2-(4-甲基吡啶-2-基)-4-十三烷基吡啶 | 85801-76-9

• 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
• 中文名称: 2-(4-甲基吡啶-2-基)-4-十三烷基吡啶
• 英文名称: 4-methyl-4′-tridecyl-2,2′-bipyridine
• 英文别名: 4-methyl-4'-tridecyl-2,2'-bipyridine；2-(4-methylpyridin-2-yl)-4-tridecylpyridine
• CAS: 85801-76-9
• 化学式: C₂₄H₃₆N₂
• 分子量: 352.563
• InChiKey: BVMBSXRIWGULSI-UHFFFAOYSA-N

物化性质

• 沸点：
  474.3±40.0 °C(Predicted)
• 密度：
  0.948±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.6
• 重原子数：
  26
• 可旋转键数：
  13
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  oxodiperoxidomolybdenum(IV) aqua 、 2-(4-甲基吡啶-2-基)-4-十三烷基吡啶 以 甲醇 为溶剂， 生成 (4-methyl-4'-tridecyl-2,2'-bipyridine)oxodiperoxidomolybdenum(VI)
  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
• 作为产物：
  描述：

  4,4'-二甲基-2,2'-联吡啶 在 cesium fluoride 、 lithium diisopropyl amide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 24.75h， 生成 2-(4-甲基吡啶-2-基)-4-十三烷基吡啶
  参考文献：
  名称：

  Synthesis of Halomethyl and Other Bipyridine Derivatives by Reaction of 4,4‘-Bis[(trimethylsilyl)methyl]-2,2‘-bipyridine with Electrophiles in the Presence of Fluoride Ion

  摘要：

  Bipyridine (bpy) ligands figure prominently in many areas of chemistry. Common precursors to many derivatives are the halomethyl-substituted analogues. This report describes a new, high yield route to these valuable compounds via a trimethylsilyl (TMS) intermediate. 4,4'-Dimethyl-2,2'-bpy was reacted with lithium diisopropylamide, and the dianion thus formed was trapped with TMSCl to generate 4,4'-bis[(trimethylsilyl)methyl]-2,2'-bp (1). The TMS group was removed using dry F- sources (TBAF/SiO2 in THF or CsF in DMF) in the presence of BrF2CCF2Br or Cl3CCCl3 to pro duce the bromide 2 or chloride 3 analogues of 4,4'-bis(halomethyl)-2,2'-bipyridine, respectively. The CsF/DMF methodology extends to other electrophiles, including benzaldehyde to give 4,4'-bis(2-hydroxy-2-phenethyl)-2,2'-bpy, 6, as well as to alkyl halides. Benzyl Br, dodecyl Br, and alpha-chloroacetonitrile gave mixtures of di- and monoalkylated products along with the diprotonated product, 4,4'-dimethyl-2,2'-bpy.

  DOI：

  10.1021/jo971685x

文献信息

• Interaction between monomers of two surfactants derived from the [Ru(2,2′-bpy)3]2+ complex and α, β and γ-cyclodextrins: formation of [2]- and [3]-pseudorotaxanes
  作者：M. Lopez-Lopez、F. Montilla、M. Olivares、J. A. Lebron、M. L. Moya、P. Lopez-Cornejo

  DOI：10.1039/c3dt32197e

  日期：——

  Two new surfactants derived from the tris(2,2′-bipyridine) ruthenium(II) complex, [Ru(2,2′-bpy)3]2+, were synthesized and characterized: the double-tailed [Ru(2,2′-bipy)2(4,4′-(C11H23)2-2,2′-bipy)]2+ surfactant (RuC11) and the mono-tailed [Ru(2,2′-bipy)2(4-(CH3)-4′-(C13H27)-2,2′-bipy)]2+ surfactant (RuC13). The main characteristic of these species is the presence of an inorganic complex as the polar head of the surfactant with interesting luminescence properties, which were used to study the interaction of these cationic surfactants with α-, β- and γ-cyclodextrins (CD). The results showed the formation of [2]- and [3]-pseudorotaxanes. The binding constant values as well as the stoichiometry of the complexes formed were obtained; the results were confirmed, from a qualitative point of view, with NMR spectra.

  我们合成并鉴定了由三(2,2â²-联吡啶)钌(II)配合物[Ru(2,2â²-bpy)3]2+衍生的两种新型表面活性剂：双尾[Ru(2,2â²-bipy)2(4,4â²-(C11H23)2-2,2â²-bipy)]2+表面活性剂（RuC11）和单尾[Ru(2,2â²-bipy)2(4-(CH3)-4â²-(C13H27)-2,2â²-bipy)]2+表面活性剂（RuC13）。这些种类的主要特征是存在一种无机复合物，作为表面活性剂的极性头，具有有趣的发光特性，我们利用这种特性研究了这些阳离子表面活性剂与δ-、δ-和δ-环糊精（CD）的相互作用。结果显示形成了 [2]- 和 [3]- 伪紫杉烷。研究获得了结合常数以及所形成复合物的化学计量学；核磁共振光谱从定性的角度证实了这些结果。
• Photoinduced electron-transfer reactions of micelle-forming surfactant ruthenium(II) bipyridyl derivatives
  作者：Farid M. el Torki、Russell H. Schmehl、Wayne F. Reed

  DOI：10.1039/f19898500349

  日期：——

  emission maximum for complexes of the type [(bpy)2 Ru(L-L]2+ L-L = surfactant bipyridine, exhibits a bathochromic shift of ca. 15 nm upon micellization. Luminescence quenching of one complex, [(bpy)2Ru(MC17)2+(MC17 = 4-methyl-4′-heptadecyl-2-2′-bipyridine), with methyl viologen (MV2+) was examined as a function of the surfactant complex concentration by both static and dynamic luminescence measurements. Quenching

  已经制备了一系列在单个联吡啶上具有一个或两个长烷基链的表面活性剂钌（II）联吡啶基衍生物。使用表面张力测定法确定复合物的氯化物盐的临界胶束浓度，并通过静态光散射测量获得聚集体数。另外，检查了复合物的光物理性质与聚集度的关系。发射最大值的类型的配合物[（联吡啶）2的Ru（LL] 2+ LL =表面活性剂联吡啶，表现出红移约15纳米时胶束。一个复杂的，[（联吡啶）的发光猝灭2的Ru（MC17 ）2+通过静态和动态发光测量，检测了具有甲基紫精（MV 2+）的（MC17 ＝ 4-甲基-4'-十七烷基-2-2'-联吡啶）作为表面活性剂复合物浓度的函数。发现胶束化复合物的淬灭比游离表面活性剂复合物的淬灭至少慢20倍。还研究了在牺牲电子供体EDTA存在下复合物对Mv 2+的光还原与[[bpy 2 Ru（MC17）] 2+浓度的关系。MV 2+光还原的量子产率为确定并与在类似条件下使用[Ru（bpy）3 ]
• Griggs, Colin G.; Smith, David J. H., Journal of the Chemical Society. Perkin transactions I, 1982, # 12, p. 3041 - 3044
  作者：Griggs, Colin G.、Smith, David J. H.

  DOI：——

  日期：——
• GRIGGS, C. G.;SMITH, D. J. H., J. CHEM. SOC. PERKIN TRANS., 1982, N 12, 3041-3043
  作者：GRIGGS, C. G.、SMITH, D. J. H.

  DOI：——

  日期：——
• 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.