3-氟偕二硝甲基-1,2,4-三唑的合成及性能

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

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)。

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 com- pounds were confirmed by IR,1H NMR, 13C NMR, elemental analysis and MS. The synthetic conditions ofoximation reac- tion were optimized, the suitable conditions were as follows： molar ratio of 3-cyano-1,2,4-triazole and hydroxylamine hydro- chloride 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） A3,Z=16,μ=0.178 mm-1, F（000）=1536. Based on thecalculated（CBS-4M） heat of formation（-8.7 kJ· mol-1） and the density （1 .81 g. cm-3）, impres-sive values for the detonation parameters such as detonation velocity（8365.0 m · s-1 ）, detonation pressure （31.1 GPa） and deto-nation energy（5614.4 kJ ·kg-1 ） were computed using Kamlet-Jacobs equations.