1,4-二硝基呋咱并[3,4-b]哌嗪(DNFP)的合成

设计合成了高能量密度材料1，4-二硝基呋咱并3，4-b]哌嗪（DNFP）。即以N，N＇-二叔丁基乙二胺为起始原料，低温条件下与二氯乙二肟缩合环化生成1，4-二叔丁基哌嗪-2，3-二酮肟（PDO—tB），而后在氢氧化钠的乙二醇溶液中高温反应脱水环化得1，4-二叔丁基呋咱并3，4-b]哌嗪，经98％硝酸和硫酸的混酸体系硝解合成出DNFP，总收率32．6％，采用红外光谱、核磁共振谱、元素分析对DNFP和中间体结构进行了表征；改进了PDO—tB的合成工艺条件，加料方式由一次性加入改为缓慢滴加，并确定了适宜的冷浴温度为-18℃；研究了不同硝解体系对反应的影响，确定了适宜的硝解体系为硝硫混酸，硝解收率为61．7％。

Synthesis of 1,4-Dinitrofurazano[3,4-b]piperazine(DNFP)

The synthesis of 1, 4-dinitrofurazano 3,4-b] piperazine( DNFP) with an overall yield of 32. 6% ,was described. The cyclizative condensation between N, N'-di-tert-butyl ethylenediamine and dichloroglyoxime at low temperature generated 1,4-di-tert-butyl piperazine-2,3 -dioxime ( PDO-tB ) , which underwent a base-promoted dehydration at high temperature to obtain 1,4-di-tert-butylfurazano3,4-b] piperazine ( FP-tB ). Furthermore, nitrolysis of FP-tB provided an efficient access to the novel explosive compound DNFP. The structures of DNFP and its intermediates were characterized by IR, ~1H NMR, ~(13)C NMR and elemental analysis. Moreover, the effects of reaction conditions on the yield of PDO-tB were studied, and the optimum reaction condition is dropwise addition at ～ 18℃. Converting FP-tB to DNFP with several nitrolysis reagents were also studied, and the nitrolysis with the mixed acid of 98% HNO_3 and H_2SO_4 provides a good yield of 61.7%.