并联双杂环化合物新合成方法的研究
发布时间：2018-10-24 17:42
【摘要】：并联双杂环化合物在人们的生活和生产中越来越常见，是医药、香精香料及生物材料等多领域中至关重要的化工原料或者合成中间体。开发并联双杂环化合物合成方法的必要性日益凸显，但到目前为止，报道合成并联双杂环化合物的方法普遍存在着收率低、反应条件苛刻、原料来源局限、操作难度大等问题。本文的研究在于进一步探索Wilkinsons催化剂催化还原性环合的机理及其通用性，探索一种简便、高效、环保的并联双杂环化合物的合成方法。 以3-噻吩甲醇为原料，可以简便合成含硫、氮并联双杂环化合物，总收率可达到30%；以乙酰乙酸乙酯和氯乙醛为原料，，合成邻羰基呋喃甲醇类的衍生物，并以此作为底物，进行Wilkinsons催化剂催化还原性环合合成含氧并联双杂环化合物及其衍生物的研究，该工作在探索中。 在Wilkinsons催化剂多功能催化还原性环合机制的研究中，本文以合成的2-乙酰基-3-噻吩甲醇类为底物，研究它在催化剂、氢气以及质子酸等反应条件下的环合反应。探索不同反应条件对反应的影响、以及通过分离鉴定反应过程中的中间体、副产物等方法，初步证实该反应机制有半缩酮脱水环合和加氢还原的过程。采用1H-NMR、13C-NMR、LC-MS鉴定所涉及的中间体、副产物及目标产物结构。
[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.
【学位授予单位】：重庆医科大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：R914.5
本文编号：2292089
[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.
【学位授予单位】：重庆医科大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：R914.5
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本文编号：2292089
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