2-methoxy[6-2H]pyridine | 170453-58-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-methoxy[6-2H]pyridine
• 英文别名: 2-Deuterio-6-methoxypyridine
• CAS: 170453-58-4
• 化学式: C₆H₇NO
• 分子量: 110.12
• InChiKey: IWTFOFMTUOBLHG-UICOGKGYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  22.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  三甲基氯硅烷 、 2-methoxy[6-2H]pyridine 在 2,2,6,6-四甲基哌啶 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 以55%的产率得到2-methoxy[6-2H]-3-pyridyl(trimethyl)silane
  参考文献：
  名称：

  Lithiation of 2-Chloro- and 2-Methoxypyridine with Lithium Dialkylamides: Initial Ortho-Direction or Subsequent Lithium Ortho-Stabilization?

  摘要：

  The lithiation pathway of 2-chloro and 2-methoxypyridine with LDA and LTMP has been investigated using deuterated probes. The availability of both H-6 and H-3 protons on the pyridine nucleus was found to be critical to ensure complete C-3 lithiation. We thus concluded that the C-3 lithiation was not a straightforward process. A mechanism involving precomplexation of lithium dialkylamides near the H-6 proton and formation of a 3,6-dilithio pyridine intermediate is proposed.

  DOI：

  10.1021/jo026559u
• 作为产物：
  描述：

  2-甲氧基吡啶 在 正丁基锂 、 diclazuril 、 Lithium-2-(dimethylamino)ethanolat 作用下， 生成 2-methoxy[6-2H]pyridine
  参考文献：
  名称：

  Aggregative activation and heterocyclic chemistry III. Unusual regioselective lithiation of 2-alkoxy-pyridines

  摘要：

  DOI：

  10.1016/0040-4039(95)00867-c

文献信息

• Aggregative activation in heterocyclic chemistry. Part 4. Metallation of 2-methoxypyridine: unusual behaviour of the new unimetal superbase BuLi–Me2N(CH2)2OLi (BuLi–LiDMAE)
  作者：Philippe Gros、Yves Fort、Paul Caubère

  DOI：10.1039/a701914i

  日期：——

  A series of potential unimetal superbases BuLi–ROLi has been studied in order to increase the basicity/nucleophilicity ratio ([B/N]R) of BuLi. The best [B/N]R ratio is found with BuLi–LiDMAE. This complex base apparently metallates 2-methoxypyridine at the unexpected C-6 position. It is shown that no actual metallated species are formed in the reaction medium, the reaction occurring as the result of a common radical precursor stabilized by an aggregate cluster. Finally, as an application, C-6 substituted 2-methoxypyridines have been obtained in good to excellent yields.

  为了提高BuLi的基本性/亲核性比率([B/N]R)，研究了一系列潜在的单金属超碱BuLi–ROLi。最佳的[B/N]R比率是在BuLi–LiDMAE中发现的。这种复合碱显然在意想不到的C-6位点对2-甲氧基吡啶进行了金属化。研究表明，在反应介质中并没有形成实际的金属化物种，该反应是由于一个通过聚集簇稳定的共同自由基前体的结果。最后，作为应用，得到了C-6取代的2-甲氧基吡啶，产率良好到优异。
• Lithiation of 2-Heterosubstituted Pyridines with BuLi−LiDMAE:  Evidence for Regiospecificity at C-6
  作者：Philippe Gros、Sabine Choppin、Julien Mathieu、Yves Fort

  DOI：10.1021/jo015855o

  日期：2002.1.1

  The determination of the initial deprotonation site of 2-chloro- and 2-methoxypyridine during reaction with BuLi-LiDMAE has been investigated. A series of experiments on deuterated regioisomers revealed a direct lithiation at C-6 excluding a potential first classical ortholithiation and lithium equilibration in the reaction medium. These results suggested that the formation of lithium aggregates at the neighboring of the pyridinic nitrogen atom favored BuLi delivery at C-6 as well as 6-lithio intermediate stabilization.
• Aggregative activation and heterocyclic chemistry III. Unusual regioselective lithiation of 2-alkoxy-pyridines
  作者：Ph. Gros、Y. Fort、G. Queguiner、P. Caubère

  DOI：10.1016/0040-4039(95)00867-c

  日期：1995.7
• Lithiation of 2-Chloro- and 2-Methoxypyridine with Lithium Dialkylamides: Initial Ortho-Direction or Subsequent Lithium Ortho-Stabilization?
  作者：Philippe Gros、Sabine Choppin、Yves Fort

  DOI：10.1021/jo026559u

  日期：2003.3.1

  The lithiation pathway of 2-chloro and 2-methoxypyridine with LDA and LTMP has been investigated using deuterated probes. The availability of both H-6 and H-3 protons on the pyridine nucleus was found to be critical to ensure complete C-3 lithiation. We thus concluded that the C-3 lithiation was not a straightforward process. A mechanism involving precomplexation of lithium dialkylamides near the H-6 proton and formation of a 3,6-dilithio pyridine intermediate is proposed.
• One-step exchange-labelling of pyridines and other N-heteroaromatics using deuterium gas: catalysis by heterogeneous rhodium and ruthenium catalysts
  作者：Efstathios Alexakis、John R. Jones、William J.S. Lockley

  DOI：10.1016/j.tetlet.2006.05.106

  日期：2006.7

  A wide range of pyridines and other nitrogen heteroaromatics can be labelled with deuterium at room temperature and pressure by isotopic exchange with deuterium gas in THF in the presence of rhodium black, ruthenium black or 5% rhodium on alumina. The labelling is rapid, isotope efficient and applicable to both electron-rich and electron-poor substrates. In a few cases, a degree of reduction accompanies the exchange. (c) 2006 Elsevier Ltd. All rights reserved.