吡啶类离子液体在汽油萃取脱硫中的应用研究

利用合成的六种吡啶类离子液体，N-丁基吡啶硝酸盐离子液体([BPy]NO3)，N-乙基吡啶硝酸盐离子液体([EPy]NO3)，N-丁基吡啶四氟硼酸盐离子液体([BPy]BF4)，N-乙基吡啶四氟硼酸盐离子液体([EPy]BF4)、N-乙基吡啶乙酸盐([EPy]Ac)、N-丁基吡啶乙酸盐([BPy]Ac)，进行了汽油萃取脱硫的应用研究。结果表明，[BPy]BF4的脱硫效果最好，[EPy]BF4的脱硫效果最差。[BPy]BF4对模型化合物单程脱硫率达到45.5％，可以有效地脱除汽油中的含硫化合物，使用过的离子液体可以通过真空加热或用四氯化碳反萃取再生。     

离子液体中钙拮抗剂尼群地平的合成

尼群地平属第二代1, 4-二氢吡啶类钙拮抗剂,2-(3-硝基亚苄基)乙酰乙酸乙酯和3-氨基-2-丁烯酸甲酯在离子液体1-丁基吡啶四氟硼酸盐中反应合成尼群地平,收率高达96％,离子液体回收套用至少5次,收率没有明显降低。     

微波法合成新的离子液体支载的二醋酸碘苯试剂

利用微波法高产率地合成了一种新的离子液体支载的二醋酸碘苯试剂——1-(4-二乙酰氧基碘苯甲基)吡啶四氟硼酸盐,其结构经1HNMR,13CNMR,FT-IR,MS和元素分析表征。     

含醛基功能化离子液体为载体液相合成氨基醚类化合物

以1-甲基咪唑、对二氯苄、对羟基苯甲醛和四氟硼酸钠为原料, 制备了一种含醛基的新型功能化离子液体1-(4-对甲酰基苯氧基亚甲基苄基)-3-甲基咪唑四氟硼酸盐(简写为[fmmim][BF4]). 为拓展功能化离子液体为载体的液相合成反应体系, 以该含醛基功能化离子液体为可溶性液相载体, 进行了Williamson醚化的合成反应, 较高产率和纯度得到了一系列氨基醚类化合物, 切割后得到的目标化合物不需要进行进一步的柱色谱纯化处理, 产率为81%～85%, 纯度为96%～99%. 回收得到的功能化离子液体可以重复套用多次而不影响其功效, 目标化合物的产率在81%～84%之间波动. 结果表明该方法可高效率地用于基于Williamson醚化反应的液相组合化学合成.     

2-取代-4(3H)-喹唑啉酮在BrФnsted酸性功能化离子液体中的微波合成

以N-甲基咪唑、吡啶为起始原料,合成了二种新型BrФnsted酸性功能化离子液体:1-(4-磺酸基)苄基-3-甲基咪唑硫酸氢根盐(3a),N-(4-磺酸基)苄基吡啶硫酸氢根盐(3b),以其作为反应介质与催化剂,研究了2-取代-4(3H)-喹唑啉酮的三组分、一锅法微波合成.结果表明,当n(2-氨基苯甲酸):n(酰氯):n(乙酸铵):n(3a或3b)=1:1.2:1.5:0.1时,反应6min即可完成,产率81%～95%.离子液体经减压蒸馏、真空干燥可重复使用3次,催化活性基本保持不变.     

2-取代-4(3H)-喹唑啉酮在Br(o)nsted酸性功能化离子液体中的微波合成

以N-甲基咪唑、吡啶为起始原料,合成了二种新型Br(o)nsted酸性功能化离子液体:1-(4-磺酸基)苄基-3-甲基咪唑硫酸氢根盐(3a),N-(4-磺酸基)苄基吡啶硫酸氢根盐(3b),以其作为反应介质与催化剂,研究了2-取代-4(3H)-喹唑啉酮的三组分、一锅法微波合成.结果表明,当n(2-氨基苯甲酸):n(酰氯):n(乙酸铵):n(3a或3b)=1:1.2:1.5:0.1时,反应6 min即可完成,产率81%～95%.离子液体经减压蒸馏、真空干燥可重复使用3次,催化活性基本保持不变.     

PVA接枝离子液体聚合物电解质的制备及性能!

