3,4-bis(tridecafluoro-n-hexyl)bromobenzene | 398466-03-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3,4-bis(tridecafluoro-n-hexyl)bromobenzene
• 英文别名: 1-bromo-3,5-bis(perfluorohexyl)benzene；3,5-bis(perfluorohexyl)bromobenzene；1,3-Bis(tridecafluorohexyl)-5-bromobenzene；1-bromo-3,5-bis(1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl)benzene
• CAS: 398466-03-0
• 化学式: C₁₈H₃BrF₂₆
• 分子量: 793.084
• InChiKey: KPKQNGJGHRHXNQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.1
• 重原子数：
  45
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  26

反应信息

• 作为反应物：
  描述：

  3,4-bis(tridecafluoro-n-hexyl)bromobenzene 在 叔丁基锂 、 三氯化硼 、 sodium chloride 作用下， 以 乙醚 、 正戊烷 、 正己烷 、 溶剂黄146 为溶剂， 反应 1.0h， 以46%的产率得到sodium tetrakis(3,5-bis(perfluorohexyl)phenyl)borate
  参考文献：
  名称：

  四{3,5-双（全氟己基）苯基}硼酸酯：高氟阴离子

  摘要：

  为寻找使催化剂可溶于氟溶剂的新可能性，描述了四{3，5-双（全氟己基）苯基}硼酸硼酸钠的钠衍生物的制备，硼酸钠是一种新型的高氟阴离子。这种弱配位的阴离子对全氟化溶剂表现出显着的亲和力，因此有望与氟双相循环技术兼容的阳离子过渡金属催化剂种类繁多。

  DOI：

  10.1016/s0040-4039(01)01716-6
• 作为产物：
  描述：

  1,3-二碘苯 在 2,2'-联吡啶 、 N-溴代丁二酰亚胺(NBS) 、 铜 作用下， 以 六氟苯 、 硫酸 、 二甲基亚砜 、 三氟乙酸 为溶剂， 反应 312.0h， 生成 3,4-bis(tridecafluoro-n-hexyl)bromobenzene
  参考文献：
  名称：

  四{3,5-双（全氟己基）苯基}硼酸酯：高氟阴离子

  摘要：

  为寻找使催化剂可溶于氟溶剂的新可能性，描述了四{3，5-双（全氟己基）苯基}硼酸硼酸钠的钠衍生物的制备，硼酸钠是一种新型的高氟阴离子。这种弱配位的阴离子对全氟化溶剂表现出显着的亲和力，因此有望与氟双相循环技术兼容的阳离子过渡金属催化剂种类繁多。

  DOI：

  10.1016/s0040-4039(01)01716-6

文献信息

• Rhodium catalysed hydroformylation of alkenes using highly fluorophilic phosphines
  作者：Dave J. Adams、James A. Bennett、David J. Cole-Hamilton、Eric G. Hope、Jonathan Hopewell、Jo Kight、Peter Pogorzelec、Alison M. Stuart

  DOI：10.1039/b510766k

  日期：——

  Highly fluorophilic phosphines incorporating at least one aromatic ring containing two directly attached perfluoroalkyl groups have been synthesised, their partition coefficients (organic phase : fluorous phase) measured and their electronic properties probed using 1JPtP data for their trans-[PtCl2L2] complexes. These phosphines have been used as modifying ligands for the rhodium catalysed hydroformylation of 1-octene in perfluorocarbon solvents. Catalyst activity, regioselectivity and the levels of rhodium leaching to the product phase vary with the substitution patterns of the modifying ligands that do not correlate with the electronic properties or partition coefficients of these ligands, but can be interpreted in terms of differences in the resting states of the catalysts.

  我们合成了含有至少一个直接连接两个全氟烷基的芳香环的高亲氟膦，测量了它们的分配系数（有机相：氟相），并利用反式[PtCl2L2]配合物的 1JPtP 数据探测了它们的电子特性。这些膦已被用作在全氟碳溶剂中铑催化 1-辛烯加氢甲酰化反应的修饰配体。催化剂活性、区域选择性和铑浸出到产物相的水平随修饰配体的取代模式而变化，这些变化与这些配体的电子特性或分配系数无关，但可以用催化剂静止状态的差异来解释。
• Compensation of London Dispersion in the Gas Phase and in Aprotic Solvents
  作者：Robert Pollice、Felix Fleckenstein、Ilya Shenderovich、Peter Chen

