黑索今的新型合成路线

以乙腈/三聚甲醛为原料合成1,3,5-三乙酰基-均-三嗪（TRAT），再硝解制备黑索今(RDX)。 聚合反应中，当n(CH3CN)∶n(C3H6O3)=2∶1，n(H2SO4)∶n(C3H6O3)=1∶7.5，反应温度75 ℃，反应3 h时，TRAT的产率为95.2%。 硝解反应中，当n(N2O5)∶n(TRAT)=7∶1，n(HNO3)∶n(N2O5)=6∶1，反应温度45 ℃，反应1 h时，RDX的产率为87.2%。 RDX的全程产率为83.0%。 该工艺简单、易于控制，废酸污染小，有望应用于工业化生产。

A New Synthetic Approach toward Hexogen

Acetonitrile-trioxymethylene was chosen to replace acetamide-paraformaldehyde for the synthesis of the intermediate hexahydro-1,3,5-triacetyl-s-triazine(TRAT), which was then nitrated by dinitrogen pentroxide to form hexogen(RDX). Under optimized synthetic conditions, a 95.2% yield of TRAT could be attained when the molar ratio of 1,3,5-trioxane to acetonitrile was 1∶2, the molar ratio of H2SO4 to 1,3,5-trioxane was 1∶7.5, the reaction temperature was 75 ℃, the reaction time was 3 h, H2SO4 was chosen as catalyst and acetonitrile was used as both reactant and solvent. In the subsequent nitration process, carried at 45 ℃ for 1 h, a 87.2% yield of RDX could be achieved when the molar ratios of TRAT to N2O5 and N2O5 to HNO3 were 1∶7 and 1∶6, respectively. The overall yield of RDX was 83.0% for this new approach. This established method might be scaled up for industrial productions of RDX due to its simpleness in terms of post treatment and environmental benign.