1-methyl-2,4-dinitroimidazole | 5213-50-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 1-methyl-2,4-dinitroimidazole
• 英文别名: 1-Methyl-2,4-dinitro-1H-imidazole
• CAS: 5213-50-3
• 化学式: C₄H₄N₄O₄
• mdl: MFCD00516994
• 分子量: 172.1
• InChiKey: GHLBJBRVTJECDP-UHFFFAOYSA-N

物化性质

• 熔点：
  144-146 °C
• 沸点：
  427.4±37.0 °C(Predicted)
• 密度：
  1.83±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  110
• 氢给体数：
  0
• 氢受体数：
  5

安全信息

• 海关编码：
  2933290090

反应信息

• 作为反应物：
  描述：

  1-methyl-2,4-dinitroimidazole 在 硫酸 、 三氧化硫 、 硝酸 作用下， 反应 2.5h， 以62.9%的产率得到1-甲基咪唑烷-2,4,5-三酮
  参考文献：
  名称：

  由1-甲基咪唑衍生物制备1-甲基-2,4,5-三硝基咪唑及其硝化条件下的氧化

  摘要：

  在这项工作中，对1-甲基咪唑及其硝基衍生物与H 2 SO 4中98％HNO 3和15％SO 3的混合物的硝化反应进行了重新研究。1-甲基咪唑，1-甲基-4-硝基咪唑，1-甲基-5-硝基咪唑或1-甲基-4,5-二硝基咪唑得到1-甲基-4,5-二硝基咪唑和1-甲基-2的混合物， HNO 3与H 2 SO 4体积比下的4,5-三硝基咪唑在80°C的温度下以1：3的浓度进行2.5小时，1-甲基-2,4,5-三硝基咪唑的最高未分离产率为2.4％。在相同条件下，由1-甲基-2-硝基咪唑，1-甲基-2,4-二硝基咪唑或1-甲基-2,5-二硝基咪唑制备1-甲基-2,4,5-三硝基咪唑，并得到收率。分别是65％，76％和82％。但是，当HNO 3与H 2 SO 4的比例比例为1：5，在120°C下反应2.5小时，从1-甲基咪唑，1-甲基-4-硝基咪唑或1-甲基-5-硝基咪唑中仅获得1-甲基-4,5-二硝基咪

  DOI：

  10.1007/s10593-020-02622-7
• 作为产物：
  描述：

  2,4-二硝基咪唑 、 硫酸二甲酯 在 碳酸氢钠 作用下， 以86%的产率得到1-methyl-2,4-dinitroimidazole
  参考文献：
  名称：

  使用铁粉选择性还原2,4-二硝基和4,5-二硝基咪唑衍生物

  摘要：

  在室温下，使用冰醋酸中的铁粉将一系列N取代的2,4-二硝基咪唑，4,5-二硝基咪唑和2-甲基-4,5-二硝基咪唑选择性还原为相应的氨基硝基咪唑衍生物。2,4-二硝基咪唑仅被还原为2-氨基-4-硝基衍生物，但是4,5-二硝基咪唑根据结构的不同给出了4-氨基-5-硝基或5-氨基-4-硝基衍生物。的ñ -取代。J.杂环化​​学。（2010）。

  DOI：

  10.1002/jhet.418

文献信息

• Study of the methylation reaction of 2,4-dinitroimidazole and potassium 2,4,5-trinitroimidazol-1-ide with dimethyl sulfate
  作者：Peng-Bao Lian、Yuan Yuan、Jian Chen、Li-Zhen Chen、Jian-Long Wang

  DOI：10.1007/s10593-020-02767-5

  日期：2020.8

  The methylation of 2,4-dinitroimidazole and potassium salt of 2,4,5-trinitroimidazole with dimethyl sulfate was reinvestigated. When the reaction system contained a weak base, the reaction products were 1-methyl-2,4-dinitroimidazole and 1-methyl-2,4,5-trinitroimidazole, respectively. However, in the absence of a base in the reaction system, the products contained oxidation byproducts 1-methylimidazolidine-2

  重新研究了2,4-二硝基咪唑和2,4,5-三硝基咪唑的钾盐与硫酸二甲酯的甲基化反应。当反应体系包含弱碱时，反应产物分别为1-甲基-2,4-二硝基咪唑和1-甲基-2,4,5-三硝基咪唑。然而，在反应体系中不存在碱的情况下，产物包含氧化副产物1-甲基咪唑烷-2,4,5-三酮，1,3-二甲基咪唑烷-2,4,5-三酮和回收的起始原料。所有产品均使用FT-IR，NMR和元素分析进行​​表征。通过单晶X射线衍射进一步确认了1-甲基咪唑烷-2,4,5-三酮和1,3-二甲基咪唑烷-2,4,5-三酮的结构。
• Strategies toward the design of energetic ionic liquids: nitro- and nitrile-substituted N,N′-dialkylimidazolium salts
  作者：Alan R. Katritzky、Hongfang Yang、Dazhi Zhang、Kostyantyn Kirichenko、Marcin Smiglak、John D. Holbrey、W. Matthew Reichert、Robin D. Rogers

  DOI：10.1039/b509260d

  日期：——

  Twelve novel 1,3-dialkylimidazolium salts containing strongly electron-withdrawing nitro- and cyano-functionalities directly appended to the cationic heterocyclic rings have been synthesized; the influences of the substituents on both formation and thermal properties of the resultant ionic liquids have been determined by DSC, TGA, and single crystal X-ray diffraction, showing that an electron-withdrawing nitro-substituent can be successfully appended and has a similar influence on the melting behaviour as that of corresponding methyl group substitution. Synthesis of di-, or trinitro-substituted 1,3-dialkylimidazolium cations was unsuccessful due to the resistance of dinitro-substituted imidazoles to undergo either N-alkylation or protonation, while 1-alkyl-4,5-dicyanoimidazoles were successfully alkylated to obtain 1,3-dialkyl-4,5-dicyanoimidazolium salts. Five crystal structures (one of each cation type) show that, in the solid state, the NO2-group has little significant effect, beyond the steric contribution, on the crystal packing.

