tri-2-pyridylchloromethane | 81940-18-3

• 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: tri-2-pyridylchloromethane
• 英文别名: 2,2',2''-trispyridylmethylchloride；2-[Chloro(dipyridin-2-yl)methyl]pyridine
• CAS: 81940-18-3
• 化学式: C₁₆H₁₂ClN₃
• 分子量: 281.744
• InChiKey: GPPXICVNSOYSBY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tri-2-pyridylchloromethane 在 三正丁基氢锡 作用下， 以 四氢呋喃 为溶剂， 以92%的产率得到tris(2-pyridyl)methane
  参考文献：
  名称：

  Strong Lewis acids derived from molybdenum and tungsten nitrosyls containing the tri-2-pyridylmethane ligand. Dynamic NMR studies of their adducts with aldehydes, ketones, and esters

  摘要：

  The doubly charged Lewis acid precursors [HC(py)3M(NO)2(CO)](SbF6)2 (M = Mo, W; HC(py)3 = tri-2-pyridylmethane) are conveniently synthesized by reaction of HC(py)3M(CO)3 and 2 equiv of NOSbF6. Facile loss of CO from the precursors generates the [HC(py)3M(NO)2](SbF6)2 Lewis acids. The Lewis acidity of the tungsten complex is greater than that of the molybdenum complex. With the H-1 NMR chemical shifts of bound crotonaldehyde as a qualitative assessment of relative acidity, the acidity of the tungsten species is comparable to that of BF3 and AlCl3, while that of the molybdenum species is similar to that of TiCl4. Analysis of the NMR spectra of the Lewis acid-organic carbonyl base adducts, which include the adducts of aldehydes, ketones, and esters, showed that eta-1-M(O = C) interactions dominate the chemistry. The barriers of rotation about the aldehyde C1-C2 bonds in the p-anisaldehyde adducts of the molybdenum and tungsten species were measured to be 12.8 and 13.7 kcal/mol, respectively, which are significantly higher than that for the free p-anisaldehyde. The exchange behavior between the E and Z isomers of the acetate adducts could be observed on the NMR time scale. The E to Z interconversion barriers of 12.2 +/- 0.1 and 12.3 +/- 0.1 kcal/mol for the methyl acetate and ethyl acetate complexes, respectively, were calculated from the results of variable-temperature proton NMR experiments. The free energy differences between the E and Z conformers of the methyl acetate and ethyl acetate adducts are 1.27 +/- 0.01 and 0.96 +/- 0.01 kcal/mol at 229 K, respectively.

  DOI：

  10.1021/ja00005a021
• 作为产物：
  描述：

  三(2-吡啶基)甲基醇 在 氯化亚砜 、 sodium hydride 作用下， 生成 tri-2-pyridylchloromethane
  参考文献：
  名称：

  Strong Lewis acids derived from molybdenum and tungsten nitrosyls containing the tri-2-pyridylmethane ligand. Dynamic NMR studies of their adducts with aldehydes, ketones, and esters

  摘要：

  The doubly charged Lewis acid precursors [HC(py)3M(NO)2(CO)](SbF6)2 (M = Mo, W; HC(py)3 = tri-2-pyridylmethane) are conveniently synthesized by reaction of HC(py)3M(CO)3 and 2 equiv of NOSbF6. Facile loss of CO from the precursors generates the [HC(py)3M(NO)2](SbF6)2 Lewis acids. The Lewis acidity of the tungsten complex is greater than that of the molybdenum complex. With the H-1 NMR chemical shifts of bound crotonaldehyde as a qualitative assessment of relative acidity, the acidity of the tungsten species is comparable to that of BF3 and AlCl3, while that of the molybdenum species is similar to that of TiCl4. Analysis of the NMR spectra of the Lewis acid-organic carbonyl base adducts, which include the adducts of aldehydes, ketones, and esters, showed that eta-1-M(O = C) interactions dominate the chemistry. The barriers of rotation about the aldehyde C1-C2 bonds in the p-anisaldehyde adducts of the molybdenum and tungsten species were measured to be 12.8 and 13.7 kcal/mol, respectively, which are significantly higher than that for the free p-anisaldehyde. The exchange behavior between the E and Z isomers of the acetate adducts could be observed on the NMR time scale. The E to Z interconversion barriers of 12.2 +/- 0.1 and 12.3 +/- 0.1 kcal/mol for the methyl acetate and ethyl acetate complexes, respectively, were calculated from the results of variable-temperature proton NMR experiments. The free energy differences between the E and Z conformers of the methyl acetate and ethyl acetate adducts are 1.27 +/- 0.01 and 0.96 +/- 0.01 kcal/mol at 229 K, respectively.

