tris[4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyloxy)phenyl]phosphane

• 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: tris[4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyloxy)phenyl]phosphane
• 英文别名: Tris[4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctoxy)phenyl]phosphane
• 化学式: C₄₂H₁₈F₄₅O₃P
• 分子量: 1456.51
• InChiKey: QBOMZNLSBFAKIG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  19.9
• 重原子数：
  91
• 可旋转键数：
  27
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  48

反应信息

• 作为反应物：
  描述：

  acetylacetonatodicarbonylrhodium(l) 、 一氧化碳 、 氢气 、 tris[4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyloxy)phenyl]phosphane 以 further solvent(s) 为溶剂， 生成 、 、 、
  参考文献：
  名称：

  Hydroformylation of 1-octene with rhodium catalysts in fluorous systems

  摘要：

  Rhodium complexes associated with the fluorous phosphine P(C6H4-4-OCH2C7F15)3 (1) are active catalysts in the hydroformylation of 1-octene in biphasic fluorous systems (TOF 380 h(-1)). Selectivity in aldehydes was as much as 99% and regioselectivity in the linear aldehyde up to a n/iso ratio of 2.8. The system was efficiently recycled for two consecutive runs without decreasing conversion or selectivity. The loss of Rh in the organic layer after the first run was 0.78%. The activity increased using perfluoromethylcyclohexane as a sole solvent (TOF 1040 h(-1)). Under pressure of CO/H-2 (40 bar) the hydrido species [RhH(CO)(1)(3)] and [RhH(CO)(2)(1)(2)] were detected by high pressure NMR spectroscopy. (C) 2003 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/s1381-1169(03)00509-0
• 作为产物：
  描述：

  2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-十五氟辛-1-醇 在 三氯硅烷 、 caesium carbonate 、 三乙胺 作用下， 以 乙醚 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 45.0h， 生成 tris[4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyloxy)phenyl]phosphane
  参考文献：
  名称：

  具有氟相亲和性的三芳基膦家族的合成

  摘要：

  已经开发出一种使用氧取代基作为引入全氟链的支化点的新型全氟官能化三芳基膦的非常有效的合成方法。这种方法能够在对位、间位和邻位引入全氟尾，从而得到含有 54 至 59 wt% 氟的三苯基膦的高度全氟化类似物。该方法已扩展到 1,2-双（二苯基膦基）乙烷的全氟类似物的合成。已经测量了一些全氟膦的氟/有机分配系数，以及它们的氧化速率。

  DOI：

  10.1002/1099-0690(20021)2002:2<269::aid-ejoc269>3.0.co;2-b
• 作为试剂：
  描述：

  双丙酮半乳糖 在 四溴化碳 、 tris[4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyloxy)phenyl]phosphane 作用下， 以 甲苯 为溶剂， 反应 7.0h， 以48%的产率得到6-bromo-6-deoxy-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose
  参考文献：
  名称：

  使用氟膦将醇类转化为溴化物

  摘要：

  在甲苯中或在两相甲苯-FC-72体系中，醇与氟代膦四溴化碳络合物反应，可得到相应的溴化物，收率很高。氟氧化膦很容易通过液-液萃取分离，为均相三苯基膦-四氯化碳转化以及聚合物负载的膦方法提供了一种替代方法。可以还原氟氧化膦，并重复使用产物。

  DOI：

  10.1016/j.tetlet.2003.08.064

文献信息

• Phosphorus(III) ligands in fluorous biphase catalysis
  作者：Pravat Bhattacharyya、Ben Croxtall、Joanne Fawcett、John Fawcett、David Gudmunsen、Eric G Hope、Ray D.W Kemmitt、Danny R Paige、David R Russell、Alison M Stuart、Dan R.W Wood

  DOI：10.1016/s0022-1139(99)00166-9

  日期：2000.2

  The synthesis, coordination chemistry and catalytic applications of a series of perfluoroalkyl-substituted phosphorus(III) ligands is illustrated.

  说明了一系列全氟烷基取代的磷（III）配体的合成，配位化学和催化应用。
• A convenient access to triarylphosphines with fluorous phase affinity
  作者：Denis Sinou、Gianluca Pozzi、Eric G. Hope、Alison M. Stuart

  DOI：10.1016/s0040-4039(98)02537-4

  日期：1999.1

  Perfluorocarbon-soluble triarylphosphines with electronic properties similar to those of tris(p-methoxyphenyl)phosphine can be easily prepared through O-alkylation of tris(p-hydroxyphenyl)phosphine oxide and subsequent reduction with trichlorosilane. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Synthesis of a Family of Triarylphosphanes with Fluorous Phase Affinity
  作者：Denis Sinou、David Maillard、Gianluca Pozzi

  DOI：10.1002/1099-0690(20021)2002:2<269::aid-ejoc269>3.0.co;2-b

  日期：2002.1

  A very efficient synthesis of new perfluoro-functionalized triarylphosphanes using an oxygen substituent as the branching point for the introduction of the perfluoro chain has been developed. This approach enabled the introduction of the perfluoro tail at the para, meta, and ortho position, giving highly perfluorinated analogues of triphenylphosphane containing between 54 and 59 wt% fluorine. This

  已经开发出一种使用氧取代基作为引入全氟链的支化点的新型全氟官能化三芳基膦的非常有效的合成方法。这种方法能够在对位、间位和邻位引入全氟尾，从而得到含有 54 至 59 wt% 氟的三苯基膦的高度全氟化类似物。该方法已扩展到 1,2-双（二苯基膦基）乙烷的全氟类似物的合成。已经测量了一些全氟膦的氟/有机分配系数，以及它们的氧化速率。
• Hydroformylation of 1-octene with rhodium catalysts in fluorous systems
  作者：Ali Aghmiz、Carmen Claver、Anna M. Masdeu-Bultó、David Maillard、Denis Sinou

  DOI：10.1016/s1381-1169(03)00509-0

  日期：2004.2

  Rhodium complexes associated with the fluorous phosphine P(C6H4-4-OCH2C7F15)3 (1) are active catalysts in the hydroformylation of 1-octene in biphasic fluorous systems (TOF 380 h(-1)). Selectivity in aldehydes was as much as 99% and regioselectivity in the linear aldehyde up to a n/iso ratio of 2.8. The system was efficiently recycled for two consecutive runs without decreasing conversion or selectivity. The loss of Rh in the organic layer after the first run was 0.78%. The activity increased using perfluoromethylcyclohexane as a sole solvent (TOF 1040 h(-1)). Under pressure of CO/H-2 (40 bar) the hydrido species [RhH(CO)(1)(3)] and [RhH(CO)(2)(1)(2)] were detected by high pressure NMR spectroscopy. (C) 2003 Elsevier B.V. All rights reserved.