2-lithio-3-methoxy-N,N-dimethylaniline | 1426256-70-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-lithio-3-methoxy-N,N-dimethylaniline
• CAS: 1426256-70-3
• 化学式: C₉H₁₂LiNO
• 分子量: 157.141
• InChiKey: FIZDNGHIAJWESC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.18
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  二苯甲酮 、 2-lithio-3-methoxy-N,N-dimethylaniline 以 环己烷 为溶剂， 以1.39 g的产率得到(2-(dimethylamino)-6-methoxyphenyl)diphenylmethanol
  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
• 作为产物：
  描述：

  3-二甲基氨基苯甲醚 在 正丁基锂 、 四甲基乙二胺 作用下， 以 环己烷 为溶剂， 反应 3.0h， 生成 2-lithio-3-methoxy-N,N-dimethylaniline
  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%.