[1]贾思媛①,张海昊①,张家荣①,等.3-叠氮基-1,3-二硝基氮杂环丁烷的合成工艺改进及性能研究[J].爆破器材,2023,52(05):1-6,13.[doi:10.3969/j.issn.1001-8352.2023.05.001]
　JIA Siyuan,ZHANG Haihao,ZHANG Jiarong,et al.Improvement of Synthesis Process and Properties of 3-Azido-1, 3-Dinitroazetidine[J].EXPLOSIVE MATERIALS,2023,52(05):1-6,13.[doi:10.3969/j.issn.1001-8352.2023.05.001]
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3-叠氮基-1,3-二硝基氮杂环丁烷的合成工艺改进及性能研究()
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《爆破器材》[ISSN:1001-8352/CN:32-1163/TJ]

卷:
52
期数:
2023年05
页码:
1-6,13
栏目:
基础理论
出版日期:
2023-10-13

文章信息/Info

Title:
Improvement of Synthesis Process and Properties of 3-Azido-1, 3-Dinitroazetidine
文章编号:
5769
作者:
贾思媛①; 张海昊①; 张家荣①; 薛琪①; 毕福强①②; 王伯周①②
①西安近代化学研究所（陕西西安，710065）
②氟氮化工资源高效开发与利用国家重点实验室（陕西西安，710065）
Author(s):
JIA Siyuan①;  ZHANG Haihao①;  ZHANG Jiarong①;  XUE Qi①;  BI Fuqiang①②;  WANG Bozhou①②
①Xi’an Modern Chemistry Research Institute (Shaanxi Xi’an, 710065)
②State key laboratory of Fluorine & Nitrogen Chemicals (Shaanxi Xi’an, 710065)
关键词:
3-叠氮基-1; 3-二硝基氮杂环丁烷; 合成; 晶体结构; 性能
Keywords:
3-azido-1; 3-dinitroazetidine;  synthesis;  crystal structure;  property
分类号:
TJ55; TQ560.7
DOI:
10.3969/j.issn.1001-8352.2023.05.001
文献标志码:
A
摘要:
3-叠氮基-1,3-二硝基氮杂环丁烷（AzDNAZ）是一种含偕叠氮硝基基团的低熔点含能化合物。AzDNAZ结构与性能研究对于新型含能化合物的设计合成具有重要的借鉴意义。采用1-叔丁基-3-硝基-3-羟甲基氮杂环丁烷盐酸盐(TNHAC)为原料，经氧化叠氮化、中和以及硝化等反应制备了AzDNAZ， 改进了合成工艺，总收率达到70% （文献中收率为37%）。采用红外光谱、1H NMR、13C NMR及元素分析等对中间体及目标化合物进行了结构表征。首次培养出了AzDNAZ的单晶。晶体结构属三斜晶系；空间群为P-1，a＝0.612 0 (6) nm，b＝0.634 5(6) nm，c＝1.019 0(9) nm，V＝0.368(6) nm3， Z＝2，Dc＝1.695 g/cm3，F(000)＝192，R1= 0.032 1，R2=0.037 2。采用Hirshfeld 表面分析方法研究了晶体分子内的相互作用，O…H和N…H的作用点占比达到51%，占主导地位。对比计算了AzDNAZ和1,3,3-三硝基氮杂环丁烷（TNAZ）的键离解能，AzDNAZ的C—NO2和N—NO2键离解能分别较TNAZ高9.63 kJ/mol和4.87 kJ/mol；实测AzDNAZ的撞击感度大于40 J。采用EXPLO5程序预估了AzDNAZ的爆轰性能：爆速为8 421 m/s；爆压为29.60 GPa。与TNAZ相比，AzDNAZ的能量性能略低。但是，丰富的分子间氢键作用以及较高的键离解能使得AzDNAZ的机械感度较低，安全性提升。
Abstract:
3-Azido-1,3-dinitroazetidine (AzDNAZ) is a low melting point energetic compound with gem-azidonitro groups. The study of its structure and properties is of important significance for the design and synthesis of new energetic compounds. Using (1-tert-butyl-3-nitroazetidin-3-yl) methanol (TNHAC) as starting material, AzDNAZ was synthesized via the reactions of oxidation-azidation, neutralization and nitration. The synthesis process was improved, and the yield was increased from 37% to 70%. The structure of intermediates as well as the final product compound was characterized by IR, 1H NMR, 13C NMR, and element analysis. The crystal structure of AzDNAZ was determined for the first time. Its crystal belongs to the triclinic system, its space group is P-1. And its crystal structure parameters are as follows: a=0.612 0 (6) nm，b=0.634 5(6) nm, c=1.019 0(9) nm, V=0.368(6) nm3, Z=2, Dc=1.695 g/cm3, F(000)=192, R1= 0.032 1, R2=0.037 2. Interactions in crystal molecules were studied using Hirshfeld surface analysis method. The dominant interactions are O…H and N…H, and the tolal proportion reaches 51%.The bond dissociation energy of C—NO2 and N—NO2 of AzDNAZ was found theoretically to be higher than that of TNAZ by 9.63 kJ/mol and 4.87 kJ/mol, respectively. The measured impact sensitivity of AzDNAZ is more than 40 J. The detonation performance was estimated by EXPLO5. The results indicate that the detonation velocity is 8 421 m/s and the detonation pressure is 29.60 GPa. In spite of the lower energy performance of AzDNAZ compared to TNAZ, the intermolecular hydrogen bonding and high bond dissociation can result in a lower mechanical sensitivity and an enhanced safety of AzDNAZ.

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备注/Memo

备注/Memo:
收稿日期：2022-10-08
第一作者：贾思媛（1981-），女，副研究员，主要从事高含能材料的合成与性能研究。E-mail: jiasiyuan125@163.com
通信作者：毕福强（1982-），男，研究员，主要从事含能材料的设计、合成与性能研究。E-mail：bifuqiang@msn.com
更新日期/Last Update: 2023-10-11