亞磺酸鹽在磺酰胺合成中的一些新的應用
發(fā)布時間：2019-06-29 12:21
【摘要】：磺酰胺類化合物廣泛存在于天然產物和藥物中,在醫(yī)藥,農藥,染料和有機合成中均具有重要的作用�；诨酋０奉惢衔锏闹匾�,化學工作者致力于研究其合成方法,而開發(fā)出新的方法制備磺酰胺類化合物具有一定的現實意義。然而,現有的合成方法具有一定的局限性,例如反應處理麻煩,起始原料有害,反應條件苛刻,反應時間長,且大多數反應使用過渡金屬,嚴重污染環(huán)境等。本文主要介紹了我們探索出的具有高效,經濟,操作簡單及環(huán)保的磺酰胺類化合物新方法。本論文主要可分為四個部分,主要內容如下:1.文獻綜述部分。主要介紹了磺酰胺類化合物的發(fā)現及其生物活性,和在醫(yī)藥、農藥方面的應用。總結了磺酰胺類化合物的合成方法,并分析了各種方法所存在的不足之處。2.碘催化亞磺酸鈉與苯并三氮唑的N-磺�；磻�。簡要介紹了單質碘作為催化劑在有機合成中應用。我們以苯并三氮唑化合物和亞磺酸鈉鹽為底物,碘為催化劑,空氣中的氧氣為氧化劑,在室溫下合成了N-磺�；讲⑷蝾惢衔�,并通過實驗驗證了該方法的可行性和適用性,同時還提出了催化循環(huán)機理。這種方法的新穎點在于單質碘與亞磺酸鈉鹽結合后經均裂反應形成相應的自由基,這也是反應的關鍵點。此外,無論從原料、反應的條件、還是反應的副產物來看,該方法都符合綠色化學的要求,且具有實際的應用價值。3.溴化物促進的苯并三氮唑的N-磺�；磻�。在上述成果的基礎上,我們又發(fā)現了一種新穎,有效的合成N-磺�；讲⑷蝾惢衔锏姆椒�:室溫下以EtOAc:MeOH=4:1為反應體系的溶劑,間氯過氧苯甲酸為氧化劑,苯亞磺酸鈉和苯并三唑在溴化鈉的作用下反應幾個小時既得到收益良好的產物。同時對反應條件進行優(yōu)化,對底物進行拓展,得到一系列相應的產物,并對反應機理進行了解釋。4.亞磺酸鈉經磺酰溴與胺一步合成磺酰胺的反應。通過一系列的反應,我們發(fā)現了一種以間氯過氧苯甲酸為氧化劑,亞磺酸鈉與胺在四丁基溴化銨促進下的親核取代反應,用該方法合成了相應的磺酰胺。通過實驗驗證了該方法的可行性和較廣的適用性,并對反應機理進行了解釋。
[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.
【學位授予單位】：浙江工業(yè)大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O623.8
本文編號：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.
【學位授予單位】：浙江工業(yè)大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O623.8
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