The Synthesis Of Benzo-1,2,3,4-tetrazine-1,3-Dioxide And Derivatives

Benzo-1,2,3,4-tetrazine-1,3-dioxide (BTDO) and its derivatives (BTDOS) are energetic nitrogen compounds. The energetic nitrogen compounds usually show large positive heat of formation, high density, high oxygen balance and high nitrogen content. And it’s friendly to the environment. Therefore, the synthesis of benzo-1,2,3,4-tetrazine-1,3-dioxide and its derivatives have great significance.This paper selected 2-nitroaniline as the raw materials to synthesize BTDO which were analysed and characterized. O-nitrosonitrobenzene was synthesized using 2-nitroaniline and caro’acid as the raw materials.2-tert-Butyl-1-(2-anilino)-diazene-l-oxide was produced from o-nitrosonitrobenzene by azo reaction, reduction reaction, that was cyclized with nitration N2O5 to give BTDO. The nitration reaction processes for the synthesis of 5-nitrobenzene-1,2,3,4-tetrazine-1,3-dioxide (5-NBTDO),7-nitrobenzene-1,2,3,4-tetrazine-1, 3-dioxide (7-NBTDO) and 5,7-dinitr obenzene-1,2,3,4-tetrazine-1,3-dioxide (DNBTDO) were investigated by using BTDO as raw material under different nitration systems. Orthogonal experiments and single factor experiments were developed to determine the optimal conditions. Besides, nitration products and material properties were predicted by molecular computation. The target compounds were identified by 1H NMR,13C NMR, IR and MS.5-NBTDO was synthesized by using BTDO as raw material, which reacted with oleum and potassium nitrate, the yield of 34.9%. The process conditions were optimized and the optimal reaction conditions were as follows:n(BTDO:n(KN03)=1:2, reaction temperature of 20℃.7-NBTDO was synthesized by using BTDO and mixed acid as raw material, the yield of 77.1%. The process conditions were optimized and the optimal reaction conditions were as follows: n(BTDO):n(HNO3)=1:3, reaction temperature of 40℃.DNBTDO was synthesized by using 5-NBTDO or 7-NBTDO as raw material, which reacted with oleum and nitric acid, the yield of 90.0%. The process conditions were optimized and the optimal reaction conditions were as follows:n(BTDO):n(HNO3)=1:9, reaction temperature of 95℃.