N-甲基二乙醇胺的异常反应研究  

Research on an Abnormal Reaction of N-Methyl-di( 2-hydroxyethyl) amine

作　　者：薛童[1] 张日成[1] 闫喜龙[1] 

机构地区：[1]天津大学化工学院,天津300072

出　　处：《化学通报》2015年第12期1162-1165,共4页Chemistry

摘　　要：在有机合成反应中常使用甲基磺酰氯与醇反应,将羟基转化为易于离去的甲磺酸酯基。在近期的实验中,我们却发现N-甲基二乙醇胺同甲基磺酰氯反应生成的是羟基被氯取代的产物。我们设计了一系列实验推测生成氯取代产物的关键原因是在反应过程中生成了三元环的氮鎓离子过渡态,而形成这一过渡态必须满足的条件是:氮原子与羟基之间相隔两个碳原子,氮原子有足够的电子云密度,氮原子周围的空间位阻不能太大。In organic synthesis, methanesulfonyl chloride was often used to react with alcohol to turn hydroxyl into a more active leaving group--methanesulfonyl. However, we have found that, when N-methyl-di （2- hydroxyethyl） amine reacted with methanesulfonyl chloride, its hydroxyl groups were both substituted by chlorine atoms. A series of designed experiments indicated that the key reason of this phenomenon is the generation of three- membered ring azonia ion transition state. The formation of this transition state must meet three requirements： there are must two carbon atoms between the nitrogen atom and hydroxyl group, nitrogen atom must have sufficient electron cloud density and the steric hindrance around nitrogen atom cannot be too high.

关 键 词：N-甲基二乙醇胺 甲基磺酰氯 氯取代 氮鎓离子 

分 类 号：O621.25[理学—有机化学]