以聚乙烯醇(PVA)、N-乙烯基咪唑(VyIm)和四氟硼酸(HBF4)为自由基接枝共聚反应的主要原料,合成了含离子液体结构的聚乙烯醇接枝N-乙烯基咪唑四氟硼酸盐(PVA-g-VyImBF4),并引入磷钨酸(PTA)和聚乙二醇(400)咪唑四氟硼酸盐离子液体(PEG400IMBF4)提高了聚合物的实用性能.采用溶液浇铸法制备了聚乙烯醇接枝N-乙烯基咪唑四氟硼酸盐/磷钨酸/离子液体聚合物电解质复合膜(PVA-g-VyImBF4/PTA/PEG400IMBF4).利用傅里叶红外光谱(FTIR)、差示扫描量热仪(DSC)、热重分析(TGA)、扫描电子显微镜(SEM)、交流阻抗及循环伏安等测试方法对聚合物电解质进行了表征.结果表明,当m(PVA-g-VyImBF4)∶m(PTA)∶m(PEG400IMBF4)=4∶2∶1.8时,所制备的聚合物电解质的室温电导率可达到3.267×10-3S/cm;电化学稳定窗口为4.4 V,具有良好的热稳定性和优良的实用性能.     

离子液体对植物水解酶抑制法测定克百威的影响

考察了N-丁基吡啶四氟硼酸盐([BPy][BF4])和1-丁基-3-甲基咪唑四氟硼酸盐([BMim][BF4])离子液体对植物水解酶抑制法测定克百威的影响(酶活性、抑制率、分析时间和检出限)。与未添加离子液体的磷酸缓冲溶液体系相比,农药对酶的抑制率在8%(V/V)[BPy][BF4]-磷酸缓冲溶液体系中提高了2.2倍,克百威的检出限降低了约1个数量级;同时加快了农药对酶的抑制速度,使分析时间缩短了4 min。添加[BMim][BF4]离子液体有类似的影响。     

微波辐射一锅法合成1-羧甲基-3-甲基咪唑四氟硼酸离子液体

以N-甲基咪唑为原料,微波辐射一锅法合成了1-羧甲基-3-甲基咪唑四氟硼酸离子液体,其结构经1HNMR和IR表征。     

功能化离子液体为载体液相合成二氢吡啶酮衍生物

在微波辐照条件下, 以甲基咪唑、氯乙醇和四氟硼酸钠为原料制备了含羟基功能化离子液体1-(2-羟乙基)-3-甲基咪唑四氟硼酸盐([2-hydemim][BF₄]), 并以其为液态载体, 首先与乙酰乙酸乙酯反应, 得到的中间体再分别和Meldrum酸、醋酸铵以及各种芳香醛反应, 最后在温和的条件下用甲醇钠进行切割反应, 得到了一系列产率和纯度较高的3,4-二氢吡啶酮衍生物, 目标化合物不需要进一步的色谱纯化处理, 纯度为95%～98%, 产率为83%～93%. 回收得到的功能化离子液体可以重复套用至少6次也不影响其活性. 表明该方法是一种高效的3,4-二氢吡啶酮衍生物的组合化学合成方法.     

Elemental fluorine, Part 23: Direct fluorination of β-ketoesters as an approach to enantioselective fluorination

Attempts to develop a direct enantioselective fluorination protocol using elemental fluorine and an appropriate Lewis acid and chiral ligand system are described.     

Industrial scale production of Selectfluor™ fluorination agent: from initial concept to full scale commercial production in a 5 year period

The Selectfluor™ electrophilic fluorination agent 1 is now produced in multi-ton per year quantities and is one of only a few fluorine-containing fine chemicals that are produced by direct fluorination with F₂ on an industrial scale. From the initial concept of the “ideal fluorination agent” to the present day industrial scale production of Selectfluor™, the route to the successful commercialization included a series of critical steps. A chronological account of the road to commercialization of Selectfluor™, noting the important product development factors, is provided herein.     

