3-氟偕二硝甲基-1,2,4-三唑的合成及性能

以3-氰基~(-1),2,4-三唑为原料,经肟化、重氮化-氯化、硝解、还原、氟化等反应合成了一种含氟偕二硝甲基官能团的新型含能化合物——3-氟偕二硝甲基~(-1),2,4-三唑(FDNMT),利用红外光谱、核磁(~1H NMR、~(13)C NMR)、元素分析和质谱等方法表征了化合物的结构;优化了肟化反应的合成条件:3-氰基~(-1),2,4-三唑和盐酸羟胺摩尔比为1∶1.15,p H值为8,反应时间为2 h,反应温度为60℃,收率为49.0%;获得了FDNMT的单晶并进行了晶体结构解析,该化合物晶体为正交晶系,空间群为Pbcn,晶体学参数为:a=7.4821(11),b=9.8106(15),c=38.683(6),V=2839.5(7)~3,Z=16,μ=0.178 mm~(-1),F(000)=1536;采用Gaussian 09程序中的CBS-4M方法计算了该化合物的生成热,基于密度和计算的生成热,利用Kamlet-Jacobs爆轰方程预估该化合物的爆轰性能:密度1.81 g·cm~(-3),生成热-8.7 k J·mol~(-1),爆速8365.0 m·s~(-1),爆压31.1 GPa,爆热为5614.4 k J·kg~(-1)。

Synthesis and Properties of 3-Fluorodinitromethyl-1,2,4-triazole

3-Fluorodinitromethyl-1,2,4-triazole(FDNMT) was synthesized using 3-cyano-1,2,4-triazole as starting material by the reactions of oximation,diazotization-chlorination,nitration,reduction and fluorination.The structures of all compounds were confirmed by IR,1H NMR,13C NMR,elemental analysis and MS.The synthetic conditions of oximation reaction were optimized,the suitable conditions were as follows: molar ratio of 3-cyano-1,2,4-triazole and hydroxylamine hydrochloride was 1:1.15,pH value was 8-9,reaction time was 2 h,reaction temperature was at 60 ℃ with a yield of 49.0%.The single crystal of FDNMT was obtained in the acetonitrile system,and the crystal of FDNMT belongs to orthorhombic system,space group Pbcn,cell parameters: a=7.4821(11) (A),b=9.8106(15) (A),c=38.683(6) (A),V=2839.5(7) (A)3,Z=16,μ=0.178 mm-1,F(000)=1536.Based on the calculated(CBS-4M) heat of formation(-8.7 kJ·mol-1) and the density (1.81 g·cm-3),impressive values for the detonation parameters such as detonation velocity(8365.0 m·s-1),detonation pressure (31.1 GPa) and detonation energy(5614.4 kJ·kg-1) were computed using Kamlet-Jacobs equations.