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氯代苯胺液相催化加氢合成环己酮

Liquid phase catalytic hydrogenation of chloroaniline into cyclohexanone

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【作者】 谢建伟项益智胡伟周兆良谢艳李小年

【Author】 XIE JianWei 1,2,XIANG YiZhi 1,HU Wei 1,2,ZHOU ZhaoLiang 1,XIE Yan 2 &LI XiaoNian 1 1 Industrial Catalysis Institute of Zhejiang University of Technology;State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology,Hangzhou 310032,China 2 Research Institute of Chemical Technology,Quzhou College,Quzhou 324000,China

【机构】 浙江工业大学工业催化研究所绿色化学合成技术国家重点实验室培养基地衢州学院化工研究所

【摘要】 提出了一种催化降解氯代苯胺高选择性合成环己酮的技术.在La修饰Pd/Al2O3催化剂作用下,通过催化加氢的方法实现了由多氯代苯胺(2,4,6-三氯苯胺和2,4,-二氯苯胺)高选择性地合成环己酮(不含环己醇).在优化的反应条件下,2,4,6-三氯苯胺加氢生成环己酮的转化率和选择性分别为100%和98.6%(没有检测到环己醇);2,4,-二氯苯胺加氢生成环己酮的转化率和选择性均为100%.氯代苯胺在Pd/La-Al2O3催化剂表面首先发生加氢脱氯/N-甲基化等反应生成苯胺、N-甲基苯胺和N,N-二甲基苯胺等中间产物,随后这些中间产物发生苯环加氢、氨基水解/醇解等反应得到环己酮;氯代苯胺上Cl元素的存在和体系中水的含量是影响环己酮选择性的重要因素.

【Abstract】 A method for the degradation of chloraniline for high selective synthesis of cyclohexanone was proposed. The cyclohexanone was synthesized from multichloraniline(2,4,6-trichloroaniline and 2,4-dichloroaniline) with a high selectivity(without cyclohexanol) over a La modified Pd/Al2O3 catalyst.The conversion of the hydrogenation of 2,4,6-trichloroaniline and 2,4-dichloroaniline are both 100%,and the corresponding selectivity of cyclohexanone are 98.6%and 100%(cyclohexanol was not detected) ,respectively,under the optimal reaction conditions. Chloraniline was first underwent hydrodechlorination/N-methylation reactions to form intermediates such as aniline,N-methylaniline,N,N-dimethylaniline,etc.on the surface of the Pd/La-Al2O3 catalyst.Then cyclohexanone was produced from the ring hydrogenation and amino-group hydrolysis/alcoholysis of these intermediates.The presence of Cl in the chloraniline molecular and water in the reaction system is important for the selectivity of cyclohexanone.

【基金】 国家自然科学基金(NSFC-20976164);浙江省自然科学基金(Y4080442);浙江省科技计划重点项目(2008C21036)资助
  • 【文献出处】 中国科学:化学 ,Scientia Sinica(Chimica) , 编辑部邮箱 ,2010年11期
  • 【分类号】TQ234.21
  • 【被引频次】1
  • 【下载频次】249
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