Chin. J. Org. Chem. ›› 2012, Vol. ›› Issue (03): 580-588.DOI: 10.6023/cjoc1108052 Previous Articles     Next Articles



李亚南a, 唐婷b, 廉鹏a, 罗义芬a, 杨威a, 王友兵a, 李辉a, 张志忠a, 王伯周a   

  1. a 西安近代化学研究所 西安 710065;
    b 西安瑞联近代电子材料有限责任公司 西安 710077
  • 收稿日期:2011-08-05 修回日期:2011-10-22 发布日期:2012-03-24
  • 通讯作者: 王伯周
  • 基金资助:

    国防基础科研创新计划(Nos. 2371000415, B09201100051)资助项目.

Synthesis, Thermal Performance and Quantum Chemistry Study on 1,4-Diamino-3,6-dinitropyrazolo[4,3-c]pyrazole

Li Yanana, Tang Tingb, Lian Penga, Luo Yifena, Yang Weia, Wang Youbinga, Li Huia, Zhang Zhizhonga, Wang Bozhoua   

  1. a Xi'an Modern Chemistry Research Instritute, Xi'an 710065;
    b Xi'an Ruilian Modern Electronic Chemicals Co., Ltd, Xi'an 710077
  • Received:2011-08-05 Revised:2011-10-22 Published:2012-03-24
  • Supported by:

    Project supported by the National Defense Fundamental Scientific Research (Nos. 2371000415, B09201100051).

Using 3,5-dimethyl-4-aminopyrazole as primary substance, 1,4-diamino-3,6-dinitropyrazolo[4,3-c]pyrazole (LLM-119) was synthesized by six steps of diazotisation, intramolecular cyclic condensation, nitration, oxidation, decarboxylation nitration and N-amination. The structures of intermediates and target compound were confirmed by means of IR, 1H NMR, 13C NMR and elemental analysis. The post-treatment method of 4-diazonium-3,5-dimethylpyrazole salt was improved, the yield was increased from 77.0% to 86.1% because of using the freezing crystallization method instead of extractive method, which could avoid the use of organic reagent and shorten operation process. The mechanism of N-amination reaction was discussed in order to analyze the reason of low-yield theoretically. Using differential scanning calorimetry (DSC) and thermogravimetric (TG) as thermal analysis methods, the thermal performance of LLM-119 was studied with thermal decomposition peak temperature of 232.05 ℃ and the results showed that LLM-119 had preferable thermal stability. The structure of LLM-119 was also estimated by a B3LYP method on 6-31G(d,p) basis set in order that its steady geometric configuration and bond order were obtained. The vibrational frequencies, IR spectra and thermodynamics properties in different temperatures of the system were obtained on the basis of vibrational analysis, the relations of the effects of temperatures on thermodynamics properties were also obtained. The density of LLM-119 calculated through the Monte-Carlo method was 1.85 g/cm3, which approached with the experiment value, and the predicted detonation velocity was 8733.94 m/s by the formula of Kamlet.

Key words: 1,4-diamino-3,6-dinitropyrazolo[4,3-c]pyrazole (LLM-119), synthesis, thermal performance, theoretical calculation, thermodynamics property