4-bromo-1,2-dimethyl-5-nitro-1H-imidazole | 21431-58-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 4-bromo-1,2-dimethyl-5-nitro-1H-imidazole
• 英文别名: 4-bromo-1,2-dimethyl-5-nitroimidazole
• CAS: 21431-58-3
• 化学式: C₅H₆BrN₃O₂
• 分子量: 220.026
• InChiKey: ZNTMHCHYIKJJMI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  63.6
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 海关编码：
  2933290090

反应信息

• 作为反应物：
  描述：

  4-bromo-1,2-dimethyl-5-nitro-1H-imidazole 在 四(三苯基膦)钯 、 氯化亚砜 、 sodium carbonate 作用下， 以 乙二醇二甲醚 、 乙醇 为溶剂， 反应 16.5h， 生成 4-(4-(chloromethyl)phenyl)-1,2-dimethyl-5-nitro-1H-imidazole
  参考文献：
  名称：

  Long distance-SRN1 in nitroimidazole series favored by temperature

  摘要：

  New reductive alkylating agents in 4- and 5-nitroimidazole series produce exclusively O-alkylation with nitronate anions under classical S(RN)1 conditions at room temperature. Electron-transfer C-alkylation is observed under microwave irradiation or under conventional heating. Furthermore, X-ray spectroscopy shows that the dihedral angles between the phenyl and imidazole rings for the two series are different, which could greatly influence reactivity in 4- and 5-nitroimidazole series. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2011.10.096
• 作为产物：
  描述：

  重氮甲烷 、 5-溴-2-甲基-4-硝基-1H-咪唑 以 乙醚 为溶剂， 反应 6.0h， 以68.6%的产率得到4-bromo-1,2-dimethyl-5-nitro-1H-imidazole
  参考文献：
  名称：

  Regioselective Nitro Group Substitution. Synthesis of Isomeric 4-Amino-5-nitro- and 5-Amino-4-nitroimidazoles

  摘要：

  On the basis of the reactions between 4,5-dinitroimidazole derivatives (1-methyl-4,5-dinitroimidazole, 1,2-dimethyl-4,5-dinitroimidazole and ethyl 2-(4,5-dinitroimidazol-1-yl)acetate) and cyclic amines (morpholine, piperidine or pyrrolidine) in mild conditions (THF or ethanolic solution), the order of nitro group substitution has been discovered for the first time. The influence of the solvent, steric effects and possibility of hydrogen bonds formation on the reaction direction has been discussed. Also, the way of formation of diamino-substitution product and interesting isomerization process is presented.

  DOI：

  10.3987/com-12-12502

文献信息

• First single electron transfer reaction on propargylic chloride in 5-nitroimidazole series
  作者：Kévin Neildé、Maxime D. Crozet、Thierry Terme、Patrice Vanelle

  DOI：10.1016/j.tetlet.2014.04.100

  日期：2014.7

  We report here the first example of an SRN1 reaction on propargylic chloride in heterocyclic series. The reaction of 4-(3-chloroprop-1-ynyl)-1,2-dimethyl-5-nitro-1H-imidazole with nitronate anions led to both the formation of the C-alkylated product through an SRN1 mechanism and the predominant ethylenic compound resulting from nitrous acid elimination on the C-alkylated product. Interestingly, in

  我们在此报告杂环系列中炔丙基氯上S RN 1反应的第一个例子。4-（3-氯丙-1-炔基）-1,2-二甲基-5-硝基-1 H-咪唑与亚硝酸根阴离子的反应导致通过S RN 1机理形成C-烷基化产物和由亚烷基消除C-烷基化产物产生的主要烯类化合物。有趣的是，与我们先前关于S RN 1反应性的研究相反，没有观察到O-烷基化的产物。
• Exploring the Synthesis and the Reactivity of 4-[4-(Chloromethyl)styryl]-1,2-dimethyl-5-nitro-1H-imidazole in TDAE Strategy
  作者：Patrice Vanelle、Nicolas Primas、Kévin Neildé、Youssef Kabri、Maxime Crozet、Thierry Terme

  DOI：10.1055/s-0033-1338572

  日期：——

  imidazoles in moderate to good yields. We describe herein the preparation of 4-[4-(chloromethyl)styryl]-1,2-dimethyl-5-nitro-1H-imidazole via a Stille cross-­coupling reaction. After determining the best reaction conditions, we investigated the reactivity of this activated chloromethyl compound in a TDAE [tetrakis(dimethylamino)ethylene] strategy toward 10 various electrophiles, obtaining 4-(4-substituted)styryl-1

