4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物的合成及性能-Synthesis and Properties of 4-Amino-1,2,3-triazolo[4,5-e]furazano[3,4-b]pyrazine 6-oxide

4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物的合成及性能

2020,28(7):664-669

李亚南, 胡建建, 陈涛, 王彬, 常佩, 王伯周

西安近代化学研究所氟氮化工资源高效开发与利用国家重点实验室

摘要：以自制的5,6-二氯呋咱并[3,4-b]吡嗪(DCFP)为原料，经取代、硝化-环化、中和、N-氨化等反应设计合成了新型N-氨基化合物——4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物(ATFPO)，采用红外光谱、核磁共振(¹H NMR、¹³C NMR)及元素分析等手段确定了中间体及目标物的结构；获得了关键中间体——1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物四乙基铵盐(TTFPO)的单晶并进行了结构解析，TTFPO晶体为单斜晶系，空间群为P2(1)/c，晶胞参数为：a=9.237(2) Å，b=22.162(5) Å，c=7.3506(17) Å，α=90°，β=98.378(4)°，γ=90°，V=1488.6(6) Å³，Z=4，μ=0.100 mm^-1，F(000)=656；采用差示扫描量热(DSC)方法研究了ATFPO的热性能，结果表明，其熔点为208.77 ℃，3个热分解峰温度分别为247.13、293.68 ℃和378.29 ℃；采用Gaussian 09程序中CBS-4M方法和Kamlet-Jacobs爆轰方程预估了目标物的爆轰性能，其生成热为705.4 kJ·mol^-1，爆速为8743 m·s^-1，爆压为34.6 GPa，爆热为5970 kJ·kg^-1；采用BAM落锤法测试了ATFPO机械感度，其撞击感度为35 J。研究结果表明，ATFPO是一种热稳定性好、钝感、爆轰性能优良的高能量密度化合物。

关键词：含能材料;4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物;合成;表征;性能

Synthesis and Properties of 4-Amino-1,2,3-triazolo[4,5-e]furazano[3,4-b]pyrazine 6-oxide

LI Ya-nan, HU Jian-jian, CHEN Tao, WANG Bin, CHANG Pei, WANG Bo-zhou

State Key Laboratory of Fluorine & Nitrogen Chemicals, Xi''an Modern Chemistry Research Institute, Xi''an 710065, China

Abstract：A novel N-amino compound—4-amino-1,2,3-triazolo[4,5-e]furazano[3,4-b]pyrazine 6-oxide (ATFPO) was designed and synthesized by the reactions of substitution, nitrification-cyclization, neutralization and N-amination using self-synthetic 3,6-dichlorinefurazano[3,4-b]pyrazine as starting material. The structures of intermediates and target compound were characterized by means of IR spectra, ¹H NMR,¹³C NMR and elemental analysis. The single crystal of key intermediate—tetraethyl ammonium 1,2,3-triazolo[4,5-e]furazano[3,4-b]pyrazine 6-oxide (TTFPO) was obtained, and the crystal structure was analyzed. The crystal of TTFPO belongs to monoclinic system，space group P2(1)/c, cell parameters: a=9.237(2) Å, b=22.162(5) Å, c =7.3506(17) Å, α=90°, β=98.378(4)°, γ=90°, V=1488.6(6) Å³, Z=4, μ=0.100 mm^-1, F(000)=656. The study on thermal stability of ATFPO by using differential scanning calorimetry (DSC) method show that its melting point is at 208.77 ℃, the thermal decomposition peak temperatures of ATFPO are 247.13 ℃, 293.68 ℃ and 378.29 ℃, respectively. Based on the calculated (CBS-4M) heat of formation and the experimental density, the detonation parameters of ATFPO were computed using Gaussian 09 program and Kamlet-Jacobs equations. The heat of formation is 705.4 kJ·mol^-1, the detonation velocity is 8743 m·s^-1, thedetonation pressure is 34.6 GPa and the detonation heat is 5970 kJ·kg^-1. The mechanical sensitivity was determined according to BAM Fall hammer method, and the impact sensitivity is 35 J. Results show that ATFPO is a novel high energy density material with good thermal stability, insensitivity and preferable detonation properties.

Key words：energetic materials;4-amino-1,2,3-triazolo[4,5-e]furazano[3,4-b]pyrazine 6-oxide;synthesis;characterization;properties

收稿日期：2020-02-29

基金项目：国家自然科学基金资助(21805222)

下载PDF全文