1,6-二溴全氟己烷 | 918-22-9

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氟化物
• 中文名称: 1,6-二溴全氟己烷
• 英文名称: 1,6-dibromo-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane
• 英文别名: 1,6-dibromododecafluorohexane；1,6-dibromoperfluorohexane；1,6-dibromo-1H,6H-dodecafluoro-hexane；1,6-dibromo-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-hexane
• CAS: 918-22-9
• 化学式: C₆Br₂F₁₂
• mdl: MFCD00153110
• 分子量: 459.855
• InChiKey: SWAPKQWKFYIOJS-UHFFFAOYSA-N

物化性质

• 沸点：
  142 °C
• 密度：
  2.10
• 闪点：
  141-142°C
• 稳定性/保质期：

  常温常压下稳定，避免与氧化物接触。

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  12

安全信息

• 危险品标志：
  Xi
• 危险类别码：
  R36/37/38
• 安全说明：
  S26,S37/39
• 储存条件：
  请将容器密封保存，并储存在阴凉干燥的地方。

反应信息

• 作为反应物：
  描述：

  1,6-二溴全氟己烷 在 phosphorus pentoxide 、 lead(II) bromide 、 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoro-octanedial 、 氢化铝 、 tin(ll) chloride 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 8.0h， 生成 (endo-H/endo-H)-1,6-Bis(methyl 2-O-cyclohexylcarbamoyl-6-deoxy-3,4-O-methylidin-α-L-altropyranoside) dodecafluorohexane
  参考文献：
  名称：

  Organofluorine compounds and fluorinating agents Part 17: Sonochemical-forced preparation of perfluoroalkanals and their use for non-conventional acetalations of carbohydrates

  摘要：

  The homologous 1-iodo-perfluoroalkanes 1a-1c and alpha,omega-dibromo-perfluoroalkanes 4a, 4b were carbonylated with DMF in the presence of Al/SnCl2 or Al/PbBr2 under sonication in a short reaction time. The hydrated aldehydes 2a-2c and 5a, 5b respectively were obtained in good yields allowing dehydration to 3a-3c and 6a, 6b. Some of the fluorinated aldehydes were selected as substrates in a Wittig-Homer olefination assisted by ultrasound and in non-conventional acetalations of methyl alpha-L-rhamnopyranoside (9). Thus, (E)-1-perfluorooctyl-2-phenylsulphonyl-ethene (8) was prepared from 3c and the phosphonate 7 by Wittig-Horner synthesis. Acetalations of 9 were carried out with the aldehydes (3a, 3b, 6a), hydrated aldehydes (2a, 2b), and the aldehyde hemiacetal 12 respectively, in the presence of dicyclohexylcarbodiimide (DCC). In all cases, a selective epimerization was observed at the C-atom 3 of the monosaccharide, i.e. polyfluoroalkylidenated 6-deoxy-alpha-L-altropyranosides 10, 11, 13, and 14 were obtained. (C) 1997 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-1139(96)03551-8
• 作为产物：
  描述：

  7H-全氟庚酰氟 以17%的产率得到
  参考文献：
  名称：

  ZAPEVALOV, A. YA.;FILYAKOVA, T. I.;PESCHANSKIJ, N. V.;KODESS, M. I.;KOLEN+, ZH. ORGAN. XIMII, 26,(1990) N, S. 265-272

  摘要：

  DOI：

文献信息

• Gold-Catalyzed Highly Selective Photoredox C(sp² )−H Difluoroalkylation and Perfluoroalkylation of Hydrazones
  作者：Jin Xie、Tuo Zhang、Fei Chen、Nina Mehrkens、Frank Rominger、Matthias Rudolph、A. Stephen K. Hashmi

  DOI：10.1002/anie.201508622

  日期：2016.2.18

  hydrazones are highly functionalized, versatile molecules. A mild reduction of the coupling products can efficiently produce gem‐difluoromethylated β‐amino phosphonic acids and β‐amino acid derivatives. In mechanistic studies, a difluoroalkyl radical intermediate was detected by an EPR spin‐trapping experiment, indicating that a gold‐catalyzed radical pathway is operating.

  据报道，使用容易获得的R F -Br试剂，gold的金催化光氧化还原C（sp 2）-H二氟烷基化和hydr的全氟烷基化。所得的宝石二氟甲基化和全氟烷基化的azo是高度官能化的多用途分子。偶合产物的轻度减少可以有效地生产出宝石-二氟甲基化的β-氨基膦酸和β-氨基酸衍生物。在机理研究中，通过EPR自旋捕获实验检测到二氟烷基自由基中间体，表明金催化的自由基途径正在起作用。
• Versatile Route to Arylated Fluoroalkyl Bromide Building Blocks
  作者：Peter T. Kaplan、David A. Vicic

  DOI：10.1021/acs.orglett.6b00032

  日期：2016.2.19

  fluoroalkylated silyl reagents have been prepared that react with silver and copper salts to afford active catalysts that can be used to synthesize arylated fluoroalkyl bromide building blocks. It has been shown that the [(phen)Ag(CF2)nBr] intermediates are capable of transferring both the phenanthroline ligand and the fluoroalkyl bromide chain to copper iodide, eliminating the need for a preligated copper salt precursor

  已经制备了与银盐和铜盐反应的新的双官能化和氟代烷基化的甲硅烷基试剂，以提供可以用于合成芳基化的氟代烷基溴化物结构单元的活性催化剂。已经显示[[（phen）Ag（CF 2）n Br]]中间体能够将菲咯啉配体和氟代烷基溴链转移到碘化铜上，从而不需要预连接的铜盐前体。该方法与氟代烷基卤官能度的各种链长相容。
• Practical and efficient synthesis of perfluoroalkyl iodides from perfluoroalkyl chlorides via modified sulfinatodehalogenation
  作者：Hai-Ping Cao、Qing-Yun Chen

  DOI：10.1016/j.jfluchem.2007.04.018

  日期：2007.10

  A novel two-step one pot synthesis of perfluoroalkyl iodides (α,ω-diiodoperfluoroalkanes) from perfluoroalkyl chlorides (α-chloro-ω-iodoperfluoroalkanes) has been developed by initial conversion to the corresponding sodium perfluoroalkanesulfinates with sodium dithionite and then subsequent oxidation by iodine.