  合成了12种新型1,3-二烷基咪唑鎓盐，其阳离子杂环上直接附加了强吸电子硝基和氰基功能团；通过DSC、TGA和单晶X射线衍射确定了取代基对所得离子液体形成和热性质的影响，结果表明吸电子硝基取代基可以成功附加，并且对熔融行为的影响与相应的甲基取代相似。由于二硝基取代的咪唑对N-烷基化或质子化的抵抗力，未能成功合成二硝基或三硝基取代的1,3-二烷基咪唑鎓阳离子，而1-烷基-4,5-二氰基咪唑成功进行了烷基化，得到了1,3-二烷基-4,5-二氰基咪唑鎓盐。五种晶体结构（每种阳离子类型各一种）显示，在固态下，NO2基团对晶体堆积的影响不大，仅限于空间贡献。
• Molten-State Nitration of Substituted Imidazoles: New Synthetic Approaches to the Novel Melt-Cast Energetic Material, 1-Methyl-2,4,5-trinitroimidazole
  作者：Raja Duddu、Reddy Damavarapu、Mao-Xi Zhang、Nathaniel Gelber

  DOI：10.1055/s-0030-1260148

  日期：2011.9

  Novel, one-step synthetic routes for the preparation of 1-methyl-2,4,5-trinitroimidazole (MTNI) are described. In addition, a new, molten-state nitration method for the synthesis of 1-methyl-2,4,5-trinitroimidazole is developed.

  描述了一种新颖的一步合成1-甲基-2,4,5-三硝基咪唑（MTNI）的方法。此外，还开发了一种新的熔融状态硝化法用于合成1-甲基-2,4,5-三硝基咪唑。
• Melt-cast explosive material
  申请人：The United States of America as represented by the Secretary of the Army

  公开号：US07304164B1

  公开（公告）日：2007-12-04

  1-Methyl-2,4,5-Trinitroimidazole is synthesized starting from 4-nitroimidazole using stepwise nitration method and further methylation using Dimethylsulphate. It is relatively insensitive to impact and its thermal stability is excellent. The calculated detonation properties indicate that its performance is about 30% better than TATB. It can be prepared easily, with reasonable yield, starting from commercially available Imidazole. Results from impact sensitivity, friction sensitivity, time-to-explosion temperature and vacuum stability tests indicate that it is less sensitive than both RDX and HMX. The good oxygen balance and measured heat of formation data of this material indicate that its propellant performance should be good.

  1-甲基-2,4,5-三硝基咪唑是从4-硝基咪唑开始使用逐步硝化方法合成的，并进一步使用二甲基硫酸酯进行甲基化。它对冲击相对不敏感，热稳定性优异。计算的爆轰性能表明，其性能比TATB好约30%。它可以从商业可获得的咪唑出发轻松制备，产率合理。冲击敏感性、摩擦敏感性、爆炸温度和真空稳定性测试结果表明，它比RDX和HMX都不敏感。该材料的氧平衡良好，测得的生成热数据表明其推进剂性能应该很好。
• Intermediates in the reduction of the antituberculosis drug PA-824, (6S)-2-nitro-6-{[4-(trifluoromethoxy)benzyl]oxy}-6,7-dihydro-5H-imidazo[2,1-b][1,3]oxazine, in aqueous solution
  作者：Robert F. Anderson、Sujata S. Shinde、Andrej Maroz、Maruta Boyd、Brian D. Palmer、William A. Denny

  DOI：10.1039/b801859f

  日期：——

  The reduction chemistry of the new anti-tuberculosis drug PA-824, together with a more water-soluble analogue, have been investigated using pulse and steady-state radiolysis in aqueous solution. Stepwise reduction of these nitroimidazo-dihydrooxazine compounds through electron transfer from the CO2˙− species revealed that, unlike related nitroimidazoles, 2-electron addition resulted in the reduction of the imidazole ring in preference to the nitro group. In mildly acidic solution a nitrodihydroimidazo intermediate was formed, which was reduced further to the amine product. In both alkaline and neutral solution, an intermediate produced on 2-electron reduction was resistant to further reduction and reverted to parent compound on extraction or mass spectrometric analysis of the solution. The unusual reduction chemistry of these nitroimidazole compounds, exhibiting ring over nitro group reduction, is associated with alkoxy substitution in the 2-position of a 4-nitroimidazole. The unique properties of the intermediates formed on the reduction of PA-824 need to be considered as playing a possible role in its bactericidal action.

  我们利用水溶液中的脉冲和稳态辐射分解法研究了新型抗结核药物 PA-824 和一种水溶性更强的类似物的还原化学性质。通过 CO2˙-物种的电子传递逐步还原这些硝基咪唑二氢恶嗪化合物，发现与相关的硝基咪唑不同，2 电子加成导致咪唑环优先于硝基还原。在弱酸性溶液中会形成硝基二氢咪唑中间体，然后进一步还原成胺产物。在碱性和中性溶液中，2 电子还原产生的中间产物无法进一步还原，在萃取或对溶液进行质谱分析时会还原成母体化合物。这些硝基咪唑化合物不寻常的还原化学性质表现出环比硝基还原，这与 4-硝基咪唑 2 位的烷氧基取代有关。需要考虑 PA-824 还原过程中形成的中间体的独特性质在其杀菌作用中可能发挥的作用。