發(fā)布時(shí)間：2019-02-18 12:23

【摘要】：鄰苯二甲酰亞胺類(lèi)化合物作為一種重要的合成原料和中間體,在醫(yī)藥、農(nóng)藥和有機(jī)材料等多個(gè)研究領(lǐng)域中都有極為重要的應(yīng)用。因此,該類(lèi)化合物的合成一直受到科學(xué)家的關(guān)注。本論文提出了一種利用多重鹵鍵活化模式,實(shí)現(xiàn)了親電試劑鹵代烴和N-鹵代酰亞胺的偶聯(lián)反應(yīng),提供了合成鄰苯二甲酰亞胺類(lèi)化合物的新思路。該合成方法具有快速高效、無(wú)需金屬參與、條件溫和、底物適用范圍廣及原子利用率高等優(yōu)點(diǎn)。當(dāng)向反應(yīng)體系中引入DBU時(shí),作為親電試劑的鹵代烴和N-鹵代酰亞胺的偶聯(lián)反應(yīng)得以發(fā)生,生成了胺化產(chǎn)物。反應(yīng)的最佳條件是以二甲基亞砜作為溶劑,N-鹵代酰亞胺(1.2倍量)、DBU(1.2倍量)與1當(dāng)量的鹵代烴在室溫下反應(yīng),以較好的產(chǎn)率(25%-93%)獲得目標(biāo)產(chǎn)物。實(shí)驗(yàn)結(jié)果表明:在反應(yīng)底物鹵代烴中,反應(yīng)活性順序?yàn)?碘代烷烴溴代烷烴氯代烷烴;反應(yīng)物N-鹵代酰亞胺的反應(yīng)活性:氯代酰亞胺的活性要高于溴代酰亞胺。在實(shí)驗(yàn)結(jié)果基礎(chǔ)上,本論文提出了由多重鹵鍵活化的偶聯(lián)反應(yīng)的反應(yīng)機(jī)理。鹵鍵的存在同時(shí)活化了N-鹵代酰亞胺和鹵代烴兩種底物,使得該偶聯(lián)反應(yīng)可以高效平穩(wěn)發(fā)生。我們的這種合成方法以及機(jī)理的提出豐富了鹵鍵化學(xué),為鹵鍵活化在有機(jī)合成中的應(yīng)用提供了新的例證。
[Abstract]:As an important synthetic raw material and intermediate, phthalimides have been widely used in many fields such as medicine, pesticide and organic materials. Therefore, the synthesis of this kind of compounds has been concerned by scientists. In this paper, a coupling reaction of electrophilic reagents halogenated hydrocarbons and N-halogenated imides is proposed by using the multiple halogenated bond activation mode, which provides a new idea for the synthesis of phthalimide compounds. The method has the advantages of fast and high efficiency, no metal participation, mild conditions, wide application range of substrates and high atomic utilization rate. When DBU was introduced into the reaction system, the coupling reaction of halogenated hydrocarbons and N-halogenimide as electrophilic reagents took place, resulting in amination products. The optimum reaction conditions were as follows: dimethyl sulfoxide was used as solvent, N-halogenated imide (1.2-fold), DBU (1.2-fold) reacted with 1 equivalent halogenated hydrocarbon at room temperature, and the target product was obtained in a better yield (25-93%). The experimental results show that the order of reaction activity of halogenated hydrocarbons is as follows: iodinated alkanes bromoalkanes chlorinated alkanes, the reactivity of N-halogenated imide is higher than that of bromoimide, and the reaction activity of N-haloimide is higher than that of bromoimide. Based on the experimental results, the mechanism of the coupling reaction activated by multiple halogen bonds was proposed. The existence of halogen bond activates both N-halogenimide and halogenated hydrocarbons, which makes the coupling reaction take place smoothly and efficiently. This method and its mechanism enrich the halogen bond chemistry and provide a new example for the application of halogen bond activation in organic synthesis.
【學(xué)位授予單位】：東北師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O621.25

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本文編號(hào)：2425834