【作者】 张亮亮；

【导师】 唐果； 赵玉芬；

【作者基本信息】 厦门大学 ， 有机化学， 2017， 硕士

【摘要】 磷、硫元素是构成生命体的两种重要元素,它们和氧、碳、氮等其他元素组成人体糖类,蛋白质,脂肪,生长因子,辅酶,激素等物质,参与到生命活动中重要的代谢过程。同时,有机磷、硫化合物应用到生产、生活中的各个环节,在生物医药,功能材料,有机合成等领域都发挥着举足轻重的作用。本文主要发展了合成3-芳基磺酰化喹啉衍生物以及硫磷酸酯(包括S’-芳基和S-烷基)的新方法。主要内容如下:第一部分:发展了一种无需金属催化剂,仅在过氧化物TBHP作用下的磺酰基自由基与不饱和炔烃的加成、环化、氧化、芳香化串联反应,进而实现3-芳基磺酰化喹啉化合物的合成。该方法经济,且环境友好,底物适用性也比较好,为一系列在药物化学和催化领域中有重要研究价值的3-芳基磺酰化喹啉衍生物的合成提供了方法。第二部分:首先发展了一种在Cu(acac)2催化作用下,二芳基碘盐、硫粉与氢亚磷酸酯三组份“一锅法”偶联反应,合成S’-芳基硫磷酸酯的新方法。此外,发展了一种无需催化剂,卤代烃、硫粉以及氢亚磷酸酯三组份“一锅法”生成S-烷基硫磷酸酯的绿色经济方法。这部分的主要优势在于:(1)操作简单,在空气中即可制备;(2)原料廉价经济,很容易制备,用量少。同时,使用硫粉作为硫源,避免了传统的刺激性有机硫化合物的使用。更多还原

【Abstract】 Phosphorus and sulfur are two important elements in living organisms.They make up carbohydrate,protein,fat,growth factor,coenzyme and hormone which play a vital role in the metabolism of living organisms together with other elements such as oxygen,carbon,nitrogen.At the same time,organophosphorus and organosulfur compounds almost spreads over all fields of producing and living,and have broad applications in the fields of biomedicine,functional materials,organic synthesis and so on.In this paper,we mainly developed new methods to synthesize 3-arylsulfonylquinolines derivatives and phosphorothioates(including S-aryl and S-alkyl).The main contents are as follows:Part 1:we have developed an efficient protocol for the preparation of various 3-arylsulfonylquinolines via tert-butyl hydroperoxide(TBHP)-mediated sulfonylation-cyclization-aromatization of various N-propargyl aromatic amine derivatives with arylsulfonylhydrazides without the addition of any metals.The TBHP oxidant system can be regarded as a metal-free,cost-effective,and environmentally benign system.Given that a wide range of substrates can be utilized for the cascade annulation,this simple protocol may provide a general approach to 3-arylsulfonylquinolines derivatives of importance in medicinal chemistry and catalytic chemistry.Part 2:Firstly,we have developed a novel Cu(acac)2-catalyzed phosphorus-sulfur-carbon(aryl)bond-forming reactions to access S-aryl phosphorothioates which proceeds in good yield via phosphorothiolation of diaryliodonium salts with P(O)H compounds and sulfur powder.Secondly,we have developed a novel,simple and efficient phosphorus-sulfur-carbon(alkyl)bond-forming reaction to access S-alkyl phosphorothioates via phosphorothiolation of alkyl chloride with P(O)H compounds and sulfur powder.without the addition of any catalysts.The main advantages of this part are:(1)the reaction is simple and easy to operate under air(2)raw materials are cheap,easy prepared and less waste.At the same time,sulfur powder is used as a source of sulfur,avoiding the pungent odorus thiols.更多还原