4-(1H-imidazol-1-yl)-N,N-dimethylaniline

• 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-(1H-imidazol-1-yl)-N,N-dimethylaniline
• 英文别名: 4-imidazol-1-yl-N,N-dimethylaniline
• 化学式: C₁₁H₁₃N₃
• 分子量: 187.244
• InChiKey: NXOXTWPURLNTDZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  21.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-(1H-imidazol-1-yl)-N,N-dimethylaniline 在 1,2,3,4,5,6,7,8-八硫杂环辛烷 、 N-溴代丁二酰亚胺(NBS) 、 sodium hydroxide 作用下， 以 1,4-二氧六环 、 乙醇 、 对二甲苯 、 水 为溶剂， 反应 3.5h， 生成 1-(4-(dimethylamino)phenyl)-3-(3-methyl-1H-indol-2-yl)-1H-imidazole-2(3H)-thione
  参考文献：
  名称：

  Betaine–Carbene Interconversions. From N-Ylides to Zwitterionic N-Heterocyclic Carbene–Borane Adducts

  摘要：

  In the presence of NBS 3-methylindole reacted with various imidazoles to give the (indol-2-yl)imidazolium salts 21a-f, which were converted in aqueous solution into the 2-(imidazolium-3-yl)-3-methylindolates 22a-f by base. These conjugated ylides-which represent a subclass of mesomeric betaines-are the exclusively detectable form in the NMR spectra taken in DMSO-d(6). A DFT calculation revealed that the betaine 22a is -9.3 kJ/mol more stable than the tautomeric N-heterocyclic carbene 23a and that the energy for the betaine-carbene interconversion is Delta G(double dagger) = 66.4 kJ/mol. The N-heterocyclic carbenes (3-methyl-indol-2-yl)imidazol-2-ylidenes, however, can be trapped by sulfur, triethylborane, and triphenylborane. Whereas the first trapping reaction yielded the expected imidazolethiones, the borates gave the first representatives of new zwitterionic borane adducts, imidazo[2',1':3,4][1,4,2]diazaborolo[1,5-a]indolium-11-ides 26a-h. We performed DFT calculations on the structures of mesomeric betaine 22a, the carbene 23a, and the mechanisms of the borane adduct formation to 26a-h, NMR spectroscopic investigations including N-15, Li-7, and B-11 NMR spectroscopy, and an X-ray single-crystal analysis of one of the borane adducts.

  DOI：

  10.1021/jo302479p
• 作为产物：
  描述：

  咪唑 、 4-溴-N,N-二甲基苯胺 在 copper(I) oxide potassium tert-butylate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 以98%的产率得到4-(1H-imidazol-1-yl)-N,N-dimethylaniline
  参考文献：
  名称：

  β-酮胺可作为含氮杂环与芳基卤化物的铜催化N-芳基化反应的有效配体

  摘要：

  已经开发出一种有效的铜催化剂体系，Cu 2 O /β-酮亚胺L 1，用于含氮杂环与芳基碘化物和溴化物的N-芳基化。该系统与富电子，-中性和-不足的芳基溴化物配合良好，从而以良好或优异的收率提供了产物。

  DOI：

  10.1016/j.tetlet.2008.05.008

文献信息

• Ligand-Free Copper-Catalyzed Arylation of Imidazole and<i>N,N</i>′-Carbonyldiimidazole, and Microwave-Assisted Synthesis of<i>N</i>-Aryl-1<i>H</i>-imidazoles
  作者：Xiao-Dong Yang、Liang Li、Hong-Bin Zhang

  DOI：10.1002/hlca.200890156

  日期：2008.8

  Microwave-assisted arylation of 1H-imidazoles and N,N′-carbonyldiimidazole under ligand-free copper-mediated conditions in tetraethyl orthosilicate is reported. Valuable evidence for understanding of the Cu-catalyzed mechanism of the Ullmann reaction is also presented.

