2-hydroxy-3,5-bis(1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl)benzaldehyde | 1040926-08-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-hydroxy-3,5-bis(1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl)benzaldehyde
• 英文别名: 2-hydroxy-3,5-bis(perfluorohexyl)benzaldehyde；3,5-bis-perfluorohexyl-salicylaldehyde；2-Formyl-4,6-bis(tridecafluorohexyl)phenol
• CAS: 1040926-08-6
• 化学式: C₁₉H₄F₂₆O₂
• 分子量: 758.198
• InChiKey: DCKRQEQMJUXSPQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.1
• 重原子数：
  47
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  28

反应信息

• 作为反应物：
  描述：

  2-hydroxy-3,5-bis(1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl)benzaldehyde 在 正丁基锂 、 potassium carbonate 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 48.5h， 生成 2-isopropoxy-3,5-bis(1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl)styrene
  参考文献：
  名称：

  Experimental and theoretical study of Hoveyda–Grubbs catalysts modified by perfluorohexyl ponytail in the alkoxybenzylidene ligand

  摘要：

  The alkoxybenzylidene ligand of Hoveyda-Grubbs 1st and 2nd generation catalysts was modified with one or two perfluorohexyl groups by Ullmann reaction with the aim to improve both the fluorophilicity and activity of the catalyst. While bis(perfluorohexylation) resulted in inability of the ligand to exchange tricyclohexylphosphine ligand of parent Grubbs catalysts, mono(perfluorohexylation) and subsequent ligand exchange resulted in the formation of complexes of light fluorous properties and substantially higher activity in model RCM reactions. Modification of the mesityl group of the unsaturated NHC ligand by polyfluoroalkyl ponytails resulted in the formation of ruthenium precatalyst furnishing active catalytic intermediate with light fluorous properties. DFT computations of the model initiation reaction of ethene with Hoveyda-Grubbs 2nd generation catalyst or its pentafluoroethylated counterpart revealed that in the latter, the intermediate ruthenacyclobutane can form and decompose with significantly lower energies, thus explaining its higher activity. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jfluchem.2013.06.001
• 作为产物：
  描述：

  methyl 3,5-diiodo-2-methoxybenzoate 在 2,2'-联吡啶 、 lithium aluminium tetrahydride 、 草酰氯 、 三溴化硼 、 铜 、 二甲基亚砜 作用下， 以 六氟苯 、 乙醚 、 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 80.0h， 生成 2-hydroxy-3,5-bis(1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl)benzaldehyde
  参考文献：
  名称：

  Experimental and theoretical study of Hoveyda–Grubbs catalysts modified by perfluorohexyl ponytail in the alkoxybenzylidene ligand

  摘要：

  The alkoxybenzylidene ligand of Hoveyda-Grubbs 1st and 2nd generation catalysts was modified with one or two perfluorohexyl groups by Ullmann reaction with the aim to improve both the fluorophilicity and activity of the catalyst. While bis(perfluorohexylation) resulted in inability of the ligand to exchange tricyclohexylphosphine ligand of parent Grubbs catalysts, mono(perfluorohexylation) and subsequent ligand exchange resulted in the formation of complexes of light fluorous properties and substantially higher activity in model RCM reactions. Modification of the mesityl group of the unsaturated NHC ligand by polyfluoroalkyl ponytails resulted in the formation of ruthenium precatalyst furnishing active catalytic intermediate with light fluorous properties. DFT computations of the model initiation reaction of ethene with Hoveyda-Grubbs 2nd generation catalyst or its pentafluoroethylated counterpart revealed that in the latter, the intermediate ruthenacyclobutane can form and decompose with significantly lower energies, thus explaining its higher activity. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jfluchem.2013.06.001

文献信息

• Photochemical direct perfluoroalkylation of phenols
  作者：Giacomo Filippini、Manuel Nappi、Paolo Melchiorre

  DOI：10.1016/j.tet.2015.02.034

  日期：2015.7

  A metal-free photochemical strategy for the direct aromatic perfluoroalkylation of phenols is reported. This operationally simple approach occurs at ambient temperature and under illumination by a fluorescent light bulb. The chemistry is driven by the ability of phenolate anions, transiently generated upon deprotonation of phenols, to directly reach an electronically excited state upon light absorption

