2,2'-Dimethoxy-3,3'-bipyridine | 95881-80-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 2,2'-Dimethoxy-3,3'-bipyridine
• 英文别名: 2-methoxy-3-(2-methoxypyridin-3-yl)pyridine
• CAS: 95881-80-4
• 化学式: C₁₂H₁₂N₂O₂
• 分子量: 216.239
• InChiKey: PHJFDFBBLZMRNT-UHFFFAOYSA-N

物化性质

• 沸点：
  272.5±35.0 °C(Predicted)
• 密度：
  1.143±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  44.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,2'-Dimethoxy-3,3'-bipyridine 在 吡啶盐酸盐 作用下， 反应 4.0h， 以84%的产率得到<3,3'-Bipyridin>-2,2'-diol
  参考文献：
  名称：

  Dehmlow, Eckehard V.; Sleegers, Arthur, Liebigs Annalen der Chemie, 1992, # 9, p. 953 - 960

  摘要：

  DOI：
• 作为产物：
  描述：

  2,3-二氯吡啶 在 三苯基膦 、 nickel dichloride 、 锌 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 生成 2,2'-Dimethoxy-3,3'-bipyridine
  参考文献：
  名称：

  Tiecco, Marcello, Bulletin des Societes Chimiques Belges, 1986, vol. 95, # 11, p. 1009 - 1020

  摘要：

  DOI：

文献信息

• Deprotonative Metalation of Aromatic Compounds by Using an Amino-Based Lithium Cuprate
  作者：Tan Tai Nguyen、Nada Marquise、Floris Chevallier、Florence Mongin

  DOI：10.1002/chem.201100990

  日期：2011.9.5

  employed to attempt the interception of the generated aryl cuprates, aroyl chlorides, iodomethane, and diphenyl disulfide efficiently reacted. In addition, different oxidative agents were identified to afford symmetrical biaryls. Finally, palladium‐catalyzed coupling with aryl halides was optimized and allowed the synthesis of different aryl derivatives in medium to good yields.

  以2,4-二甲氧基嘧啶和2-甲氧基吡啶为底物，以苯甲酰氯为亲电子试剂，对基于氨基的铜酸锂对芳香族化合物的去质子化进行了优化。[（tmp）2 CuLi]（+2 LiCl）（tmp = 2,2,6,6-四甲基哌啶子基）被确定为最佳试剂，其应用范围已扩展到苯甲醚，1,4-二甲氧基苯，其他取代的吡啶，呋喃，噻吩及其衍生物和N -Boc-吲哚（Boc =叔-丁氧羰基）。在试图拦截所生成的芳基铜酸酯的亲电试剂中，芳酰氯，碘甲烷和二苯基二硫化物有效地反应了。另外，鉴定出不同的氧化剂以提供对称的联芳基。最后，优化了钯催化与芳基卤化物的偶联，并以中等收率合成了不同的芳基衍生物。
• Palladium-Catalyzed, <i>tert-</i> Butyllithium-Mediated Dimerization of Aryl Halides and Its Application in the Atropselective Total Synthesis of Mastigophorene A
  作者：Jeffrey Buter、Dorus Heijnen、Carlos Vila、Valentín Hornillos、Edwin Otten、Massimo Giannerini、Adriaan J. Minnaard、Ben L. Feringa

  DOI：10.1002/anie.201510328

  日期：2016.3.7

  A palladium‐catalyzed direct synthesis of symmetric biaryl compounds from aryl halides in the presence of tBuLi is described. In situ lithium–halogen exchange generates the corresponding aryl lithium reagent, which undergoes a homocoupling reaction with a second molecule of the aryl halide in the presence of the palladium catalyst (1 mol %). The reaction takes place at room temperature, is fast (1 h)

