苦味酸氨化产物的合成及其性能研究

兵工学报 ›› 2010, Vol. 31 ›› Issue (10): 1341-1345.

苦味酸氨化产物的合成及其性能研究

张学梅¹, 董海山², 周智明¹, 李海华¹

(1.北京理工大学化工与环境学院，北京 100081；2.中国工程物理研究院化工材料研究所，四川绵阳 621900）

收稿日期:2009-02-26 修回日期:2009-02-26 上线日期:2014-05-04
通讯作者: 张学梅 E-mail:zh_xuemei@126.com
作者简介:张学梅(1979—)，女，博士研究生
基金资助:
中国工程物理研究院重大科学技术发展基金项目（2007A03002）

Synthesis and Properties of 3-Amino-246-Trinitrophenol and 35-Diamino-246-Trinitrophenol

ZHANG Xue-mei¹, DONG Hai-shan², ZHOU Zhi-ming¹, LI Hai-hua¹

（1.School of Chemical Engineering and the Environment, Beijing Institute of Technology, Beijing 100081, China;2.Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang 621900, Sichuan, China)

Received:2009-02-26 Revised:2009-02-26 Online:2014-05-04
Contact: ZHANG Xue-mei E-mail:zh_xuemei@126.com

摘要/Abstract

摘要： 苦味酸经4-氨基-1,2,4-三氮唑替代亲核取代(VNS)氨化，在不同条件下，分别合成了一氨基苦味酸和二氨基苦味酸，两者的产率分别为81%和78%. 产物的结构通过傅里叶红外光谱、核磁共振氢谱、元素分析进行了表征。利用DTA-TG研究了两种化合物的热分解过程，并对其撞击感度进行了测试。研究表明：一氨基苦味酸和二氨基苦味酸的热分解峰值温度分别为243.7 ℃和286.9 ℃；一氨基苦味酸和二氨基苦味酸的特性落高h₅₀值分别为42.8 cm和56.1 cm；氨基的引入使热分解峰值温度升高、撞击感度降低。

关键词: 有机化学, 合成, 替代亲核取代, 氨化反应, 3-氨基-2, 4, 6-三硝基苯酚, 3, 5-二氨基-2, 4, 6-三硝基苯酚, 特性落高

Abstract: 3-amino-2,4-trinitrophenol and 3,5-diamino-2,4,6-trinitrophenol were obtained by vicarious nucleophilic substitution (VNS) amination of picric acid under the different conditions in the yield of 81% and 78% respectively, which used 4-amino-1,2,4-triazole as the aminating reagent. The structures of the products were identified by IR, ₁HNMR, and elemental analysis. The thermal decomposition processes were studied by DTA-TG, and their shock sensitivities were tested. The results show that the peak temperatures of thermal decomposition of 3-amino-picric acid and 3,5-diamino-picric acid are 243.7 ℃ and 286.9 ℃, respectively, and their characteristic fall heights are 42.8 cm and 56.1 cm, respectively. The peak temperature of thermal decomposition increases and the shock sensitivity is lowered when amino group is introduced into the molecular of picric acid.

Key words: organic chemistry, synthesis, vicarious nucleophilic substitution, aminating reaction, 3-amino-2,4,6-trinitrophenol, 3,5-diamino-2,4,6-trinitrophenol, characteristic fall height

中图分类号:

TJ55
O62

张学梅, 董海山, 周智明, 李海华. 苦味酸氨化产物的合成及其性能研究[J]. 兵工学报, 2010, 31(10): 1341-1345.

ZHANG Xue-mei, DONG Hai-shan, ZHOU Zhi-ming, LI Hai-hua. Synthesis and Properties of 3-Amino-246-Trinitrophenol and 35-Diamino-246-Trinitrophenol[J]. Acta Armamentarii, 2010, 31(10): 1341-1345.

参考文献

［1］ Pagoria P F, Lee G S,Mitchell A R, et al. A review of energetic materials synthesis［J］. Thermochimica Acta, 2002, 384(1-2):187-204.
［2］ van Duin C F, van Lennep B C Robters. Modern brisant nitro explosives［J］. Recueildes Travaux Chimiques des Pays-Bas et de la Belgique, 1920, 39:145-177.
［3］ Koppes William M, Lawrence G William, Sitzmann Michael E, et al. Reaction of 1,3,5-trifluorotrinitrobenzene with nucleophiles［J］. Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry, 1981,(7):1815-1820.
［4］ Mitchell A R, Pagoria P F, Schmidt R D. Amination of electrophilic aromatic compounds by vicarious nucleophilic substitution for preparation of insensitive high explosives: US 6069277［P］.2000-05-30.
［5］ Mitchell A R, Coburn M D, Lee G S, et al. Preparation of trinitrophloroglucinol and triaminotrinitrobenzene (TATB) from picric acid via diaminopicric acid: US 2005070743［P］. 2005-03-31.
［6］张熙和，丁来欣，朱广军. 炸药实验室制备方法［M］.北京：兵器工业出版社，1997.
ZHANG Xi-he, DING Lai-xin, ZHU Guang-jun. Preparation of explosives in laboratory［M］. Beijing: The Publishing House of Ordnance Industry, 1997. (in Chinese)
［7］ Schmidt R D, Mitchell A R, Lee G S, et al. New synthesis of TATB: scale-up and product characterization［C］∥31st International Annual Conference of ICT. Karlsruhe, Germany: Fraunhofer Institute for Chemical Technology, 2000.
［8］ Mitchell A R, Pagoria P F, Schmidt R D, et al. 1,1,1–trimethylhydrazinium iodide: a novel, highly ractive reagent for aromatic amination via vicarious nucleophilic substitution of hydrogen［J］. Journal of Organic Chemistry, 1996, 61: 2934-2935.
［9］ Katritzky A R, Laurenzo K S. Alkylaminonitrobenzenes by vicarious nucleophilic amination with 4-(alkylamino)-1,2,4-triazoles［J］. Journal of Organic Chemistry, 1988, 53: 3978-3982.
［10］ Makosza M, Kwast A. Vicarious nucleophilic substitution of hydrogen. mechanism and orientation［J］. Journal of Physical Organic Chemistry, 1998, 11 (5): 341-349.
［11］ Makosza M, Winiarski J. Vicarious nucleophilic substitution of hydrogen［J］. Accounts of Chemical Research, 1987, 20 (8): 282-289.
［12］ Battacharjee S K, Ammon H L. Crystallographic studies of high-density organic crystals, 3,5-diamino-2,4, 6-trinitrophenol［J］. Acta Crystallographica, 1981,B37:2082-2085.

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