3-硝基胍-6-(3,5-二甲基吡唑)-1,2,4,5-四嗪的晶体结构及热行为

doi:10.11944/j.issn.1000-0518.2016.01.150211

摘要/Abstract

摘要：

合成了3-硝基胍-6-(3,5-二甲基吡唑)-1,2,4,5-四嗪(NDT),在二甲基甲酰胺(DMF)中培养出NDT的单晶(NDT·DMF),该晶体属于三斜晶系,P-1空间群,晶胞参数为a=0.7070(4) nm,b=0.8468(6) nm,c=1.4123(9) nm,α=73.281(8)°,β=80.423(11)°,γ=81.740(9)°,Z=2。利用DSC和TG-DTG研究了NDT的热分解行为,其放热过程的表观活化能和指前因子分别为288.245 kJ/mol和10^29.04 s^-1。对NDT的热安全性进行了研究,获得NDT的自加速分解温度T_SADT为212.19 ℃,热点火温度T_be为213.52 ℃,热爆炸临界温度T_bp为214.95 ℃,绝热至爆时间范围在5.43~6.26 s。

关键词: 硝基胍-(二甲基吡唑)-四嗪, 晶体结构, 热行为, 绝热至爆时间

Abstract:

3-Nitroguanyl-6-(3,5-dimethylpyrazol-1yl)-1,2,4,5-tetrazine(NDT) was synthesized and its crystal structure was determined by X-ray diffraction analysis. Crystals of NDT·DMF have the following parameters:triclinic, space group P-1, a=0.7070(4) nm, b=0.8468(6) nm, c=1.4123(9) nm, α=73.281(8)°, β=80.423(11)°, γ=81.740(9)°, Z=2. Thermal decomposition behavior of NDT was studied by DSC and TG-DTG analysis. The apparent activation energy and pre-exponential constant of the exothermic decomposition reaction were obtained as 288.25 kJ/mol and 10^29.04 s^-1, respectively. The self-accelerating decomposition temperature(T_SADT), the thermal ignition temperature(T_be) and the critical temperature of thermal explosion(T_bp) are 212.19 ℃, 213.52 ℃and 214.95 ℃, respectively. The adiabatic time-to-explosion was also estimated to be 5.43~6.26 s.

Key words: nitroguanyl-(dimethylpyrazol-1yl)-tetrazine, crystal structure, thermal behavior, adiabatic time-to-explosion

李帅磊, 胡拥鹏, 胡荣祖, 马海霞. 3-硝基胍-6-(3,5-二甲基吡唑)-1,2,4,5-四嗪的晶体结构及热行为[J]. 应用化学, 2016, 33(1): 39-46.

LI Shuailei, HU Yongpeng, HU Rongzu, MA Haixia. Crystal Structure and Thermal Behavior of 3-Nitroguanyl-6-(3,5-dimethylpyrazol-1yl)-1,2,4,5-tetrazine[J]. Chinese Journal of Applied Chemistry, 2016, 33(1): 39-46.