  摘要 我们在本文中描述了通过Stille交叉偶联反应制备4- [4-（氯甲基）苯乙烯基] -1，2-二甲基-5-硝基-1 H-咪唑。确定最佳反应条件后，我们研究了该活化的氯甲基化合物在TDAE [四（二甲基氨基）乙烯]策略中对10种不同亲电试剂的反应性，获得了4-（4-取代）苯乙烯基-1,2-二甲基-5-硝基-1 H-咪唑的产率中等至良好。 我们在本文中描述了通过Stille交叉偶联反应制备4- [4-（氯甲基）苯乙烯基] -1，2-二甲基-5-硝基-1 H-咪唑。确定最佳反应条件后，我们研究了该活化的氯甲基化合物在TDAE [四（二甲基氨基）乙烯]策略中对10种不同亲电试剂的反应性，获得了4-（4-取代）苯乙烯基-1,2-二甲基-5-硝基-1 H-咪唑的产率中等至良好。
• Nucleophilic Displacements of Imidazoles. I. Oxygen, Nitrogen and Carbon Nucleophiles
  作者：S Kulkarni、MR Grimmett、LR Hanton、J Simpson

  DOI：10.1071/ch9871399

  日期：——

  4(5)- Bromo - and - iodo-imidazoles, activated by an adjacent nitro substituent, undergo nucleophilic displacement with methoxide, phenoxide , cyclic secondary chines and cyanide. The regiochemistry of the reactions of 5-iodo-4-nitroimidazole with methoxide has been confirmed by spectroscopic and X-ray methods, and a number of erroneous structures from the literature have been revised. Some apparently anomalous reactions of methoxide with 5-halo-1,2-dimethyl-4- nitroimidazoles, and of cyanide with 4-halo-1-methyl-5-nitroimidazole have been noted. The crystal and molecular structure of 5-methoxy-1-methyl-4-nitroimidazole has been determine: by direct methods. Crystals are monoclinic, P21/c, a 10.929(3), b 8 899(2), c 7.290(2) �; β 92.87(2)�; Z 4. The structure was refined to R = 0.095 for 818 reflections (I > 2σI).

  4(5)-溴-和-碘-咪唑在邻近硝基取代基的活化下，与甲醇、苯酚、环仲胺和氰化物发生亲核置换反应。光谱和 X 射线方法证实了 5-碘-4-硝基咪唑与甲醇反应的区域化学性质，并修正了文献中一些错误的结构。还注意到甲醇与 5-卤代-1,2-二甲基-4-硝基咪唑以及氰化物与 4-卤代-1-甲基-5-硝基咪唑的一些明显异常反应。通过直接方法确定了 5-甲氧基-1-甲基-4-硝基咪唑的晶体和分子结构。晶体为单斜晶系，P21/c，a 10.929(3)，b 8 899(2)，c 7.290(2) �；β 92.87(2)�；Z 4。818 个反射（I > 2σI）的结构精制为 R = 0.095。
• Nucleophilic Displacements of Imidazoles. II. Displacements of Halogen by S-Nucleophiles and Displacements of Mesyl Groups Activated by Nitro; Oxidation of Imidazolethiols
  作者：S Kulkarni、MR Grimmett

  DOI：10.1071/ch9871415

  日期：——

  In basic medium arylthiols displace bromo and iodo groups activated by nitro substituents in 5(4)-halo-4(5)- nitroimidazoles . The bromo compounds are slightly more reactive than the iodo analogues. Substituents at C5 are more readily displaced than those at C4. Methylsulfonyl groups, similarly activated by an adjacent nitro substituent, are displaced by a variety of nucleophiles. The imidazolethiol products are readily oxidized to the sulfones.

  在碱性介质中，芳基硫醇取代了 5(4)- 卤-4(5)- 硝基咪唑中由硝基取代基活化的溴基和碘基。溴代化合物的活性略高于碘代类似物。位于 C5 的取代基比位于 C4 的取代基更容易被取代。甲基磺酰基也同样被邻近的硝基取代基激活，并被各种亲核剂置换。咪唑硫醇产物很容易被氧化成砜。
• Synthese von thienoanalogen Zimtsäurederivaten mit Hilfe der Heck Reaktion [1]
  作者：Thomas Erker、Norbert Handler

  DOI：10.3797/scipharm.aut-04-02

  日期：——

  entsprechenden Bromthiophenderivat und Acrylsaurederivat wurden die optimalen Bedingungen fur eine Heck-Reaktion erarbeitet. Dabei wurde der Einfluss der Mengenverhaltnisse der Reaktanden bzw. des Katalysators und Co-Katalysators sowie des Losungsmittels und der Temperatur auf die Umsetzung untersucht.

  加强了对溴化苯丙交酯的抗性和对丙烯的保护，使Heck-Reaktion erarbeitet成为最佳选择。Dabei wurde der Einfluss der Mengenverhaltnisse der Reaktandenbzw。催化器和辅助催化器，以及在未受污染的环境下的低温和低温。