全氟烷基磺酰氟诱导羧酸与1,3-二羰基化合物的酰基化或烯醇酯化反应以及诱导醇与二苯基膦氧的膦酸酯化反应

发布时间：2018-07-12 17:33

本文选题：全氟烷基磺酰氟 + 羧酸　；参考：《南昌大学》2017年硕士论文

【摘要】：全氟烷基磺酰氟(以R_fSO_2F表示,下同,如n-C_4F_9SO_2F和n-C_8F_(17)SO_2F)是一类性能优异的羟基活化试剂。最近十年,针对全氟烷基磺酰氟在有机合成化学中的应用,课题组进行了不断的研究。我们课题组的实验结果表明,R_fSO_2F不仅可以活化醇的羟基而广泛应用于构建C-F,C-O,C-N和C-S键中,而且可以作为优良的缩合试剂用于活化有机羧酸的羟基而发生酯化、酰胺化和酸酐化反应。当全氟烷基磺酰氟用于活化酮肟的羟基时,能顺利引发贝克曼重排反应而生成酰胺产物;用于活化醛肟的羟基时则生成相应的消除产物腈。因此R_fSO_2F在有机合成上的应用价值正在慢慢地体现出来。继续深入探讨R_fSO_2F在有机合成化学中的应用就显得十分必要。在课题组已有实验结果的基础上,本论文开展了两部分内容的研究工作。在第一部分工作中,我们研究了全氟烷基磺酰氟用于诱导羧酸和1,3-二羰基化合物之间的酰基化或烯醇酯化反应,结果以45-65%的产率生成了相应的三羰基化合物产物或烯醇酯产物。我们考察了溶剂、反应温度、碱、试剂配比和反应时间对反应的影响,提出了一种可行的反应机理。所考察的反应条件温和、副产物少、后处理简便和产物易于纯化。研究结果丰富了烯醇酯的合成方法。在第二部分工作中,我们研究了全氟烷基磺酰氟诱导醇和二苯基磷氧之间的Atherton-Todd型膦酸酯化反应,结果以52-78%的产率生成了相应的二苯基膦酸酯产物。同样我们考察了溶剂、反应温度、碱、试剂配比和反应时间对反应的影响。提出了一种可行的反应机理用于解释反应现象。温和、非金属的反应条件和无毒稳定的全氟烷基磺酰氟试剂的使用,是该反应的特色和亮点。为有机膦酸酯的制备提供了一种高效、实用的方法。
[Abstract]:Perfluoroalkyl sulfonyl fluoride (expressed in Rstufso _ 2F, the same as n-C _ 4F _ 9S _ 2F and n-C _ 8F _ (17) so _ 2F) is a kind of hydroxyl activating reagents with excellent properties, for example, n-C _ 4F _ 9S _ 2F and n-C _ 8F _ (17) so _ (2F). In the last ten years, the application of perfluoroalkyl sulfonyl fluoride in organic synthesis chemistry has been studied. The experimental results of our research group show that rsfSO2F can not only activate the hydroxyl groups of alcohols, but also be widely used in the construction of C-FFC-ON-C-N and C-S bonds. It can also be used as an excellent condensation reagent for the esterification, amidation and anhydride reaction of organic carboxylic acids. When perfluoroalkyl sulfonyl fluoride is used to activate the hydroxyl group of ketone oxime, it can initiate Beckmann rearrangement reaction to produce amide product, and the corresponding elimination product nitrile is formed when the hydroxyl group of aldoxime is activated. As a result, the application value of RSP 2 F in organic synthesis is slowly coming out. It is necessary to further discuss the application of RfSO2F in organic synthesis chemistry. On the basis of the experimental results, two parts of research work have been carried out in this paper. In the first part, we studied the effects of perfluoroalkyl sulfonyl fluoride on the acylation or esterification of carboxylic acids with 1 ~ (3) -dicarbonyl compounds. As a result, the corresponding products of tricarbonyl compounds or enol esters were obtained in 45-65% yields. The effects of solvent, reaction temperature, alkali, reagent ratio and reaction time on the reaction were investigated, and a feasible reaction mechanism was proposed. The reaction conditions are mild, the byproducts are few, the post-treatment is simple and the product is easy to be purified. The results enrich the synthesis of enolates. In the second part, we studied the esterification of Atherton-Todd phosphonic acid between perfluoroalkyl sulfonyl fluoride and diphenyl phosphoric acid. The corresponding diphenylphosphonate was obtained in 52-78% yield. The effects of solvent, reaction temperature, alkali, reagent ratio and reaction time on the reaction were also investigated. A feasible reaction mechanism is proposed to explain the reaction phenomenon. Mild, non-metallic reaction conditions and the use of non-toxic and stable perfluoroalkyl sulfonyl fluoride reagents are the characteristics and highlights of the reaction. It provides an efficient and practical method for the preparation of organic phosphonate.
【学位授予单位】：南昌大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25

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