【作者】 陈保华；

【导师】 李记太；

【作者基本信息】 河北大学 ， 分析化学， 2014， 博士

【摘要】 多组分反应是指由三种或三种以上的反应物以一锅煮的反应方式形成一个包含所有组分主要结构片段的新化合物的过程，是一类重要的有机化学反应。由于其高度的原子经济性、收敛性和出色的产率等特性以及在新药设计与合成、组合化学和天然产物合成等方面的重要应用，一锅多组分反应的研究越来越受到合成化学家们的重视。超声辐射在有机合成中的应用研究近年来发展非常迅速，同传统的合成方法相比，其具有反应条件温和，操作简便，反应速度快，产率高等优点，为在一般条件下难以进行或不可能实现的化学反应提供了一种新的途径。论文对超声波的作用原理及在有机化学中的应用做了简单介绍，综述了近年来超声辐射在多组分一锅法合成中的应用，利用超声辐射下的一锅法反应合成了四类含氮化合物并对其结构进行了表征。在25~28oC超声辐射下，以芳香醛、芳香酮、乙酰氯和乙腈为原料，硫酸钴为催化剂，通过多组分一锅法高产率合成了β-乙酰氨基酮类化合物。考察了催化剂用量对反应的影响，并与传统的加热回流反应进行对照。结果表明，超声法的反应效果要明显优于传统的加热回流法。在超声辐射和NaOH存在下，利用一锅法，由芳醛肟与芳基磺酰氯在室温CH2Cl2中反应15~60min合成相应的O-芳磺酰基芳醛肟，收率56%~94%。对影响反应的因素如反应物的用量、催化剂种类及超声频率等进行了研究。方法操作简便，反应条件温和，时间短，产率高，为同类化合物的合成提供了一种简便有效的方法。以对甲苯磺酸为催化剂，在乙醇溶剂中，由1-哌啶基-1,3-丁二酮、芳香醛和硫脲在室温超声辐射下，通过三组分一锅法有效地合成了系列含哌啶酰胺基的2-硫代-二氢嘧啶衍生物。反应时间1~2h，产物收率81%~91%，与传统的加热回流方法对比，反应时间明显缩短，产物收率高。在超声辐射和十二烷基苯磺酸催化下，利用三组分一锅法由靛红酸酐、芳香醛和胺在水介质中合成了系列2,3-二取代-2,3-二氢喹唑啉-4(1H)-酮衍生物，反应温度40~42oC，反应时间1~2h，收率80%~92%。本方法操作和处理步骤简便，反应条件温和，避免使用有机溶剂，对环境友好。更多还原

【Abstract】 Multi-component reactions are an important class of organic synthesis reaction, bywhich three or more reactants can form a compound containing the main structural fragmentof all components with one-pot method. Because of its high atom economy, convergence,excellent yield and the important applications in design and synthesis of new drug,combinatorial chemistry and synthesis of natural products, the study of one-potmulti-component reactions are getting more and more attention to the synthetic chemists.In recent years, the application of ultrasound irradiation in organic synthesis developedrapidly. Compared with traditional methods, many organic reactions can be carried out undermild conditions, simple operation, in short reaction time with high yield under ultrasoundirradiation. It is a more versatile and facile in many types of chemical reactions, especially thereactions difficult or impossible to occur under normal conditions. In this paper, the principleof sonochemistry and some applications in organic synthesis were introduced, and theapplications of ultrasound in one-pot multi-component reactions were reviewed. Four kindsof nitrogenous compounds were syntheisized by one-pot synthesis under ultrasoundirradiation and characterized by their spectral data.Ultrasound-promoted synthesis of β-acetamido ketones catalyzed by cobalt sulfateheptahydrate via one-pot multi-component reaction coupling of aromatic aldehyde,acetophenone and acetyl chloride in acetonitrile was carried out in excellent yields at25~28oC. The effect of the amount of the catalyst on the reaction was investigated, and the resultsunder different conditions were compared. It indicated that the results of the reaction underultrasound irradiation were obviously superior to those under reflux condition.One-pot synthesis of O-arylsulfonyl arylaldoximes was carried out in56%~94%yieldswithin15~60min via the condensation of arylaldoxime with aromatic sulfonyl chloride in thepresence of sodium hydroxide at room temperature in dichloromethane under ultrasoundirradiation. The effect factors on the reaction such as the molar ratio of the reactant, the kindsof catalyst, and the frequency of ultrasound irradiation were studied. The advantages of this methodology are convenient operation, mild conditions, short reaction times, and high yields.It provides a simple and efficient method for the similar compounds.A convenient and efficient one-pot synthesis of2-thioxo-dihydropyrimidine derivativesbearing piperidinylamide moiety was carried out in81%~91%yields within1~2h via thecondensation of1-(piperidin-1-yl)butane-1,3-dione with aromatic aldehyde and thiourea inethanol catalyzed by p-toluenesulfonic acid at room temperature under ultrasound irradiation.Comparing with the results under traditional refluxing conditions, the advantages of thismethodology are shorter reaction times and higher yields.A series of2,3-disubstituted-2,3-dihydroquinazolin-4(1H)-one derivatives weresynthesized in80%~92%yields within1~2h by one-pot three-component condensation ofisatoic anhydride, aromatic aldehyde and amine using dodecylbenzenesulfonic acid ascatalyst in aqueous medium at40~42oC under ultrasound irradiation. Simple experimentaland work-up procedures, mild reaction conditions, avoid the use of organic solvents, andfriendly to environment are the salient features of this protocol.更多还原