發(fā)布時(shí)間：2018-11-18 14:58

【摘要】：砜類化合物的應(yīng)用十分廣泛,它不僅是醫(yī)藥和農(nóng)藥的活性成分,在復(fù)雜的化學(xué)合成反應(yīng)中還是關(guān)鍵的中間體。此外,還可以用作特種材料和食品添加劑。砜類化合物因具有廣譜生物活性引起人們對(duì)它的關(guān)注,若是在不同的化合物結(jié)構(gòu)中引入砜基基團(tuán),通過結(jié)構(gòu)修飾就能產(chǎn)生很多種具有廣譜生物活性的化合物。砜類化合物的生物活性,讓它在新型超高效農(nóng)藥創(chuàng)制中發(fā)揮出的作用越來越不可替代。本文從四個(gè)方面對(duì)砜類化合物的應(yīng)用研究進(jìn)行了分類綜述,分別是醫(yī)藥、農(nóng)藥、材料、化工等方面,簡(jiǎn)述了不同砜類化合物的應(yīng)用。比如芳基砜類化合物,這類化合物有多種生物活性,有些已經(jīng)商品化,可以用來治療人類疾病,如萬(wàn)絡(luò),氨苯砜和抗雄激素康士得。各種芳基砜類衍生品因?yàn)樗鼈兊纳锘钚砸约霸谧鳛檫^渡金屬有用的配體方面有很重要的作用,最近也備受關(guān)注。有機(jī)合成方面,在經(jīng)典的Ramberg-Backlund反應(yīng)和Jolia烯化反應(yīng)中,砜也是萬(wàn)能的中間體。有很多生成砜類化合物的方法,經(jīng)典的就是通過氧化硫化物或者由親核試劑與親電試劑的反應(yīng)來制得。但是這些方法有很大的局限性,比如使用氧化途徑的話就限制了對(duì)氧化劑敏感的官能團(tuán)的存在,使用親電/親核試劑的話就要有反應(yīng)前體的制備,還要考慮立體選擇性。研究表明,直接用有機(jī)金屬試劑與磺酰氯進(jìn)行反應(yīng)是生成砜類化合物的一種非常簡(jiǎn)便的方法。當(dāng)使用有機(jī)鋅試劑時(shí),在反應(yīng)性和官能團(tuán)的兼容性這方面是一個(gè)非常理想的有機(jī)金屬試劑。我們課題組曾經(jīng)報(bào)道過有機(jī)鋅試劑與磺酰氯生成砜的反應(yīng),因催化劑為金屬催化劑,考慮對(duì)其改良�；谖覀冋n題小組長(zhǎng)時(shí)間探究有機(jī)鋅在合成砜類化合物中的應(yīng)用,我們希望有機(jī)鋅試劑能與磺酰氯在合適的配體及非金屬催化劑存在的條件下能進(jìn)行加成反應(yīng)。本文選用有機(jī)鋅試劑與磺酰氯為研究對(duì)象,研究它們之間的反應(yīng),用于合成高官能團(tuán)化的砜類化合物。本文主要研究了官能團(tuán)化的有機(jī)鋅試劑與磺酰氯在三苯基氧膦催化下發(fā)生親核加成生成砜類化合物的反應(yīng)。反應(yīng)條件溫和,室溫下即可生成攜帶多種官能團(tuán)的砜類化合物,產(chǎn)率也很高。本方法為硫化學(xué)的研究提供了一種新穎、簡(jiǎn)單和有潛在應(yīng)用價(jià)值的合成官能團(tuán)化的砜類化合物的方法。
[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.
【學(xué)位授予單位】：蘭州交通大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O621.251

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