两种新型多氨基多硝基吡啶衍生物的合成与表征(英文)  

Synthesis and Characterization of Two New Energetic Polyamino and Nitro Pyridine Derivatives

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作  者:马丛明[1] 刘祖亮[2] 姚其正[2,3] 

机构地区:[1]南京理工大学环境与生物工程学院,江苏南京210094 [2]南京理工大学化工学院,江苏南京210094 [3]中国药科大学药学院,江苏南京210009

出  处:《含能材料》2015年第12期1176-1180,共5页Chinese Journal of Energetic Materials

基  金:the National Natural Science Foundation of China(21102125)

摘  要:以2-氯-4-氨基吡啶(1)为原料,经硝化反应合成出一种新的偶氮桥吡啶衍生物(E)-1,2-双(2-氯-3-硝基吡啶基-4-基)二氮烯(3)和2-氯-4-氨基-3,5-二硝基吡啶(2),随后经胺化反应分别得到(E)-1,2-双(2-氨基-3-硝基吡啶基-4-基)二氮烯(5)和2,4-二氨基-3,5-二硝基吡啶(4),总的得率分别为69%和18%。室温下,用氯仿作溶剂得到化合物3的红色晶体用于X-射线衍射分析。用Kamlet-Jacobs经验方程计算了化合物4和5的爆轰性能。结果表明,化合物3为单斜晶系,空间群P21/N,晶胞参数为:a=9.965(2),b=6.3190(13),c=10.737(2),β=93.75(3)°,V=674.6(2)~3,D_c=1.689 g·cm-3,C_(10)H_4Cl_2N_6O_4,M_r=171.55,F(000)=344,μ(Mo Kα)=0.510 mm^(-1),Z=4。化合物4的爆轰性能与2,4,6-三硝基甲苯(TNT)相当,而化合物5的爆轰性能不佳。A new azo-bridged pyridine derivative (E) -1,2-bis (2-chloro-3-nitropyrJdin-4-yl) diazene (3) and 2-chloro-4-amine-3,5-dinitropyridine (2) were synthesized through a direct nitration reaction using 2-chloro-4-aminopyridine(1 ) as a primary material, followed by a simple am ination reaction to give (E) -1,2-bis ( 2-amino-3-nitro-pyridin-4-yl ) diazene ( 5 ) and 2,4-diamino-3,5-dinitropyridine ( 4 ), with a total yield of 69 % and 18%, respectively. Red colored crystals of compound 3 growing from CHCI3 solvent at room temperature were used for X-ray diffraction analysis. The detonation performances of compounds 4 and 5 were calculated by Kamlet-Jacobs empirical equations. The results show that the crystal of com- pound 3 is monoclinic, space group P21/N with crystal parameters of a=9.965(2) A, b=6.3190(13)A, c=10.737(2) A,β= 93.75(3)°, V= 674.6(2) A, Dc=1.689 g cm-3, CwH4CI2N604, Mr=171.55, F(000)= 344, p,(Mo Ka)=0.510 mm-1 , and Z=4. The detonation performance of compound 4 is similar to 2, 4, 6-trinitrotoluene (TNT), whereas the detonation performance of compound 5 is poor.

关 键 词:合成 晶体结构 吡啶衍生物 偶氮化合物 爆轰性能 

分 类 号:TQ560.1[化学工程—炸药化工]

 

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