【摘要】：由于含氟化合物獨(dú)特的物理化學(xué)性質(zhì)以及生理活性,使得含氟化合物在藥物化學(xué),材料和生命科學(xué)等領(lǐng)域得到了廣泛的應(yīng)用。尤其是含有二氟亞甲基的化合物表現(xiàn)出特殊的生物活性。在這些化合物中,由于含二氟亞甲基苯甲酰類化合物具有合成應(yīng)用價(jià)值和潛在的生物活性,此類化合物的研究引起了人們廣泛的興趣。在過去的幾年,盡管大量高效的二氟烷基化方法被報(bào)道,但是對(duì)于構(gòu)建含二氟苯甲酰類化合物的研究較少。本論文首先合成了一類官能團(tuán)化的含氟砌塊:α,α,α-碘二氟丙酮類化合物,并以其為含氟試劑與炔烴進(jìn)行自由基反應(yīng),我們還研究了其與炔烴,苯硼酸的三組分反應(yīng),為合成含二氟亞甲基苯甲酰類化合物提供了一種的新方法。本論文的第2章中,我們合成了一類α,α,α-碘二氟丙酮類化合物,并研究了其與不同種類的炔烴的加成反應(yīng),篩選出了最優(yōu)的反應(yīng)條件,即使用20 mol% AIBN為自由基引發(fā)劑,無溶劑,在氮?dú)獗Ｗo(hù)下80℃反應(yīng)12小時(shí),以高達(dá)88%產(chǎn)率和高的立體選擇性得到了官能團(tuán)化二氟取代的烯基碘化物,在Pd催化劑下,該加成產(chǎn)物能進(jìn)一步發(fā)生偶聯(lián)反應(yīng)得到官能團(tuán)化的多取代含二氟亞甲基苯甲酰類化合物。最后,我們對(duì)加成反應(yīng)的機(jī)理進(jìn)行了初步的討論。本章共合成9個(gè)含氟砌塊,19個(gè)加成產(chǎn)物和2個(gè)偶聯(lián)產(chǎn)物。本論文的第3章中,我們研究了 α,α,α-碘二氟丙酮類化合物與苯硼酸,炔烴的三組分反應(yīng),我們對(duì)反應(yīng)的催化劑,堿,溶劑和溫度等進(jìn)行了篩選,最終確定了最優(yōu)反應(yīng)條件,即使用5 mol%Pd(PPh3)4為催化劑,K3P04(2equiv)為堿,甲苯為溶劑,在氮?dú)獗Ｗo(hù)下60℃反應(yīng)12小時(shí),以良好的產(chǎn)率得到了目標(biāo)產(chǎn)物。本章共合成10個(gè)官能團(tuán)化二氟亞甲基苯甲酰類化合物。
[Abstract]:Because of the unique physical and chemical properties and physiological activities of fluorinated compounds, fluorinated compounds have been widely used in the fields of pharmaceutical chemistry, materials and life sciences. In particular, compounds containing difluoromethylenes exhibit special biological activity. Among these compounds, the research of difluoromethylbenzoyl compounds has attracted extensive interest because of their potential biological activity and synthesis value. In the past few years, although a large number of highly efficient difluoroalkylation methods have been reported, there have been few studies on the construction of difluorobenzoyl compounds. In this paper, a class of functional fluorinated blocks, 偽 -iodifluoroacetone compounds, were synthesized and reacted with alkynes by free radical reaction with alkynes and phenyboric acids. A new method for the synthesis of difluoromethylene benzoyl compounds is provided. In chapter 2 of this thesis, we synthesized a class of 偽, 偽 -iodifluoroacetone compounds, studied their addition reaction with different kinds of alkynes, and screened out the optimal reaction conditions, that is, using 20 mol% AIBN as free radical initiator, solvent free. At 80 鈩，

本文編號(hào)：2256905