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  

Improvement of Synthesis Process and Properties of 3-Azido-1,3-Dinitroazetidine

作　　者：贾思媛[1] 张海昊[1] 张家荣[1] 薛琪[1] 毕福强[1,2] 王伯周 JIA Siyuan;ZHANG Haihao;ZHANG Jiarong;XUE Qi;BI Fuqiang;WANG Bozhou(Xi’an Modern Chemistry Research Institute,Shaanxi Xi’an,710065;State key laboratory of Fluorine&Nitrogen Chemicals,Shaanxi Xi’an,710065)

机构地区：[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

出　　处：《爆破器材》2023年第5期1-6,13,共7页Explosive Materials

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、13 C 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=0.6120(6)nm,b=0.6345(6)nm,c=1.0190(9)nm,V=0.368(6)nm 3,Z=2,D c=1.695 g/cm 3,F(000)=192,R 1=0.0321,R 2=0.0372。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—NO 2和N—NO 2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8421 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。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,13 C 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=0.6120(6)nm,b=0.6345(6)nm,c=1.0190(9)nm,V=0.368(6)nm 3,Z=2,D c=1.695 g/cm 3,F(000)=192,R 1=0.0321,R 2=0.0372.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—NO 2 and N—NO 2 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 8421 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.

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 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] TQ560.7[化学工程—炸药化工]