Control of Reactivity and Selectivity through Elucidiation of Activation Mechanisms of Sonochemical Reactions

通过阐明声化学反应的激活机制来控制反应性和选择性

• 批准号: 04453021
• 负责人: ANDO Takashi
• 金额: $ 3.52万
• 依托单位: SHIGA UNIVERSITY OF MEDICAL SCIENCE
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04453021/
• 关键词: Sonochemistry; Ultrasound; Lead Tetraacetate; Photochemistry; 光反応; テトラヒドロフラン; ヒドロペルオキシド; 標準化; 光化学; 二酸化マンガン; 担持試薬

Mechanisms of sonochemical activation in several reactions were studied in order to establish it as the novel and general method of controlling the reactivity and selectivity of chemical reactions. Results are summarized below :1. In several reactions of lead tetraacetate, we found that : (1) stirenes whose reaction courses become more radical at higher temperatures showed the acceleration in their rates with more radical products under ultrasonic irradiation ; (2) a triarylmethane which reacts by increasing ionic mechanisms at higher temperatures showed no definite results ; and (3) 2-octanol whose reactivity does not change at higher temperatures does not show any clear effect of ultrasound. The results showed that the effect of ultrasound originates from the thermal effect.2. Thermodynamic study on the reaction of lead tetraacetate with trans-beta-methylylstirene indicated that the chain propagation step involving methyl radical occurs at a temperature only slightly higher than that … More determined by a thermocouple. The result indicated that the cite of the reaction is not in the interface but in the bulk liquid.3. Catalytic reactions of active manganese dioxide with mixtures of different classes of compounds showed the characteristic selectivity based of the adsorption on the surface.4. Sonochemical switching from aliphatic nucleophilic substitution to aromatic electrophilic substitution by selective poisoning of the basic cites on the alumina surface with acidic salts by accelerating solid-solid interaction with ultrasonic irradiation was tried in the mixtures of organic halides, salts, and alumina in aromatic solvents without much success.5. Simultaneous irradiation of a tetrahydrofuran solution of benzophebnone with ultrasound and UV light gave tetrahydrofuran hydroperoxide, while their separate of sequential irradiation did not. The mechanisms are not clear yet.6. Standardization of the power of ultrasound was studied by using calorimetry and the Weissler reaction. Less

为了使声化学活化成为控制化学反应活性和选择性的一种新的通用方法，对几种反应的声化学活化机理进行了研究。研究结果如下：1.在四乙酸铅的几个反应中，我们发现：（1）在超声波辐射下，反应过程在较高温度下变得更加自由基的苯乙烯反应速率加快，生成更多的自由基产物;和（3）在较高温度下反应性不改变的2-辛醇没有显示出任何明显的超声效应。结果表明，超声波的作用主要来源于热效应.对四乙酸铅与反式-β-甲基苯乙烯反应的热力学研究表明，甲基自由基参与链增长的温度仅略高于 ...更多信息 由热电偶确定。结果表明，反应的发生点不在界面上，而在本体液体中.活性二氧化锰与不同种类化合物的混合物的催化反应显示出基于表面吸附的特征选择性.在有机卤化物、盐和氧化铝的芳香族溶剂混合物中，通过超声辐射加速固-固相互作用，用酸性盐选择性毒化氧化铝表面的碱性位点，尝试了从脂肪族亲核取代到芳香族亲电取代的超声化学转换，但没有太大成功.用超声和紫外光同时照射苯并菲酮的四氢呋喃溶液，可得到四氢呋喃过氧化氢，而它们单独依次照射则不能。其机制尚不清楚。利用量热法和Weissler反应对超声功率的标准化进行了研究。少

项目成果

Takashi Ando: Inorganic Solid Supported Reagents as Acid and Bases, in "Acid-Base catalysis II" , ed by, H.Hatton, M.Misono, and Y.Ono. Kodansha, 9-20 (1994)

Takashi Ando：作为酸和碱的无机固体支撑试剂，在“酸碱催化 II”中，由 H.Hatton、M.Misono 和 Y.Ono 编辑。

Takashi Ando: "Effect of Ultrasound on the Reaction of trans-β-Methylstyrene with Lead Tetraacetate" Ultrasonics Sonochemistry. 1. 33-35 (1994)

Takashi Ando：“超声波对反式-β-甲基苯乙烯与四乙酸铅反应的影响”超声波声化学。1. 33-35 (1994)

David G.Cork: "Improved Fluorination with Supported Fluoride Reagents" Bulletin of Shiga University of Medical Science(General Education). 4. (1993)

David G.Cork：“用支持的氟化物试剂改进氟化”滋贺医科大学公告（通识教育）。

Takahide Kimura: "Selectivity in Catalytic Dehydrogenation with Active Manganese Dioxide" Bulletin of the Chemical Society of Japan. 65. 1149-1150 (1992)

Takahide Kimura：“活性二氧化锰催化脱氢的选择性”日本化学会通报。

Hajime Sohmiya: "Novel One-Step Synthesis of Sulfonyl Chlorides from Sulfides with Iodosobenzene and Hydrogen Chloride-Treated Silica Gel" Chemistry Letters. 1931-1932 (1992)

Hajime Sohmiya：“用碘代苯和氯化氢处理的硅胶从硫化物新型一步合成磺酰氯”化学快报。