2,6-bis(trimethylsilylmethyl)pyridine | 85932-62-3

• 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: 2,6-bis(trimethylsilylmethyl)pyridine
• 英文别名: 2,6-Bis(trimethylsilylmethyl)pyridine；trimethyl-[[6-(trimethylsilylmethyl)pyridin-2-yl]methyl]silane
• CAS: 85932-62-3
• 化学式: C₁₃H₂₅NSi₂
• 分子量: 251.519
• InChiKey: GQBJXKKVMXLULP-UHFFFAOYSA-N

物化性质

• 沸点：
  272.2±30.0 °C(Predicted)
• 密度：
  0.880±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.92
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,6-bis(trimethylsilylmethyl)pyridine 在 正丁基锂 作用下， 以 乙醚 为溶剂， 反应 84.0h， 生成
  参考文献：
  名称：

  Kinetically Controlled Protonation of a Cyclic Phosphamethanide Complex to a PH-Phosphonium Ylide

  摘要：

  DOI：

  10.1002/1521-3773(20020916)41:18<3367::aid-anie3367>3.0.co;2-7
• 作为产物：
  描述：

  2,6-二甲基吡啶 、 二(三甲基硅基)氯甲烷 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以52%的产率得到2,6-bis(trimethylsilylmethyl)pyridine
  参考文献：
  名称：

  Olefin epoxidation in solventless conditions and apolar media catalysed by specialised oxodiperoxomolybdenum complexes

  摘要：

  The epoxidation of olefin substrates, in both apolar organic media and under solventless conditions, with aqueous hydrogen peroxide and catalysed by molybdenum complexes has been investigated. The catalysts compounds employed were the oxodiperoxomolybdenum complexes of several pyridine, 2,2'-bipyridine and pyrazole ligands with apolar functions (alkyl chains, alkyl-trimethylsilyl groups and polydimethylsiloxanyl polymer), which showed enhanced solubility in relatively apolar organic media. Both the isolated complexes and in situ preparations were catalytically active. The solubility of the new catalyst complexes appears to facilitate the catalytic activity in these systems, since activity was not observed for the analogous, insoluble complexes of unfunctionalised ligands. In these systems, the oxidant, aqueous hydrogen peroxide, forms a separate phase and the catalyst resides in the organic phase. From a green chemistry and economic perspective the elimination of organic solvents and co-catalysts from a reaction system would present advantages and, consequently, the epoxidation reaction was also investigated under solventless conditions. The 3-hexyl-5-methylpyrazole and 3-hexyl-5-heptylpyrazole complexes were found to show heightened activities, the latter being particularly efficient in these conditions, whilst bipyridines apparently inhibit the epoxidation. In addition, the mechanism of the epoxidation reaction was studied through DFT calculations for the model olefin substrate ethylene with the oxodiperoxomolybdenum complex of 3-hexyl-5-heptylpyrazole. The oxo-transfer reaction occurred by interaction of the ethylene with the peroxo ligand via the spirocyclic transition state proposed by Sharpless. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2011.02.004

文献信息

• Nickel-phosphine complex-catalyzed Grignard coupling—II
  作者：K. Tamao、S. Kodama、I. Nakajima、M. Kumada、A. Minato、K. Suzuki

  DOI：10.1016/0040-4020(82)80117-8

  日期：1982.1

  A general, versatile method for alkylation and arylation of haloheterocyclic compounds is reported. In the presence of a catalytic quantity of [NiCl2(dppp)], where dppp stands for Ph2P(CH2)3PPh2, bromothiophenes, halopyridines, haloquinoline, and haloisoquinolines reacted with alkyl and aryl Grignard reagents at room temperature or at ether refluxing temperature to give the cross-coupling products

