基于亚磺酸盐的全氟烷基硫化反应

发布时间：2018-06-13 05:53

  本文选题：合成 + 亚磺酸盐　； 参考：《南京理工大学》2017年硕士论文

【摘要】：有机含氟化合物由于其特殊的理化性质在生物医药、农药、染料、材料等行业有着十分广泛的应用,其中三氟甲硫基(SCF3)具有强吸电子性、亲油性(πR=1.44)和稳定的C-F键等特性,能够显著改变含三氟甲硫基化合物的酸性、偶极矩、极性、两亲性及其代谢速率和化学稳定性。硫全氟烷基(SRF)除了具有三氟甲硫基的特性以外还能有助于稳定母体化合物,因而含SCF3或 SRF化合物在学术领域以及药物研发领域受到广泛关注。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机氟化学研究的热点与难点。论文研究了三氯化铁(FeCl_3)活化下,以亚磷酸二乙酯为还原剂,用三氟甲基亚磺酸钠或全氟烷基亚磺酸钠在芳环以及吲哚类化合物上进行亲电三氟甲硫基化和全氟烷基硫化。最佳反应条件为:1.5倍当量的三氟甲基亚磺酸钠(CF_3SO_2Na)或全氟烷基亚磺酸钠(RFS0_2Na),1.5倍当量的三氯化铁,2.0倍当量的亚磷酸二乙酯,反应温度95℃C,反应时间为24 h,反应溶剂为1,2-二氯乙烷,产物收率最高可达95%。该体系下芳环上含有多个供电基在产率上远大于含吸电基或单卤素取代,吲哚上有供电基取代时有利于反应。论文通过改良实验操作成功实现了全氟烷基亚磺酸钠(C2F5SO2NaC4F9SO2Na,C6F13S02Na,C8F17S02Na)的合成,并且实现了在芳环和吲哚类化合物上的全氟烷基硫化。合成的化合物均进行了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，

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