【作者】 张志国；

【导师】 刘群；

【作者基本信息】 东北师范大学 ， 有机化学， 2010， 博士

【摘要】 众所周知,在目前有机合成化学向绿色化学和节约型化学方向发展的趋势下,如何利用便宜、易得的化学化工原料高效的合成对人类有用的化合物是化学工作者在实验设计、实施过程中需要考虑的主要问题。乙酰乙酰芳胺及其衍生物是重要的有机合成试剂,在染料工业及有机合成中有相当广泛的应用。经过百年的研究,乙酰乙酰芳胺及其衍生物化学也已经发展到日臻完美的地步,发展乙酰乙酰芳胺及其衍生物的高效的、原子经济性的合成化学值得期待。本论文主要论述了乙酰乙酰芳胺及其衍生物在有机合成中的崭新应用,详细阐述了以易于制备的乙酰乙酰芳胺烷基化衍生物通过分子内串联反应分别制备几类具有重要应用价值的并杂环类天然产物母核结构的方法,并对其机理进行了深入细致的研究。我们认为这些研究成果可以为合成其它并杂环化合物提供更合理、更有效的设计方案奠定基础。在具体的研究过程中,我们主要完成了以下两项工作:1)通过催化剂、溶剂、反应温度等条件的筛选、优化确定了最佳的反应条件并且在优化条件下合成了几个系列的并杂环类化合物。2)深入细致的研究了反应的机理,为了合成其它并杂环类化合物提供依据。传统的并杂环合成往往需要多步完成,不但周期长而其产品的总产率会因反应步骤的增加而降低。通过官能团修饰的乙酰乙酰芳胺衍生物一步合成有重要应用价值的天然产物母核结构具有挑战性。我们的实验设计及合成优点如下:(1)原料易得、价格便宜:乙酰乙酰芳胺类化合物是重要的化学化工原料,合成简单,价格便宜,储存和运输都很方便。(2)官能化衍生物易于制备:制备的一系列烷基化的乙酰乙酰芳胺是以具有活泼亚甲基的乙酰乙酰胺类化合物、碱、卤代烷为原料一锅合成的。条件相当温和,易于控制烷基化产物,产率较高,分离和储存都很容易。(3)反应选择性好,产率高:从实验结果可以确定以官能化衍生物为原料的并杂环化合物的合成表现出了很好的化学选择性和区域选择性,且产率高。(4)高原子经济性:我们从一类简单、易得的合成前体出发,高原子经济性的构筑多种并杂环分子体系尤其是杂环并喹啉类化合物。原料中几乎所有原子都保留在产物中,只有副产物水生成,达到最大的原子经济性。(5)为合成其他并杂环提供理论指导:我们充分利用了乙酰乙酰芳胺烷基化衍生物分子内官能团的高选择性成键方式来实施一步、高效的多米诺反应,构建并杂环衍生物。该方法可能提供一种合成并杂环类化合物的通用新合成方法。并为合成其它并杂环类化合物提供依据。更多还原

【Abstract】 It is well-known that the green chemistry and chemical-saving are direction of the current organic synthetic chemistry. How to use cheap, readily available reagent to facile and efficient synthesis of useful compounds for humans is a major problem, which needs to be considered for chemical workers in the experimental design and the implementation process. Acetoacetarylamides and its derivatives are important reagents in organic synthesis. They have more active sites and a wide range of applications, especially in the dye industry and pharmaceutical chemistry. Acetoacetarylamides and their derivatives chemistry have also been more perfect than ever in a century of research, so developing efficient and atom-economy chemistry is worth the wait.This paper mainly discusses the new applications of acetoacetarylamides and its derivatives in organic synthesis, including their preparation and reactions of common derivatives, and also detailed the preparation of several important core of natural products by the intramolecular tandem reaction of readily available acetoacetarylamide alkylated derivatives on the basis of the literature and our previous work, these mechanisms were also in-depth study. We believe that these findings can be theoretical guidance for the synthesis of other heterocyclic compounds. During the specific research process, we mainly have completed the following two tasks: 1) we determined the optimizing conditions through screening of the catalyst, solvent, temperature etc., and several series heterocyclic compounds were synthesized under optimal conditions. 2) In order to provide a theoretical support for synthesis of other heterocyclic compounds, the reaction mechanisms were in-depth studiedThe traditional synthesis of fused-heterocyclic compounds are often require multi-step, not only needs a long time and the total yield of the products increases due to multi-step reaction. It is quite a challenging task for the synthesis of the core structure of valuable natural products by functionalized acetoacetarylamide derivatives. In contrast, the advantages of our synthesis are:(1) Ready-made, low-cost raw materials: Acetoacetarylamides are important chemical raw materials, synthetic simple, cheap, and very convenient for transport and storage.(2) Easy preparation of functionalized derivatives: Preparation of the series of alkylated acetoacetarylamides is one-pot protocol by using acetoacetamides, alkali and haloalkanes under mild conditions. the reaction is easy to control and the product yield is satisfactory, easy separation and storage.(3) High selectivity and high yield: The reaction showed high chemical selectivity, regioselectivity and high yield during the fuseheterocyclic synthesis process via functionalized derivatives of acetoacetarylamide.(4) High atom economy: we obtained some of heterocyclic moleculars by high atom economy from a series of simple functionalized derivatives of acetoacetarylamide. All the atoms of raw materials are almost retained in the product, the only by-product is water. We achieved the greatest atom economy.(5) Provide theoretical guidance to synthesize other heterocycles: We have made full use of functional groups of alkylated derivatives of acetoacetarylamide to build fuseheterocyclic derivatives by domino reaction with highly regioselective. This method may provide a novel and common methods for synthesis of heterocyclic compounds. And aslo, it can provide a theoretical basis for the synthesis of other heterocyclic compounds.更多还原