  DOI：

  10.1021/ja00005a021

文献信息

• Polymer supported magnesium anthracene: application in the synthesis of benzylic Grignard reagents
  作者：Tania R. van der Ancker、Steven Harvey、Colin L. Raston

  DOI：10.1016/0022-328x(95)05688-l

  日期：1995.10

  Reactions of polystyrene supported magnesium anthracene containing radical anion and dianion sites, 7, 7′, with benzylic chlorides or bromides, affords Grignard reagents, RMgX, in modest to high yields, in THF at −10°C to 20°C. Novel benzylic-type Grignard reagents prepared in high yield include those of 2,6-(dichloromethyl)pyridine, 2,6-(dibromomethyl)pyridine, 2,2′2″-trispyridylmethylchloride, 2

  聚苯乙烯负载的含自由基阴离子和二价阴离子位点7、7'的蒽镁与苄基氯化物或溴化物的反应在-10°C至20°C的THF中以中等至高收率的方式提供了格氏试剂RMgX。高产率制备的新型苄基格氏试剂包括2,6-（二氯甲基）吡啶，2,6-（二溴甲基）吡啶，2,2'2''-三吡啶基甲基氯化物，2-甲氧基-3-甲基-1-苯甲酰氯，2,4-二甲氧基-5-甲基-1-苄基氯，3,5-二甲氧基-4-苄基氯，2,4,6-三甲氧基-3-甲基-1-苄基氯和2,5-二甲氧基苄基氯。所选的烯丙基卤化物类似地产生格氏试剂。
• Strong Lewis acids derived from molybdenum and tungsten nitrosyls containing the tri-2-pyridylmethane ligand. Dynamic NMR studies of their adducts with aldehydes, ketones, and esters
  作者：J. W. Faller、Yinong Ma

  DOI：10.1021/ja00005a021

  日期：1991.2

  The doubly charged Lewis acid precursors [HC(py)3M(NO)2(CO)](SbF6)2 (M = Mo, W; HC(py)3 = tri-2-pyridylmethane) are conveniently synthesized by reaction of HC(py)3M(CO)3 and 2 equiv of NOSbF6. Facile loss of CO from the precursors generates the [HC(py)3M(NO)2](SbF6)2 Lewis acids. The Lewis acidity of the tungsten complex is greater than that of the molybdenum complex. With the H-1 NMR chemical shifts of bound crotonaldehyde as a qualitative assessment of relative acidity, the acidity of the tungsten species is comparable to that of BF3 and AlCl3, while that of the molybdenum species is similar to that of TiCl4. Analysis of the NMR spectra of the Lewis acid-organic carbonyl base adducts, which include the adducts of aldehydes, ketones, and esters, showed that eta-1-M(O = C) interactions dominate the chemistry. The barriers of rotation about the aldehyde C1-C2 bonds in the p-anisaldehyde adducts of the molybdenum and tungsten species were measured to be 12.8 and 13.7 kcal/mol, respectively, which are significantly higher than that for the free p-anisaldehyde. The exchange behavior between the E and Z isomers of the acetate adducts could be observed on the NMR time scale. The E to Z interconversion barriers of 12.2 +/- 0.1 and 12.3 +/- 0.1 kcal/mol for the methyl acetate and ethyl acetate complexes, respectively, were calculated from the results of variable-temperature proton NMR experiments. The free energy differences between the E and Z conformers of the methyl acetate and ethyl acetate adducts are 1.27 +/- 0.01 and 0.96 +/- 0.01 kcal/mol at 229 K, respectively.