基于氮杂环氨基定向引入方法构建高能氮杂多环化合物的研究

The synthesis of amino-containing heterocyclic compounds is the research priority in the field of high energy density materials (HEDMs). At present, the methods of introducing amino groups to the nitrogen heterocyclic rings are mainly limited to C-amination and N-amination reaction. However, there have some problems in the amination reactions, such as low yield and poor selectivity, which cannot meet the synthetic needs of amino-containing heterocyclic compounds. Based on preliminary studies in our research group, three effective methods of directing the orientation of amino group into the nitrogen heterocyclic were mainly focused on: (1) Studies on the formation of 5-amino-1,2,4-triazole by Coupled-Annulation reaction using carboxyl or ester group on heterocyclic with 1-aminoguanidine. (2) Studies on the formation of 4,5-amino-1,2,4-triazole by Coupled-Annulation reaction using carboxyl group on heterocyclic with diaminoguanidine. (3) Studies on the formation of 5-amino-1,2,4-oxadiazole by Coupled-Annulation reaction using amidoximino group on heterocyclic with cyanogen bromide. (4) High energy groups can be introduced into the heterocyclic rings by the functionalization of amino to synthesize novel structural nitrogen heterocyclic energetic compounds. These three methods will break though the traditional amino-introduced model. Moreover, it provides an effective method for the synthesis of high energy, low sensitivity energetic materials. Finally, we expect to obtain 1-3 promising high energy and low sensitivity materials by the study of structure-activity relationship.

氨基氮杂环类化合物的合成是新型高能低感含能材料的研究重点。目前氮杂环上氨基引入方法主要限于C-胺化和N-胺化技术，存在收率低、选择性差等问题，无法满足氨基氮杂环类化合物的合成需求。项目基于前期研究基础，对三类氮杂环上氨基的定向引入方法及高能氮杂环含能化合物的构建进行研究：（1）基于氮杂环上羧基或羧酸酯与氨基胍的偶联关环反应构建5-氨基-1,2,4-三唑环的方法研究；（2）基于氮杂环上羧基与二氨基胍的偶联关环反应构建4,5-二氨基-1,2,4-三唑环的方法研究；（3）基于氮杂环上氨肟与溴化氰的偶联关环反应构建5-氨基-1,2,4-噁二唑环的方法研究;（4）基于氨基活性位点引入致爆基团构建高能氮杂多环化合物。通过这三类氨基定向引入方法，突破限于传统的C-胺化、N-胺化的氨基引入模式，并为高能低感含能材料的合成提供有效合成方法。通过构效关系研究,得到1-3个具有应用前景的高能低感材料。

氨基氮杂环类化合物的合成是新型高能低感含能材料的研究重点。目前氮杂环上氨基引入方法主要限于C-胺化和N-胺化技术，存在收率低、选择性差等问题，无法满足氨基氮杂环类化合物的合成需求。项目基于前期研究基础，实现了四类有效的氮杂环上氨基的定向引入方法，包括1) 基于氮杂环上酰肼类的分子间偶联-碱性关环反应技术构建3-硝氨基-1,2,4-三唑含能骨架的方法研究；2) 基于氮杂环上羧酸酯与氨基胍的偶联关环反应构建5-氨基-1,2,4-三唑含能骨架的方法研究; 3)氧化呋咱联噁二唑环上氨基的定向引入方法学研究. 4)基于氮杂环上羧基与二氨基胍的偶联关环反应构建4,5-二氨基-1,2,4-三唑含能骨架的方法研究。并基于氮杂环的氨基构建高能氮杂多环化合物包括高密度的不敏感炸药3,3’-双(4-硝基-1,2,5-噁二唑-2-氧-3-基)-5,5’-偶氮1,2,4-噁二唑（化合物2）和硝3,3’-双(5-硝胺基-1,2,4-噁二唑-3-基)-4,4’-偶氮氧化呋咱（化合物3）。其中含能化合物2的爆速达9666 m·s-1，爆压42.8 GPa，与CL-20能量相当，撞击感度达12 J，以及化合物4-硝基-3,5-双(1,2,4-3三唑-3-硝胺基-5-基)吡唑(29) 和4-硝基-3,5-双(1,2,4-3-三唑-3-硝基-5-基)吡唑(30)。其中化合物29的密度为1.92 g·cm-3，爆速为9009 m·s-1，撞击感度为20 J。其能量水平接近HMX，感度优于TNT，具备成为新型高能钝感炸药的潜力。突破限于传统的C-胺化、N-胺化的氨基引入模式，建立氮杂环氨基定向引入的方法学体系, 为高能低感高氮含能材料的合成提供新的有效合成方法，通过构效关系研究,得到2个具有应用前景的高能低感材料。