7H-三呋咱并[3,4-b:3',4'-f:3'',4''-d]氮杂环庚三烯及衍生物的合成与表征  

Synthesis and Characterization of 7H-Trifurazano-[3,4-b:3',4'-f:3'',4''-d]azepine and Its Analogues

作　　者：贾思媛[1] 张海昊[1] 周诚[1] 来蔚鹏[1] 李祥志[1] 王伯周[1] 

机构地区：[1]西安近代化学研究所,西安710065

出　　处：《有机化学》2015年第4期851-857,共7页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.21243007)资助项目~~

摘　　要：以3,4-双（3＇-氨基呋咱-4＇-基）呋咱（BATF）为原料,经Caro’s acid氧化制备了3,4-双（3＇-硝基呋咱-4＇-基）呋咱（BNTF）,收率为93%;基于BNTF分子中的NO2反应性,与水合肼、氨水等发生亲核取代、环化反应,合成了含能化合物7H-三呋咱并[3,4-b：3＇,4＇-f：3＂,4＂-d]氮杂环庚三烯（HTFAZ）和7-氨基-三呋咱并[3,4-b：3＇,4＇-f：3＂,4＂-d]氮杂环庚三烯（ATFAZ）.在硝酸-醋酐体系中氧化HTFAZ得到新化合物7,7＇-二（呋咱[3,4-b：3,4＇-d：3＂,4＂-f]氮杂环庚三烯）（BTFZ）,采用红外光谱、核磁共振、元素分析和质谱等进行了结构表征.培养了HTFAZ单晶,X射线单晶衍射分析表明：HTFAZ晶体结构属单斜晶系,空间群为P2（1）/n,a=0.7252（15）nm,b=0.6458（14）nm,c=1.6814（4）nm,V=0.7781（3）nm3,Z=4,Dc=1.871 g·cm^-3,F（000）=440,R1=0.0353,w R2=0.0895.开展了HTFAZ,ATFAZ和BTFZ的物化、爆轰性能和热性能研究,其中HTFAZ密度1.871 g·cm^―3、生成焓733.7kJ·mol^-1、熔点193.1℃、分解点345.1℃、爆速8416.5 m·s^-1、爆压为32.9GPa;ATFAZ密度1.788 g·cm^-3、生成焓831.2kJ·mol^-1、熔点204～207℃、分解点323.7℃、爆速8300 m·s^-1、爆压为30 GPa;BTFZ密度1.862 g·cm^-3、生成焓1752.4kJ·mol^-1、分解点280.2℃、爆速7924.5 m·s^-1、爆压为28.42 GPa.Using 3,4-bis（4＇-aminofurazano-3＇-yl）furazan （BATF） as the starting material, 3,4-bis（4＇-nitrofurazano-Y-yl）- fura- zan （BNTF） was synthesized by Caro＇s acid oxidation with a yield of 93%. Based on the reactivity of NO2 in BNTF, two en- ergetic material 7H-trifurazano[3,4-b：3＇,4＇-f：3＂,4＂-d]azepine （HTFZA） and 7-aminotrifurazano[3,4-b：3＇,4＇-j53＂,4＂-d]azepine （ATFAZ） were designed and synthesized from BNTF and NH3oH20 or NHENH2·H2O via the nucleophilic substitution and cyclization, then HTFAZ was nitrated in the system of HNO3-AczO to firstly obtain a novel compound 7,7＇-bis（terfurazan [3,4-b：3,4＇-d：3＂,4＂-f]azepine） （BTFZ）. The above three compounds were characterized by the means of IR, 1H NMR, 13C NMR, MS and elemental analysis. The single crystal of HTFAZ was studied by X-ray single crystal diffraction. Its crystal belongs to orthorhombic, space group is P2（1）/n with a=0.7252（15） rim, b=0.6458（14） nm, c= 1.6814（4） nm, V=0.7781（3） nm3, Z=4, Dc= 1.871 g·cm^-3, F（000）=440, R1=0.0353 and wR2=0.0895. The properties of HTFAZ, ATFAZ and BTFZ were measured and followed as： HTFAZ： the density was 1.871 g·cm^-3, the enthalpy of formation was 733.7 ·mol^-1, the melt point was 193.1℃, the decomposition point was 345.1 ℃, the explosion velocity was 8416.5 m·s^-1, the detonation pressure was 32.9 GPa; ATFAZ： the density was 1.788 g·cm-3, the enthalpy of formation was 831.2 kJ·mol^-1, the melt point was 204～207 ℃, the decomposition point was 323.7 ℃, the explosion velocity was 8300 mos-1, the detonation pressure was 30 GPa; BTFZ： the density was 1.862 g·cm^-3, the enthalpy of formation was 1752.4 kJ·mol^-1, the decomposition point was 280.2 ℃, the explo- sion velocity was 7924.5 m·s^-1, the detonation pressure was 28.42 GPa.

关 键 词：7H-三呋咱并[3 4-b:3' 4'-f:3' 4'-d]氮杂环庚三烯 衍生物 合成 晶体结构 性能 

分 类 号：O626[理学—有机化学]