發(fā)布時(shí)間：2018-10-24 17:42

【摘要】：并聯(lián)雙雜環(huán)化合物在人們的生活和生產(chǎn)中越來(lái)越常見(jiàn)，是醫(yī)藥、香精香料及生物材料等多領(lǐng)域中至關(guān)重要的化工原料或者合成中間體。開(kāi)發(fā)并聯(lián)雙雜環(huán)化合物合成方法的必要性日益凸顯，但到目前為止，報(bào)道合成并聯(lián)雙雜環(huán)化合物的方法普遍存在著收率低、反應(yīng)條件苛刻、原料來(lái)源局限、操作難度大等問(wèn)題。本文的研究在于進(jìn)一步探索Wilkinsons催化劑催化還原性環(huán)合的機(jī)理及其通用性，探索一種簡(jiǎn)便、高效、環(huán)保的并聯(lián)雙雜環(huán)化合物的合成方法。 以3-噻吩甲醇為原料，可以簡(jiǎn)便合成含硫、氮并聯(lián)雙雜環(huán)化合物，總收率可達(dá)到30%；以乙酰乙酸乙酯和氯乙醛為原料，，合成鄰羰基呋喃甲醇類的衍生物，并以此作為底物，進(jìn)行Wilkinsons催化劑催化還原性環(huán)合合成含氧并聯(lián)雙雜環(huán)化合物及其衍生物的研究，該工作在探索中。 在Wilkinsons催化劑多功能催化還原性環(huán)合機(jī)制的研究中，本文以合成的2-乙�；�-3-噻吩甲醇類為底物，研究它在催化劑、氫氣以及質(zhì)子酸等反應(yīng)條件下的環(huán)合反應(yīng)。探索不同反應(yīng)條件對(duì)反應(yīng)的影響、以及通過(guò)分離鑒定反應(yīng)過(guò)程中的中間體、副產(chǎn)物等方法，初步證實(shí)該反應(yīng)機(jī)制有半縮酮脫水環(huán)合和加氫還原的過(guò)程。采用1H-NMR、13C-NMR、LC-MS鑒定所涉及的中間體、副產(chǎn)物及目標(biāo)產(chǎn)物結(jié)構(gòu)。
[Abstract]:Parallel double heterocyclic compounds are more and more common in people's life and production. They are important chemical raw materials or synthetic intermediates in many fields such as medicine, flavor and biomaterials. It is necessary to develop the synthetic method of parallel double heterocyclic compounds, but up to now, it is reported that the synthesis methods of parallel double heterocyclic compounds have many problems, such as low yield, harsh reaction conditions, limited source of raw materials, difficult operation and so on. The purpose of this paper is to explore the mechanism and generality of catalytic reduction cyclization of Wilkinsons catalyst, and to explore a simple, efficient and environmentally friendly method for the synthesis of parallel double heterocyclic compounds. Using 3-thiophene methanol as raw material, the sulfur and nitrogen parallel heterocyclic compounds can be synthesized in an overall yield of 30%, and the derivatives of o-carbonyl furanol are synthesized from ethyl acetoacetate and chloroacetaldehyde as raw materials. The synthesis of oxygen-containing parallel bisheterocyclic compounds and their derivatives by catalytic reductive cyclization of Wilkinsons catalyst was studied. In the study of the mechanism of multi-functional catalytic reduction cyclization of Wilkinsons catalyst, the cyclization of 2-acetyl-3-thiophene methanol was studied under the conditions of catalyst, hydrogen and proton acid. The effects of different reaction conditions on the reaction were explored, and the process of dehydration and cyclization and hydrogenation reduction of Ketal was preliminarily confirmed by means of separation and identification of intermediates and by-products in the reaction process. The intermediates, by-products and target products were identified by 1H-NMR-13C-NMR-LC-MS.
【學(xué)位授予單位】：重慶醫(yī)科大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2014
【分類號(hào)】：R914.5

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