醋酸镱催化异佛尔酮二胺甲氧羰基化反应  

Methoxycarbonylation of Isophorone Diamine Catalyzed by Ytterbium Acetate

作　　者：谭学峰[1,2] 王越[1] 李建国[1] 胡晓佳[1] 王公应[1] 

机构地区：[1]中国科学院成都有机化学研究所,四川成都610041 [2]中国科学院研究生院,北京100049

出　　处：《石油化工》2012年第9期1011-1016,共6页Petrochemical Technology

摘　　要：在常压、无溶剂条件下,研究了以异佛尔酮二胺(IPDA)和碳酸二甲酯(DMC)为原料合成异佛尔酮二氨基甲酸甲酯(IPDC)的甲氧羰基化反应。考察了多种金属醋酸盐的催化活性,实验结果表明,稀土金属醋酸盐的Lewis酸性越强,IPDC的收率和选择性越高,其中醋酸镱的活性最高。以醋酸镱为催化剂考察了反应温度、原料配比、催化剂用量和反应时间对甲氧羰基化反应的影响,得到最优的反应条件:反应温度90℃、反应时间6 h、n(DMC)∶n(IPDA)=4、n(催化剂)∶n(IPDA)=0.025,在此条件下,IPDA转化率为94.3%,IPDC收率为54.2%,IPDC选择性为57.5%。探讨了甲氧羰基化反应的可能机理,醋酸镱催化IPDA与DMC的甲氧羰基化历程符合SN2亲核取代反应机理。The solvent-free catalytic methoxycarbonylation of isophorone diamine（IPDA） with dimethyl carbonate（DMC） to methyl N-（3- { [ （methoxycarbonyl）amino] methyl}-3, 5, 5-trimethylcyclohexyl） carbamate（IPDC） under atmospheric pressure was studied. The catalytic activity of various metal acetates for the methoxycarbonylation was investigated. It was found that the stronger the Lewis acidity of rare earth metal acetates, the higher the yield and selectivity of IPDC within a certain range. Among the various metal acetates, ytterbium acetate showed the highest catalytic activity for the methoxycarbonylation. The effects of reaction temperature, mole ratio between the reactants, catalyst dosage and reaction time on the methoxycarbonylation were discussed. Under the optimal conditions： reaction temperature 90 ~C, n（DMC） ： n（IPDA） 4, n（catalyst） ： n（IPDA） 0.025 and reaction time 6 h, the conversion of IPDA, and the yield and selectivity of IPDC are 94.3%, 54.2% and 57.5%, respectively. A possible reaction mechanism of the methoxycarbonylation in the presence of ytterbium acetate was proposed, which is a SN2 nucleophilic substitution.

关 键 词：异佛尔酮二胺 碳酸二甲酯 异佛尔酮二氨基甲酸甲酯 甲氧羰基化 醋酸镱催化剂 

分 类 号：TQ426[化学工程]