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Sonochemistry : The Establishment and the Strategic Applications of the Idea of Physical Control of Chemical Reactivity

声化学:化学反应物理控制思想的建立及其战略应用

基本信息

批准号：
11640531
负责人：
ANDO Takashi
金额：
$ 2.24万
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 Scientific Research (C)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2001
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640531/
关键词：
Sonochemistry Ultrasound Photochemistry Lead Tetraacetate Vapor Pressure Iodination 沃素化反応機構スチレン

项目摘要

We carried out our studies with a view to clarify the factors governing the sonochemical reactivity and to establish the idea of 'physical control of chemical reactivity' in sonochemistry. The results we obtained are as follows:(1) Sonochemistry and photochemistry were compared in the decomposition of bromotrichloromethane in the presence and absence of 1-alkenes. It became clear that photochemistry occurs in the homogeneous and dispersed phase while sonochemistry occurs in heterogeneous and local phase, although both are described by the same chemical equation. Dependence of the sonochemical reactivity on the surface tension was also established.(2) Radical reactivity in the reaction of lead tetraacetate (LTA) with styrene showed a good linear free energy relationship (LFER) with the calculated vapor pressure of styrenes. Production of radicals from styrenes under sonication in the absence of LTA also showed the same type of LFER with the vapor pressure. These results indicate the rate-determining vaporization of styrenes into the cavity in the sonochemical reaction.(3) The reactivity of a liquid-liquid two-phase oxidation of alkyl- and arylthiols in water-isopropanol depends on the vapor pressure and surface activity of the thiols.(4) Iodination of simple hydrocarbons with iodoform and solid sodium hydroxide issonochemically accelerated. Bromination with tetrabromomethane was also sonochemically accelerated.

本研究旨在阐明声化学反应的影响因素，确立声化学中“化学反应的物理控制”的思想。主要研究结果如下：(1)比较了声化学和光化学在1-烯烃存在和不存在的情况下对溴三氯甲烷的分解。很明显，光化学发生在均相和分散相中，而声化学发生在非均相和局部相中，尽管两者都用相同的化学方程式描述。(2)四乙酸铅(LTA)与苯乙烯反应的自由基反应性与计算的苯乙烯蒸汽压呈良好的线性自由能关系。在没有LTA的情况下，超声波作用下由苯乙烯产生的自由基也显示出与蒸汽压相同类型的LFER。这些结果表明，在声化学反应中，苯乙烯类化合物汽化进入空腔的速率是决定性的。(3)烷基硫醇和芳基硫醇在水-异丙醇中的液-液两相氧化反应的活性取决于硫醇的蒸汽压和表面活性。(4)简单碳氢化合物与碘仿和固体氢氧化钠的同位化学加速。与四溴甲烷的溴化反应也得到了声化学加速。