Experimental and Theoretical Investigation of the Reaction of Secondary Amines with Maleic Anhydride
作者:Manjinder Kour、Raakhi Gupta、Raj K. Bansal
DOI:10.1071/ch17206
日期:——
The reaction of secondary amines, namely 1-methylpiperazine, pyrrolidine, morpholine, 2-methylpiperidine, and diethylamine, with maleic anhydride has been investigated experimentally and theoretically at the DFT level. Under kinetic control, i.e. at −78°C or −15°C, amines add across the C=O functionality exclusively and the initially formed addition products isomerize to the corresponding N-substituted
已在DFT级别上通过实验和理论研究了仲胺(即1-甲基哌嗪,吡咯烷,吗啉,2-甲基哌啶和二乙胺)与马来酸酐的反应。在动力学控制下,即在-78°C或-15°C下,胺仅跨C = O官能团加成,初始形成的加成产物异构化为相应的N-取代的马来酸衍生物。与无环的α,β-不饱和羰基化合物相反,即使在热力学控制下,胺也不会在C = C官能团中加成胺。可以基于局部稠合的Fukui功能来合理化马来酸酐的这种行为,这表明马来酸酐中的羰基碳原子比无环α,β-不饱和羰基化合物如丙烯醛中的硬得多。