Department of Chemistry, Energetic Materials Research, Ludwig-Maximilian University, Butenandtstr. 5-13 (D), 81377 München, Germany.
Chem Asian J. 2013 Jan;8(1):148-59. doi: 10.1002/asia.201200903. Epub 2012 Nov 21.
In this work we report on the syntheses of energetic salts of cyanotetrazolate-1- and -2-oxides; this offers a unique ability to compare the effects of tetrazole 1- versus 2-oxidation. 5-Cyanotetrazolate-2-oxide can be synthesized by oxidation of the 5-cyanotetrazolate anion with Oxone, while the corresponding 1-oxide was synthesized by the rearrangement of azidoaminofurazan. Both chemical (multinuclear NMR, IR, and Raman spectroscopies, mass spectrometry, etc.) as well as explosive (impact, friction, and static sensitivities) properties are reported for these energetic salts. Calculated explosive performances using the EXPLO5 computer code are also reported. We furthermore detail the chemistry of these two anions, and their ability to form tetrazole-carboxamides, dihydrotetrazines, and tetrazines. The ability to hydrolyze cyanotetrazole oxides to their amides was demonstrated by two copper complexes. Several crystal structures of these species are presented in addition to full chemical characterization. Finally, the unique 1,4,-bis(2-N-oxidotetrazolate)-1,2,4,5-tetrazine anion was characterized as an energetic material as its ammonium salt.
在这项工作中，我们报告了氰基四唑-1-和-2-氧化物的高能盐的合成；这提供了一个独特的能力来比较四唑 1-与 2-氧化的影响。5-氰基四唑-2-氧化物可以通过用 Oxone 氧化 5-氰基四唑阴离子来合成，而相应的 1-氧化物则通过叠氮氨基呋咱的重排来合成。这些高能盐的化学性质（多核 NMR、IR 和拉曼光谱、质谱等）和爆炸性质（冲击、摩擦和静态敏感性）都有报道。使用 EXPLO5 计算机代码计算的爆炸性能也有报道。此外，我们还详细介绍了这两种阴离子的化学性质，以及它们形成四唑酰胺、二氢四嗪和四嗪的能力。通过两个铜配合物证明了氰基四唑氧化物水解为酰胺的能力。除了完整的化学表征外，还介绍了这些物质的几个晶体结构。最后，作为一种高能材料，其铵盐形式的独特的 1,4-双（2-N-氧化四唑）-1,2,4,5-四嗪阴离子被表征。
