| 刘伟娜,王智,杨金辉,彭亚晶.化学通报,2022,85(6):751-754. |
| 3-氨基-4-硝基氧化呋咱含能化合物的设计合成研究 |
| Study on the Design and Synthesis of 3-amino-4-nitro-furoxan Energetic Compound |
| 投稿时间：2021-10-13 修订日期：2021-11-19 |
| DOI： |
| 中文关键词: 氧化呋咱 含能材料 合成反应 密度泛函理论 CCSD方法 |
| 英文关键词:furoxan energetic materials synthesis reaction density functional theory CCSD method |
| 基金项目:(20180550510)；辽宁省高等学校创新人才支持计划项目(LR2019004),辽宁省普通高等学校校际合作项目(XJXM2020005)资助2020-02-02收稿,2020-03-03接受 * |
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| 中文摘要: |
| 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Coupled Cluster Singles and Doubles(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N2后进行Curtious重排产生异氰酸酯；异氰酸酯经水解、羟基扭转、CO2的脱离形成产物。反应的决速步为CO2的脱离，能垒为44 kcal/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。 |
| 英文摘要: |
| 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 was mainly divided into two stages: 3-acyl azide-4 nitrofuroxan sloughs N2 followed by Curtious rearrangement to produce isocyanate; isocyanate is formed by hydrolysis, hydroxyl torsion, and CO2 detachment. The rate-determining step of the reaction is CO2 detachment, with a barrier of 44 kcal/mol. So heating is necessary to complete the synthesis reaction. Water is not only green, but also involved in the reaction. Therefore, water is the optimal solvent for the synthesis. These results provide a necessary theoretical basis for the experimental synthesis of 3-amino-4-nitro-furoxan. |
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