5,5’-bis(CF3CH2OCH2)-2,2’-bipyridine | 1290640-16-2

• 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: 5,5’-bis(CF3CH2OCH2)-2,2’-bipyridine
• 英文别名: 5,5'-bis(CF3CH2OH2)-2,2'-bpy；5,5'-Bis[(2,2,2-trifluoroethoxy)methyl]-2,2'-bipyridine；5-(2,2,2-trifluoroethoxymethyl)-2-[5-(2,2,2-trifluoroethoxymethyl)pyridin-2-yl]pyridine
• CAS: 1290640-16-2
• 化学式: C₁₆H₁₄F₆N₂O₂
• 分子量: 380.29
• InChiKey: ALSFNFRKZFIOBL-UHFFFAOYSA-N

物化性质

• 熔点：
  120 °C(Solv: dimethyl sulfoxide (67-68-5))
• 沸点：
  400.9±45.0 °C(Predicted)
• 密度：
  1.332±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  44.2
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  potassium tetrachloroplatinate(II) 、 5,5’-bis(CF3CH2OCH2)-2,2’-bipyridine 以 二甲基亚砜 为溶剂， 反应 4.0h， 以83%的产率得到
  参考文献：
  名称：

  热形条件下短链铂络合物催化氢化硅烷化：冰温下的异相分离

  摘要：

  均相催化剂 PtCl2[5,5'-bis-(n-ClCF2(CF2)3CH2OCH2)-2,2'-bpy] (2A) 和 PtCl2[5,5'-bis-(n-HCF2(CF2)3CH2OCH2) -2,2'-bpy] (2B) 含有短的氟链，被合成并用于催化炔烃的氢化硅烷化。在这些反应中，通过利用冰温下的异相分离，热变形模式被有效地用于从反应混合物中回收这些催化剂，最多八个循环。这种催化作用以前在含约 50% F 含量的铂的含氟催化剂中被观察到，但在这项工作中，F 含量的百分比降低到仅约 30%，因此我们将它们称为“非常轻的含氟” . 我们的新型含氟量有限的催化剂被认为是含氟技术领域的重要发现，因为氟原子数量的减少将有助于符合 EPA 8-碳规则。反应后的金属浸出量已通过ICP-MS检测，检测结果表明残留金属的浸出量极少。此外，将这些结果与我们之前的工作进行比较，当使用不同氟链长度的催化剂

  DOI：

  10.3390/molecules26020378
• 作为产物：
  描述：

  2,2,2-三氟乙醇 、 5,5'-二溴甲基-2,2'-联吡啶 在 甲醇 、 sodium methylate 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以75%的产率得到5,5’-bis(CF3CH2OCH2)-2,2’-bipyridine
  参考文献：
  名称：

  Synthesis and characterization of polyfluorinated 2,2′-bipyridines and their palladium and platinum complexes, [MX2(bis(RfCH2OCH2)-2,2′-bpy)] (X=Cl, Br)

  摘要：

  The fluorous-ponytailed bpy ligands at 4,4' and 5,5'-positions, 4,4'-bis(RfCH2OCH2)-2,2'-bpy and 5,5'-bis(RfCH2OCH2)-2,2'bpy, were prepared. Then these two differently positioned bpy ligands with varying fluorous lengths were treated with [PdCl2(CH3CN)(2)], [PtCl2(CH3CN)(2)], or the simple PtBr2 salt to result in the corresponding 4,4'- or 5,5'-metal halide-containing complexes, [MX2(bis(RfCH2OCH2)-2,2'-bpy)] [M = Pd or Pt; X = Cl or Br]. All of these ligands and metal complexes were fully characterized by multi-nuclei NMR (H-1, F-19 and C-13) and FTIR spectroscopy and mass spectrometry (GC/MS, EI and CI, or FAB). Additionally, single crystals of the Pd and Pt complexes with two bpy ligands were successfully obtained, and their X-ray structures are compared with their analogues. (c) 2012 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jfluchem.2012.02.009

