| Project/Area Number |
03453082
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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 |
工業物理化学・複合材料
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| Research Institution | The University of Tokyo |
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Principal Investigator |
MISONO Makoto Faculty of Engineering, Department of Synthetic Chemistry, Professor, 工学部, 教授 (20011059)
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| Co-Investigator(Kenkyū-buntansha) |
HASHIMOTO Masato Faculty of Engineering, Department of Synthetic Chemistry, Research Assistant, 工学部, 助手 (50237947)
OKUHARA Toshio Faculty of Engineering, Department of Synthetic Chemistry, Associated Professor, 工学部, 助教授 (40133095)
李 寛栄 東京大学, 工学部, 助手 (70222792)
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| Project Period (FY) |
1991 – 1992
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| Project Status |
Completed (Fiscal Year 1992)
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| Budget Amount *help |
¥6,500,000 (Direct Cost: ¥6,500,000)
Fiscal Year 1992: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1991: ¥5,300,000 (Direct Cost: ¥5,300,000)
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| Keywords | Pseudoliquid Phase / Heteropolyacids / Solid Acid Catalysts / Solid-state NMR / Alkylation / X-ray Structure Determination / Dehydration of Ethanol / Ethoxy Group / アルチル化反応 / ピナコール転位反応 / 部分酸性塩 / アルコ-ル脱水反応 / ^<13>C NMR / プロトン化アルコ-ル / フェノ-ルのアルキル化 / 極性分子 |
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| Research Abstract |
The aims of this study are (i) to elucidate the pseudoliquid phase behavior in catalysis, (ii) to reveal the activated state of the molecules in pseudoliquid phase, and (iii) to construct the new catalytic reaction systems, utilizing the pseudoliquid phase of heteropoly compounds.
The results are summarized as follows:
(1) The pseudoliquid phase brought about the high catalytic activity for dehydration of alcohols, since nearly all protons in the bulk takes part in catalysis. In addition, unique selectivity for the reaction of polar molecules due to the pseudoliquid phase was obtained.
(2) The reaction mechanism of dehydration of ethanol in the pseudoliquid phase of H_3PW_<12>O_<40> was elucidated by using IR and solid state NMR. Protonated ethanol dimer (intermediate for diethyl ether),protonated monomer, and ethoxy group (intermediate for ethylene) were directly detected by ^<13>C solid state NMR.
(3) The crystal structure of the complex, [(C_5H_5N)_2H]_3PW_<12>O_<40> was determined by the single crystal X-ray diffraction method, where pyridine molecules are paired forming the (C_5H_5N)-H^+-(NC_5H_5) cation in the structure.
(4) By the pseudoliquid phase, the activity of liquid-phase alkylation of phenol was greatly enhanced. H_3PW_<12>O_<40> was much more active than ordinary solid acids and H_2SO_4.
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