2,4,6-三硝基-2,4,6-三氮杂环己酮生成历程的~(15)N NMR研究

由DPT与脲或硝基脲在硝化剂中反应可以合成2,4,6-三硝基-2,4,6-三氮杂环己酮。本文用~(15)N示踪原子对DPT分子中不同位置的氮原子分别进行标记,用~(15)N NMR谱图来考察~(15)N标记的反应物和产物分子中标记原子的位置及丰度。结果表明,与脲或硝基脲缩合的DPT硝解碎片为非硝基取代的N,N-二羟甲基胺,硝基脲上硝基与硝化剂之间存在着交换反应。

Studies on the Reaction Mechanism of 2,4,6-Trinitro-2,4,6- triazacyclohexanone with ~(15)N NMR Spectra

2,4,6-Trinitro-2,4,6-triazacyclohexanone could be synthesized via the condensation of the nitrolytic fragments of DPT and urea (or nitrourea) in the nitrolytic medium. In this paper the nitrogen atoms in different positions of DPT were labelled with 15N atoms respectively. With the help of 15N NMR spectra, the isotope distribution and abundance of 15N labelled atoms in the product and re-actant molecules could be determined. The results indicate that the nitrolytic fragments condensed with urea (or nitrourea) are N,N-dihydroxymethylamines without the nitro-substituent, and there exists a exchanging process between the nitro-groups in the nitrourea and in the nitrolysis agent.