  报道了在原硅酸四乙酯中在无配体的铜介导条件下1 H-咪唑和N，N'-羰基二咪唑的微波辅助芳基化反应。还提供了宝贵的证据，以了解Ullmann反应的Cu催化机理。
• Synthesis of substituted benzo[ij]imidazo[2,1,5-de]quinolizine by rhodium(<scp>iii</scp>)-catalyzed multiple C–H activation and annulations
  作者：Qingmei Ge、Bin Li、Baiquan Wang

  DOI：10.1039/c5ob02515j

  日期：——

  The cascade oxidative annulation reactions of aryl imidazoles with two molecules of alkynes via multiple C–H activation proceed efficiently in the presence of [Cp*RhCl2]2 and Cu(OAc)2·H2O to give substituted benzo[ij]imidazo[2,1,5-de]quinolizine-based polyheteroaromatic compounds. This method is compatible with various functional groups, which are very useful for further synthetic transformations.

  在[Cp * RhCl 2 ] 2和Cu（OAc）2 ·H 2 O的存在下，芳基咪唑与两个炔烃的分子通过多重C–H的级联氧化环化反应有效进行，得到取代的苯并[ ij ]咪唑[2,1,5- de ]喹啉嗪基多杂芳族化合物。该方法与各种官能团兼容，这些官能团对于进一步的合成转化非常有用。
• Synthesis of unsymmetrical imidazolium salts by direct quaternization of N-substituted imidazoles using arylboronic acids
  作者：Shiqing Li、Fan Yang、Taiyong Lv、Jingbo Lan、Ge Gao、Jingsong You

  DOI：10.1039/c4cc00474d

  日期：——

  Imidazolium salts were conveniently prepared by direct aryl quaternization using arylboronic acids. This process features the tolerance of a broad range of functional groups and excellent chemoselectivity, and is especially effective for the synthesis of unsymmetrical imidazolium salts.

  咪唑盐可通过直接芳基季铵化反应方便地制备，该反应采用芳基硼酸作为原料。该方法具有对多种官能团的耐受性和优异的化学选择性，尤其适用于非对称咪唑盐的合成。
• Novel bisimidazolium pincers as low loading ligands for in situ palladium-catalyzed Suzuki–Miyaura reaction in the ambient atmosphere
  作者：Chao Gao、Hongjun Zhou、Siping Wei、Yinsong Zhao、Jingsong You、Ge Gao

  DOI：10.1039/c2cc36375e

  日期：——

  A series of novel triazinonide-bridged bisimidazolium pincers were easily synthesized by quaternization of functionalized N-phenylimidazoles with highly reactive cyanuric chloride under mild conditions. The pincer 3c was proven to be a very efficient ligand for in situ Pd-catalyzed Suzuki–Miyaura reaction with ppm-level catalyst loading.

  一系列新型三嗪酮桥联双咪唑鎓夹钳通过在温和条件下用高度活性的氰尿酰氯对功能化N-苯基咪唑进行季铵化轻松合成。夹钳3c被证明是一种非常高效的配体，可用于催化剂负载量低至ppm级别的原位钯催化的铃木-宫浦反应。
• Remote Ligand Modifications Tune Electronic Distribution and Reactivity in Site-Differentiated, High-Spin Iron Clusters: Flipping Scaling Relationships
  作者：Charles H. Arnett、Jens T. Kaiser、Theodor Agapie

  DOI：10.1021/acs.inorgchem.9b02470

  日期：2019.12.2

  characterization, and reactivity of [LFe3O(RArIm)3Fe][OTf]2, the first Hammett series of a site-differentiated cluster. The cluster reduction potentials and CO stretching frequencies shift as expected on the basis of the electronic properties of the ligand: electron-donating substituents result in more reducing clusters and weaker C-O bonds. However, unusual trends in the energetics of their two sequential CO binding

  我们报告[LFe3O（RArIm）3Fe] [OTf] 2的合成，表征和反应性，站点分化簇的第一个哈米特系列。根据配体的电子性质，团簇还原电位和CO拉伸频率发生了预期的变化：给电子取代基导致更多的还原团簇和较弱的CO键。但是，观察到了两个连续的CO取代事件（具有取代基σp参数）的能量学上的异常趋势。具体地，给电子取代基的引入抑制了第一个CO结合事件（ΔΔH高达7.9kcal mol-1），但是增强了第二个（ΔΔH高达1.9kcal mol-1）。X射线晶体学，包括多波长异常衍射，穆斯堡尔光谱和SQUID磁强计，