基于苯炔的二氢喹啉及氧杂蒽化合物的合成研究

发布时间：2018-04-14 20:26

本文选题：苯炔 + 喹啉　；参考：《石河子大学》2016年硕士论文

【摘要】：喹啉、异喹啉、亚磷酸酯、氧杂蒽以及它们的衍生物具有重要的生物和药物活性,在天然产物和药物合成中有着广泛的应用,因此,科学家们对这些组分的串联和苯并杂环的合成产生了很大的兴趣。苯炔作为一种具有很高反应活性的有机中间体,因其特殊的结构和高反应活性,在有机合成化学和天然产物的合成领域中有着广泛的应用。本论文着重研究了基于苯炔参与的串联反应和环化反应,主要内容包括以下三个部分:1.“一锅法”制备基于苯炔去芳构磷化的杂环化合物。把2-(三甲基硅烷基)苯基三氟甲烷磺酸酯作为苯炔前体,在氟源离子的作用下原位生成苯炔,然后与喹啉、异喹啉和亚磷酸酯通过插入串联反应制备去芳构磷化的产物。通过对反应条件的优化,以50%-90%的产率得到21种不同取代的去芳构磷化化合物。通过进一步对实验结果的分析,提出了氟离子参与制备的苯炔与喹啉和亚磷酸酯经过串联生成多取代的去芳构磷化化合物的反应机理。2.“一锅法”制备基于苯炔去芳构氯化的杂环化合物。以2-(三甲基硅烷基)苯基三氟甲烷磺酸酯作为苯炔前体,在氟源离子作用下原位生成苯炔,然后与喹啉、异喹啉和二氯甲烷、三氯甲烷通过插入串联反应制备不同取代的去芳构氯化的产物。通过对反应条件的优化,以45%-86%的产率得到17种不同取代的去芳构氯化化合物。3.苯并吡喃化合物的合成。以2-(三甲基硅烷基)苯基三氟甲烷磺酸酯作为苯炔前体,在氟源离子作用下原位生成苯炔,经过与邻甲基苯醌衍生物的4+2环化反应,目前以54%-89%的产率制备了8种苯并吡喃化合物。综上,通过对苯炔的插入-环化串联反应进行研究,发展了合成去芳构磷化、去芳构氯化的三组分串联产物以及苯并吡喃化合物的高效方法,拓宽了苯炔的应用范围,发展新的杂环合成方法学。
[Abstract]:Quinoline, isoquinoline, phosphite, oxyanthracene and their derivatives have important biological and pharmaceutical activities, and are widely used in the synthesis of natural products and drugs.Scientists are interested in the series of these components and the synthesis of benzo heterocycles.As a kind of organic intermediates with high reactive activity, phenylacetylene has been widely used in the field of organic synthesis chemistry and natural products synthesis because of its special structure and high reactive activity.This thesis focuses on the series reaction and cyclization reaction based on the participation of phenyne. The main contents include the following three parts: 1: 1.Heterocyclic compounds based on phenylacetylene dearylphosphating were prepared by one pot method.2-( trimethylsilyl) phenyltrifluoromethane sulfonic acid ester was used as the precursor of phenylacetylene, and in situ was synthesized by fluorine source ion, and then was connected with quinoline, isoquinoline and phosphite in series to prepare the product of dearylphosphating.By optimizing the reaction conditions, 21 different substituted dearomatization compounds were obtained in the yield of 50%-90%.Based on the analysis of the experimental results, the reaction mechanism of phenylacetylene, quinoline and phosphite prepared by fluorine ion in series to form multi-substituted dearylphosphating compounds was put forward.One-pot method is used to prepare heterocyclic compounds based on the dearomatization of phenyne.Using 2-( trimethylsilyl) phenyl trifluoromethane sulfonic ester as the precursor of phenylacetylene, benzene acetylene was produced in situ under the action of fluorine source ions, and then with quinoline, isoquinoline and dichloromethane.Different substituted dearomeric chlorination products were prepared by intercalation series reaction of trichloromethane.By optimizing the reaction conditions, 17 different substituted dearomeric chlorinated compounds. 3 were obtained in the yield of 45-86%.Synthesis of benzopyran compounds.Using 2-( trimethylsilyl) phenyl trifluoromethane sulfonic ester as the precursor of phenylacetylene, benzene acetylene was synthesized in situ under the action of fluorine source ion, and reacted with 4 2 cyclization of o-methyl benzoquinone derivative.Eight benzopyran compounds were prepared in 54-89% yield.In summary, by studying the intercalation-cyclization series reaction of benzenes, the efficient methods of synthesizing dearylphosphating, three component series products of dearomatization and benzopyran compounds have been developed, and the range of applications of benzenes has been widened.To develop a new method of heterocyclic synthesis.
【学位授予单位】：石河子大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O626

【相似文献】