  报道了卤代杂环化合物的烷基化和芳基化的通用方法。在催化量[NiCl 2（dppp）]（其中dppp代表Ph 2 P（CH 2）3 PPh 2）的存在下，溴噻吩，卤代吡啶，卤代喹啉和卤代异喹啉在室温或室温下与烷基和芳基格氏试剂反应在乙醚回流温度下得到交叉偶联产物。偶联反应已应用于异喹啉生物碱的合成。还研究了2-噻吩基和2-吡啶基格氏试剂的反应性。
• 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。
• 2,6-Bis(lithiumtrimethylsilylmethyl)pyridine · 2TMEDA: A monomeric dilithio compound exhibiting electrostatic charge communication
  作者：Roland Hacker、Paul von Rague Schleyer、Gabriele Reber、Gerhard Müller、Lambert Brandsma

  DOI：10.1016/0022-328x(86)82094-0

  日期：1986.11
• Synthesis and crystal structures of novel lithium- and palladium-1-azaallyls
  作者：Richard J. Bowen、Manuel A. Fernandes、Marcus Layh

  DOI：10.1016/j.jorganchem.2004.01.018

  日期：2004.4

  Treatment of (RH2C)(2)C5H3N-2,6 (R = SiMe3) with Bu"Li followed by addition of Me3SiCl gave the tetrasilyl pyridine derivative (R2HC)(2)C5H3N-2,6 1 in high yield. Further lithiation of 1 with Bu"Li and reaction of the intermediate with PhCN led to the new lithium-1-azaallyl [LiN(R)C(Ph)C(R)(C5H3N-2,6)(CHR2)}](2) 2, while metallation of the previously described di-lithium compounds [LiN(R)C(R')CH}(2)(C5H3-2,6)]Li(tmen)(n) (R = SiMe3, R' = Bu', n = 1 or R = SiMe3, R' = Ph, n = 2) with PdCl2(PhCN)(2) yielded the novel metallacycles [PdN(H)(R)C(R')CH} N(SiMe2CH2)C(R')CH}C5H3N-2,6}] 3 (R' = Bu') and [PdN(R)C(R')CH}N(R)-(H)C(R')CH} C5H3N-2,6}(2)] (R' = Ph) 4 in moderate to low yield. Compound 3 is unusual in being the first example of a crystallographically characterised PdNSiC heterocycle which is believed to be formed via an intramolecular CH-activation of a trimethylsilyl group by Pd(II). All four compounds were fully characterised by NMR-spectroscopy, microanalysis (not 4) and X-ray diffraction. (C) 2004 Elsevier B.V. All rights reserved.
• Olefin epoxidation in solventless conditions and apolar media catalysed by specialised oxodiperoxomolybdenum complexes
  作者：Matthew Herbert、Francisco Montilla、Agustín Galindo

  DOI：10.1016/j.molcata.2011.02.004

  日期：2011.2.15

  The epoxidation of olefin substrates, in both apolar organic media and under solventless conditions, with aqueous hydrogen peroxide and catalysed by molybdenum complexes has been investigated. The catalysts compounds employed were the oxodiperoxomolybdenum complexes of several pyridine, 2,2'-bipyridine and pyrazole ligands with apolar functions (alkyl chains, alkyl-trimethylsilyl groups and polydimethylsiloxanyl polymer), which showed enhanced solubility in relatively apolar organic media. Both the isolated complexes and in situ preparations were catalytically active. The solubility of the new catalyst complexes appears to facilitate the catalytic activity in these systems, since activity was not observed for the analogous, insoluble complexes of unfunctionalised ligands. In these systems, the oxidant, aqueous hydrogen peroxide, forms a separate phase and the catalyst resides in the organic phase. From a green chemistry and economic perspective the elimination of organic solvents and co-catalysts from a reaction system would present advantages and, consequently, the epoxidation reaction was also investigated under solventless conditions. The 3-hexyl-5-methylpyrazole and 3-hexyl-5-heptylpyrazole complexes were found to show heightened activities, the latter being particularly efficient in these conditions, whilst bipyridines apparently inhibit the epoxidation. In addition, the mechanism of the epoxidation reaction was studied through DFT calculations for the model olefin substrate ethylene with the oxodiperoxomolybdenum complex of 3-hexyl-5-heptylpyrazole. The oxo-transfer reaction occurred by interaction of the ethylene with the peroxo ligand via the spirocyclic transition state proposed by Sharpless. (C) 2011 Elsevier B.V. All rights reserved.