双呋咱并[3,4-b:3',4'-f]氧化呋咱并[3″,4″-d]氮杂环庚三烯及衍生物的合成和表征  

Synthesis and Characterization of 7H-Difurazano[3,4-b:3',4'-f]furoxano[3 ",4"-d]azepine and Derivatives

作　　者：夏成波[1] 郑春梅[1] 张涛[1] 胥立文 魏文杰[1] 王风云[1] 雷武[1] 夏明珠[1] 

机构地区：[1]南京理工大学化工学院,江苏南京210094

出　　处：《含能材料》2015年第11期1089-1094,共6页Chinese Journal of Energetic Materials

摘　　要：以3,4-双(4'-硝基呋咱-3'-基)氧化呋咱(BNFF)为原料,合成9种不同取代基的双呋咱并[3,4-b:3',4'-f]氧化呋咱并[3″,4″-d]氮杂环庚三烯(a^i),探究了成环反应的SN2机理,并采用核磁、红外、质谱等对其进行了表征。将7-(2-氨基-1-乙基)-双呋咱并[3,4-b':4'-f]氧化呋咱并[3″,4″-d]氮杂环庚三烯(c)与2,4-二硝基氯苯、2,4,6-三硝基-3-氨基氯苯反应合成出两种未见文献报道的化合物,N-(2',4'-二硝基苯基)-和N-(3'-氨基-2',4',6'-三硝基苯基)-7-(2-氨基-1-乙基)-双呋咱并[3,4-b':4'-f]氧化呋咱并[3″,4″-d]氮杂环庚三烯(j和k),通过差示扫描量热法研究这两种物质的热性能,结果表明,化合物j的第1、2阶段热分解放热峰分别为258.03℃和329.92℃,化合物k的第1、2阶段放热峰分别为275.35℃和360.24℃,表明多硝基苯基的引入可提高含能化合物的热稳定性。理论预测了其爆轰性能:j的理论密度、爆速、爆压分别为1.68 g·cm-3、6945 m·s-1、21 GPa,k为1.74 g·cm-3、6438 m·s-1、18 GPa。Nine kinds of 7H-difurazano[3,4-b：3＇,4＇-f]furoxano[3＂,4＂-d]azepine（a- i） were synthesized with 3,4-bis（3-nitro- furazan-4-yl）furoxan （BNFF） as starting materials, and the SN2 mechanism of cyclization was discussed. The structure of these compounds were characterized bylH NMR, ℃ NMR, IR and MS. Then 7-（2-amino-1-methyl）-difurazano[3,4-b：3＇,4＇-flfurox- ano[3＂,4＂-dlazepine （c） was used to synthesize two new compounds, N-（2＇,4＇-dinitrophenyl）- and N-（3＇-amino-2＇,4＇,6＇-tri- nitrophenyl ） -7-（ 2-amino-1 -methyl ） -difurazano[ 3,4-b： 3＇ ,4 ＇-f]furoxano[3＂ ,4＂-d ] azepine （ j, k） , by reacting with 2,4-dinitro- chlorobenzene, 3-amino-2,4,6-trinitrochloro- benzene. The thermal properties j and k were analyzed by differential scanning cal- orimetry. Results show that the first and second exothermic peak of compound j are at 258.03 ℃ and 329.92 ℃, and for com- pound k, they are at 275.35 ℃ and 360.24 ℃, indicating that the introduction of nitrobenzene can increase the thermal stability. The detonation performances were estimated as follows： density, detonation velocity and detonation pressure of j and k are 1.68 g. cm-3, 6945 m· s-1, 21 GPa; 1.74 g. cm-3, 6438 m ·s-1, 18 GPa, respectively.

关 键 词：含能材料 呋咱 氧化呋咱 氮杂环庚三烯 热稳定性 

分 类 号：TQ560.1[化学工程—炸药化工]