2-甲基-4,5-二硝基三唑-1-氧化物的合成及其结构表征

以乙二醛、甲基肼和盐酸羟胺为起始原料,经缩合、肟化得到中间体肟基甲腙;该中间体不经分离直接加入到硫酸铜-吡啶-水体系中,经缩合环化得到2-甲基三唑-1-氧化物(MTO);随后用混酸(硝酸+硫酸)硝化得到目标产物2-甲基-4,5-二硝基三唑-1-氧化物(DNMTO);初步探讨了环化反应的机理,研究了反应温度与时间等因素对硝化反应的影响,确定了最佳硝化反应条件.与此同时,利用红外光谱、核磁共振、质谱及元素分析等分析了中间产物和DNMTO的组成和结构.结果表明,目标产物的总收率为16%,纯度为99%;最佳硝化反应温度为100℃,最佳硝化反应时间为0.5h.

Synthesis of 2-methyl-4,5-dinitro-1,2,3-triazole-1-oxide and characterization of its structure

Oxalic aldehyde, methyl hydrazine and hydroxylamine hydrochloride were used as starting materials to prepare oxime methyl hydrazone intermediate via condensation and oxima- tion. As-obtained intermediate was then directly added into copper sulfate-pyridine-water sys- tem to afford 2-methyl-triazole-1-oxide （denoted as MTO） via condensation and cyclization. As-obtained MTO was finally nitrified with the mixed acid （nitric acid plus sulfuric acid） to af- ford target product 2-methyl-4,5-dinitro-1,2,3-triazole-1-oxide （denoted as DNMTO）. The cy- clization mechanism was primarily investigated, the effects of temperature and time on the ni- trification reaction were examined, and the optimal reaction conditions were established. In the meantime, the composition and structure of as-prepared intermediate and target product were analyzed by means of infrared spectrometry, nuclear magnetic resonance spectrometry, mass spectrometry, and elemental analysis. Results indicate that the final target product is obtained with a purity of 99% and an overall yield of 16%; and the optimal nitrification reaction temper- ature and time are suggested as 100 ℃ and 0.5 h.