6-lithio-2-methyl anisole

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 6-lithio-2-methyl anisole
• 英文别名: 6-lithio-2-methylanisole
• 化学式: C₈H₉LiO
• 分子量: 128.1
• InChiKey: UBKHNQSLLUTYOF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.42
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  三甲基氯硅烷 、 6-lithio-2-methyl anisole 以 四氢呋喃 为溶剂， 以65%的产率得到2-methyl-6-triemthylsilyl anisole
  参考文献：
  名称：

  锂原子与茴香醚的缩聚反应：反应途径的实验和理论研究

  摘要：

  锂原子与纯茴香醚的缩聚反应导致邻位CH活化并形成氢化锂。这种简单的两组分系统允许研究包含供体分子的反应机理。因此，在较早的光谱研究中鉴定出的两个茴香醚和一个二锂分子被认为是反应路径的计算方法。

  DOI：

  10.1016/j.jorganchem.2004.12.016
• 作为产物：
  描述：

  2-甲基苯甲醚 在 正丁基锂 、 四甲基乙二胺 作用下， 以 环己烷 为溶剂， 反应 1.0h， 生成 6-lithio-2-methyl anisole
  参考文献：
  名称：

  ortho-Lithiations Reassessed: the Advantages of Deficiency Catalysis in Hydrocarbon Media

  摘要：

  Hydrocarbon media based metalation procedures involving "deficiency catalysis" are described for the ortho-lithiation of anisole (A), p-chloroanisole (p-ClA), o-, m-, p-methylanisoles (o-, m-, p-MA), the three dimethoxybenzenes (DMB's), dimethylaniline (DMA), dimethybenzylamine (DMBA), m-methoxydimethylaniline (m-MeODM.A), and tetramethyl-p-phenylenediamine (p-TMPDA). These procedures involve certain mechanistic considerations, which must be fine-tuned to maximize the extent of metalation (EoM). Our working hypothesis is that a controlled deoligomerization of the n-BuLi hexamer found in hydrocarbon media will afford a "sweet spot" of deoligomerization such that a maximally efficient metalation medium can be formed. In many eases, a substoichiometric ratio of equivalent TMEDA to n-BuLi is 0.1-0.2:1.0, but certain substrates suffer multiple sites of metalation under these conditions, so different promoted hydrocarbon media systems incorporating measured equivalents of an ether have been formulated. This paper represents the summary of our successful efforts to render ortho-lithiations safer, greener, and more atom-economical by use of hydrocarbon solvent media. EoM's of 11 of the 12 substrates under these atom-economical conditions range from 87 to 97%.

  DOI：

  10.1021/om301120e

文献信息

• ortho-Lithiations Reassessed: the Advantages of Deficiency Catalysis in Hydrocarbon Media
  作者：D. W. Slocum、Thomas K. Reinscheld、Christopher B. White、Michael D. Timmons、Philip A. Shelton、Matthew G. Slocum、Rebecca D. Sandlin、Erica G. Holland、Damir Kusmic、John A. Jennings、Kristen C. Tekin、Quang Nguyen、Steven J. Bush、Julia M. Keller、Paul E. Whitley

  DOI：10.1021/om301120e

  日期：2013.3.25

  Hydrocarbon media based metalation procedures involving "deficiency catalysis" are described for the ortho-lithiation of anisole (A), p-chloroanisole (p-ClA), o-, m-, p-methylanisoles (o-, m-, p-MA), the three dimethoxybenzenes (DMB's), dimethylaniline (DMA), dimethybenzylamine (DMBA), m-methoxydimethylaniline (m-MeODM.A), and tetramethyl-p-phenylenediamine (p-TMPDA). These procedures involve certain mechanistic considerations, which must be fine-tuned to maximize the extent of metalation (EoM). Our working hypothesis is that a controlled deoligomerization of the n-BuLi hexamer found in hydrocarbon media will afford a "sweet spot" of deoligomerization such that a maximally efficient metalation medium can be formed. In many eases, a substoichiometric ratio of equivalent TMEDA to n-BuLi is 0.1-0.2:1.0, but certain substrates suffer multiple sites of metalation under these conditions, so different promoted hydrocarbon media systems incorporating measured equivalents of an ether have been formulated. This paper represents the summary of our successful efforts to render ortho-lithiations safer, greener, and more atom-economical by use of hydrocarbon solvent media. EoM's of 11 of the 12 substrates under these atom-economical conditions range from 87 to 97%.
• The cocondensation reaction of lithium atoms and anisole: an experimental and theoretical study of the reaction pathway
  作者：Oscar Mendoza、Laurence P. Cuffe、Franz-Josef K. Rehmann、Matthias Tacke

  DOI：10.1016/j.jorganchem.2004.12.016

  日期：2005.3

  The cocondensation reaction of lithium atoms and pure anisole leads to an ortho CH activation and the formation of lithium hydride. This simple two-component system allows the investigation of the reaction mechanism with included donor molecules. Therefore two anisole and one dilithium molecule, which was identified in an earlier spectroscopic study, were considered for the reaction pathway calculations

  锂原子与纯茴香醚的缩聚反应导致邻位CH活化并形成氢化锂。这种简单的两组分系统允许研究包含供体分子的反应机理。因此，在较早的光谱研究中鉴定出的两个茴香醚和一个二锂分子被认为是反应路径的计算方法。