权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Direct Introduction of Functional Groups into Hydrocarbons by Using Low-Temperature Plasma

利用低温等离子体将官能团直接引入碳氢化合物中

基本信息

批准号：
01550679
负责人：
TEZUKA Meguru
金额：
$ 1.09万
依托单位：
Saitama Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1989
资助国家：
日本
起止时间：
1989 至 1990
项目状态：
已结题

项目摘要

Recent advance in synthetic chemistry has enabled the tailormade preparation of a diversity of organic compounds. However, direct introduction of functional groups into the carbon skeletons still remains a problem to be solved. In this study, the application of low-temperature plasma was investigated to introduce oxygen-containing groups such as hydroxyl or carbonyl group into hydrocarbons. The plasma was generated by means of radiofrequency discharge of oxygen gas flowing through a Pyrex reactor tube. Organic substrates were distilled together with oxygen through the reactor into cold traps on liquid nitrogen under reduced pressure.Some aromatic hydrocarbons were effectively oxidized in a gaseous oxygen plasma. Benzene and naphthalene were partially oxidized to give phenol and naphthol as a single volatile organic product, respectively. When alkylbenzene were reacted, the oxidation of alkyl groups competed with ring hydroxylation. Thus, toluene gave benzaldehyde and benzyl alcohol as well as phenol and three isomeric cresols. With increase in size of alkyl groups, alkyl oxidation became preferential. Based on the result that the oxidation favorably took place on the alpha-carbons, the reaction scheme involving autoxidation of benzyl radicals formed through electron collision onto starting material molecules. From the substrate having olefinic double bond, e. g. styrene, the epoxide or its derivatives, mainly ketones, were obtained in fairly good yields. There, seemingly, atomic oxygen played a significant role.The oxidation of saturated hydrocarbons was also examined. Cycloalkanes (C_5-C_8) gave the corresponding cycloalkanol and cycloalkanone in almost equimolar amounts, although their yields were unsatisfactory.

合成化学的最新进展使量身定做多种有机化合物成为可能。然而，在碳骨架中直接引入官能团仍然是一个有待解决的问题。本研究探讨了低温等离子体在碳氢化合物中引入羟基或羰基等含氧基团的应用。等离子体是由流经热阻反应管的氧气射频放电产生的。在减压条件下，将有机底物与氧气一起通过反应器蒸馏到液氮冷阱中。一些芳烃在气态氧等离子体中被有效氧化。苯和萘被部分氧化，分别得到苯酚和萘酚作为单一的挥发性有机产物。烷基苯反应时，烷基的氧化反应与环羟基化反应相竞争。因此，甲苯得到苯甲醛和苯甲醇以及苯酚和三个异构体甲酚。随着烷基尺寸的增大，烷基氧化反应优先。基于对α -碳有利氧化的结果，反应方案涉及通过电子碰撞在起始物质分子上形成的苯基自由基的自氧化。从具有烯烃双键的底物，如苯乙烯，可以得到环氧化物或其衍生物，主要是酮类，收率相当高。在那里，氧原子似乎起了重要作用。饱和碳氢化合物的氧化也进行了研究。环烷烃（C_5-C_8）生成的环烷醇和环烷酮几乎是等量的，但产率不理想。