|本期目录/Table of Contents|

[1]耿勇亮,王鹏程,林秋汉,等.1,1’-二羟基-5,5’-联四唑合成机理的理论计算[J].火炸药学报,2019,42(2):120-124,140.[doi:10.14077/j.issn.1007-7812.2019.02.003]
 GENG Yong-liang,WANG Peng-cheng,LIN Qiu-han,et al.Theoretical Calculation on the Synthetic Mechanism of 1,1’-Dihydroxy-5,5’-bitetrazole[J].,2019,42(2):120-124,140.[doi:10.14077/j.issn.1007-7812.2019.02.003]
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1,1’-二羟基-5,5’-联四唑合成机理的理论计算()
     
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《火炸药学报》[ISSN:1007-7812/CN:61-1310/TJ]

卷:
42卷
期数:
2019年第2期
页码:
120-124,140
栏目:
出版日期:
2019-04-30

文章信息/Info

Title:
Theoretical Calculation on the Synthetic Mechanism of 1,1’-Dihydroxy-5,5’-bitetrazole
作者:
耿勇亮 王鹏程 林秋汉 陆明 周宝晶
南京理工大学化工学院, 江苏 南京 210094
Author(s):
GENG Yong-liang WANG Peng-cheng LIN Qiu-han LU Ming ZHOU Bao-jing
School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China
关键词:
有机化学11’-二羟基-55’-联四唑(H2DHBT)密度泛函理论(DFT)二叠氮基乙二肟(DAzGO)溶剂效应
Keywords:
quantum chemistry11’dihydroxy-55’-tetrazole(H2DHBT)density functional theory(DFT)diazidoglyoxime(DAzGO)solvent effect
分类号:
TJ55;O62
DOI:
10.14077/j.issn.1007-7812.2019.02.003
文献标志码:
-
摘要:
为了研究由二叠氮基乙二肟(DAzGO)合成1,1’-二羟基-5,5’-联四唑(H2DHBT)的反应机理,采用密度泛函理论(DFT),在B3LYP/6-31G(d)基组水平上计算了酸性条件下DAzGO分子成环反应的反应物、过渡态和产物结构,获得反应能垒。结果表明,DAzGO分子的成环为两步成环的亲电反应,其中第一个基元反应是决速步,反应能垒为86.94 kJ/mol;氢离子和水分子的存在将反应能垒降低了30.46 kJ/mol,氢离子和水分子可以促进成环反应。DAzGO的成环反应在丙酮、水、乙醚中的决速步能垒分别为87.03、90.08、72.59 kJ/mol;溶剂的极性越小,对DA2GO分子成环反应的促进作用越大,乙醚为最佳反应溶剂。
Abstract:
To study the synthetic mechanism of 1,1’-dihydroxy-5,5’-bitetrazole (H2DHBT) from diazidoglyoxime (DAzGO), the density functional theory(DFT) method was employed to calculate the reactants, transition state and product structure of the cyclization reaction of DAzGO molecule under acidic conditions were calculated by density functional theory(DFT) at the level of B3LYP/6-31G(d) basis set, and the reaction energy barrier was obtained. The results show that the cyclization reaction of DAzGO molecule is a two-step cyclization electrophilic reaction. The first elementary reaction is rate-determining step, the reaction energy barrier is 86.94 kJ/mol. The presence of hydrogen ions and water molecules reduces the reaction energy barrier by 30.46 kJ/mol, the hydrogen ions and water molecules can promote the cyclization reaction. The energy barriers of rate-determining step for the cyclization reaction of DAzGO in acetone, water and ether are 87.03,90.08 and 72.59 kJ/mol. The smaller of the polarity of solvent, the greater of promotion to cyclization reaction of DAzGO molecule, and ether is the best reaction solvent.

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备注/Memo

备注/Memo:
收稿日期:2018-7-3;改回日期:2018-11-19。
基金项目:国家自然科学基金青年基金(No.11702141)
作者简介:耿勇亮(1994-),男,硕士研究生,从事化学反应的理论计算研究。E-mail:njustgyl@163.com
更新日期/Last Update: 1900-01-01