1-phospha-4,5-dimethyl-3,6-diphenylnorbornadienylphosphonic acid | 176976-98-0

• 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: 1-phospha-4,5-dimethyl-3,6-diphenylnorbornadienylphosphonic acid
• 英文别名: (4,5-Dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)phosphonic acid
• CAS: 176976-98-0
• 化学式: C₂₀H₂₀O₃P₂
• 分子量: 370.325
• InChiKey: MYNQQCRRCNSVEU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  57.5
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-phospha-4,5-dimethyl-3,6-diphenylnorbornadienylphosphonic acid 在 硝酸 作用下， 以 甲醇 为溶剂， 反应 0.25h， 以55%的产率得到1-oxo-1-phospha-4,5-dimethyl-3,6-diphenylnorbornadienylphosphonic acid
  参考文献：
  名称：

  新型混合双齿配体作为智能催化剂的前体。

  摘要：

  将1-膦基降冰片二烯衍生物接枝到各种周期性组织的介孔粉末上，包括通过气溶胶技术合成的新型氧化锆/二氧化硅混合氧化物。与[Rh（CO）2] +片段络合后，这些材料在烯烃加氢中的活性高于同质材料。根据理论模型讨论了这种较高活动的原因。各种表面处理（例如酯化，干燥和用PhSi（OEt）3进行功能化）为了解活性物种的性质和形成机理提供了见识。发现基于氧化锆的材料在内部烯烃加氢甲酰化中具有活性。对这一反应机理的研究表明，异构化步骤是由路易斯酸性载体催化的，而加氢甲酰化步骤是由铑催化剂驱动的。这两个步骤的分离导致活性的增强。

  DOI：

  10.1002/chem.200500542
• 作为产物：
  描述：

  1-苯基-3,4-二甲基膦杂环戊二烯) 在 盐酸 、 水 作用下， 以 四氢呋喃 为溶剂， 反应 18.25h， 生成 1-phospha-4,5-dimethyl-3,6-diphenylnorbornadienylphosphonic acid
  参考文献：
  名称：

  Phosphanorbornadienephosphonates as a New Type of Water-Soluble Phosphines for Biphasic Catalysis

  摘要：

  The reaction of (phenylethynyl)phosphonates or- phosphonamides with 1-phenyl-3,4-dimethylphosphole at 140 degrees C affords the corresponding alpha-P(O)-substituted 1-phosphanorbornadienes (1-3). The corresponding PO3Na2 salt (5) displays some solubility in water (20 g/L) but is a poor ligand both for the rhodium-catalyzed hydrogenation and hydroformylation of olefinic bonds. The reaction of an unsubstituted ethynylphosphonamide with the same phosphole yields a 3:1 mixture of alpha- and beta-P(O)-substituted 1-phosphanorbornadienes 7 and 8. The beta-PO3Na2 salt (10) is a good ligand for the hydrogenation of (Z)-alpha-(N-acetamido)cinnamic acid and displays a high solubility in water (230 g/L). The chelation of rhodium by the alpha-P(O)-substituted 1-phosphanorbornadienes probably explains the loss of hydrogenation efficiency for [RhL(2)](+) when L = 5.

  DOI：

  10.1021/jo9521716

文献信息

• Process for the partial hydrogenation of fatty acid esters
  申请人：Papadogianakis Georgios

  公开号：US20100022664A1

  公开（公告）日：2010-01-28

  Suggested is a process for the manufacture of unsaturated fatty acid alkyl esters or glycerides having a total content of C 18:1 of about 30 to about 80 Mol-% by partial hydrogenation of unsaturated fatty acid esters having a total content of (C18:2+C18:3) of at least 65 Mol-%—calculated on the total amount of C18 moieties in the ester—which is characterised in that the hydrogenation is conducted in an aqueous/organic two phase system in the presence of a water soluble catalyst consisting of a Group VIII metal and a hydrophilic ligand.
• US8263794B2
  申请人：——

  公开号：US8263794B2

  公开（公告）日：2012-09-11
• New Hybrid Bidentate Ligands as Precursors for Smart Catalysts
  作者：Frédéric Goettmann、Cédric Boissière、David Grosso、François Mercier、Pascal Le Floch、Clément Sanchez

  DOI：10.1002/chem.200500542

  日期：2005.12.9

  grafted onto various periodically organized mesoporous powders, including a new zirconia/silica mixed oxide synthesized by aerosol techniques. After complexation with the [Rh(CO)2]+ fragment, these materials were revealed to be more active in olefin hydrogenation than their homogeneous counterparts. The reasons for this higher activity are discussed in the light of theoretical modeling. Various surface treatments

  将1-膦基降冰片二烯衍生物接枝到各种周期性组织的介孔粉末上，包括通过气溶胶技术合成的新型氧化锆/二氧化硅混合氧化物。与[Rh（CO）2] +片段络合后，这些材料在烯烃加氢中的活性高于同质材料。根据理论模型讨论了这种较高活动的原因。各种表面处理（例如酯化，干燥和用PhSi（OEt）3进行功能化）为了解活性物种的性质和形成机理提供了见识。发现基于氧化锆的材料在内部烯烃加氢甲酰化中具有活性。对这一反应机理的研究表明，异构化步骤是由路易斯酸性载体催化的，而加氢甲酰化步骤是由铑催化剂驱动的。这两个步骤的分离导致活性的增强。
• Phosphanorbornadienephosphonates as a New Type of Water-Soluble Phosphines for Biphasic Catalysis
  作者：Stéphane Lelièvre、François Mercier、François Mathey

  DOI：10.1021/jo9521716

  日期：1996.1.1

  The reaction of (phenylethynyl)phosphonates or- phosphonamides with 1-phenyl-3,4-dimethylphosphole at 140 degrees C affords the corresponding alpha-P(O)-substituted 1-phosphanorbornadienes (1-3). The corresponding PO3Na2 salt (5) displays some solubility in water (20 g/L) but is a poor ligand both for the rhodium-catalyzed hydrogenation and hydroformylation of olefinic bonds. The reaction of an unsubstituted ethynylphosphonamide with the same phosphole yields a 3:1 mixture of alpha- and beta-P(O)-substituted 1-phosphanorbornadienes 7 and 8. The beta-PO3Na2 salt (10) is a good ligand for the hydrogenation of (Z)-alpha-(N-acetamido)cinnamic acid and displays a high solubility in water (230 g/L). The chelation of rhodium by the alpha-P(O)-substituted 1-phosphanorbornadienes probably explains the loss of hydrogenation efficiency for [RhL(2)](+) when L = 5.