【摘要】：喹唑啉類化合物是一類重要的含氮雜環(huán)化合物,具有廣泛的生物和藥理活性,其骨架存在于多種生物活性分子和天然產(chǎn)物之中,是合成各種功能材料的重要中間體,受到人們?cè)絹?lái)越多的關(guān)注。本論文在前人研究基礎(chǔ)上提供了一種硝基甲苯類化合物參與的C-N氧化偶聯(lián)合成喹唑啉的方法,并在其研究過(guò)程中意外發(fā)現(xiàn)硝基甲苯類化合物的自身C-C氧化偶聯(lián)反應(yīng)。而氧化偶聯(lián)反應(yīng)作為構(gòu)建碳碳及各類碳雜鍵強(qiáng)有力的化學(xué)工具,研究成果廣泛應(yīng)用于生物、醫(yī)藥、農(nóng)藥、仿生、材料、天然產(chǎn)物全合成等各個(gè)領(lǐng)域當(dāng)中,極大地促進(jìn)了有機(jī)化學(xué)的發(fā)展。因此,本論文的另一研究目的在于發(fā)展一種新型的氧化偶聯(lián)策略以實(shí)現(xiàn)1,2-二芳基乙酮/醇和2-[2-(喹啉-2-基)乙烯基]-喹啉類化合物的合成。主要研究?jī)?nèi)容包括以下三個(gè)部分:1.硝基甲苯類參與的C-N氧化偶聯(lián)反應(yīng)合成喹唑啉類化合物。以2-硝基甲苯和芐胺為原料,經(jīng)氧化縮合實(shí)現(xiàn)喹唑啉的合成,并對(duì)其反應(yīng)條件進(jìn)行優(yōu)化,以及底物拓展研究,得到了一系列含有不同取代基的喹唑啉類化合物。該方法具有原料廉價(jià)易得、反應(yīng)條件溫和、操作簡(jiǎn)單等優(yōu)點(diǎn)。2.硝基甲苯類化合物參與的C-C氧化偶聯(lián)反應(yīng)。在喹唑啉的合成研究中,發(fā)現(xiàn)硝基甲苯類化合物在堿和DMSO體系中可以發(fā)生自身氧化偶聯(lián)反應(yīng),其化學(xué)選擇性可以通過(guò)控制堿的種類調(diào)控。30°C下,在KOtBu/DMSO體系中獲得唯一產(chǎn)物1,2-二芳基乙酮類化合物;在K2CO3/DMSO體系中進(jìn)行反應(yīng)時(shí),僅產(chǎn)生1,2-二芳基乙醇類化合物。該方法避免了過(guò)渡金屬催化劑的使用,為1,2-二芳基乙酮/醇類化合物的合成提供了一種新的途徑。3.硝基甲苯類化合物C-C氧化偶聯(lián)反應(yīng)的衍生。受2-硝基甲苯在堿性條件下自身可以發(fā)生氧化偶聯(lián)反應(yīng)的啟示,本論文嘗試以與2-硝基甲苯電子效應(yīng)及結(jié)構(gòu)類似的2-甲基喹啉為底物來(lái)實(shí)現(xiàn)其自身氧化偶聯(lián)反應(yīng)。實(shí)驗(yàn)證明該理論是成立的,成功得到了2-甲基喹啉類化合物的自身氧化偶聯(lián)產(chǎn)物2-[2-(喹啉-2-基)乙烯基]-喹啉類化合物。
[Abstract]:Quinazoline compounds are a kind of important nitrogen-containing heterocyclic compounds, which have a wide range of biological and pharmacological activities. Their skeletons exist in a variety of bioactive molecules and natural products, and they are important intermediates for the synthesis of various functional materials. Get more and more attention. In this paper, based on previous studies, a method of C-N oxidative coupling of nitrotoluene compounds to quinazoline was proposed, and the self-C-C oxidative coupling reaction of nitrotoluene compounds was discovered by accident. However, oxidative coupling reaction is a powerful chemical tool for the construction of carbon and all kinds of carbon heterogeneity bonds. The research results have been widely used in biology, medicine, pesticides, bionics, materials, natural products, etc. It greatly promoted the development of organic chemistry. Therefore, another aim of this thesis is to develop a novel oxidative coupling strategy for the synthesis of 1- [(quinoline-2-vinyl) vinyl] -quinoline compounds. The main research contents include the following three parts: 1. Quinazoline compounds were synthesized by C-N oxidative coupling reaction involving nitrotoluene. Quinazoline was synthesized by oxidative condensation of 2-nitrotoluene and benzylamine. The reaction conditions were optimized and the substrate was developed. A series of quinazoline compounds containing different substituents were obtained. The method has the advantages of cheap raw material, mild reaction conditions, simple operation and so on. 2. C-C oxidative coupling reaction of nitrotoluene compounds. In the study of the synthesis of quinazoline, it was found that nitrotoluene compounds can undergo autooxidative coupling reaction in alkali and DMSO system, and their chemical selectivity can be controlled by controlling the type of base at 30 擄C. In the KOtBu/DMSO system, the unique product, 1h2- diarylethanone, was obtained. When the reaction is carried out in the K2CO3/DMSO system, only 1o 2-diaryl alcohol compounds are produced. This method avoids the use of transition metal catalysts and provides a new way for the synthesis of 1 ~ (2) -diarylacetone / alcohols. Derivation of C-C oxidative Coupling reaction of Nitrotoluene compounds. Inspired by the oxidative coupling reaction of 2-nitrotoluene in alkaline condition, this paper attempts to realize the self-oxidative coupling reaction by using 2-nitrotoluene as substrate with electronic effect and similar structure of 2-methylquinoline. It is proved that this theory is true and the self-oxidative coupling product of 2-methylquinoline compounds 2- [2- (quinoline-2-yl) vinyl] -quinoline compounds has been successfully obtained.
【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.25
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本文編號(hào)：2400200