亚磺酸盐在磺酰胺合成中的一些新的应用
发布时间：2019-06-29 12:21
【摘要】：磺酰胺类化合物广泛存在于天然产物和药物中,在医药,农药,染料和有机合成中均具有重要的作用。基于磺酰胺类化合物的重要性,化学工作者致力于研究其合成方法,而开发出新的方法制备磺酰胺类化合物具有一定的现实意义。然而,现有的合成方法具有一定的局限性,例如反应处理麻烦,起始原料有害,反应条件苛刻,反应时间长,且大多数反应使用过渡金属,严重污染环境等。本文主要介绍了我们探索出的具有高效,经济,操作简单及环保的磺酰胺类化合物新方法。本论文主要可分为四个部分,主要内容如下:1.文献综述部分。主要介绍了磺酰胺类化合物的发现及其生物活性,和在医药、农药方面的应用。总结了磺酰胺类化合物的合成方法,并分析了各种方法所存在的不足之处。2.碘催化亚磺酸钠与苯并三氮唑的N-磺酰化反应。简要介绍了单质碘作为催化剂在有机合成中应用。我们以苯并三氮唑化合物和亚磺酸钠盐为底物,碘为催化剂,空气中的氧气为氧化剂,在室温下合成了N-磺酰基苯并三氮唑类化合物,并通过实验验证了该方法的可行性和适用性,同时还提出了催化循环机理。这种方法的新颖点在于单质碘与亚磺酸钠盐结合后经均裂反应形成相应的自由基,这也是反应的关键点。此外,无论从原料、反应的条件、还是反应的副产物来看,该方法都符合绿色化学的要求,且具有实际的应用价值。3.溴化物促进的苯并三氮唑的N-磺酰化反应。在上述成果的基础上,我们又发现了一种新颖,有效的合成N-磺酰基苯并三氮唑类化合物的方法:室温下以EtOAc:MeOH=4:1为反应体系的溶剂,间氯过氧苯甲酸为氧化剂,苯亚磺酸钠和苯并三唑在溴化钠的作用下反应几个小时既得到收益良好的产物。同时对反应条件进行优化,对底物进行拓展,得到一系列相应的产物,并对反应机理进行了解释。4.亚磺酸钠经磺酰溴与胺一步合成磺酰胺的反应。通过一系列的反应,我们发现了一种以间氯过氧苯甲酸为氧化剂,亚磺酸钠与胺在四丁基溴化铵促进下的亲核取代反应,用该方法合成了相应的磺酰胺。通过实验验证了该方法的可行性和较广的适用性,并对反应机理进行了解释。
[Abstract]:Sulfonamides widely exist in natural products and drugs and play an important role in medicine, pesticides, dyes and organic synthesis. Based on the importance of sulfonamides, chemists devote themselves to the synthesis of sulfonamides, and it is of practical significance to develop a new method to prepare sulfonamides. However, the existing synthesis methods have some limitations, such as troublesome reaction treatment, harmful initial raw materials, harsh reaction conditions, long reaction time, and most of the reactions use transition metals, seriously polluting the environment and so on. This paper mainly introduces a new method of sulfonamide compounds with high efficiency, economy, simple operation and environmental protection. This paper can be divided into four parts, the main contents are as follows: 1. The part of literature review. This paper mainly introduces the discovery and biological activity of sulfonamides, and their applications in medicine and pesticides. The synthesis methods of sulfonamides were summarized, and the shortcomings of various methods were analyzed. Iodine catalyzed N-sulfonylation of sodium sulfite with benzotriazole. The application of iodine as catalyst in organic synthesis is briefly introduced. Using benzotriazole compounds and sodium sulfite as substrate, iodine as catalyst and oxygen in air as oxidant, N-sulfonylbenzotriazole compounds were synthesized at room temperature. The feasibility and applicability of the method were verified by experiments, and the catalytic cycle mechanism was also put forward. The novelty of this method is that after the combination of simple iodine and sodium sulfite, the corresponding free radicals are formed by homogeneous reaction, which is also the key point of the reaction. In addition, whether from the raw materials, the reaction conditions, or the by-products of the reaction, the method meets the requirements of green chemistry, and has practical application value. 3. N-sulfonylation of benzotriazole promoted by bromine. On the basis of the above results, we have found a novel and effective method for the synthesis of N-sulfonylbenzotriazole compounds: at room temperature, EtOAc:MeOH=4:1 as the solvent of the reaction system, m-chloroperoxybenzoic acid as oxidant, sodium benzenesulfonate and benzotriazole in the action of sodium bromide for several hours. At the same time, the reaction conditions were optimized, the substrate was expanded, a series of corresponding products were obtained, and the reaction mechanism was explained. 4. One-step synthesis of sulfonamide from sodium sulfite by sulfonyl bromide and amine. Through a series of reactions, we found a nucleophilic substitution reaction of sodium sulfite with amine promoted by tetrabutylammonium bromide with m-chloroperoxybenzoic acid as oxidant, and the corresponding sulfonamide was synthesized by this method. The feasibility and wide applicability of the method are verified by experiments, and the reaction mechanism is explained.
