锰催化肉桂酸脱羧合成芳基不饱和砜的研究
发布时间：2019-02-21 08:35
【摘要】：乙烯砜类(α,β-不饱和砜)是重要的有机分子,它们是很多药物中的重要结构片段,如半胱氨酸蛋白酶(cysteine proteases)抑制剂,膜蛋白转肽酶(SrtA(sortase A))抑制剂等。而且,在有机化学中,它们广泛用作Michael受体。由于它们的合成用途和潜在的生物活性,近些年,芳基乙烯砜类化合物的合成研究吸引了大批有机化学家的关注。已报道的合成芳基乙烯砜类涉及到约十余种不同反应方法,结合已报道的相关方法,我们提出了本课题,以肉桂酸与苯亚磺酸钠为原料合成芳基乙烯砜类,进行了如下的实验探究：第一、简要介绍了偶联反应的发展历程和综述了一些已经报道的有关偶联反应合成芳基乙烯砜类的研究方法；第二、通过对催化剂的种类、溶剂、反应温度、反应环境等的筛选,进行了一系列的实验探究,得到了反应的最优条件：5 mol% Mn(OAc)2,1.0 equiv肉桂酸,3.0 equiv苯亚磺酸钠,2.0 mL DMSO,空气条件下,110℃下反应12h,在此反应条件下得到产物芳基不饱和砜,产率达到86%。第三、在获得了最优反应条件之后,我们探索了本脱羧反应的底物范围。发现以不同的肉桂酸参与反应时,产率范围从57%-80%。底物含吸电子基或供电子基如甲基、甲氧基、氟、氯、溴、硝基等时,得到了预期的产物和满意的产率。邻、间、对位取代的的硝基肉桂酸产率变化不大。苯亚磺酸钠进行底物扩展,反应产率范围53%-76%。而对于烷基磺酸钠甲基磺酸钠参加反应,实验结果发现没能得到预期的产物。根据反应过程中产生的一些现象,给出了一些合理的分析解释。最后,根据实验的结果和已报道的相关文献分析提出可能的反应机理并对其进行了简要的解释。
[Abstract]:Ethylene sulfone (伪, 尾 -unsaturated sulfone) is an important organic molecule, which is an important structural fragment in many drugs, such as cysteine protease (cysteine proteases) inhibitor, membrane protein transpeptidase (SrtA (sortase A) inhibitor and so on. Moreover, they are widely used as Michael receptors in organic chemistry. Due to their synthetic uses and potential biological activities, the synthesis of aryl ethylene sulfone has attracted the attention of a large number of organic chemists in recent years. The synthesis of aryl ethylene sulfone has been reported, which involves about ten different reaction methods. In combination with the reported methods, we have put forward the subject of synthesizing aryl ethylene sulfone from cinnamic acid and sodium benzenesulfonate as raw materials, and the synthesis of aryl ethylene sulfone from cinnamic acid and sodium benzenesulfonate has been studied. The following experiments were carried out: first, the development of coupling reactions and some reported research methods on the synthesis of aryl ethylene sulfone were briefly introduced. Secondly, through the screening of catalyst, solvent, reaction temperature, reaction environment and so on, a series of experiments were carried out. The optimum reaction conditions were obtained as follows: 5 mol% Mn (OAc) 21.0 equiv cinnamic acid, 3. 0 equiv sodium benzenesulfonic acid, 2. 0 mL DMSO, air, 12 h reaction at 110 鈩，
本文编号：2427390
[Abstract]:Ethylene sulfone (伪, 尾 -unsaturated sulfone) is an important organic molecule, which is an important structural fragment in many drugs, such as cysteine protease (cysteine proteases) inhibitor, membrane protein transpeptidase (SrtA (sortase A) inhibitor and so on. Moreover, they are widely used as Michael receptors in organic chemistry. Due to their synthetic uses and potential biological activities, the synthesis of aryl ethylene sulfone has attracted the attention of a large number of organic chemists in recent years. The synthesis of aryl ethylene sulfone has been reported, which involves about ten different reaction methods. In combination with the reported methods, we have put forward the subject of synthesizing aryl ethylene sulfone from cinnamic acid and sodium benzenesulfonate as raw materials, and the synthesis of aryl ethylene sulfone from cinnamic acid and sodium benzenesulfonate has been studied. The following experiments were carried out: first, the development of coupling reactions and some reported research methods on the synthesis of aryl ethylene sulfone were briefly introduced. Secondly, through the screening of catalyst, solvent, reaction temperature, reaction environment and so on, a series of experiments were carried out. The optimum reaction conditions were obtained as follows: 5 mol% Mn (OAc) 21.0 equiv cinnamic acid, 3. 0 equiv sodium benzenesulfonic acid, 2. 0 mL DMSO, air, 12 h reaction at 110 鈩，
本文编号：2427390
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