發(fā)布時(shí)間：2018-06-13 05:53

  本文選題：合成 + 亞磺酸鹽　； 參考：《南京理工大學(xué)》2017年碩士論文

【摘要】：有機(jī)含氟化合物由于其特殊的理化性質(zhì)在生物醫(yī)藥、農(nóng)藥、染料、材料等行業(yè)有著十分廣泛的應(yīng)用,其中三氟甲硫基(SCF3)具有強(qiáng)吸電子性、親油性(πR=1.44)和穩(wěn)定的C-F鍵等特性,能夠顯著改變含三氟甲硫基化合物的酸性、偶極矩、極性、兩親性及其代謝速率和化學(xué)穩(wěn)定性。硫全氟烷基(SRF)除了具有三氟甲硫基的特性以外還能有助于穩(wěn)定母體化合物,因而含SCF3或 SRF化合物在學(xué)術(shù)領(lǐng)域以及藥物研發(fā)領(lǐng)域受到廣泛關(guān)注。因此探索三氟甲硫基以及硫全氟烷基化合物的合成一直是有機(jī)氟化學(xué)研究的熱點(diǎn)與難點(diǎn)。論文研究了三氯化鐵(FeCl_3)活化下,以亞磷酸二乙酯為還原劑,用三氟甲基亞磺酸鈉或全氟烷基亞磺酸鈉在芳環(huán)以及吲哚類(lèi)化合物上進(jìn)行親電三氟甲硫基化和全氟烷基硫化。最佳反應(yīng)條件為:1.5倍當(dāng)量的三氟甲基亞磺酸鈉(CF_3SO_2Na)或全氟烷基亞磺酸鈉(RFS0_2Na),1.5倍當(dāng)量的三氯化鐵,2.0倍當(dāng)量的亞磷酸二乙酯,反應(yīng)溫度95℃C,反應(yīng)時(shí)間為24 h,反應(yīng)溶劑為1,2-二氯乙烷,產(chǎn)物收率最高可達(dá)95%。該體系下芳環(huán)上含有多個(gè)供電基在產(chǎn)率上遠(yuǎn)大于含吸電基或單鹵素取代,吲哚上有供電基取代時(shí)有利于反應(yīng)。論文通過(guò)改良實(shí)驗(yàn)操作成功實(shí)現(xiàn)了全氟烷基亞磺酸鈉(C2F5SO2NaC4F9SO2Na,C6F13S02Na,C8F17S02Na)的合成,并且實(shí)現(xiàn)了在芳環(huán)和吲哚類(lèi)化合物上的全氟烷基硫化。合成的化合物均進(jìn)行了1H NMR,13C NMR,19F NMR和HRMS表征。
[Abstract]:Organic fluorinated compounds have been widely used in biomedicine, pesticides, dyes and materials because of their special physical and chemical properties. Among them, trifluoromethylthio (SCF3) has strong electron absorption, lipophilicity (蟺 R ~ (1.44) and stable C-F bond. The acidity, dipole moment, polarity, amphiphilicity, metabolic rate and chemical stability of trifluoromethylthio compounds were significantly changed. Sulfur perfluoroalkyl group (SRF) can help to stabilize the parent compounds in addition to the properties of trifluoromethylthio, so SCF3 or SRF compounds have attracted wide attention in academic fields and drug research and development fields. Therefore, to explore the synthesis of trifluoromethylthio and sulfur perfluoroalkyl compounds has been a hot and difficult point in organofluorochemistry. In this paper, the electrophilic trifluoromethylation and perfluoroalkyl sulfidation of aromatic and indole-like compounds with trifluoromethylene sulfonate or perfluoroalkylene sulfonate under the activation of FeClS _ 3) and diethyl phosphite were studied. The optimum reaction conditions were as follows: 1: 1.5 times equivalent sodium trifluoromethylene sulfonate (CFS _ 3SO _ 2Na) or perfluoroalkylsulfonic acid sodium perfluoroalkyl sulfonic acid sodium sulfonate (RFS02NaO) 1.5 times equivalent triferric chloride 2.0 times equivalent diethyl phosphite, reaction temperature 95 鈩，

本文編號(hào)：2012965