3-氨基-4-硝基氧化呋咱含能化合物的设计合成

Study on the Design and Synthesis of 3-Amino-4-nitro-furoxan Energetic Compound

在氧化呋咱环上引入氨基或硝基等功能基团,可提高含能化合物的能量密度和爆炸性能。为了获得更高能量密度的新型含能化合物,本文利用密度泛函理论(DFT)和单、双激发的耦合簇(CCSD)方法探索了以3-酰基叠氮基-4硝基氧化呋咱为起始材料,在二氧六环和水混合溶剂中合成3-氨基-4硝基氧化呋咱的反应机理,给出了反应的势能曲线。结果表明,该反应主要分为两个阶段:3-酰基叠氮基-4硝基氧化呋咱脱N_(2)后进行Curtious重排产生异氰酸酯;异氰酸酯经水解、羟基扭转、CO_(2)的脱离形成产物。反应的决速步为CO_(2)的脱离,能垒为44kcal/mol。因此,加热是实现该合成反应的必要条件。水既绿色环保,又参与反应,是该反应的最佳溶剂。这些结果为3-氨基-4-硝基氧化呋咱的实验合成提供了必要的理论依据。

The energy density and explosive properties of energetic compounds can be improved if introducing the functional groups such as amino or nitro groups into the furoxan ring. Here, in order to obtain novel energetic compounds with a higher energy density, the density functional theory(DFT) and the Coupled Cluster Singles and Doubles(CCSD) method are used to explore the formation mechanism of 3-amino-4-nitro-furoxan using 3-acyl azide-4 nitro-furoxan as starting material in the mixed solvent of dioxane and water. The potential energy profile of the reaction is given. The results show that the synthesis reaction is mainly divided into two stages: 3-acyl azide-4 nitrofuroxan sloughs N_(2) followed by Curtious rearrangement to produce isocyanate;isocyanate is formed by hydrolysis, hydroxyl torsion, and CO_(2)detachment. The rate-determining step of the reaction is CO_(2)detachment, with a barrier of 44 kcal/mol. So heating is necessary to complete the synthesis reaction. Water is not only as solvent but also participates in the reaction, it is the best solvent for this reaction. These results provide a necessary theoretical basis for the experimental synthesis of 3-amino-4-nitro-furoxan.