文献信息

• Structure and emission studies of dimorphic crystals of [PtBr₂(5,5′-bis(CF₃CH₂OCH₂)-2,2′-bpy)] (1)
  作者：Norman Lu、Lauren M. Hight、David R. McMillin、Jyun-Wei Jhuo、Wei-Cheng Chung、Kwan-Yu Lin、Yuh-Sheng Wen、Ling-Kang Liu

  DOI：10.1039/c3dt52713a

  日期：——

  The yellow (1y) and orange (1o) crystalline polymorphs of [PtBr2(5,5′-bis(CF3CH2OCH2)-2,2′-bipyridine)] exhibit surprisingly short nearest neighbour Pt⋯Pt separations of 3.526 Å and 3.590 Å, respectively, at 295 K. Both distances are much shorter than those found in structures of the unsubstituted [PtBr2(2,2′-bipyridine)] analogue. Consistent with a linear chain structure in 1o and dimer formation in 1y, both solids exhibit emission spectra shifted to much longer wavelengths than that exhibited by the monomer in a low-temperature glass. Furthermore, the emission spectra of 1o and 1y shift to even longer wavelengths as the temperature decreases and the Pt⋯Pt separations contract. Till now delocalized emission of this type has been considered to be restricted to [PtCl2(diimine)] systems and implausible in PtBr2-containing analogues for steric reasons. Ironically, in the system at hand the bulky 5,5′-substituents apparently promote delocalization of the emission by forming a network of hydrogen-bonding-like C–H⋯F–C interactions that help shape the packing.

  在 295 K 下，[PtBr2(5,5â²-双(CF3CH2OCH2)-2,2â²-联吡啶)]的黄色（1y）和橙色（1o）结晶多晶体的近邻铂间距分别为 3.526 à 和 3.590 Ã。与 1o 中的线性链结构和 1y 中的二聚体形成相一致的是，这两种固体的发射光谱都偏移到了比低温玻璃中的单体所显示的更长波长。此外，随着温度的降低和 Ptâ¯Pt 间距的收缩，1o 和 1y 的发射光谱会向更长的波长移动。迄今为止，人们一直认为这种类型的非局域发射仅限于 [PtCl2(二亚胺)] 系统，而由于立体原因，在含 PtBr2 的类似物中是不可能发生的。具有讽刺意味的是，在本研究中，笨重的 5,5â²-取代基形成了一个类似于氢键的 CâHâ¯FâC 作用网络，有助于形成堆积，从而明显促进了发射的分散。
• The (2,2′-bipyridine)PtI2 complex with 5,5′-modification of fluorous side chains: Orthogonal skeleton
  作者：Ling-Kang Liu、Yi-Jing Lu、Norman Lu、Ting-You Li、Jia-Yu Huang、Chia-Her Lin、Yuh-Sheng Wen、Colin D. McMillen、Joseph S. Thrasher

  DOI：10.1016/j.jfluchem.2017.12.002

  日期：2018.2

  Two polyfluorinated PtI2-containing complexes, [5,5'-bis(RfCH2OCH2)-2,2'-bPY]PtI2 [R-f = CF3- (5,5'-3F-PtI2), HCF2CF2- (5,5'-4F-PtI2)], have been successfully synthesized. Interestingly, these two fluorous Pt-diimine complexes show two different types of structural features. For example, one fluorinated derivative 5,5'-4F-PtI2 along with 5,5'-3F-PtBr2, which has been reported before, bear similarity to the C2/c (bpy)MX2 platform. This simple (bpy)MX2 platform with C2/c symmetry consists of orthogonal synthons in maintaining the synthons as columns and belts to accompany the introduced fluorous interactions. In contrast, the other fluorinated derivative 5,5'-3F-PtI2 has been found to be completely different in the solid state. Its pattern of pi center dot center dot center dot pi a interactions is a repetition of three molecular planes with the direction of the columns normal to the molecular planes, and its C3,3'-H center dot center dot center dot I interactions are partially kept though extensively modified. The dimer-monomer units utilize pi center dot center dot center dot pi stacking along the c-direction and C-H center dot center dot center dot I hydrogen bonds along approximately the b-direction. The less dispersive fluorous components fill in space between the layers of 5,5'-3F-PtI2 molecules parallel to bc-planes, where weak C-H center dot center dot center dot F interactions are then enabled. Additionally, the electrical properties of 5,5'-3F-PtI2 and two polymorphic 5,5'-3F-PtBr2 vs. temperature have been studied. It can be easily seen that the fluorous side chain plays an important role in influencing their molecular packing, which in turn determine their electrical properties.
• Synthesis and characterization of polyfluorinated 2,2′-bipyridines and their palladium and platinum complexes, [MX2(bis(RfCH2OCH2)-2,2′-bpy)] (X=Cl, Br)
  作者：Norman Lu、Yu-Meng Ou、Tsung-Yao Feng、Wei-Jen Cheng、Wen-Han Tu、Han-Chang Su、Xiao Wang、Liu Liu、Matthew D. Hennek、Todd S. Sayler、Joseph S. Thrasher

