有机锌试剂与磺酰氯在三苯基氧膦催化下的反应研究

发布时间：2018-11-18 14:58

【摘要】：砜类化合物的应用十分广泛,它不仅是医药和农药的活性成分,在复杂的化学合成反应中还是关键的中间体。此外,还可以用作特种材料和食品添加剂。砜类化合物因具有广谱生物活性引起人们对它的关注,若是在不同的化合物结构中引入砜基基团,通过结构修饰就能产生很多种具有广谱生物活性的化合物。砜类化合物的生物活性,让它在新型超高效农药创制中发挥出的作用越来越不可替代。本文从四个方面对砜类化合物的应用研究进行了分类综述,分别是医药、农药、材料、化工等方面,简述了不同砜类化合物的应用。比如芳基砜类化合物,这类化合物有多种生物活性,有些已经商品化,可以用来治疗人类疾病,如万络,氨苯砜和抗雄激素康士得。各种芳基砜类衍生品因为它们的生物活性以及在作为过渡金属有用的配体方面有很重要的作用,最近也备受关注。有机合成方面,在经典的Ramberg-Backlund反应和Jolia烯化反应中,砜也是万能的中间体。有很多生成砜类化合物的方法,经典的就是通过氧化硫化物或者由亲核试剂与亲电试剂的反应来制得。但是这些方法有很大的局限性,比如使用氧化途径的话就限制了对氧化剂敏感的官能团的存在,使用亲电/亲核试剂的话就要有反应前体的制备,还要考虑立体选择性。研究表明,直接用有机金属试剂与磺酰氯进行反应是生成砜类化合物的一种非常简便的方法。当使用有机锌试剂时,在反应性和官能团的兼容性这方面是一个非常理想的有机金属试剂。我们课题组曾经报道过有机锌试剂与磺酰氯生成砜的反应,因催化剂为金属催化剂,考虑对其改良。基于我们课题小组长时间探究有机锌在合成砜类化合物中的应用,我们希望有机锌试剂能与磺酰氯在合适的配体及非金属催化剂存在的条件下能进行加成反应。本文选用有机锌试剂与磺酰氯为研究对象,研究它们之间的反应,用于合成高官能团化的砜类化合物。本文主要研究了官能团化的有机锌试剂与磺酰氯在三苯基氧膦催化下发生亲核加成生成砜类化合物的反应。反应条件温和,室温下即可生成携带多种官能团的砜类化合物,产率也很高。本方法为硫化学的研究提供了一种新颖、简单和有潜在应用价值的合成官能团化的砜类化合物的方法。
[Abstract]:Sulfone compounds are widely used not only as active components of medicine and pesticides but also as key intermediates in complex chemical synthesis reactions. In addition, it can also be used as special materials and food additives. Sulfone compounds have attracted much attention because of their broad-spectrum biological activities. If sulfone groups are introduced into different compounds, many kinds of broad-spectrum bioactive compounds can be produced by structural modification. Sulfone compounds play a more and more irreplaceable role in the creation of new super-efficient pesticides because of their biological activity. In this paper, the application of sulfone compounds is reviewed in four aspects: medicine, pesticide, material and chemical industry. The applications of different sulfone compounds are briefly described. Aryl sulfone compounds, for example, have a variety of biological activities, some of which have been commercialized to treat human diseases such as Vioxx, dapsone and androgen. A variety of aryl sulfone derivatives have recently attracted attention because of their biological activity and their important role as ligands used as transition metals. In organic synthesis, sulfone is also a potent intermediate in classical Ramberg-Backlund reaction and Jolia alkenylation reaction. There are many ways to form sulfone compounds, typically by oxidation of sulfides or reaction of nucleophilic reagents with electrophilic reagents. However, these methods have great limitations, for example, the use of oxidation pathway limits the existence of oxidant sensitive functional groups, the use of electrophilic / nucleophilic reagents requires the preparation of reaction precursors, and stereoselectivity should be considered. It is shown that direct reaction of organometallic reagents with sulfonyl chloride is a very simple method for the formation of sulfone compounds. When organic zinc reagent is used, it is an ideal organometallic reagent in the aspect of reactivity and functional group compatibility. Our team has reported the reaction of organic zinc reagents with sulfonyl chloride to form sulfone, because the catalyst is a metal catalyst, consideration should be given to its improvement. Based on the application of organozinc in the synthesis of sulfone compounds, we hope that the addition reaction of organozinc reagents with sulfonyl chloride can be carried out in the presence of suitable ligands and non-metallic catalysts. In this paper, the reaction between organic zinc reagent and sulfonyl chloride was studied, which was used to synthesize sulfone compounds with high functional groups. In this paper, the nucleophilic addition of functional organic zinc reagents with sulfonyl chloride catalyzed by triphenyl phosphine oxide to form sulfone compounds was studied. Under mild reaction conditions, sulfone compounds with various functional groups can be formed at room temperature, and the yield is very high. This method provides a novel, simple and potentially useful method for the synthesis of functional sulfone compounds.
【学位授予单位】：兰州交通大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251

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