参考文献

[1]	Chavez D E,Hiskey M A,Naud D L. Tetrazine Exposives[J]. Propell Explos Pyrot,2004,29(4):209-215.
[2]	Hiskey M A,Chavez D E. Insensitive High-Nitrogen Compounds:DE,2001776133[P],2001.
[3]	DONG Haishan. The Development and Countermeasure of High Energy Density Materials[J]. Chinese J Energy Mater,2004,12:1-11(in Chinese). 董海山. 高能量密度材料的发展及对策[J]. 含能材料,2004,12:1-11.
[4]	JU Ronghui,FAN Xuezhong,WEI Hongjian,et al.Research Progress in Application of Tetrazine-based Energetic Compounds[J]. Chem Propell Polym Mater,2013,11(4):23-28(in Chinese). 巨荣辉,樊学忠,蔚红建,等. 四嗪含能化合物的应用研究进展[J]. 化学推进剂与高分子材料,2013,11(4):23-28.
[5]	Ali A N,Son S F,Hiskey M A,et al.Novel High Nitrogen Propellant Use in Solid Fuel Micropropulsion[J]. J Propul Power,2004,20(1):120-126.
[6]	FENG Jinling,ZHANG Jianguo,WANG Kun,et al.Crystal Structure and Theoretical Studies of 3,6-Dihydrazino-1,2,4,5-Tetrazine[J]. Chem J Chinese Univ,2011,32(7):1519-1525(in Chinese). 冯金玲,张建国,王昆,等. 3,6-二肼基-1,2,4,5-四嗪的晶体结构及理论研究[J]. 高等学校化学报,2011,32(7):1519-1525.
[7]	Chavez D E,Hiskey M A,Gilardi R D. 3,3'-Azobis(6-Amino-1,2,4,5-Tetrazine):A Novel High-Nitrogen Energetic Material[J]. Angew Chem,2000,112(10):1861-1863.
[8]	Saikia A,Sivabalan R,Polke B G,et al.Synthesis and Characterization of 3,6-Bis(1H-1,2,3,4-tetrazol-5-ylamino) -1,2,4,5-tetrazine(BTATz):Novel High-Nitrogen Content Insensitive High Energy Material[J]. J Hazard Mater,2009,170(1):306-313.
[9]	Son S F,Berghout H L,Bolme C A,et al.Burn Rate Measurements of HMX, TATB, DHT, DAAF, and BTATz[J]. P Combust Inst,2000,28(1):919-924.
[10]	Chavez D E,Parrish D A. New Heterocycles from Tetrazines and Oxadiazoles[J]. J Heterocycl Chem,2009,46(1):88-90.
[11]	Saracoglu N. Recent Advances and Applications in 1,2,4,5-Tetrazine Chemistry[J]. Tetrahedron,2007,63(20):4199-4236.
[12]	Chavez D E,Hanson S K,Veauthier J M,et al.Electroactive Explosives: Nitrate Ester-Functionalized 1,2,4,5-Tetrazines[J]. Angew Chem Int Edit,2013,52(27):6876-6879.
[13]	CHEN Hui,ZHENG Caixia,YANG Yufeng,et al.Synthesis and Anti-cancer Activities of Novel[1,2,4]Triazolo[4,3-b] [1,2,4,5]Tetrazine Derivatives[J]. Chinese J Synth Chem,2012,20(4):475-478(in Chinese). 陈辉,郑彩霞,杨玉峰,等. 新型[1,2,4]三唑[4,3-b]均四嗪类化合物的合成及其抗癌活性[J]. 合成化学,2012,20(4):475-478.
[14]	YANG Zhenzhen,XU Feng,CHEN Hongyun,et al.Synthesis and Antitumor Activities of 6-(2-(1,2,4,5-tetrazin-3-yl) hydrazinyl) -1,3,5-Triazine Derivatives[J]. Appl Chem Ind,2014,43(2):241-244(in Chinese). 杨珍珍,徐峰,陈红云,等. 6-[2-(1,2,4,5-四嗪-3-基)肼基]-1,3,5-三嗪类化合物的合成和抗肿瘤活性研究[J]. 应用化工,2014,43(2):241-244.
[15]	Zhao D,Lyu M F,Cai C. Study on the Azido-Tetrazolo Tautomerizations of 3,6-Bis(azido)-1,2,4,5-tetrazine[J]. Propell Explos Pyrot,2015,40(5):627-631.
[16]	Coburn M D,Buntain G A,Harris B W,et al.An Improved Synthesis of 3,6-Diamino-1,2,4,5-Tetrazine.Ⅱ.From Triaminoguanidine and 2,4-Pentanedione[J]. J Heterocycl Chem,1991,28(8):2049-2050.
[17]	MAI Tao. Synthesis, Characterization, Structural Analysis, Theoretical Calculations, Thermal Behavior and Thermodynamic Study of 1,2,4,5-Tetrazine Salts[D]. Xi'an:Northwest University,2012(in Chinese). 买涛. 1,2,4,5-四嗪盐的合成、表征、结构解析、理论计算、热行为以及热力学研究[D]. 西安:西北大学,2012.
[18]	Chavez D E,Hiskey M A,Gilardi R D. Novel High-Nitrogen Materials Based on Nitroguanyl-Substituted Tetrazines[J]. Org Lett,2004,6(17):2889-2891.
[19]	Sheldrick G M. SHELXS 97, Program for Crystal Structure Solution[CP],University of Göttingen,Göttingen, Germany,1997.
[20]	Sheldrick G M. SHELXL 97, Program for Crystal Structure Refinement[CP],University of Göttingen,Göttingen, Germany,1997.
[21]	HU Yongpeng,ZHAO Xufang,ZHAO Ningning,et al.Non-isothermal Thermal Decomposition Kinetics and Thermal Safety of DNGTz[J]. Chinese J Energ Mater,2014,22(6):767-773(in Chinese). 胡拥鹏,赵旭芳,赵宁宁,等. DNGTz的非等温热分解动力学及热安全性[J]. 含能材料,2014,22(6):767-773.
[22]	Kissinger H E. Reaction Kinetics in Differential Thermal Analysis[J]. Anal Chem,1957,29(11):1702-1706.
[23]	Ozawa T. A New Method of Analyzing Thermogravimetric Data[J]. Bull Chem Soc Jpn,1965,38(11):1881-1886.
[24]	MA Haixia,YAN Bao,LI Zhaona,et al.Preparation, Non-Isothermal Decomposition Kinetics, Heat Capacity and Adiabatic Time-to-Explosion of NTO DNAZ[J]. J Hazard Mater,2009,169(1/2/3):1068-1073.
[25]	Zhang T L,Hu R Z,Xie Y,et al.The Estimation of Critical Temperature of Thermal Explosion for Energetic Materials Using Non-Isothermal DSC[J]. Thermochim Acta,1994,244(2):171-176.
[26]	Zhang H,Xu K Z,Gao S,et al.Characterization and Thermal Properties of 2-(Dinitromethylene)-1,3-Diazacyclopentane Guanidine Salt[J]. Indian J Chem,2013,52(4):473-479.
[27]	XU Kangzhen, ZUO Xian'gang, SONG Jirong, et al. Preparation, Crystal Structure and Thermal Behavior of K(FOX-7) H2O[J]. Chem J Chinese Univ,2010,31(4):638-643(in Chinese). 徐抗震,左现刚,宋纪蓉,等. K(FOX-7)·H2O的合成、晶体结构和热行为[J]. 高等学校化学报,2010,31(4):638-643.