A Computational Study on Water-assisted Ammonolysis of N-Methyl β-Sultam  

作　　者：HE Mao-xia FENG Da-cheng YU Ling-juan CAI Zheng-ting 

机构地区：[1]Institute of Theoretical Chemistry, Shandong University, Jinan 250100, P. R. China

出　　处：《Chemical Research in Chinese Universities》2006年第1期94-98,共5页高等学校化学研究（英文版）

基　　金：SupportedbytheNationalNaturalScienceFoundationofChina(Nos.20373034and20173032)andPh.D.SpecialResearchFoundationoftheMinistryofEducationofChina.

摘　　要：The ring opening of β-sultam v/a an H2O-assisted ammonolysis process was studied by using Density Functional Theory（DFT） method at the B3LYP/6-31G level as a further step in the theoretical investigation of the ammonolysis reaction of β-sultams. The calculated pathways are analogous to those previously described for the non-assisted ammonolysis reaction. Solvent effects were assessed by using the polarized continuum model（PCM） method. The results show that mode 1 and pathway a in channel Ⅱ are the most favorable ones in both the cases. The energy barrier of the cleavage of C-S bonds producing P1 is the highest among all the energy barriers. The presence of a solvent in the continuum model disfavors the reaction, whereas the participation of water in the ammonolysis reaction plays a positive role and reduces the active energy greatly. The relative energies of all the transition states in the assisted ammonolysis are 20-80 kJ/mol lower than those for the non-assisted reaction.The ring opening of β-sultam v/a an H2O-assisted ammonolysis process was studied by using Density Functional Theory（DFT） method at the B3LYP/6-31G level as a further step in the theoretical investigation of the ammonolysis reaction of β-sultams. The calculated pathways are analogous to those previously described for the non-assisted ammonolysis reaction. Solvent effects were assessed by using the polarized continuum model（PCM） method. The results show that mode 1 and pathway a in channel Ⅱ are the most favorable ones in both the cases. The energy barrier of the cleavage of C-S bonds producing P1 is the highest among all the energy barriers. The presence of a solvent in the continuum model disfavors the reaction, whereas the participation of water in the ammonolysis reaction plays a positive role and reduces the active energy greatly. The relative energies of all the transition states in the assisted ammonolysis are 20-80 kJ/mol lower than those for the non-assisted reaction.

关 键 词：AMMONOLYSIS Water-assisted mechanism Density Functional Theory（DFT） β-Sultam 

分 类 号：O623.626[理学—有机化学]