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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
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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

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国家自然科学基金资助(21805222)


Synthesis and Properties of 4-Amino-1,2,3-triazolo[4,5-e]furazano[3,4-b]pyrazine 6-oxide
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State Key Laboratory of Fluorine & Nitrogen Chemicals, Xi''an Modern Chemistry Research Institute, Xi''an 710065, China

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    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) Å3Z=4,μ=0.100 mm-1F(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。

    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, the detonation 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.

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李亚南,胡建建,陈涛,等.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[J].含能材料, 2020, 28(7):664-669. DOI:10.11943/CJEM2020043.
LI Ya-nan, HU Jian-jian, CHEN Tao, et al. Synthesis and Properties of 4-Amino-1,2,3-triazolo[4,5-e]furazano[3,4-b]pyrazine 6-oxide[J]. Chinese Journal of Energetic Materials, 2020, 28(7):664-669. DOI:10.11943/CJEM2020043.

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历史
  • 收稿日期: 2020-02-29
  • 最后修改日期: 2020-04-25
  • 录用日期: 2020-04-08
  • 在线发布日期: 2020-04-21
  • 出版日期: 2020-07-25