| 薛童,张日成,闫喜龙.化学通报,2015,78(12):1162-1165. |
| 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 |
| 投稿时间：2015-04-24 修订日期：2015-07-07 |
| DOI： |
| 中文关键词: N-甲基二乙醇胺,甲基磺酰氯,氯取代,氮鎓离子 |
| 英文关键词:N-methyl-di(2-hydroxyethyl)amine, methanesulfonyl chloride, chloride substituted, azonia ion |
| 基金项目: |
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| 中文摘要: |
| 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：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。 |
| 英文摘要: |
| In organic synthesis, methanesulfonyl chloride often used to react with alcohol to turn hydroxyl into a more active leaving group—methanesulfonyl. However, during our recent study, we found that, when N-methyl-di(2-hydroxyethyl)amine reacted with methanesulfonyl chloride, it’s hydroxyl was substituted by chlorine. We designed a series of experiments and found the key reason 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 electronScloudSdensity and the steric hindrance around nitrogen atom cannot be too high. |
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