(E)-1-methyl-2-(3,3,4,4,5,5,6,6,6-nonafluoro-hexen-1-yl)-benzene | 1374105-06-2

• 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: (E)-1-methyl-2-(3,3,4,4,5,5,6,6,6-nonafluoro-hexen-1-yl)-benzene
• 英文别名: 1-methyl-2-(3,3,4,4,5,5,6,6,6-nonafluorohex-1-en-1-yl)benzen；1-methyl-2-[(E)-3,3,4,4,5,5,6,6,6-nonafluorohex-1-enyl]benzene
• CAS: 1374105-06-2
• 化学式: C₁₃H₉F₉
• 分子量: 336.2
• InChiKey: PLDLOODVKNEQNH-VOTSOKGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  1,3-bis(1-iodo-3,3,4,4,5,5,6,6,6-nonafluorohexan-1-yl)tetramethyldisiloxane 在 三氟化硼乙醚 、 四丁基氟化铵 、 palladium diacetate 、 二乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 180.0h， 生成 (E)-1-methyl-2-(3,3,4,4,5,5,6,6,6-nonafluoro-hexen-1-yl)-benzene
  参考文献：
  名称：

  Hiyama coupling reaction of fluorous alkenyl-fluorosilanes: Scope and mechanistic considerations

  摘要：

  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.

  DOI：

  10.1016/j.jfluchem.2012.03.007

文献信息

• Photoinduced selective perfluoroalkylation of terminal alkynes <i>via</i> electron donor–acceptor complexes
  作者：Xiaolin Shi、Bo Yu、Xin Zhou、Yong Yang

  DOI：10.1039/d4cc00105b

  日期：——

  terminal alkynes driven by the noncovalent interaction between a thymol anion and fluoroalkyl iodides. By precisely tuning the reaction solvent, a wide range of 37 structurally diverse perfluoroalkylated alkynes and alkenes, including ibuprofen, empagliflozin, galactose, isoxepac and indomethacin, were obtained in up to 92% yields. Mechanistic studies reveal the formation of EDA complexes between the

  在此，我们报道了由百里酚阴离子和氟烷基碘之间的非共价相互作用驱动的末端炔烃的光诱导选择性全氟烷基化。通过精确调节反应溶剂，获得了 37 种结构不同的全氟烷基化炔烃和烯烃，包括布洛芬、恩格列净、半乳糖、异氧派和吲哚美辛，收率高达 92%。机理研究揭示了百里酚阴离子和氟烷基碘之间形成 EDA 复合物。该策略可以为制备有用的全氟烷基化炔烃和烯烃的传统方法提供重要的补充。
• Siloxane based syntheses of fluorous ethenes and their tandem Heck reactions with aryl iodides
  作者：Ágnes Csapó、József Rábai

  DOI：10.1016/j.jfluchem.2012.07.010

  日期：2012.12

  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.