1-二叠氮甲基亚氨基-5-叠氮四唑的合成与理论研究

Synthesis and Theoretical Study of 1-Diazidecarboni-midoyl-5-azidotetrazole

以三氨基胍盐酸盐为原料,经重氮化取代反应和环化反应合成了1-二叠氮甲基亚氨基-5-叠氮四唑(DACAT)。用IR、13C NMR和14N NMR鉴定了它的结构。考察了三氨基胍盐酸盐/亚硝酸钠摩尔比、反应温度、反应时间、体系的pH对反应收率的影响。用密度泛函理论,在B3LYP/6-31G(d,p)基组水平下优化了DACAT的几何结构。用Monte-Carlo法、完全基组法(CBS-4M)和Kamlet-Jacobs公式分别计算了DACAT的理论密度()、气相生成焓(ΔθfHθg,m)、固相生成焓(ΔfH s,m)、爆速(D)和爆压(p)。结果表明,最佳反ρ应条件为:n(三氨基胍盐酸盐)∶n(亚硝酸钠)=1∶2,重氮化取代反应温度为0℃,环化反应温度为20℃,pH值为8.0,重氮化反应和环化反应时间各为30min。两步反应的总收率为12.6%。所得DACAT的、ΔfHθg,m、ΔfHθs,m、D和p值分别为1.7628g·cm-3、ρ1590.42kJ·mol-1、1435.44kJ·mol-1、8725m·s-1和34.52GPa。

1-Diazidecarbonimidoyl-5-azidotetrazole（DACAT）was prepared via diazotized substitution reaction and cyclization reaction using triaminoguanidinium as raw material.Its structure was confirmed by IR,13 C NMR and 14 N NMR.The influence of triaminoguanidinium/sodium nitrite molar ratio,reaction temperature,reaction time and pH of system on the yield of reaction was examined.The geometry of DACAT were optimized at the B3LYP/6-31G（d,p）basis set level using a density functional theory（DFT）Theoretical density（ρ）,enthalpy of formation of gas phaseΔfHθg,m,enthalpy of formation of solid phaseΔfHθs,m,detonation velocity（D）and detonation pressure（p）for DACAT were calculated by Monte-Carlo method,complete base set method（CBS-4 M）and Kamlet-Jacobs formula,respectively.Results show that the optimized process conditions were determined as：n（triaminoguanidinium）∶n（sodium nitrite）=1∶2,diazotized substitution reaction temperature 0 ℃,cyclization reaction temperature 20 ℃,pH=8.0,diazotization reaction time 30 min and cyclization reaction time 30 min.The total yield of the two steps reactions was 12.6%.The obtained values ofρ,ΔfHθg,m,ΔfHθs,m,Dand p are 1.7628 g·cm^-3,1590.42 kJ·mo^l-1,1435.44 k1J·mol^-1,8725 m·s- and 34.52 GPa,respectively.