pH-Controlled forms of 1-amino-1-hydrazino-2,2-dinitroethylene (HFOX): selective reactivity of amine and hydrazinyl groups with aldehydes or ketones
pH-Controlled forms of 1-amino-1-hydrazino-2,2-dinitroethylene (HFOX): selective reactivity of amine and hydrazinyl groups with aldehydes or ketones
复制标题
pH 控制形式的 1-氨基-1-肼基-2,2-二硝基乙烯 (HFOX)：胺和肼基与醛或酮的选择性反应
DOI：
10.1039/d2ma00307d
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发表时间：
2022
影响因子：
5
通讯作者：
Shreeve, Jean’ne M.
中科院分区：
文献类型：
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作者：
Chinnam, Ajay Kumar;Staples, Richard J.;Shreeve, Jean’ne M.
1-氨基-1-肼基-2，2-二硝基乙烯（HFOX）是一类潜在的新型含能材料的反应中间体。现在我们描述它与各种羰基化合物在酸性和碱性催化剂存在下的缩合反应。HFOX与α-二酮和β-二酮的缩合得到了许多感兴趣的产物。α-二酮在碱存在下发生环化反应，形成六元环产物，而β-二酮在酸存在下环化为五元环产物。其中一个令人兴奋的反应是形成（5，6-二甲基-1，2，4-三嗪-3-基）二硝基甲烷铵盐5c，其通过使用氨水作为亲核碱分离。所有新化合物均通过先进的光谱技术进行了充分表征。5、5c、5e、9、11和12 a的结构由单晶X射线衍射分析支持。大多数新的六元环化合物具有良好的热稳定性（>200 °C），而氟化的五元环化合物12 b在25 °C时具有最高密度2.04 g cm−3。用Gaussian 03和EXPLO 5软件计算了生成热和爆轰特性。几乎所有的新化合物都具有很好的爆轰性能，特别是三嗪盐，5e（Dv = 7513 m s−1; P = 24.45 GPa），和5f（Dv = 7948 m s-1; P = 26.27 GPa）以及叠氮化物衍生物11（Dv = 8166 m s−1; P = 25.48 GPa），其上级优于TNT（Dv = 6824 m s−1; P = 19.40 GPa）。这些发现为新型高性能含能材料的合成提供了新的视角。
1-Amino-1-hydrazino-2,2-dinitroethylene (HFOX) is a potential reactive intermediate for a new class of energetic materials. Now we describe its condensation with various carbonyl compounds in the presence of acidic and basic catalysts. Condensation of HFOX with α-diones and β-diones gives products of much interest. α-Diones undergo cyclization in the presence of base to form six-membered ring products, while β-diones cyclize to five-membered ring products in the presence of acid. One of the exciting reactions is the formation of ammonium (5,6-dimethyl-1,2,4-triazin-3-yl)dinitromethanide salt, 5c, which was isolated by using aqueous ammonia as a nucleophilic base. All new compounds were fully characterized by advanced spectroscopic techniques. The structures of 5, 5c, 5e, 9, 11, and 12a are supported by single crystal X-ray diffraction analysis. Most of the new six membered ring compounds have good thermostabilities (>200 °C), while the fluorinated five membered ring compound, 12b, has the highest density of 2.04 g cm−3 at 25 °C. Heats of formation and detonation properties were calculated by using Gaussian 03 and EXPLO5 software programs. Nearly all new compounds have very good detonation properties, especially, triazine salts, 5e (Dv = 7513 m s−1; P = 24.45 GPa), and 5f (Dv = 7948 m s−1; P = 26.27 GPa) as well as azide derivative 11 (Dv = 8166 m s−1; P = 25.48 GPa), which are superior to TNT (Dv = 6824 m s−1; P = 19.40 GPa). These findings provide a new perspective for the synthesis of novel high performing energetic materials.