2-methoxy-5-(1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl)styrene

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-methoxy-5-(1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl)styrene
• 英文别名: 2-Ethenyl-1-methoxy-4-(1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl)benzene；2-ethenyl-1-methoxy-4-(1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl)benzene
• 化学式: C₁₅H₉F₁₃O
• 分子量: 452.215
• InChiKey: KVFBCMLQIJUUGA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  29
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  Grubbs catalyst first generation 、 2-methoxy-5-(1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl)styrene 在 copper(l) chloride 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以81.4%的产率得到dichloro[2-methoxy-5-(1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl)benzylidene](tricyclohexylphosphine)ruthenium(IV)
  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：

  2-methoxy-5-(1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl)benzaldehyde 、 甲基三苯基溴化膦 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.0h， 以90.3%的产率得到2-methoxy-5-(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

文献信息

• 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.