尿素法合成甲苯-2,4-二氨基甲酸正丙酯反应  

Synthesis of Dipropyl Toluene-2,4-dicarbamate via Urea Route

作　　者：耿艳楼[1] 方鸿刚[1] 安华良[1] 王桂荣[1] 赵新强[1] 王延吉[1] 

机构地区：[1]河北工业大学化工学院绿色化工与高效节能河北省重点实验室,天津300130

出　　处：《石油学报（石油加工）》2013年第3期494-500,共7页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学基金项目(20976035);河北省自然科学基金项目(B2010000019);天津市自然科学基金项目(12JCYBJC12800)资助

摘　　要：以2,4-二氨基甲苯(TDA)、尿素和正丙醇(PrOH)为原料,非催化合成了甲苯-2,4-二氨基甲酸正丙酯(TDC-P),考察了反应条件对该合成反应的影响,并基于反应产物的液相色谱-质谱分析结果,推测了可能的反应路径。结果表明,该反应适宜的反应条件为n(TDA)/n(Urea)=1/3、n(TDA)/n(PrOH)=1/84、反应温度170℃、反应压力0.6MPa、反应时间4h。此时,TDA转化率95.3%,TDC-P产率66.1%、选择性69.4%。合成TDC-P可能的反应路径有3条,(1)经过氨基甲酸正丙酯和3-氨基-4-甲基苯氨基甲酸正丙酯或2-甲基-5-氨基苯氨基甲酸正丙酯生成TDC-P的反应路径;(2)以2,4-甲苯二脲为中间产物的反应路径;(3)以3-脲基-4-甲基苯氨基甲酸正丙酯或2-甲基-5-脲基苯氨基甲酸正丙酯为中间产物的反应路径。Dipropyl toluene-2,4-dicarbamate （TDC-P） was synthesized successfully by using 2,4- diamino toluene （TDA）, urea and propanol （PrOH） as raw materials in the absence of catalyst. The effects of reaction conditions on the synthesis of TDC-P were studied. The plausible reaction paths existed in this synthesis were speculated based on the result of HPLC-MS analyses. The results showed that the suitable reaction conditions for this synthesis were TDA/urea molar ratio of 1/3, TDA/PrOH molar ratio of 1/84, reaction temperature of 170℃, reaction pressure of 0.6 MPa and reaction time of 4 h, under which TDA conversion, TDC-P yield and selectivity were 95.3%, 66.1% and 69.4%, respectively. There existed three possible reaction paths in the TDC-P synthesis, which were （ 1 ） through propyl carbamate and propyl 2-methyl-5-amino-N- phenylcarbamate or propyl 3-amino-4-methyl-N phenylcarbamate, （2） via toluene 2,4-bisurea as an intermediate, （3） via propyl 3-ureido-4-methyl-N-phenylearbamate or propyl 2-methyl-5-ureido-N- phenylcarbamate as an intermediate.

关 键 词：2 4-二氨基甲苯 尿素 正丙醇 甲苯-2 4-二氨基甲酸正丙酯 反应路径 

分 类 号：TQ246.3[化学工程—有机化工]