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  本文選題：全氟烷基磺酰氟 + 羧酸�。� 參考：《南昌大學(xué)》2017年碩士論文

【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)是一類性能優(yōu)異的羥基活化試劑。最近十年,針對全氟烷基磺酰氟在有機(jī)合成化學(xué)中的應(yīng)用,課題組進(jìn)行了不斷的研究。我們課題組的實(shí)驗(yàn)結(jié)果表明,R_fSO_2F不僅可以活化醇的羥基而廣泛應(yīng)用于構(gòu)建C-F,C-O,C-N和C-S鍵中,而且可以作為優(yōu)良的縮合試劑用于活化有機(jī)羧酸的羥基而發(fā)生酯化、酰胺化和酸酐化反應(yīng)。當(dāng)全氟烷基磺酰氟用于活化酮肟的羥基時,能順利引發(fā)貝克曼重排反應(yīng)而生成酰胺產(chǎn)物;用于活化醛肟的羥基時則生成相應(yīng)的消除產(chǎn)物腈。因此R_fSO_2F在有機(jī)合成上的應(yīng)用價值正在慢慢地體現(xiàn)出來。繼續(xù)深入探討R_fSO_2F在有機(jī)合成化學(xué)中的應(yīng)用就顯得十分必要。在課題組已有實(shí)驗(yàn)結(jié)果的基礎(chǔ)上,本論文開展了兩部分內(nèi)容的研究工作。在第一部分工作中,我們研究了全氟烷基磺酰氟用于誘導(dǎo)羧酸和1,3-二羰基化合物之間的�；蛳┐减セ磻�(yīng),結(jié)果以45-65%的產(chǎn)率生成了相應(yīng)的三羰基化合物產(chǎn)物或烯醇酯產(chǎn)物。我們考察了溶劑、反應(yīng)溫度、堿、試劑配比和反應(yīng)時間對反應(yīng)的影響,提出了一種可行的反應(yīng)機(jī)理。所考察的反應(yīng)條件溫和、副產(chǎn)物少、后處理簡便和產(chǎn)物易于純化。研究結(jié)果豐富了烯醇酯的合成方法。在第二部分工作中,我們研究了全氟烷基磺酰氟誘導(dǎo)醇和二苯基磷氧之間的Atherton-Todd型膦酸酯化反應(yīng),結(jié)果以52-78%的產(chǎn)率生成了相應(yīng)的二苯基膦酸酯產(chǎn)物。同樣我們考察了溶劑、反應(yīng)溫度、堿、試劑配比和反應(yīng)時間對反應(yīng)的影響。提出了一種可行的反應(yīng)機(jī)理用于解釋反應(yīng)現(xiàn)象。溫和、非金屬的反應(yīng)條件和無毒穩(wěn)定的全氟烷基磺酰氟試劑的使用,是該反應(yīng)的特色和亮點(diǎn)。為有機(jī)膦酸酯的制備提供了一種高效、實(shí)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.
【學(xué)位授予單位】：南昌大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O621.25

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