碳酸铯催化胺与CO_(2)有效转化制备有机脲类化合物  

Preparation of organic urea compounds by efficient conversion of amines and CO_(2) catalyzed by cesium carbonate

作　　者：熊南妮 王春蓉 陈阳 周明东[1] XIONG Nanni;WANG Chunrong;CHEN Yang;ZHOU Mingdong(School of Petrochemical Engineering,Liaoning Petrochemical University,Fushun 113001,Liaoning,China)

机构地区：[1]辽宁石油化工大学石油化工学院,辽宁抚顺113001

出　　处：《精细化工》2024年第9期2082-2088,共7页Fine Chemicals

基　　金：辽宁省博士科研启动基金资助项目(2021-BS-249);辽宁省自然科学基金资助项目(LJKZ0373)。

摘　　要：以CO_(2)和有机胺为原料直接制备有机脲类化合物,反应过程中无任何脱水剂参与,考察反应的温度、压力、反应物浓度、时间、溶剂、催化剂与助剂种类及用量对反应的影响,得到的最佳反应条件为:温度190℃、CO_(2)压力4.5 MPa、以无机盐碳酸铯(Cs_(2)CO_(3))为碱性催化剂、溴化四正丁铵(n-Bu4NBr)为助剂、N-甲基吡咯烷酮(NMP)为溶剂、有机胺的浓度为6.67 mol/L、反应时间6 h(部分24 h),在该条件下制备了15种对称型不同烷基或芳基取代的有机脲类化合物,气相色谱(GC)分离产率可达42%~80%,采用^(1)HNMR和^(13)CNMR对所得产物的结构进行了表征,并分析了可能的反应机理。该法具有方便高效、环境友好和原子经济的特点。Organic urea compounds were prepared directly from CO_(2)and organic amines without any dehydrating agent participating in the reaction process.With regulation of factors such as temperature,pressure,reactant concentration,time,solvent,type and dosage of catalysts and additives,the optimal reaction conditions were obtained as follows:temperature of 190℃,carbon dioxide pressure of 4.5 MPa,inorganic salt Cs_(2)CO_(3)as catalyst,n-Bu4NBr as additive,and N-methyl pyrrolidone(NMP)as solvent,amine of 6.67 mol/L,reaction time of 6 h(certain reaction 24 h),15 symmetric organic urea compounds with different alkyl or aryl substitutions prepared under the optimal reaction conditions exhibited separation yields ranging from 42%to 80%.The compounds obtained were then characterized by^(1)HNMR and^(13)CNMR,and analyzed for possible reaction mechanism exploration.This method showed characteristics of convenience,efficiency,environmental friendliness,and atomic economy.

关 键 词：二氧化碳 有机胺 无机盐碳酸铯 对称型有机脲 机理 精细化工中间体 

分 类 号：O622[理学—有机化学]