新型双呋咱并[3,4-b∶3',4'-f]氧化呋咱并[3″,4″-d]氧杂环庚三烯的合成与量子化学研究  

Synthesis and Quantum Chemistry Study of Novel Bifurazano [3,4-b∶3′,4′-f]furoxano[3″,4″-d]oxacyclohetpatriene

作　　者：周彦水[1] 王伯周[1] 王锡杰[1] 周诚[1] 宁艳利[1] 廉鹏[1] 李建康[1] 张叶高[1] 

机构地区：[1]西安近代化学研究所,陕西西安710065

出　　处：《合成化学》2012年第2期147-152,共6页Chinese Journal of Synthetic Chemistry

基　　金：国防科研基础计划项目(B0920110005)

摘　　要：以3,4-双(4'-硝基呋咱-3'-基)氧化呋咱为原料,设计并合成了新型双呋咱并[3,4-b∶3',4'-f]氧化呋咱并[3″,4″-d]氧杂环庚三烯(1),收率50.1%,其结构经13C NMR,15N NMR,IR,MS和元素分析表征。最佳的反应条件为:以无水碳酸钠为催化剂,乙腈(含水量0.04%)为溶剂,于80℃反应3.5 h。用B3LYP方法在6-31G**基组水平上对1的结构进行了计算,得到了稳定的几何构型和键级。在振动分析的基础上求得体系在不同温度下的热力学性质,得到了温度对热力学性能影响的关系式。1的性能研究表明,1的m.p.92℃～94℃,爆速8 256m.s-1(1.85 g.cm-3),摩擦感度0%(90°摆角),撞击感度12%(10 kg,25 cm),特性落高H50=57.5 cm(5 kg)。Novel bifurazano[3,4-b∶3′,4′-f]furoxano[3″,4″-d]oxacyclohetpatriene（1） in yield of 50.1% was designed and synthesized from 3,4-bis（4′-nitrofurazano-3′-yl）furoxan.The structure was characterized by 13C NMR,15N NMR,IR,MS and elemental analysis.The optimum reaction conditions at 80 ℃ for 3.5 h were as follows： catalyzer was anhydrous sodium carbonate,acetonitril（moisture content of 0.04%） was solvent.The molecular structure of 1 was estimated by B3LYP method based on 6-31G＊＊ basis set and the stable geometric configuration and bond order were obtained.The thermodynamics properties at different temperatures were obtained from vibrational analysis,and the relationship between temperature and thermodynamics properties was deducted.The properties of 1 had been tested in our experiments,the results showed that density was 1.870 g·cm-3,melting point was 92 ℃~94 ℃,detonation velocity was 8 256 m·s-1（ρ=1.85 g·cm-3）,friction sensitivity was 0%（90 deg）,impact sensitivity was 12%（10 kg,25 cm）,H50 was 57.5 cm（5 kg）.

关 键 词：双呋咱并[3 4-b∶3' 4'-f]氧化呋咱并[3″ 4″-d]氧杂环庚三烯 合成 表征 量子化学研究 

分 类 号：O625.6[理学—有机化学]