Theoretical study on the azido-cyclization of 3,6-diazido-1,2,4,5-tetrazine (DAT) with the dimethylsulfoxide (DMSO) solvent

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.

参考文章(36)
My Hang V. Huynh, Michael A. Hiskey, David E. Chavez, Darren L. Naud, Richard D. Gilardi, Synthesis, characterization, and energetic properties of diazido heteroaromatic high-nitrogen C-N compound. Journal of the American Chemical Society. ,vol. 127, pp. 12537- 12543 ,(2005) , 10.1021/JA0509735
Nelli Rahanyan, Anthony Linden, Kim K. Baldridge, Jay S. Siegel, Diels–Alder reactions of 3,6-disubstituted 1,2,4,5-tetrazines. Synthesis and X-ray crystal structures of diazafluoranthene derivatives Organic and Biomolecular Chemistry. ,vol. 7, pp. 2082- 2092 ,(2009) , 10.1039/B820551E
Rajendra P. Singh, Rajendar D. Verma, Dayal T. Meshri, Jean'ne M. Shreeve, Energetic nitrogen-rich salts and ionic liquids. Angewandte Chemie. ,vol. 45, pp. 3584- 3601 ,(2006) , 10.1002/ANIE.200504236
Thomas M. Klapötke, Carles Miró Sabaté, Matthias Rasp, Synthesis and properties of 5-nitrotetrazole derivatives as new energetic materials Journal of Materials Chemistry. ,vol. 19, pp. 2240- 2252 ,(2009) , 10.1039/B818925K
Anton Hammerl, Thomas M. Klapötke, Reginaldo Rocha, Azide-tetrazole ring-chain isomerism in polyazido-1,3,5-triazines, triazido-s-heptazine, and diazidotetrazines European Journal of Inorganic Chemistry. ,vol. 2006, pp. 2210- 2228 ,(2006) , 10.1002/EJIC.200600100
Hossein A. Dabbagh, Walter Lwowski, Equilibria of the 5-substituted-1,2-acylated tetrazoles and imidoyl azides Journal of Organic Chemistry. ,vol. 65, pp. 7284- 7290 ,(2000) , 10.1021/JO000267G
Anna Katrusiak, Urszula Skierska, Andrzej Katrusiak, Azido-tetrazolo tautomers of methylated azolopyridazines Journal of Molecular Structure. ,vol. 751, pp. 65- 73 ,(2005) , 10.1016/J.MOLSTRUC.2005.04.025
Yang Zhou, Xinping Long, Yuanjie Shu, None, Theoretical Study on the Azido-cyclization of 3,6-Di(azido)-1,2,4,5-tetrazine Chinese Journal of Chemistry. ,vol. 28, pp. 2123- 2129 ,(2010) , 10.1002/CJOC.201090352
Thierry Lioux, Gilles Gosselin, Christophe Mathé, Azido/Tetrazole Tautomerism in 2‐Azidoadenine β‐D‐Pentofuranonucleoside Derivatives European Journal of Organic Chemistry. ,vol. 2003, pp. 3997- 4002 ,(2003) , 10.1002/EJOC.200300274