3-(4′-methoxyphenyl)-ortho-carborane | 1159494-40-2

• 英文名称: 3-(4′-methoxyphenyl)-ortho-carborane
• 英文别名: 3-para-methoxyphenyl-o-carborane
• CAS: 1159494-40-2
• 化学式: C₉H₁₈B₁₀O
• 分子量: 250.351
• InChiKey: WHQAGEZBPOPFRG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  4-溴苯甲醚 、 3-iodo-o-carborane 在 3-氯丙烯 、 三氟乙酸 、 cobalt(II) bromide 、 锌 、 bis-triphenylphosphine-palladium(II) chloride 作用下， 以 乙腈 为溶剂， 以77 %的产率得到3-(4′-methoxyphenyl)-ortho-carborane
  参考文献：
  名称：

  具有敏感官能团的 3-Aryl-ortho-carboranes 的合成

  摘要：

  使用原位生成的3-碘-邻-碳硼烷和芳基溴化锌，开发了一种简单有效的方法，用于一锅合成具有敏感官能团的邻-碳硼烷的 3-芳基衍生物。一系列 3-芳基-邻-碳硼烷，包括含有腈和酯基的那些，3-RC 6 H 4 -1,2-C 2 B 10 H 11 (R = p -Me, p -NMe 2 , p - OCH 2 OMe, p -OMe, o -CN, p -CN, o -COOEt,m -COOEt, p -COOEt) 是使用这种方法合成的。3-RC 6 H 4 -1,2-C 2 B 10 H 11 (R = p -OMe、o -CN 和p -CN)的固态结构由单晶 X 射线衍射确定。讨论了涉及芳环的邻位取代基和碳硼烷的CH和BH基团的分子内氢键。

  DOI：

  10.3390/molecules26237297

文献信息

• Magnesium-assisted intramolecular demethylation utilizing carborane C–H geometry
  作者：Kiminori Ohta、Hiroto Yamazaki、Yasuyuki Endo

  DOI：10.1016/j.jorganchem.2008.11.044

  日期：2009.5

  A novel type of demethylation reaction was designed in the Pd-catalyzed coupling reaction of iodocarboranes with several Grignard reagents, CH3OPhMgBr. 3-Iodo-o-carborane 1 reacted with 2-CH3OPhMgBr to afford the corresponding phenol compound 4b in 78% yield. However, when compound 1 was reacted with the other Grignard reagents, the corresponding methoxyl compounds 5a and 6a were obtained in excellent yields. 2-Iodo-p-carborane 3 reacted with 2-CH3OPhMgBr to afford the corresponding phenol 8b in 50% yield and the methoxyl compound 8a in 41% yield. The carborane C-H geometry, which can form an intramolecular C-H center dot center dot center dot O hydrogen bonding, seems to be an important factor in the demethylation process. To examine the mechanism of the demethylation, compounds 1 and 4a were treated with CH3MgBr and quenched with D2O. While the two C-Hs of compound 1 were completely deuterated, compound 4a showed a replacement of one C-H with C-D. Therefore, we propose a mechanism involving intramolecular C-Mg center dot center dot center dot O interaction instead of intramolecular C-H center dot center dot center dot O interaction, via the generation of 3-iodo-o-carboranyl(MgBr)(2), 11. Since it is also possible to replace the C-Hs with various metals other than Mg, new applications of carboranes in coordination and metal catalyst chemistry can be expected. (C) 2008 Elsevier B.V. All rights reserved.