 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)
本山 幸弘 豊橋技術科学大学, 工学部, 助手 (20283492)
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| Project Period (FY) |
2002 – 2004
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| Project Status |
Completed (Fiscal Year 2004)
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| Budget Amount *help |
¥13,300,000 (Direct Cost: ¥13,300,000)
Fiscal Year 2004: ¥2,800,000 (Direct Cost: ¥2,800,000)
Fiscal Year 2003: ¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 2002: ¥7,300,000 (Direct Cost: ¥7,300,000)
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| Keywords | mesoporous silica / silica / adsorption heats / adsorption / calorimetry / zeolite / 不斉合成 / 環境融和型触媒 / アルデヒド / 不斉シクロプロバン化 / 不斉アリル化 / シアノ化 |
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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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