  报道了苯酚的直接芳族全氟烷基化的无金属光化学策略。这种操作简单的方法发生在环境温度和荧光灯照明下。化学反应是由酚去质子时瞬间生成的酚酸根阴离子在吸收光后直接达到电子激发态的能力驱动的，同时又触发了由全氟烷基碘化物形成反应性自由基的形成。初步的力学研究已报道。
• Direct perfluoroalkylation of non-activated aromatic C–H bonds of phenols
  作者：Masato Matsugi、Masakazu Hasegawa、Shohei Hasebe、Shohei Takai、Ryusuke Suyama、Yusuke Wakita、Kanako Kudo、Hiromi Imamura、Toshiya Hayashi、Seiichi Haga

  DOI：10.1016/j.tetlet.2008.04.106

  日期：2008.6

  A simple procedure for the perfluoroalkylation of the aromatic ring of phenols under mildly basic conditions is described. Treatment of a variety of phenols with perfluoroalkyl iodide in the presence of the radical initiator V-70L and Cs2CO3 provided the corresponding perfluoroalkylated products in moderate to good yields. Generally, the reaction proceeded smoothly at room temperature to yield regioselectively

  描述了在温和碱性条件下苯酚芳环全氟烷基化的简单程序。在自由基引发剂V-70L和Cs 2 CO 3的存在下用全氟烷基碘处理各种酚，以中等至良好的产率提供了相应的全氟烷基化产物。通常，反应在室温下平稳进行，得到区域选择性的全氟烷基化产物。
• [EN] FLUOROUS METAL CHELATES COMPOSITIONS<br/>[FR] COMPOSITIONS DE CHÉLATES MÉTALLIQUES FLUORITIQUES
  申请人：THE REGENTS OF THE UNIVEFISITY OF CALIFORNIA

  公开号：WO2020118307A1

  公开（公告）日：2020-06-11

  This disclosure provides compositions of SALTAME core containing compounds and associated methods for use in tracking cells by magnetic resonance imaging (MRI), computed tomography (CT), positron emission tomography (PET), and related methods.

  这份披露提供了含有盐核心的化合物组合物以及用于通过核磁共振成像（MRI）、计算机断层扫描（CT）、正电子发射断层扫描（PET）和相关方法追踪细胞的方法。
• FLUOROUS METAL CHELATES COMPOSITIONS
  申请人：The Regents of the University of California

  公开号：US20220033424A1

  公开（公告）日：2022-02-03

  This disclosure provides compositions of SALTAME core containing compounds and associated methods for use in tracking cells by magnetic resonance imaging (MRI), computed tomography (CT), positron emission tomography (PET), and related methods.
• Experimental and theoretical study of Hoveyda–Grubbs catalysts modified by perfluorohexyl ponytail in the alkoxybenzylidene ligand
  作者：Jaroslav Kvíčala、Martin Schindler、Vendula Kelbichová、Mario Babuněk、Markéta Rybáčková、Magdalena Kvíčalová、Josef Cvačka、Anna Březinová

  DOI：10.1016/j.jfluchem.2013.06.001

  日期：2013.9

  The alkoxybenzylidene ligand of Hoveyda-Grubbs 1st and 2nd generation catalysts was modified with one or two perfluorohexyl groups by Ullmann reaction with the aim to improve both the fluorophilicity and activity of the catalyst. While bis(perfluorohexylation) resulted in inability of the ligand to exchange tricyclohexylphosphine ligand of parent Grubbs catalysts, mono(perfluorohexylation) and subsequent ligand exchange resulted in the formation of complexes of light fluorous properties and substantially higher activity in model RCM reactions. Modification of the mesityl group of the unsaturated NHC ligand by polyfluoroalkyl ponytails resulted in the formation of ruthenium precatalyst furnishing active catalytic intermediate with light fluorous properties. DFT computations of the model initiation reaction of ethene with Hoveyda-Grubbs 2nd generation catalyst or its pentafluoroethylated counterpart revealed that in the latter, the intermediate ruthenacyclobutane can form and decompose with significantly lower energies, thus explaining its higher activity. (C) 2013 Elsevier B.V. All rights reserved.