  DOI：10.1016/j.jfluchem.2012.02.009

  日期：2012.5

  The fluorous-ponytailed bpy ligands at 4,4' and 5,5'-positions, 4,4'-bis(RfCH2OCH2)-2,2'-bpy and 5,5'-bis(RfCH2OCH2)-2,2'bpy, were prepared. Then these two differently positioned bpy ligands with varying fluorous lengths were treated with [PdCl2(CH3CN)(2)], [PtCl2(CH3CN)(2)], or the simple PtBr2 salt to result in the corresponding 4,4'- or 5,5'-metal halide-containing complexes, [MX2(bis(RfCH2OCH2)-2,2'-bpy)] [M = Pd or Pt; X = Cl or Br]. All of these ligands and metal complexes were fully characterized by multi-nuclei NMR (H-1, F-19 and C-13) and FTIR spectroscopy and mass spectrometry (GC/MS, EI and CI, or FAB). Additionally, single crystals of the Pd and Pt complexes with two bpy ligands were successfully obtained, and their X-ray structures are compared with their analogues. (c) 2012 Elsevier B.V. All rights reserved.
• Short-Chained Platinum Complex Catalyzed Hydrosilylation under Thermomorphic Conditions: Heterogeneous Phase Separation at Ice Temperature
  作者：Chiao-Fan Chiu、Jinn-Hsuan Ho、Eskedar Tessema、Yijing Lu、Chia-Rui Shen、Chang-Wei Lin、Norman Lu

  DOI：10.3390/molecules26020378

  日期：——

  chain lengths of the catalysts are used. It has been found that there exists fluorous chain assisted better selectivity towards β-(E) form in the Pt-catalyzed hydrosilylation of non-symmetric terminal alkyne when the Pt catalyst contains short fluorous chain (i.e., 4 Cs). Phenyl acetylenes showed the opposite regioselectivity due to pi-pi interaction while using the same catalyst via Markovnikov’s addition

  均相催化剂 PtCl2[5,5'-bis-(n-ClCF2(CF2)3CH2OCH2)-2,2'-bpy] (2A) 和 PtCl2[5,5'-bis-(n-HCF2(CF2)3CH2OCH2) -2,2'-bpy] (2B) 含有短的氟链，被合成并用于催化炔烃的氢化硅烷化。在这些反应中，通过利用冰温下的异相分离，热变形模式被有效地用于从反应混合物中回收这些催化剂，最多八个循环。这种催化作用以前在含约 50% F 含量的铂的含氟催化剂中被观察到，但在这项工作中，F 含量的百分比降低到仅约 30%，因此我们将它们称为“非常轻的含氟” . 我们的新型含氟量有限的催化剂被认为是含氟技术领域的重要发现，因为氟原子数量的减少将有助于符合 EPA 8-碳规则。反应后的金属浸出量已通过ICP-MS检测，检测结果表明残留金属的浸出量极少。此外，将这些结果与我们之前的工作进行比较，当使用不同氟链长度的催化剂