【作者】 贾晓洁；

【导师】 马恒昌； 雷自强；

【作者基本信息】 西北师范大学 ， 高分子化学与物理， 2011， 硕士

【摘要】 本论文由以下四部分组成:第一章:综述从醇在金属催化剂作用下的催化氧化和在非金属催化剂作用下的催化氧化两个方面分别综述了当前醇催化氧化研究领域的进展。在金属催化部分,分别从金属钌催化体系、金属铬催化体系、金属铁催化体系、金属锰催化体系、双金属催化体系和其它过渡金属（钯、金、钒、铜）催化体系几个方面介绍了醇在金属催化剂作用下的催化氧化研究进展。在非金属催化氧化部分,重点介绍了最常用的催化剂TEMPO催化体系以及其它非金属催化体系（例如碘等）在醇非金属催化氧化研究中的应用。另外,全面介绍了最近新发现的催化剂“碳催化剂”。第二章: Me₂SiCl₂对醇的催化氧化性能研究以小分子有机硅试剂Me₂SiCl₂为催化剂,以30 % H₂O₂为氧化剂,对醇的氧化表现出很好的催化性能,苯甲醇或二苯甲醇及其衍生物均能被30 % H₂O₂高转化率和高选择性地氧化为相应的醛或酮。并在此基础上进行了在此反应体系中反应活性的关联性分析,得到了Me₂SiCl₂催化氧化醇的Hammett曲线。并进一步对该反应的机理进行了探索。第三章: Me₂Si（OH）₂和PEG催化的醇氧化反应以Me₂Si（OH）₂为溶剂和催化剂,对醇的催化氧化性能进行了研究,得到了很好的催化效果。并在此基础上对炔烃的氧化反应进行了研究,发现在此催化体系下,炔烃发生的是环二聚反应,得到了几种环二聚产物并合成了两种氘代试剂。以PEG-600为溶剂和催化剂,以空气中的氧气为氧化剂,120℃下反应24 h,使各种醇转化为相应的羰基化合物,催化性能良好。以（18）^O标记的苯甲醇的氧化反应跟踪了反应历程,生成的苯甲醛中的（16）^O来自于氧化剂空气氧,并进一步从不同方面对反应机理进行了探讨。更多还原

【Abstract】 The thesis consists of the following four chapters:ChapterⅠ: ReviewsIt reviewed the catalytic oxidation of alcohols with both metal catalysts and metal-free catalysts in this chapter. For the metal-catalyzed oxidation, the research progress were reviewed, such as: ruthenium, iron, manganese, bimetallic catalyst and other transition metal catalyst system （palladium, gold, vanadium and copper）. In the second section, the applications of TEMPO and its derivatives as well as other no-metal-catalyst system （such as iodine） in the catalytic oxidation of alcohols were well discussed. And also, the new concept of“carbocatalyst”was introduced.ChapterⅡ: Oxidation of alcohols catalyzed by dichlorodimethylsilane with hydrogen peroxideUsing hydrogen peroxide （30 %） as sole oxidant, organosilicon dichlorodimethylsilane was applied to the transformation of benzyl alcohol to benzaldehyde. The results showed that it was excellent catalyst for the oxidation of alcohols. A series of benzyl alcohols and benzhydrol derivatives were oxidized to the corresponding aldehydes and ketones with high coversion and selectivity using 30 % H₂O₂ as oxidant. On the base of that, the reactivity of substituted aromatic compounds in the oxidation of alcohols catalyzed by dichlorodimethylsilane was clarified and Hammett plot was designed in this oxidation system. Meanwhile, the mechanism of the reaction was postulated.ChapterⅢ: Oxidation of alcohols catalyzed by dimethylsilanediol and Polyethylene glycolIn the solvent of dimethylsilanediol, for the oxidation of alcohols, dimethylsilanediol displayed good catalytic behivior. We studied the oxidation of alkyne as well as the oxidation of alcohols, and it was found that cyclodimerization for alkynes was occurred. On the base of the result, two deuterium substituted reagents were synthesized. Also the possible mechanism was postulated.Using PEG-600 as solvent and catalyst, at 120℃, oxidation transformation of alcohols to the corresponding aldehydes and ketones in the presence of air was studied. The results show that PEG-600 is good catalyst for the oxidation of alcohols. Oxidation of （18）^O enriched benzyl alcohol transformed to （16）^O benzaldehyde which shows that （16）^O come from the air oxygen. Also we postulated the mechanism of the reaction from different point of view.更多还原