2,6-二乙酰氨基吡嗪-1-氧化物硝化反应研究

研究了2,6-二乙酰氨基吡嗪-1-氧化物在硝硫混酸和发烟硝酸/酸性离子液体中的硝化反应。在混酸硝化体系中,考察了混酸硝化剂类型对产物2,6-二氨基-3,5-二硝基吡嗪-1-氧化物(LLM-105)收率和纯度的影响。在发烟硝酸/N,N,N-三甲基-N-丙磺酸基-硫酸氢铵(TMPSHSO4)硝化体系中,考察了在酸性离子液体催化条件下酸性离子液体使用量、硝解反应温度、酸性离子液体重复使用次数对LLM-105收率和纯度的影响。结果表明:混酸硝化体系中,2,6-二乙酰氨基吡嗪-1-氧化物的最佳硝化剂为KNO3和质量分数20%发烟硫酸,LLM-105的收率为72.5%,质量分数为98.6%。发烟硝酸/酸性离子液体硝化体系中,最佳反应条件为:TMPSHSO4与2,6-二乙酰氨基吡嗪-1-氧化物的物质的量的比为0.051.00,硝解温度为75℃,LLM-105收率为64.8%,质量分数为98.5%,TMPSHSO4经回收可重复使用3次。相对而言,以发烟硝酸/TMPSHSO4为硝化剂合成LLM-105更具优势。用1H NMR、IR和MS对LLM-105的结构进行了表征。

Study on the Nitration Reaction of 2,6-Diacetamidopyrazine-l-Oxide

Nitration reactions of 2, 6-diacetamidopyrazine-l-oxide in mix acid or fuming nitric acid/acidic ionic liquid were researched. In the mixed acid nitration system, effects of mixed acid nitration agent types on the yield and purity of the product LLM-105 were investigated. In the fuming nitric acid and N, N, N-trimethyl-N-propanesulfonic acid ammonium hydrogen sulfate （ TMPSHSO4 ） nitration system, the effects of acidic ionic liquid quantity, nitration temperature and acidic ionic liquid recycle times on the yield and purity of LLM-105 were investigated in the catalyst condition of acidic ionic liquid. The results show that, in the mixed acid nitration system, the best nitrating agent of 2, 6-diacetamidopyrazinc- 1-oxide are KNO3 and 20% oleum, the product yield is 72.5% , and the purity is 98.6%. In the fuming nitric acid and TMPSHSO4 nitration system, optimal reaction conditions are that molar ratio of TMPSHSO4 and 2,6-diacetamidopyrazine-1- oxide is O. 05 ： 1.00, reaction temperature is 75 ℃, the product yield is 64.8% , the purity is 98.5% , and TMPSHSO4 could be recovered and used repeatedly for three times. Nitration of 2,6-diacetamidopyrazine-l-oxide by fuming nitric acid and TMPSHSO4 has more advantages. The structure of LLM-105 was also characterized by 1H NMR, IR and MS.