作者: Piao He , Jian-Guo Zhang , Kun Wang , Xin Yin , Tong-Lai Zhang
DOI: 10.1016/J.COMPTC.2015.06.017
关键词:
摘要: Abstract The density functional theory (DFT) with B3LYP/6-311G ∗ level was used to study the azido-cyclization of 3,6-diazido-1,2,4,5-tetrazine (DAT) dimethylsulfoxide (DMSO) solvent based on self-consistent reaction field (SCRF). cyclization DAT mainly occurs in conversion azido → tetrazole, which molecular and electronic structure change significantly. electrostatic potential introduced predict sites where could be vulnerable attacks by electrophile. thermodynamic analysis shows that all reactions are endothermic non-spontaneous DMSO solvent. And makes products more stable than gas phase, while there is a little decrease barrier. barriers first second 24 28 kcal/mol, most possible path may connect ap -DAT -DAT2c. isomeric ( -DAT2c sp- DAT2c) coexist due extremely low azido-rotation (about 7 8 kcal/mol). Finally, rate constants Arrhenius equation were evaluated between temperature ranges 200 1000 K.