亲电氟化反应的新进展

介绍了自八十年代以来亲电氟化反应的最新进展, 其中包括众多的N-F类电氟化试剂的制备, 它们和各种底物的反应以及此类亲电氟化反应可能的机理。     

Selective fluorination of an aryl triazolinone herbicide intermediate

Fluoroaryl 1,2,4-triazolin-5-ones are an important class of herbicidal compounds useful in a variety of crop protection applications, primarily for the control of grassy and broad-leaf plant species. While a number of different synthetic strategies can be used for the step-wise preparation of these complex molecules, it is generally preferred to introduce fluorine later in the synthetic pathway, since the presence of fluorine and other halogens has a dominant effect on all subsequent synthetic steps. We have investigated the reactions that occur between aryl triazolinones and a variety of fluorination agents, including F₂/N₂, XeF₂, (CF₃SO₂)₂NF, Selectfluor^®, CF₂(OF)₂, CF₃OF, CH₃COOF, and CF₃COOF, and have used this knowledge to develop several alternative high-yielding routes to fluoroaryl 1,2,4-triazolin-5-ones. The fluorine introduction strategy and experimental results for a representative example of this important class of compounds are discussed herein.     

含氟内酯化合物的合成方法研究进展

内酯化合物广泛存在于天然产物和具有生理活性的物质中, 因此, 内酯化合物的合成一直是人们非常关心的一个研究领域, 不仅作为天然产物的重要合成砌块, 也用来合成一些精细化工产品和医药中间体. 将氟原子或含氟基团引入到内酯化合物分子中, 可使其生理活性发生改变. 就含氟内酯化合物合成方法的研究进展进行了综述.     

含氟卟啉的研究进展

综述了近几年国内外含氟卟啉的合成及其研究进展. 含氟卟啉合成方法分为直接氟化法和间接氟化法. 直接法主要采用无机氟化试剂直接对卟啉环进行氟化; 间接法主要采用含氟砌块法引入氟基团. 由于合成卟啉环比较复杂, 目前氟化学家主要采用间接氟化法合成含氟卟啉化合物.     

Innovative Syntheses of Cyano(fluoro)borates: Catalytic Cyanation,Electrochemical and Electrophilic Fluorination

Different types of high-yield, easily scalable syntheses for cyano(fluoro)borates Kt[BF_n(CN)_4−n] (n=0–2) (Kt=cation), which are versatile building blocks for materials applications and chemical synthesis, have been developed. Tetrafluoroborates react with trimethylsilyl cyanide in the presence of metal-free Brønsted or Lewis acid catalysts under unprecedentedly mild conditions to give tricyanofluoroborates or tetracyanoborates. Analogously, pentafluoroethyltrifluoroborates are converted into pentafluoroethyltricyanoborates. Boron trifluoride etherate, alkali metal salts, and trimethylsilyl cyanide selectively yield dicyanodifluoroborates or tricyanofluoroborates. Fluorination of cyanohydridoborates is the third reaction type that includes direct fluorination with, for example, elemental fluorine, stepwise halogenation/fluorination reactions, and electrochemical fluorination (ECF) according to the Simons process. In addition, fluorination of [BH(CN)₂{OC(O)Et}]⁻ to result in [BF(CN)₂{OC(O)Et}]⁻ is described.     

Electrolytic partial fluorination of organic compounds: 89: Regioselective anodic fluorination of tetrazolyl sulfides

Anodic fluorination of five-membered nitrogen-containing heterocyclic sulfides like tetrazolyl sulfides was comparatively studied. The anodic fluorination of tetrazolyl sulfides having α-electron-withdrawing groups was successfully carried out to provide α-monofluorinated tetrazolyl derivatives in moderate yields. This is in sharp contrast to the low efficient anodic fluorination of triazolyl sulfides. Thus, it was found that the efficiency of anodic fluorination is greatly affected by the basicity of the heterocyclic groups of the starting heterocyclic sulfides.     

Electrolytic partial fluorination of organic compounds. Part 78: Regioselective anodic fluorination of 2-oxazolidinones

Various 2-oxazolidinones were galvanostatically electrooxidized in the presence of various fluoride salts. It was found that a fluorine atom was introduced to the α-position of the nitrogen atom of N-acyl- and N-alkoxycarbonyl-2-oxazolidinones to provide the corresponding α-fluorinated products in moderate to good yields. In the case of N-phenoxycarbonyl derivative, fluorination took place on the phenyl group selectively.     

电化学氟化的新进展

电化学氟化是利用电极反应将氟直接引入有机或无机物的一种重要方法。有机物的电化学氟化方法有两种: 一是Simons于1941年发明的, 用镍作阳极, 在无水氟化氢溶液中, 电解制备全氟化合物的方法。此方法在近年来有不少改进。另一是1970年Rozhkov提出的, 以有机溶剂(如含Et3N.3HF的MeCN)为介质, 在铂阳极上,氧化得到单氟化产物的方法。本文全面地综述了这两种方法, 并着重于最新民发展。