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有机化学
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有机化学 ›› 2011, Vol. 31 ›› Issue (11): 1893-1900. 上一篇    下一篇

研究论文

2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯的合成、晶体结构及性能研究

毕福强1，姚君亮2，王伯周*1，樊学忠1，葛忠学1，许诚1，刘庆1，康冰1   

  1. (1西安近代化学研究所 西安 710065)
    (2同济大学化学系 上海 200092)
  • 收稿日期:2011-04-11 修回日期:2011-06-19 发布日期:2011-07-14
  • 通讯作者: 王伯周 E-mail:wbz600@163.com

Synthesis, Crystal structure and Properties of 2,3-Bis(hydroxymethyl)- 2,3-dinitro-1,4-butanediol Tetranitrate

Bi Fuqiang1 Yao Junliang2 Wang Bozhou*1 Fan Xuezhong1 Ge Zhongxue1 Xu Cheng1 Liu Qing1 Kang Bing1   

  1. (1 Xian Modern Chemistry Research Institute, Xian 710065)
    (2 Department of Chemistry, Tongji University, Shanghai 200092)
  • Received:2011-04-11 Revised:2011-06-19 Published:2011-07-14

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被引次数

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以硝基甲烷为起始原料, 经缩合、环化、氧化耦合、脱缩酮及硝化等5步反应合成了2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯(BHDBT), 总收率为36.1%, 并采用核磁共振谱、红外光谱以及元素分析等进行了结构表征. 用浓盐酸代替氯化氢气体, 改进了关键中间体2,3-二羟甲基-2,3-二硝基-1,4-丁二醇(BHDB)的合成方法, 并确定最佳反应条件为: n(浓盐酸)∶n(BDND)＝1.1∶1, 反应温度55 ℃, 时间4 h, 收率为94.8%. 首次发现了BHDB和BHDBT的亚甲基质子具有磁不等价性, 并从理论上分析其产生的原因. 培养了BHDBT单晶, 四元衍射晶体结构解析表明：BHDBT属于单斜晶系, 空间群P2(1)/n, 晶胞参数: a＝0.81944(11) nm, b＝2.3365(3) nm, c＝0.85838(11) nm, α＝90°, β＝113.501(2)°, γ＝90°, V＝1.5072(3) nm3, Z＝4, Dc＝1.852 g•cm－3, μ＝0.189 mm－1, F(000)＝856. BHDBT熔点为86.37 ℃, 分解峰温度为185.79 ℃ (DSC), 摩擦感度为100% (3.92 MPa, 90°), 特性落高H50为10.0 cm (5 kg).

关键词: 2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯, 合成, 晶体结构, 性能

Starting from nitromethane, 2,3-bis(hydroxymethyl)-2,3-dinitro-1,4-butanediol tetranitrate (BHDBT) was synthesized by the condensation, cyclization, oxidative dimerization, deketalization and nitration in total yield of 36.1%. The structures of BHDBT and its intermediates were characterized by means of 1H NMR, 13C NMR, FT-IR and elemental analysis. The synthetic process for 2,3-bis(hydroxymethyl)-2,3-dinitro- 1,4-butanediol (BHDB) was improved by using concentrated hydrochloric acid instead of HCl gas. It was found that the optimum conditions for the synthesis of BHDB were as follows: the molar ratio of concentrated hydrochloric acid to BDND is 1.1∶1, the reaction temperature is 55 ℃, the reaction time is 4 h, and the yield is up to 94.8%. It was experimentally first found that the protons in BHDB and BHDBT are magnetic nonequivalent. The crystal structure of BHDBT was determined by X-ray single crystal diffractometer. It was shown that the crystal is monoclinic and P2(1)/n space group with unit cell dimensions of a＝0.81944(11) nm, b＝2.3365(3) nm, c＝0.85838(11) nm, α＝90°, β＝113.501(2)°, γ＝90°, V＝1.5072(3) nm3, Z＝4, Dc＝1.852 g•cm－3, μ＝0.189 mm－1, F(000)＝856. Furthermore, the thermal decomposition performance of BHDBT was tested by DSC and TG, and its sensitive properties such as friction sensitivity and impact sensitivity were also investigated. The results showed that the melting point and decomposition peak of BHDBT, which can be used for castable explosive componets and high energy plasticizer for the propellants, are 86.37 and 185.79 ℃, respectively. The friction sensitivity and impact sensitivity (H50) of BHDBT are 100% (3.92 MPa, 90°) and 10.0 cm (5 kg), respectively.

Key words: 2,3-bis(hydroxymethyl)-2,3-dinitro-1,4-butanediol tetranitrate, synthesis, crystal structure, property