CHINESE JOURNAL OF ENERGETIC MATERIALS
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Brφnsted酸性离子液体中芳烃硝化反应的研究
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岳彩波(1976-),男,在读博士研究生,从事离子液体中有机合成反应的研究。e-mail: yuecaibo@163.net

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Nitration of Aromatic Compounds in Brnsted Acidic Ionic Liquid
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    摘要:

    以BrØnsted酸性离子液体[Hmim][CF3COO](三氟乙酸根甲基咪唑盐)和[Hmim][HSO4](硫酸氢根甲基咪唑盐)作为溶剂和催化剂,硝酸铵为硝化剂,研究了烷基苯和卤苯等芳香化合物的硝化反应。在0 ℃到室温的硝化条件下,烷基苯和卤苯都能被硝化成一硝基化合物,收率为40%~80%。甲苯等烷基苯的硝化选择性与硝硫混酸中的硝化选择性相当; 卤苯硝化的对位选择性则远高于硝硫混酸中的硝化结果。其中氯苯在18 ℃下反应8 h,三氟乙酸酐(TFAA)/硝酸铵为4时产物的对邻比达到6.2,而溴苯在0 ℃下反应8 h,TFAA/硝酸铵为5时产物的对邻比可达到14.0,并且生成的对硝基溴苯可以从反应液中析出,得到对硝基溴苯含量为98%的产物。

    Abstract:

    Various aromatic compounds,including alkyl and halo benzenes,were nitrated to mononitro compounds in reasonable yields (40%-80%) with NH4NO3 from 0 ℃ to room temperature in Brnsted acidic ionic liquids with [Hmim][CF3COO] and [Hmim][HSO4] as solvent and catalyst respectively. The isomer ratios for nitration of toluene in Brnsted acidic ionic liquids were comparable to that obtained in mixed acid nitration. Isomer ratios for the nitration of halo benzenes in Brnsted acidic ionic liquids are different from that obtained in mixed acid nitration,usually,with higher para selectivity. The para-/ortho- product isomer ratio is 6.2 for the nitration of chlorobenzene at 18 ℃ for 8 h with n(TFAA)/n(NH4NO3)=5. The para-/ortho- product isomer ratio is 14.0 for the nitration of bromobenzene at 0 ℃ for 8 h with n(TFAA)/n(NH4NO3)=5. The para-product, p-nitrobromobenzene, from the nitration of bromobenzene in [Hmim][HSO4] under 0 ℃ precipitates with 98% purity, which facilitates the separation of the pure isomert.

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岳彩波,魏运洋,吕敏杰. Brφnsted酸性离子液体中芳烃硝化反应的研究[J].含能材料, 2007, 15(2):118-121.
YUE Cai-bo, WEI Yun-yang, Lü Min-jie. Nitration of Aromatic Compounds in Brnsted Acidic Ionic Liquid[J]. Chinese Journal of Energetic Materials, 2007, 15(2):118-121.

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  • 收稿日期: 2006-05-26
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  • 在线发布日期: 2011-10-31
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