【学位授予单位】：浙江工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O623.8
本文编号：2507813
[Abstract]:Sulfonamides widely exist in natural products and drugs and play an important role in medicine, pesticides, dyes and organic synthesis. Based on the importance of sulfonamides, chemists devote themselves to the synthesis of sulfonamides, and it is of practical significance to develop a new method to prepare sulfonamides. However, the existing synthesis methods have some limitations, such as troublesome reaction treatment, harmful initial raw materials, harsh reaction conditions, long reaction time, and most of the reactions use transition metals, seriously polluting the environment and so on. This paper mainly introduces a new method of sulfonamide compounds with high efficiency, economy, simple operation and environmental protection. This paper can be divided into four parts, the main contents are as follows: 1. The part of literature review. This paper mainly introduces the discovery and biological activity of sulfonamides, and their applications in medicine and pesticides. The synthesis methods of sulfonamides were summarized, and the shortcomings of various methods were analyzed. Iodine catalyzed N-sulfonylation of sodium sulfite with benzotriazole. The application of iodine as catalyst in organic synthesis is briefly introduced. Using benzotriazole compounds and sodium sulfite as substrate, iodine as catalyst and oxygen in air as oxidant, N-sulfonylbenzotriazole compounds were synthesized at room temperature. The feasibility and applicability of the method were verified by experiments, and the catalytic cycle mechanism was also put forward. The novelty of this method is that after the combination of simple iodine and sodium sulfite, the corresponding free radicals are formed by homogeneous reaction, which is also the key point of the reaction. In addition, whether from the raw materials, the reaction conditions, or the by-products of the reaction, the method meets the requirements of green chemistry, and has practical application value. 3. N-sulfonylation of benzotriazole promoted by bromine. On the basis of the above results, we have found a novel and effective method for the synthesis of N-sulfonylbenzotriazole compounds: at room temperature, EtOAc:MeOH=4:1 as the solvent of the reaction system, m-chloroperoxybenzoic acid as oxidant, sodium benzenesulfonate and benzotriazole in the action of sodium bromide for several hours. At the same time, the reaction conditions were optimized, the substrate was expanded, a series of corresponding products were obtained, and the reaction mechanism was explained. 4. One-step synthesis of sulfonamide from sodium sulfite by sulfonyl bromide and amine. Through a series of reactions, we found a nucleophilic substitution reaction of sodium sulfite with amine promoted by tetrabutylammonium bromide with m-chloroperoxybenzoic acid as oxidant, and the corresponding sulfonamide was synthesized by this method. The feasibility and wide applicability of the method are verified by experiments, and the reaction mechanism is explained.
【学位授予单位】：浙江工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O623.8
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