本文選題：雜環(huán)化合物 + 5-氨基吡唑�。� 參考：《蘭州大學(xué)》2016年博士論文

【摘要】：雜環(huán)化學(xué)是近現(xiàn)代有機化學(xué)的重要組成部分,也是有機化學(xué)領(lǐng)域近年來研究最為活躍的領(lǐng)域之一。雜環(huán)化合物存在于大量的天然產(chǎn)物和具有生物活性的化合物中,其總數(shù)已超過已知有機化合物的三分之一,而含氮雜環(huán)化合物是雜環(huán)化合物中數(shù)量最多的一類。吡唑和吡咯衍生物是兩類重要的含氮雜環(huán)化合物,他們存在于許多有生物活性的化合物和人工合成的功能材料中。因此,很多化學(xué)合成工作者們的興趣也一直聚焦在對含氮雜環(huán)結(jié)構(gòu)的化合物的構(gòu)建和功能改造上。當(dāng)今社會需要的化學(xué)合成方法不僅僅是傳統(tǒng)地對化學(xué)、區(qū)域和立體選擇性做出要求,而且對新方法也有一些要求,總結(jié)如下:1.使用簡單且容易制備的原料;2.實驗操作簡單可行;3.有利的經(jīng)濟因素:包括原材料、人力資源和能源的成本;4.對環(huán)境的影響小:包括減少溶劑的使用,催化劑的可重復(fù)利用以及原子經(jīng)濟等。利用簡單易得的原料制備有機化合物是當(dāng)今有機合成工作者們面臨的巨大挑戰(zhàn)之一,以及在一個單一的操作中創(chuàng)建多個新化學(xué)鍵的形成,也已經(jīng)成為一個更具吸引力的目標(biāo)。另外,探索更為環(huán)境友好的合成方法也是化學(xué)工作者們的重要任務(wù)。本論文主要致力于用簡單易得的原料合成含氮雜環(huán)化合物的方法研究。我們用高效、綠色的方法合成了5-氨基吡唑衍生物和吡咯衍生物,具體包含如下兩個章節(jié):第一章:我們對5-氨基吡唑類化合物在醫(yī)藥、農(nóng)業(yè)和合成中的應(yīng)用以及對近年來報道的合成5-氨基吡唑衍生物的方法進行了文獻綜述。在此基礎(chǔ)上,我們以乙腈和腙的衍生物為底物,發(fā)展了一種用醋酸鈀和乙酰丙酮銅聯(lián)合催化通過C-C鍵和C-N鍵的形成高效合成5-氨基吡唑衍生物的新方法,該方法具有反應(yīng)物簡單易得,操作簡便和反應(yīng)條件溫和等優(yōu)點。利用該反應(yīng)體系,各種取代的乙腈和腙都能順利參與反應(yīng)并且給出良好的產(chǎn)品收率。相比于脂肪族和芳香雜環(huán)取代的底物,芳香基取代的底物表現(xiàn)出了更好的反應(yīng)活性。產(chǎn)物5-氨基吡唑的氨基還可以作為反應(yīng)官能團與其他分子進行衍生化反應(yīng),比如氨基磺酰化,氨基羰基化和重氮化反應(yīng)。第二章:我們對吡咯衍生物在醫(yī)藥、農(nóng)藥、高分子材料等領(lǐng)域的應(yīng)用及吡咯類化合物的合成方法研究做了介紹,同時對微波和蒙脫土K10在有機合成中的應(yīng)用也進行了文獻綜述。在此基礎(chǔ)上,我們研究了一種用α-氨基酮衍生物和苯乙醛衍生物通過C-C鍵和C-N鍵的形成高效合成多取代吡咯化合物的新方法,此方法通過微波輻射、蒙脫土K10催化來實現(xiàn)。該方法對帶有各種取代基的底物適用性良好,并且可以得到中等至良好的收率,最高產(chǎn)率可達98%。與常規(guī)加熱反應(yīng)方式相比,該方法具有無污染、反應(yīng)速率快、產(chǎn)品產(chǎn)率高且產(chǎn)物易于分離的特點,是一種環(huán)境友好并可能有廣泛應(yīng)用前景的合成方法。
[Abstract]:Heterocyclic chemistry is an important part of modern organic chemistry and one of the most active fields in the field of organic chemistry in recent years. Heterocyclic compounds are found in a large number of natural products and biologically active compounds. The total number of heterocyclic compounds is more than 1/3 of known organic compounds, while the heterocyclic compounds containing nitrogen are the most numerous heterocyclic compounds. Pyrazole and pyrrole derivatives are two important nitrogen-containing heterocyclic compounds. They exist in many bioactive compounds and synthetic functional materials. Therefore, the interest of many chemical synthesizers has been focused on the construction and functional transformation of nitrogen-containing heterocyclic compounds. The chemical synthesis methods that are needed in today's society are not only traditionally required for chemical, regional and stereoselectivity, but also for new methods, as summarized below: 1: 1. Use simple and easily prepared raw materials. The experiment is simple and feasible. Favorable economic factors: including raw materials, human resources and energy costs. Small environmental impact: reducing the use of solvents, catalyst reuse and atomic economy. The preparation of organic compounds from simple and easily available raw materials is one of the great challenges faced by organic synthesis workers today, and the formation of multiple new chemical bonds in a single operation has become a more attractive goal. In addition, exploring more environmentally friendly synthetic methods is also an important task for chemists. This paper is devoted to the synthesis of heterocyclic compounds containing nitrogen from simple and easily available raw materials. We have synthesized 5-aminopyrazole derivatives and pyrrole derivatives in a highly efficient and green way, including the following two chapters: chapter 1: we have a response to 5-aminopyrazole derivatives in medicine, The applications of agriculture and synthesis and the methods of synthesis of 5-aminopyrazole derivatives reported in recent years were reviewed. On this basis, we developed a novel method for the efficient synthesis of 5-aminopyrazole derivatives by the formation of C-C bond and C-N bond using palladium acetate and copper acetylacetone as the substrates of acetonitrile and Hydrazone derivatives. The method has the advantages of simple and easy to obtain reactants, simple operation and mild reaction conditions. With this reaction system, all substituted acetonitrile and Hydrazone can participate in the reaction smoothly and give a good yield. Compared with aliphatic and aromatic heterocyclic substrates, aromatic substrates exhibit better reactivity. The amino of 5-aminopyrazole can also be used as a functional group for the derivation of other molecules, such as amino sulfonylation, amino carbonylation and diazotization. Chapter 2: we introduce the applications of pyrrole derivatives in medicine, pesticides, polymer materials and the synthesis of pyrrole compounds. At the same time, we review the application of microwave and montmorillonite K10 in organic synthesis. On this basis, we have studied a new method of synthesis of polysubstituted pyrrole compounds by the formation of C-C bond and C-N bond by 偽 -aminoketone derivative and phenylacetaldehyde derivative. This method is realized by microwave irradiation and montmorillonite K10 catalysis. The method is suitable for substrates with various substituents and can obtain moderate to good yield with the highest yield of 98%. Compared with the conventional heating reaction method, this method has the advantages of no pollution, fast reaction rate, high product yield and easy separation. It is an environmentally friendly synthesis method with potential application prospects.
【學(xué)位授予單位】：蘭州大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：O626
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本文編號：1786906