1599446-02-2Relevant academic research and scientific papers
An experimental and theoretical reinvestigation of the Michael addition of primary and secondary amines to dimethyl acetylenedicarboxylate
Gurjar, Asha,Poonia, Priyadarshni,Sinha, Pragya,Bansal, Raj K.
, p. 2504 - 2507 (2014)
Theoretical calculations of the Michael addition of diethylamine, pyrrolidine, and benzylamine to DMAD at the DFT (B3LYP/6-31+G-) level indicate that the reaction follows a stepwise mechanism via a zwitterionic intermediate. The reactions have low activation barriers, 13-15 kcal mol -1 and are exothermic, ΔH° = -29 to -44 kcal mol -1. The detailed investigation of the reaction of benzylamine with DMAD reveals participation of the reactant-, transition structure-, and the product-complexes and that the 1,3-prototropic shift occurs through the benzylamine molecule. It also predicts formation of dimethyl 2-(N-benzylimino)butane-1,4-dicarboxylate as one of the products, which has been duly isolated and characterized experimentally.
