2-ethynyl-1-(phenylethynyl)-1H-imidazole | 486999-99-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 2-ethynyl-1-(phenylethynyl)-1H-imidazole
• 英文别名: 2-ethynyl-1-phenylethynyl-1H-imidazole；2-Ethynyl-1-(2-phenylethynyl)imidazole
• CAS: 486999-99-9
• 化学式: C₁₃H₈N₂
• 分子量: 192.22
• InChiKey: WYRZZAXVYSUELY-UHFFFAOYSA-N

物化性质

• 熔点：
  107-108 °C
• 沸点：
  367.9±25.0 °C(Predicted)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  17.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-ethynyl-1-(phenylethynyl)-1H-imidazole 在 1,4-环己二烯 、 氯苯 作用下， 反应 24.0h， 以27%的产率得到5-chloro-8-phenyl-imidazo[1,2-a]pyridine
  参考文献：
  名称：

  Synthesis and Thermolysis of Heterocyclic 3-Aza-3-ene-1,5-diynes¹

  摘要：

  [GRAPHICS]Simple, acyclic 3-aza-3-ene-1,5-diynes undergo an aza-Bergman rearrangement to a fleeting 2,5-didehydropyridine (2,5-ddp) intermediate that rapidly ring-opens to beta-alkynylacrylonitrile products. In an effort to access longer-lived 2,5-ddp intermediates, we have prepared heterocyclic 3-aza-3-ene-1,5-diynes. The thermolysis of one such heterocyclic aza-enedlyne does not afford products derived from trapping a 2,5-ddp intermediate but rather cyclopropanes that appear to arise from a carbene intermediate and a product that appears to be a trapping product from a 2,3-ddp intermediate.

  DOI：

  10.1021/ol027100p
• 作为产物：
  描述：

  1-phenylethynyl-2-[(triisopropylsilanyl)-ethynyl]imidazole 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 生成 2-ethynyl-1-(phenylethynyl)-1H-imidazole
  参考文献：
  名称：

  Intra- and intermolecular trapping of cyclopentapyrazine carbenes derived from 1,2-dialkynylimidazoles

  摘要：

  The thermolysis of 1,2-dialkynylimidazoles in benzene solution affords high yields of 7-pheiiyl-5H-cyclopentapyrazines, which presumably form by solvent trapping of cyclopentapyrazine carbene intermediates. In cases where dialkynylimidazole contains side chains that can participate in intramolecular carbene C-H insertion or olefin addition, these processes compete with solvent addition to afford novel tri- and tetracyclic pyrazines, which can be obtained in good yield when the thermolysis is carried out in hexafluoro benzene. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.11.010

文献信息

• Cytotoxic 1,2-Dialkynylimidazole-Based Aza-Enediynes: Aza-Bergman Rearrangement Rates Do Not Predict Cytotoxicity
  作者：Christophe Laroche、Jing Li、Sean M. Kerwin

  DOI：10.1021/jm200289j

  日期：2011.7.28

  synthesized: the 1,2-dialkynylimidazoles. The aza-Bergman rearrangement of these 1,2-dialkynylimidazoles has been investigated theoretically at the B3LYP/6-31G(d,p) level and experimentally by measuring the kinetics of rearrangement in 1,4-cyclohexadiene. There is a good correlation between the theoretical and experimental results; subtle substituent effects on the initial aza-Bergman cyclization barrier predicted

  由烯二炔抗肿瘤抗生素启发而来的一类新的潜在抗肿瘤药已被合成：1,2-二烷基炔基咪唑。从理论上在B3LYP / 6-31G（d，p）水平研究了这些1,2-二炔基咪唑的aza-Bergman重排，并通过测量1,4-环己二烯的重排动力学进行了实验研究。理论和实验结果之间有很好的相关性；实验证实了理论上预测的对初始氮杂-伯格曼环化屏障的微妙取代基作用。然而，尽管这些1，2-二酮基咪唑在相对温和的条件下能够发生Bergman重排成双自由基/卡宾中间体的能力，但Bergman环化速率与对A459细胞的细胞毒性之间没有相关性。此外，细胞毒素1 2-二炔基咪唑不会引起超螺旋质粒DNA的切口或牛血清白蛋白的裂解。细胞毒性的另一种机制涉及意外的选择性硫醇添加到提出了某些1，2-二乙炔基咪唑的N-乙炔基。
• Synthesis and Thermolysis of Heterocyclic 3-Aza-3-ene-1,5-diynes¹
  作者：Asha K. Nadipuram、Wendi M. David、Dalip Kumar、Sean M. Kerwin

  DOI：10.1021/ol027100p

  日期：2002.12.1

  [GRAPHICS]Simple, acyclic 3-aza-3-ene-1,5-diynes undergo an aza-Bergman rearrangement to a fleeting 2,5-didehydropyridine (2,5-ddp) intermediate that rapidly ring-opens to beta-alkynylacrylonitrile products. In an effort to access longer-lived 2,5-ddp intermediates, we have prepared heterocyclic 3-aza-3-ene-1,5-diynes. The thermolysis of one such heterocyclic aza-enedlyne does not afford products derived from trapping a 2,5-ddp intermediate but rather cyclopropanes that appear to arise from a carbene intermediate and a product that appears to be a trapping product from a 2,3-ddp intermediate.
• Intra- and intermolecular trapping of cyclopentapyrazine carbenes derived from 1,2-dialkynylimidazoles
  作者：Asha K. Nadipuram、Sean M. Kerwin

  DOI：10.1016/j.tetlet.2005.11.010

  日期：2006.1

  The thermolysis of 1,2-dialkynylimidazoles in benzene solution affords high yields of 7-pheiiyl-5H-cyclopentapyrazines, which presumably form by solvent trapping of cyclopentapyrazine carbene intermediates. In cases where dialkynylimidazole contains side chains that can participate in intramolecular carbene C-H insertion or olefin addition, these processes compete with solvent addition to afford novel tri- and tetracyclic pyrazines, which can be obtained in good yield when the thermolysis is carried out in hexafluoro benzene. (c) 2005 Elsevier Ltd. All rights reserved.
• Thermal cyclization of 1,2-dialkynylimidazoles to imidazo[1,2-a]pyridines
  作者：Asha K. Nadipuram、Sean M. Kerwin

  DOI：10.1016/j.tet.2005.11.084

  日期：2006.4

  Thermolysis of 1,2-dialkynylimidazoles in chlorinated solvents leads to 5-chloroimidazo[1,2-a]-pyridine products, which are also formed in DMF containing 1 equiv of HCI. Deuterium labeling of the starting dialkynylimidazoles indicates that reaction may proceed by multiple pathways, depending upon conditions and substituents. Dialkynylimidazoles can also give rise to 5-diethylamino-substituted imidazopyridines when the thermolysis is carried out in the presence of diethylamine. (c) 2006 Elsevier Ltd. All rights reserved.