  DOI：10.1002/anie.201905436

  日期：2019.10

  importance of London dispersion for structure and stability of molecules with less than about 200 atoms has been established in recent years but the quantitative understanding is still largely based on computations because of a persistent lack of suitable experimental data. We herein report a comprehensive computational and experimental study of the compensation of London dispersion in proton-bound dimer

  近年来，伦敦分散体对于少于200个原子的分子的结构和稳定性的重要性已经确立，但由于持续缺乏合适的实验数据，对定量的理解仍主要基于计算。我们在此报告了质子结合的二聚体解离中伦敦色散补偿的综合计算和实验研究，结果表明，极性和非极性非质子溶剂中的总补偿在很大范围内都具有很大的不变性。此外，我们发现在典型的实验温度下，溶剂补偿（约40％至80％）比气相补偿（约0％至40％）在很大程度上占优势。
• New Media for Classical Coordination Chemistry: Phase Transfer of Werner and Related Polycations into Highly Nonpolar Fluorous Solvents
  作者：Subrata K. Ghosh、Ann Sullivan Ojeda、Juan Guerrero-Leal、Nattamai Bhuvanesh、John A. Gladysz

  DOI：10.1021/ic400945u

  日期：2013.8.19

  Optimized procedures for the previously reported conversions of 1,3-diiodobenzene and perfluorohexyliodide (Rf6I; copper, DMSO, 140 degrees C) to 1,3-C6H4(R-f6)(2) (3; 86-70%) and 3 to Br(3,5-C6H3(R-f6)(2) (2; NBS, H2SO4/CF3CO2H; 88-75%) are described. The latter is converted (t-BuLi, BCl3) to the "fluorous BArf" salt NaB(3,5-C6H3(R-f6)(2))(4) (1 or NaBArf6; 77-70%), as given earlier. When orange aqueous solutions of [Co(en)(3)]Cl-3 (en = ethylenediamine) are treated with perfluoro(methylcyclohexane) (PFMC) solutions of 1 (1:3 mol ratio), the aqueous phase decolorizes and [Co(en)(3)](BArf6)(3) can be isolated from the fluorous phase (96%). Similar reactions with the trans-1,2-cyclohexanediamine analogue [Co(R,R-chxn)(3)]Cl-3 and [Ru(bipy)(3)]Cl-2 give [Co(R,R-chxn)(3)](BArf6)(3) (92%) and [Ru(bipy)(3)] (BArf6)(2) (95%). All of these salts are isolated as hydrates and exhibit toluene/PFMC partition coefficients of <= 1:>= 99, establishing that the anion BArf6- can efficiently transport polar polycations into highly nonpolar fluorous phases. When equal volumes of CH2Cl2 and PFMC are charged with the "nonfluorous" BArf (B(3,5-C6H3-(CF3)(2))(4)) salt [Co(en)(3)](BArf)(3) and 3.0 equiv of the fluorous salt NaBArf6, the cobalt trication partitions predominantly into the fluorous phase (64:36). The arene 2 crystallizes in a polar space group (tetragonal, I4, Z = 8) with fluorous and nonfluorous domains and all eight bromine atoms located essentially on one face of the unit cell.
• Fluorous Bulk Membranes for Potentiometric Sensors with Wide Selectivity Ranges:  Observation of Exceptionally Strong Ion Pair Formation
  作者：Paul G. Boswell、Philippe Bühlmann

  DOI：10.1021/ja052403a

  日期：2005.6.1

  Potentiometric sensors based on fluorous membranes doped with a fluorophilic tetraphenylborate derivative are shown to have a remarkably wide range of selectivities that exceeds the selectivity range of conventional polymeric membranes by 8 orders of magnitude. The fluorous character of these sensing membranes explains the formation of ion pairs of unprecedented strength. Ion pair formation constants in perfluoroperhydrophenanthrene, as measured in this work, are on the order of 1020 and exceed previously reported values for ion pair formation in nonpolar solvents by 6 orders of magnitude. The low solubility of lipids in such fluorous phases makes them very promising for the reduction of biofouling.
• CHEMICAL SENSOR
  申请人：The Regents of the University of Minnesota

  公开号：EP1888330A2

  公开（公告）日：2008-02-20