本文選題：三氟甲基化　切入點：雙官能團化　出處：《哈爾濱工業(yè)大學》2016年碩士論文

【摘要】：三氟甲基特殊的物理性質(zhì)和化學性質(zhì),使得其廣泛應用于醫(yī)藥、農(nóng)化學品和材料等領域。因此,向有機分子引入三氟甲基已成為當今有機合成的熱點研究領域。幾十年來,化學家實現(xiàn)了各種不同類型的引入方法,但有些方法存在反應條件苛刻,原料難得及選擇性差等缺點。近年來,隨著有機光化學研究的發(fā)展,三氟甲基化反應的研究取得了重大突破。烯烴的雙官能團化反應,即通過雙鍵向有機分子引入兩種官能團的反應,在有機合成中具有無限的潛能。實現(xiàn)烯烴的雙官能團化重要反應策略之一是通過烯烴的三氟甲基化,在構建C-CF3鍵時,引入C-X,C-C,C-H,C-O,C-N或C-S鍵。本文主要研究利用光化學反應,向烯烴引入三氟甲基實現(xiàn)烯烴的雙官能團化,并構建分子內(nèi)的C-C鍵。α,β-不飽和芳香酮作反應原料,通過對三氟甲基試劑、溶劑、光敏劑和光源等反應條件進行篩選優(yōu)化,確定最優(yōu)反應條件:在N2保護下,三氟甲基亞磺酸鈉(CF3SO2Na)提供三氟甲基源,二苯甲酮(BP)作光敏劑,干燥乙腈為溶劑,在500 W中壓汞燈紫外光照射下合成一系列三氟甲基化菲酚類衍生物。在最優(yōu)條件下,拓展了25種含有不同官能團的α,β-不飽和芳香酮,均取得良好收率,進而研究不同官能團對該反應的影響。通過加入自由基捕獲劑TEMPO的控制實驗,氣相-質(zhì)譜儀檢測到TEMPOCF3,推測該方法可能的反應機理:三氟甲基試劑在光敏劑和紫外光誘導下產(chǎn)生三氟甲基自由基(CF3.),和光照底物α,β-不飽和芳香酮的雙鍵發(fā)生自由基加成,形成以碳為中心的自由基,然后進攻另一苯環(huán)鄰位進行分子內(nèi)環(huán)合,形成苯基自由基,最后,伴隨羰基的烯醇化和氫質(zhì)子的離去,生成目標產(chǎn)物。
[Abstract]:Because of its special physical and chemical properties, trifluoromethyl is widely used in medicine, agricultural chemicals and materials.Therefore, the introduction of trifluoromethyl to organic molecules has become a hot research field of organic synthesis.In recent decades, chemists have realized a variety of different methods of introduction, but some methods have some shortcomings such as harsh reaction conditions, rare raw materials and poor selectivity.In recent years, with the development of organic photochemistry, the study of trifluoromethylation has made a great breakthrough.The bifunctional reaction of olefins, that is, the introduction of two functional groups to organic molecules by double bonds, has unlimited potential in organic synthesis.One of the important strategies for the bifunctional reaction of olefin is the trifluoromethylation of olefin. When the C-CF3 bond is constructed, C-XG C-C, C-H, C-O, C-N or C-S bonds are introduced.In this paper, using photochemical reaction to introduce trifluoromethyl to olefin to realize difunctional group of olefin and to construct intramolecular C-C bond. 偽, 尾 -unsaturated aromatic ketone is used as raw material.The reaction conditions such as Guang Min and light source were screened and optimized to determine the optimum reaction conditions: under the protection of N2, sodium trifluoromethylene sulfonate (CF3SO2Na) provided trifluoromethyl source, benzophenone BP) as Guang Min agent, and dry acetonitrile as solvent.A series of trifluoromethylphenolic derivatives were synthesized by UV irradiation of 500 W medium pressure mercury lamp.Under the optimum conditions, 25 kinds of 偽, 尾 -unsaturated aromatic ketones with different functional groups were developed and the yield was good. The effect of different functional groups on the reaction was studied.By adding free radical trapping agent TEMPO to control experiment,TEMPOCF3 was detected by gas phase mass spectrometer, and the possible reaction mechanism of this method was speculated: trifluoromethyl radical was induced by Guang Min and ultraviolet light, and free radical addition was produced by double bond of 偽, 尾 -unsaturated aromatic ketones.Carbon-centered free radicals were formed, and then attacked another benzene ring for intramolecular cyclization to form phenyl radical. Finally, with the enolation of carbonyl group and the departure of hydrogen proton, the target product was formed.
【學位授予單位】：哈爾濱工業(yè)大學
【學位級別】：碩士
【學位授予年份】：2016
【分類號】：O621.25

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