Direct Introduction of Hetero Atoms into Hydrocarbons in Plasmas

本研究旨在通过常规化学方法生成超活性物质并将其引入烃类中。不仅对气态等离子体反应，而且对等离子体诱导的溶液相有机反应，即辉光放电电解（gde）也给予了特别的关注。1995年，研究了在射频等离子体中芳香烃与氧的氧化。当各种烷基苯进入气态等离子体时，苯环的羟基化与烷基的氧化相竞争。另一方面，烯烃双键优先被氧化成相应的环氧化物。1996年，用gde方法对溶解在水溶液中的有机物进行了氧化降解。因此，苯酚最终被分解成二氧化碳和水。中间产物为对苯二酚和儿茶酚。它们依次被氧化为邻苯三酚和羟基对苯二酚。苯核的裂解随后产生多种羧酸，如草酸或甲酸。据推测，由水分子解离产生的羟基自由基是导致氧化的主要原因。尝试了gde方法在有机溶剂体系中的应用。乙腈的主要产物是丙腈、丙烯腈和丁二腈。提出了一种涉及离子种类（可能是乙腈阳离子）的反应方案，这种离子可以在放电区产生，并可能进入溶液表面层以分解几个溶剂分子。由此产生的自由基，即甲基自由基和氰基自由基，应相互重组，以产生上述产物。

In this study, The creation super-reactive species which might be formrd by conventional chemical methods and its introduction into hydrocarbons has been aimed. Special attention has been paied not only to gaseous plasma reactions but also solution-phase organic reactions induced by plasma, namely glow discharge electrolysis (gde).In 1995, the oxidation of aromatic hydrocarbons with oxygen in a radio-frequency plasma was examined. When a variety of alkylbenzenes were fed into the gaseous plasma, the hydroxylation of benzene rings competed with the oxidation of alkylgroups. On the other hand, the olefinic double bonds were preferentially oxidized to the corresponding epoxides.In 1996, the oxidative degradation of organic substances dissolved in an aqueous solution was conducted by means of gde. Thus, phenols was eventually decomposed to carbon dioxides and water. As the intermediate products, hydroquinone and catechol were formed. Successively, they were oxidized to pyrogallol and hydroxyhydroquinone. The cleavage of benzene nucleus subsequently occurred to yield a diversity of carboxylic acids such as oxalic or formic acids. It was assumed that hydroxyl radical resulting from the dissociation of water molecule should be responsible for the pxidation.the application of gde methods to organic solvent system was attempted. In the gde of acetonitrile, propionitrile, acrylonitrile and succinonitrile were obtained as major products in the solution-phase. The reaction scheme involving the ionic species, probably acetonitrile cation, which could be generated in the discharge zone and might ruch into the solution surface layr to break up several solvent molecules, was proposed. The resulting radical, that is methyl and cyano radicals, should be mutually recombined to give rise to the above-mentioned products.