Dynamics of Pseudoliquid Phase of Heteropolyacids and Design of New Catalytic Reactions

杂多酸拟液相动力学及新催化反应设计

• 批准号: 03453082
• 负责人: MISONO Makoto
• 金额: $ 4.16万
• 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: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-03453082/
• 关键词: 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

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.

本研究旨在阐明杂多化合物的准液相催化行为，揭示准液相中分子的活化状态，以及利用杂多化合物的准液相构建新的催化反应体系，主要结果如下：（1）准液相对醇脱水反应具有高的催化活性，因为本体中几乎所有的质子都参与了催化作用。此外，由于假液相，获得了对极性分子反应的独特选择性。(2)用<12><40>红外光谱和固体核磁共振等方法对PW_3O_2准液相中乙醇脱水反应机理进行了研究。质子化的乙醇二聚体（乙醚的中间体）、质子化的单体和乙氧基（乙烯的中间体）通过13 <13>C固态NMR直接检测。(3)用单晶X射线衍射法测定了配合物[（C_5H_5N）_2H]_3PW_O_的晶体结构<12><40>，其中吡啶分子成对形成（C_5H_5N）-H^+-（NC_5H_5）阳离子。(4)假液相的存在大大提高了苯酚液相烷基化反应的活性。<12>H_3PW_O_2<40>的催化活性远高于普通固体酸和H_2SO_4。

项目成果

M. Misono: "New Catalytic Aspects of Heteropolyacids and Related Compounds - To the Molecular Design of Practical Catalysis" Proceedings of 10th International Congress on Catalysis.

M. Misono：“杂多酸和相关化合物的新催化方面 - 实用催化的分子设计”第十届国际催化大会论文集。

Hiroo MORI: "Factors Controlling the Selectivity of the Oxidation of Acetaldehyde over Heteropoly Compounds" Journal of Catalysis. 131. 133-142 (1991)

Hiroo MORI：“控制乙醛氧化相对杂多化合物选择性的因素”催化杂志。

H. Mori, N. Mizuno, and M. Misono: "Factors Controlling the Selectivity of the Oxidation of Acetaldehyde over Heteropoly Compounds" Journal of Catalysis. 131. 133-142 (1991)

H. Mori、N. Mizuno 和 M. Misono：“控制乙醛氧化相对杂多化合物选择性的因素”催化杂志。

T. Okuhara, T. Nishimura, H. Watanabe, and M. Misono: "Insoluble Heteropoly Compounds as Highly Active Catalysts for Liquid Phase Reactions" Journal of Molecular Catalysis. 74. 247-256 (1992)

T. Okuhara、T. Nishimura、H. Watanabe 和 M. Misono：“不溶性杂多化合物作为液相反应的高活性催化剂”《分子催化杂志》。

Toru NISHIMURA: "High Catalytic Activity of an Insuluble Acidic Caecium Sult of Dodecatunystophosphoic Acid for Liguid Phase Alkylation" Applied Catalysis. 73. L7-L11 (1991)

Toru NISHIMURA：“十二磷酸磷酸铯产物对液相烷基化的高催化活性”应用催化。