3，6-二硝基吡唑［4，3-c］并吡唑（DNPP）百克量合成及DNPP·H2 O晶体结构

摘要

The synthesis of 3,6-dinitropyrazolo[4,3-c]pyrazole(DNPP)was optimized at 100 g level with total yield increase from 9.3% to 17.9%. The structures of intermediates and DNPP were confirmed by IR,1H NMR,13C NMR,elemental analysis and MS. The mechanism and safety of cyclization and reduction one pot method were discussed. Freezing crystallization technics, instead of extractive technics,which could avoid organic reagant and shorten operation process,was used to post-process 4-diazoni-um-3,5-dimethylpyrazole,increasing the yield from 77. 0% to 86. 1%. The single crystal of DNPP·H2 O was obtained in the water system. The crystal of DNPP·H2 O belongs to monoclinic system,space group P2(1)/c,cell parameters:a=0. 3480(4)nm,b=1.4134(16)nm,c=0.9027(11)nm,α=90°,β=94.327(16)°,γ=90°,V=0.4427(9)nm3,Z=4,Dc =1.756 g·cm -3,μ=0. 164 mm -1 ,F(000)=240,R1 =0. 0503,wR2 =0. 1391.%研究了3，6-二硝基吡唑[4，3-c]并吡唑（ DNPP）的百克量级合成工艺，总收率由9．3％提高到17．9％。采用 IR、1 H NMR、13 C NMR、元素分析、质谱等方法对中间体及 DNPP的结构进行了表征。探讨了环化、还原“一锅法”反应机理及反应安全性；改进了重氮盐中间体的后处理方法：采用冷冻结晶法代替萃取法，操作简单，避免大量使用有机溶剂，收率从77．0％提高到86．1％；培养了 DNPP·H2O 单晶，晶体结构分析表明，DNPP·H2O 为单斜晶系，空间群为 P2（1）/c，晶体学参数为：a ＝0．3480（4）nm，b ＝1．4134（16）nm，c＝0．9027（11）nm，α＝90°，β＝94．327（16）°，γ＝90°，V ＝0．4427（9）nm3，Z ＝4，Dc ＝1．756g·cm -3，μ＝0．164 mm -1，F（000）＝240，R1＝0．0503，wR2＝0．1391。