1-benzhydryl-3-(3-methyl-1H-indol-2-yl)-1H-imidazole-2(3H)-thione | 1419209-62-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-benzhydryl-3-(3-methyl-1H-indol-2-yl)-1H-imidazole-2(3H)-thione
• 英文别名: 1-benzhydryl-3-(3-methyl-1H-indol-2-yl)imidazole-2-thione
• CAS: 1419209-62-3
• 化学式: C₂₅H₂₁N₃S
• 分子量: 395.528
• InChiKey: JWHDCBUUHHMPGJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  1-benzhydryl-3-(3-methyl-1H-indol-2-yl)-1H-imidazolium bromide 在 1,2,3,4,5,6,7,8-八硫杂环辛烷 、 sodium hydroxide 作用下， 以 乙醇 、 对二甲苯 、 水 为溶剂， 反应 3.0h， 生成 1-benzhydryl-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

文献信息

• Betaine–Carbene Interconversions. From N-Ylides to Zwitterionic N-Heterocyclic Carbene–Borane Adducts
  作者：Nazar Pidlypnyi、Jan C. Namyslo、Martin H. H. Drafz、Martin Nieger、Andreas Schmidt

  DOI：10.1021/jo302479p

  日期：2013.2.1

  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.