  通过先用连二亚硫酸钠转化为相应的全氟烷磺酸亚磺酸钠，然后再用碘氧化，开发了一种新颖的两步一锅合成法，由全氟烷基氯化物（α-氯-ω-碘全氟烷烃）合成全氟烷基碘（α，ω-二碘全氟烷烃）。 。
• Halogen bonding in a series of Br(CF₂)_<i>n</i>Br–DABCO adducts (<i>n</i> = 4, 6, 8)
  作者：Alan K. Brisdon、Abeer M. T. Muneer、Robin G. Pritchard

  DOI：10.1107/s2053229617013663

  日期：2017.11.1

  Halogen bonding (XB) is a highly-directional class of intermolecular interactions that has been used as a powerful tool to drive the design of crystals in the solid phase. To date, the majority of XB donors have been iodine-containing compounds, with many fewer involving brominated analogues. We report the formation of adducts in the vapour phase from a series of dibromoperfluoroalkyl compounds, BrCF₂(CF₂) _n CF₂Br (n = 2, 4, 6), and 1,4-diazabicyclo[2.2.2]octane (DABCO). Single-crystal X-ray diffraction studies of the colourless crystals identified 1,4-diazabicyclo[2.2.2]octane–1,4-dibromoperfluorobutane (1/1), C₄Br₂F₈·C₆H₁₂N₂, (I), 1,4-diazabicyclo[2.2.2]octane–1,6-dibromoperfluorohexane (1/1), C₆Br₂F₁₂·C₆H₁₂N₂, (II), and 1,4-diazabicyclo[2.2.2]octane–1,8-dibromoperfluorooctane (1/1), C₈Br₂F₁₆·C₆H₁₂N₂, (III), each of which displays a one-dimensional halogen-bonded network. All three adducts exhibit N...Br distances less than the sum of the van der Waals radii, with butane analogue (I) showing the shortest N...Br halogen-bond distances yet reported between a bromoperfluorocarbon and a nitrogen base [2.809 (3) and 2.818 (3) Å], which are 0.58 and 0.59 Å shorter than the sum of the van der Waals radii.

  卤素键（XB）是一类高度定向的分子间相互作用，已被用作推动固相晶体设计的有力工具。迄今为止，大多数 XB 给体都是含碘化合物，而涉及溴化类似物的则较少。我们报告了一系列二溴全氟烷基化合物 BrCF2(CF2) n CF2Br（n = 2、4、6）和 1,4-二氮杂双环[2.2.2]辛烷 (DABCO)。无色晶体的单晶 X 射线衍射研究确定了 1,4-二氮杂双环[2.2.2]辛烷-1,4-二溴全氟丁烷 (1/1)，C4Br2F8-C6H12N2，(I)，1,4-二氮杂双环[2.2.2]辛烷-1,6-二溴全氟己烷 (1/1)，C6Br2F12-C6H12N2，(II) 和 1,4-二氮杂双环[2.2.2]辛烷-1,8-二溴全氟辛烷 (1/1)，C8Br2F16-C6H12N2，(III)，它们都显示出一维卤素键网络。所有这三种加合物的 N...Br 间距都小于范德华半径之和，其中丁烷类似物 (I) 显示了迄今所报道的溴全氟碳和氮基之间最短的 N...Br 卤素键距离 [2.809 (3) 和 2.818 (3) Å]，比范德华半径之和短 0.58 和 0.59 Å。
• Tetrafluoroethylene telomerization using dibromohaloethanes as telogens
  作者：I. Wlassics、V. Tortelli

  DOI：10.1016/j.jfluchem.2005.11.011

  日期：2006.2

  route to α,ω-dibromo perfluoroalkanes Br(CF2)nBr with n = 2, 4, 6 and 8. The selectivity of the CMT products versus those from “normal” telomerization depends mainly on the choice of telogen and on its ability to act as ‘bromine donor’ in the radical telomerization. These perfluoroalkyl dibromides are useful intermediates for other derivatives, for example, perfluorinated mono- and diolefins, Br(CF2)nCHCH2

  已经根据CMT和“正常”端粒化产生的产物分布评估了C 2 F 4和溴氯氟乙烷之间的载体介导的端粒化（CMT）。研究了引发剂和调质剂类型，TFE压力和温度等参数对反应的影响。过氧化氢引发的二溴代卤代乙烷与C 2 F 4的端粒化提供了一种简便的合成路线，可将α，ω-二溴全氟烷烃Br（CF 2）n Br与n = 2、4、6和8。CMT产品相对于“正常”端粒化产品的选择性主要取决于端粒的选择及其在自由基端粒化中充当“溴供体”的能力。这些全氟烷基二溴化物是其他衍生物的有用中间体，例如，全氟单烯烃和二烯烃Br（CF 2）n CHCH 2和CH 2 CH（CF 2）n CHCH 2。

表征谱图