1-benzyl-3-(3-methyl-1H-indol-2-yl)-1H-imidazole-2(3H)-thione | 1419209-58-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 1-benzyl-3-(3-methyl-1H-indol-2-yl)-1H-imidazole-2(3H)-thione
• 英文别名: 1-benzyl-3-(3-methyl-1H-indol-2-yl)imidazole-2-thione
• CAS: 1419209-58-7
• 化学式: C₁₉H₁₇N₃S
• 分子量: 319.43
• InChiKey: UCYDCERLQDQZID-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.11
• 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：

  2-(1-benzyl-1H-imidazolium-3-yl)-3-methylindolate 在 1,2,3,4,5,6,7,8-八硫杂环辛烷 作用下， 以 对二甲苯 为溶剂， 反应 3.0h， 以96%的产率得到1-benzyl-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

• N-Heterocyclic carbenes from ylides of indolyl-imidazolium, azaindolyl-imidazolium, and indolyl-triazolium salts, and their borane adducts
  作者：Nazar Pidlypnyi、Sebastian Wolf、Ming Liu、Kari Rissanen、Martin Nieger、Andreas Schmidt

  DOI：10.1016/j.tet.2014.09.035

  日期：2014.11

  Their tautomeric N-heterocyclic carbenes (NHCs) were trapped by sulfur to give imidazole-2-thiones. Treatment of the ylides with triethylborane resulted in the formation of zwitterionic borane adducts. An analogous sequence of reactions was performed with 8-azaindol-2-yl-imidazolium salts, which served as precursor to prepare first representatives of a new heterocyclic ring system on reaction of their

  在吲哚环的N1处使吲哚-2-基-咪唑鎓盐去质子化，得到酰化物。他们的互变异构N-杂环卡宾（NHCs）被硫捕获，得到咪唑-2-硫酮。用三乙基硼烷处理该酰基化物导致两性离子硼烷加合物的形成。用8-氮杂吲哚-2-基-咪唑鎓盐进行类似的反应序列，其用作前体以在其NHC-互变异构体与三乙基硼烷反应上制备新的杂环体系的第一代表。同样，检查了吲哚-2-基-1,2,4-三唑鎓盐的叶立德-NHC互变异构和捕获反应。吲哚-3-胺与1,3,4-恶二唑盐的亲核环转化得到吲哚-3-基-三唑鎓盐，其通过捕获其叶立德的互变异构N-杂环卡宾而转化为三唑硫酮。