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

doi:10.6023/cjoc201409006

有机化学 ›› 2015, Vol. 35 ›› Issue (4): 851-857.DOI: 10.6023/cjoc201409006 上一篇下一篇

研究论文

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

贾思媛, 张海昊, 周诚, 来蔚鹏, 李祥志, 王伯周

西安近代化学研究所西安 710065

收稿日期:2014-09-05 修回日期:2014-10-11 发布日期:2014-12-15
通讯作者: 王伯周 E-mail:wbz600@163.com
基金资助:
国家自然科学基金(No. 21243007)资助项目.

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

Jia Siyuan, Zhang Haihao, Zhou Cheng, Lai Weipen, Li Xiangzhi, Wang Bozhou

Xi'an Modern Chemistry Research Instritute, Xi'an 710065

Received:2014-09-05 Revised:2014-10-11 Published:2014-12-15
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21243007).

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摘要/Abstract

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, D_c=1.871 g· cm^-3, F(000)=440, R₁=0.0353, wR₂=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733.7 kJ·mol^-1、熔点193.1 ℃、分解点345.1 ℃、爆速8416.5 m·s^-1、爆压为32.9 GPa; ATFAZ密度1.788 g·cm^-3、生成焓831.2 kJ·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1752.4 kJ·mol^-1、分解点280.2 ℃、爆速7924.5 m·s^-1、爆压为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

Using 3,4-bis(4'-aminofurazano-3'-yl)furazan (BATF) as the starting material, 3,4-bis(4'-nitrofurazano-3'-yl)- furazan (BNTF) was synthesized by Caro's acid oxidation with a yield of 93%. Based on the reactivity of NO₂ in BNTF, two energetic material 7H-trifurazano[3,4-b:3',4'-f:3",4"-d]azepine (HTFZA) and 7-aminotrifurazano[3,4-b:3',4'-f:3",4"-d]azepine (ATFAZ) were designed and synthesized from BNTF and NH₃·H₂O or NH₂NH₂·H₂O via the nucleophilic substitution and cyclization, then HTFAZ was nitrated in the system of HNO₃-Ac₂O 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) nm, b=0.6458(14) nm, c=1.6814(4) nm, V=0.7781(3) nm³, Z=4, D_c=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 kJ·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 m·s^-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 explosion velocity was 7924.5 m·s^-1, the detonation pressure was 28.42 GPa.

Key words: 7-aminotrifurazano[3,4-b:3',4'-f:3",4"-d]azepine, analogues, synthesis, crystal structure, property

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贾思媛, 张海昊, 周诚, 来蔚鹏, 李祥志, 王伯周. 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[J]. 有机化学, 2015, 35(4): 851-857.

Jia Siyuan, Zhang Haihao, Zhou Cheng, Lai Weipen, Li Xiangzhi, Wang Bozhou . Synthesis and Characterization of 7H-Trifurazano-[3,4-b:3',4'-f:3",4"-d]azepine and Its Analogues[J]. Chin. J. Org. Chem., 2015, 35(4): 851-857.

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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

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