苯并1,2,3,4-四嗪-1,3-二氧化物的硝化工艺

Nitration Process of Benzo-1,2,3,4-tetrazine-1,3-dioxide

以苯并1,2,3,4-四嗪-1,3-二氧化物(BTDO)为原料,合成了5-硝基苯并1,2,3,4-四嗪-1,3-二氧化物(5-NBTDO)、7-硝基苯并1,2,3,4-四嗪-1,3-二氧化物(7-NBTDO)。并在此基础上,分别以5-NBTDO或7-NBTDO为原料合成了5,7-二硝基苯并1,2,3,4-四嗪-1,3-二氧化物(DNBTDO)。用1H NMR,13C NMR,IR和MS表征了合成化合物的结构。考察了硝化体系、物料比(n(BTDO)∶n(NO-3))与反应温度对不同硝化产物产率的影响。理论预测了可能的硝化产物,并用高效液相色谱测定了产物收率。结果表明,确定合成3种物质的最佳工艺条件为:发烟硫酸/硝酸钾体系、n(BTDO)∶n(KNO3)=1∶2、反应温度为40℃,5-NBTDO产率为34.9%;硝硫混酸体系、n(BTDO)∶n(HNO3)=1∶3、温度为20℃,7-NBTDO产率为77.1%;发烟硫酸/硝酸体系、n(NBTDO)∶n(HNO3)=1∶8、温度95℃,DNBTDO产率可达90%。实验过程中BTDO作为原料一步法合成3种硝化产物的难易程度与理论预测结果相一致,7-NBTDO产率最高,5-NBTDO次之,DNBTDO最少。

5-Nitrobenzene-1 , 2, 3, 4-tetrazine-1 , 3-dioxide （ 5-NBTDO ） and 7-nitrobenzene-1 , 2, 3,4-tetrazine-1 , 3-dioxide （7-NBTDO） were synthesized using benzo-1,2,3,4-tetrazine-l,3-dioxide （BTDO） as raw materials. Then the 5,7-dinitrobenzene-1,2,3,4-tetrazi ne-1,3-dioxide （DNBTDO） was synthesized by 5-NBTDO and 7-NBTDO as raw materials. The structures of synthesized compounds were characterized by ^1H NMR, ^13C NMR, IR and MS. The effects of nitration system, material ratio n（BTDO） ： n（NO1^-） and reaction temperature on the yields of different nitrating products were explored. Possible nitration products were predicted through theoretical method. The yields of the products were detected by HPLC. Results show that the optimum process conditions of synthesizing three substances were determined as ： for oleum-KNO3 nitration system, n（BTDO） ： n（ KNO3 ） = 1 ： 2 , reaction temperature 40 ℃, with yield of 5-NBTDO 34.9% ; for nitric acid-sulfuric acid mixed system, n（BTDO） ： n（HNO3）=1 ： 3, reaction temperature 20℃,with yield of 7-NBTDO 77. 1%; for oleum-nitric acid system, n（NBTDO） ： n（HNO3）=1 ：8, and reaction temperature 95℃,with yield of DNBTDO 90%. The yield of three kinds of nitration products, synthesized via one-step method using BTDO, is consistent with the theory prediction. The order of yield is 7-NBTDO〉5-NBTDO 〉DNBTDO.