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Ionic Liquids 离子液体

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邓友全,杜正银
619.40 KB

本发明公开了一种室温离子液体中酮肟经贝克曼重排反应制备酰胺的清洁催化合成方法。本发明的催化剂选自酰氯化合物,酮肟在室温离子液体中温和的反应条件下 高转化高选择性地生成相应的酰胺,产物可以用水萃取,离子液体能够循环使用。这种催化重排方法简单,无污染,不产生固体废物,是一种绿色清洁催化过程,具 有较好的工业应用前景。

邓友全,杜正银,李作鹏. 一种酮肟经贝克曼重排反应制备酰胺的方法. 200510096932.1. 2008.

杜正银 / 邓友全
163.99 KB

Several novel sulfonyl chloride functionalized ionic materials were used as media and catalysts for Beckmann rearrangement of cyclohexanone oxime and satisfactory results were achieved under mild conditions. The effects of all parameters were discussed. Moreover, the deactivation of ionic liquid catalytic system during the recycle was investigated by using FTIR spectroscopy and mass balance calculation. The trapping of acidic ionic material with basic product is proved to be mainly responsible for the difficulties encountered in the reuse of this type of material. A possible mechanism was conjectured.

★★★☆☆ Keywords: Beckmann rearrangement; Cyclohexanone oxime; Caprolactam; Sulfonyl chloride functionalized ionic materials; IR investigation

★★★☆☆ Z. Du et al. / Journal of Molecular Catalysis A: Chemical 237 (2005) 80–85.

杜正银 / 邓友全
128.55 KB

Novel lactam-cation-based Bronsted acid ionic liquids (ILs) were prepared through a simple and atom-economic neutralization reaction between a lactam, such as caprolactam and butyrolactam, and a Bronsted acid, HX, where X is BF4-, CF3COO-, phCOO(-), ClCH2COO-, NO3-, or H2PO4-. The density, viscosity, acidic scale, electrochemical window, temperature dependency of ionic conductivity, and thermal property of these ILs were measured and investigated in detail. The results show that protonated caprolactam tetrafluoroborate (CPBF) has a relatively strong acidity with -0.22 of Hammett acidic scale Ho and caprolactam trifluoroacetate (CPTFA) and pyrrolidonium trifluoroacetate (PYTFA) ILs possess very low viscosities, that is, 28 cP and 11 cP, respectively. An investigation of thermal property showed that a wide liquid range (up to -90 degrees C), moderate thermal stability (up to 249 degrees C for 10% of decomposition), and complex polymorphism were observed in these ILs. In comparison to imidazolium-cation-based ILs, the lactam-cation-based Bronsted acid ILs have a relatively lower cost, lower toxicity, and comparable ion conductivity and heat storage density (more than 200 MJ/m(3)). They have wide applicable perspectives for fuel cell devices, thermal transfer fluids, and acid-catalyzed reaction media and catalysts as replacements of conventional inorganic acids.

★★★★☆ Zhengyin Du, Zuopeng Li, Shu Guo, Juan Zhang, Laiying Zhu, and Youquan Deng. J. Phys. Chem. B 2005, 109, 19542-19546