CAJ | 학술논문

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%.
설계합성료고능량밀도재료1,4-이초기부찰병[3,4-b]고진(DNFP).즉이N, N′-이숙정기을이알위기시원료,저온조건하여이록을이우축합배화생성1, 4-이숙정기고진-2,3-이동우(PDO-tB),이후재경양화납적을이순용액중고온반응탈수배화득1, 4-이숙정기부찰병[3,4-b]고진,경98%초산화류산적혼산체계초해합성출DNFP,총수솔32.6%,채용홍외광보、핵자공진보、원소분석대DNFP화중간체결구진행료표정;개진료PDO-tB적합성공예조건,가료방식유일차성가입개위완만적가,병학정료괄의적랭욕온도위-18 ℃;연구료불동초해체계대반응적영향,학정료괄의적초해체계위초류혼산,초해수솔위61.7%.
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-butylfurazano[3,4-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%.