1,3-bis(1-iodo-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctan-1-yl)tetramethyldisiloxane | 1374104-95-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 1,3-bis(1-iodo-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctan-1-yl)tetramethyldisiloxane
• CAS: 1374104-95-6
• 化学式: C₂₀H₁₈F₂₆I₂OSi₂
• 分子量: 1078.3
• InChiKey: ZBOWXVXKJUSXNU-UHFFFAOYSA-N

物化性质

• 沸点：
  408.8±45.0 °C(Predicted)
• 密度：
  1.747±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  12.36
• 重原子数：
  51.0
• 可旋转键数：
  16.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  1,3-bis(1-iodo-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctan-1-yl)tetramethyldisiloxane 在 potassium fluoride 、 水 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以70%的产率得到1H,1H,2H-全氟-1-辛烯
  参考文献：
  名称：

  Siloxane based syntheses of fluorous ethenes and their tandem Heck reactions with aryl iodides

  摘要：

  Perfluoroalkyl-ethenes (RfnCH=CH2, 6a-c; a, n = 4; b, n = 6; c, n = 8) were prepared in good isolated yields (67-89%) and high purity (GC assay > 98%) from various fluorinated organosilanes in fluoride-anion assisted protodesilylation reactions. The environmentally more benign 'KF/NEt3/H2O' reagent combination introduced here was found as an effective substitute for the commonly used tetrabutylammonium-fluoride trihydrate (TBAF center dot 3H(2)O) as a fluoride source. Fluorous styrenes ((E)-RfnCH=CH-Ar, 8) were then prepared in good isolated yields (58-93%/iodoarene) and purities (GC assay > 95%) with the Pd(0) catalyzed Heck coupling of iodoarenes (Ar-1, 7) and perfluoroalkyl-ethenes generated in situ by the fluoride assisted cleavage of (beta-perfluoroalkyl-alpha-iodo-ethyl)-siloxane ((RfnCH2CH(I)SiMe2](2)O, 3) precursors in DMF solution at elevated temperatures. They are accessible by the one-pot reaction of dimethylvinylchlorosilane (CH2=CHSiMe2Cl, 2) and perfluoroalkyl iodides (R-I, 1) as we reported earlier. Similarly, the radical chain addition of C8F17I to CH2=CHSi(OMe)(3) (9) gave (beta-perfluorooctyl-alpha-iodo-ethyl)-trimethoxysilane ([C8F17CH2CH(I)]Si(OMe)(3), 10) in good yield, which then was reacted with silica gel in dry toluene to obtain an SiO2-bonded (perfluorooctyl)ethene surrogate [silica(-O-)(3)Si-CH(I)CH2C8F17, 11]. The fluoride assisted cleavage of 11 and tandem Heck reaction with iodobenzene afforded the appropriate cross-coupled product (E)-C8F17CH=CHPh. (C) 2012 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jfluchem.2012.07.010
• 作为产物：
  描述：

  四甲基二乙烯基二硅氧烷 、 全氟己基碘烷 在 sodium dithionite 、 碳酸氢钠 作用下， 以 水 、 乙腈 为溶剂， 反应 2.0h， 以70%的产率得到1,3-bis(1-iodo-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctan-1-yl)tetramethyldisiloxane
  参考文献：
  名称：

  单电子转移反应合成具有C˭C和C-C桥连基团的全氟烷基硅氧烷

  摘要：

  图形摘要 摘要 全氟烷基碘与乙烯基硅氧烷在乙腈-水混合物中由连二亚硫酸钠引发的反应在温和条件下有效进行。结果，全氟烷基键合到硅氧烷末端或侧链的 C˭C 上。随后消除或减少 C-I 桥接基团在硅氧烷上产生相应的 RfCH˭CH- 或 RfCH2CH2- 取代基团。所有氟硅氧烷均通过 FT-IR、1H NMR、19F NMR 和 EI-MS 进行表征。通过原子力显微镜和X射线光电子显微镜进一步观察了氟硅氧烷薄膜的形貌和微观结构。

  DOI：

  10.1080/10426507.2014.965814

文献信息

• Hiyama coupling reaction of fluorous alkenyl-fluorosilanes: Scope and mechanistic considerations
  作者：Ágnes Csapó、Andrea Bodor、József Rábai

  DOI：10.1016/j.jfluchem.2012.03.007

  日期：2012.5

  Novel fluorous alkenyl-fluorosilanes (CnF2n+1CH=CHSiMe2F; n = 4, 6, 8; 5a-c) were synthetized in a three step procedure from perfluoroalkyliodides and dimethylvinylchlorosilane. They were first reacted with iodobenzene at room temperature in Hiyama coupling reaction (DMF, Pd(OAc)(2), TBAF, 72 h) to afford the appropriate omega-perfluoroalkyl-styrenes (CnF2n+1CH=CHC6H5, n = 4, 6, 8): then the reactivity of 5a with monosubstituted iodobenzenes was studied. The coupling reaction of Sa with o-substituted iodobenzenes usually failed, while that of with the m- and p-substituted ones gave fluorous styrenes [m- or p-(C4F9CH=CH)C6H4X], independently of the electronic effect of their substituent (X = Br, CF3, CH3, OCH3). These volatile products can easily be isolated by steam-distilltaion and purified further by distillation. The mechanism of the above coupling reactions was a pure Hiyama type involving fluoride-ion induced transmetallation without any Heck type contribution, since no coupling product of C6F13CH=CH2 and C6H5I was observed in blank control experiments using similar conditions (DMF, TBAF, Pd(OAc)(2), 72 h, 25 degrees C). (c) 2012 Elsevier B.V. All rights reserved.