Direct Introduction of Hetero Atoms into Hydrocarbons in Plasmas

本研究的目的是创造常规化学方法可能形成的超活性物种，并将其引入烃类中。不仅对气相等离子体反应，而且对由等离子体诱导的液相有机反应，即辉光放电电解（gde）反应也给予了特别的关注。1995年，在射频等离子体中，研究了芳烃与氧气的氧化反应。当各种烷基苯进料到气态等离子体中时，苯环的羟基化与烷基的氧化竞争。另一方面，烯双键优先被氧化成相应的环氧化物。1996年，通过gde对溶解在水溶液中的有机物进行了氧化降解。因此，酚类最终分解为二氧化碳和水。中间产物为对苯二酚和邻苯二酚。在琥珀酸中，它们被氧化成焦性没食子酸和羟基氢醌。随后发生苯核的裂解，产生多种羧酸，如草酸或甲酸。推测水分子解离产生的羟基自由基是氧化反应的主要原因，并尝试将气相色谱法应用于有机溶剂体系。在乙腈的gde中，溶液相中主要得到丙腈、丙烯腈和丁二腈。提出了在放电区产生的离子物种（可能是乙腈阳离子）可能进入溶液表面层分解几个溶剂分子的反应方案。所得到的自由基，即甲基和氰基自由基，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.