  描述了在t BuLi存在下钯催化芳基卤化物直接合成对称联芳基化合物的方法。原位锂-卤素交换生成相应的芳基锂试剂，该试剂在钯催化剂（1摩尔％）存在下与第二个芳基卤分子进行均偶联反应。反应在室温下进行，反应快速（1小时），并以良好至极好的收率得到相应的联芳基化合物。该方法的应用已证明了高效的igo草烯A的不对称全合成。由于催化剂诱导的远程点对轴手性转移，手性联芳基轴的抗选择性为9：1。
• Deprotonative metalation of substituted aromatics using mixed lithium–cobalt combinations
  作者：Gandrath Dayaker、Floris Chevallier、Philippe C. Gros、Florence Mongin

  DOI：10.1016/j.tet.2010.09.053

  日期：2010.11

  The deprotonation of anisole was attempted using different homo- and heteroleptic TMP/Bu mixed lithium–cobalt combinations. Using iodine to intercept the metalated anisole, an optimization of the reaction conditions showed that in THF at room temperature 2 equiv of base were required to suppress the formation of the corresponding 2,2′-dimer. The origin of the dimer was not identified, but its formation

  苯甲醚的去质子化尝试使用不同的均配和杂配的TMP / Bu混合锂钴混合物。使用碘截留金属化的茴香醚，反应条件的优化表明，在室温下的THF中，需要2当量的碱才能抑制相应的2,2'-二聚体的形成。二聚体的来源尚未确定，但烯丙基溴作为亲电子试剂有利于其形成。使用碘，茴香醛和氯二苯膦有效地捕集金属化的苯甲醚，并适当使用二苯甲酮和苯甲酰氯。类似地将1，2-，1，3-和1，4-二甲氧基苯区域选择性地转化为相应的碘化物。观察到2-甲氧基-和2，当进行类似处理时，6-二甲氧基吡啶比相应的苯更易于二聚。苯甲酸乙酯在金属化-碘化过程中的参与表明，该方法不适用于对具有反应性功能的底物进行功能化。
• A Convenient Synthesis of Bipyridines by Nickel-Phosphine Complex-Mediated Homo Coupling of Halopyridines
  作者：M. Tiecco、L. Testaferri、M. Tingoli、D. Chianelli、M. Montanucci

  DOI：10.1055/s-1984-30951

  日期：——
• Deprotonative metalation of aromatic compounds using mixed lithium–iron combinations
  作者：Elisabeth Nagaradja、Floris Chevallier、Thierry Roisnel、Viatcheslav Jouikov、Florence Mongin

  DOI：10.1016/j.tet.2012.02.019

  日期：2012.4

  The deprotonation of 2-methoxypyridine was attempted using putative (TMP)(3)FeLi prepared from different iron sources. Using iodine to intercept the metalated 2-methoxypyridine, the best result was obtained from FeBr2 (1 equiv) using THF at room temperature: nevertheless, in addition to the expected iodide, the corresponding 2,2'-dimer was obtained (86% total yield). The origin of the competitive formation of the 2,2'-dimer was not identified but mechanisms were suggested to explain its formation. It was observed that the nature of the electrophile employed to trap the 3-metalated 2-methoxypyridine has a strong impact on this dimer formation, the latter being favored using iodine (35% yield), but also benzophenone (28%), benzoyl chloride (22%), methyl iodide (27%), allyl bromide (15%), benzyl bromide (41%), and tetramethylthiuram disulphide (36%); for this reason, the yields of the expected derivatives were only 51, 15, 62, 0, <5, 18, and 0%, respectively. In contrast, using aldehydes readily led to the expected pyridine alcohols without dimerization (59% yield using 3,4,5-trimethoxybenzaldehyde and 66% yield using pivalaldehyde). 2,6-Dimethoxypyridine (in 68% yield), anisole (47%), 2,4-dimethoxypyrimidine (50% at C5 and 3% at C6), 2-fluoropyridine (64%), and thiophene (49%) were similarly converted into the corresponding alcohols after subsequent trapping with pivalaldehyde. Using iodine to trap the 2-metalated anisole did not lead to dimer formation, and 2-iodoanisole was isolated in 71% yield. (C) 2012 Elsevier Ltd. All rights reserved.