(N-bis(N',N'-diethyl-2-aminoethyl)-4-aminomethylphenyl)diphenylphosphine | 258885-11-9

• 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: (N-bis(N',N'-diethyl-2-aminoethyl)-4-aminomethylphenyl)diphenylphosphine
• 英文别名: 4-((bis(2-diethylaminoethyl)aminomethyl)phenyl)diphenylphosphine；{4-[bis(2-diethylaminoethyl)aminomethyl]diphenyl}phosphine；(4-[bis(diethylaminoethyl)aminomethyl]diphenyl)phosphine；N3P；N'-[2-(diethylamino)ethyl]-N'-[(4-diphenylphosphanylphenyl)methyl]-N,N-diethylethane-1,2-diamine
• CAS: 258885-11-9
• 化学式: C₃₁H₄₄N₃P
• 分子量: 489.684
• InChiKey: BRMGCMDGNNENHN-UHFFFAOYSA-N

物化性质

• 沸点：
  546.2±40.0 °C(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  35
• 可旋转键数：
  15
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  9.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  cis-dichlorobis(propiononitrile)platinum(II) 、 (N-bis(N',N'-diethyl-2-aminoethyl)-4-aminomethylphenyl)diphenylphosphine 以 二氯甲烷 为溶剂， 以90%的产率得到dichloroplatinum;N'-[2-(diethylamino)ethyl]-N'-[(4-diphenylphosphanylphenyl)methyl]-N,N-diethylethane-1,2-diamine
  参考文献：
  名称：

  Synthesis, characterisation and ligand properties of a new amphiphilic triphenylphosphine analogue †

  摘要：

  {4-[双（2-二乙氨基乙基）氨基甲基]二苯基}膦，N3P，一种具有两亲性的三苯基膦（TPP）类似物，已被合成并表征。制备了其金属配合物[Rh(CO)(N3P)(acac)]和顺式[PtCl2(N3P)2]，并确定了前者的晶体结构。此外，还证明了[Rh(CO)2(acac)]和 N3P 原位形成的催化剂在均相和双相条件下对 1-己烯进行加氢甲酰化反应的可行性。

  DOI：

  10.1039/a908077e
• 作为产物：
  描述：

  N,N,N′,N′-四乙基二乙烯三胺 在 碘 、 magnesium 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 2.0h， 生成 (N-bis(N',N'-diethyl-2-aminoethyl)-4-aminomethylphenyl)diphenylphosphine
  参考文献：
  名称：

  Synthesis, characterisation and ligand properties of a new amphiphilic triphenylphosphine analogue †

  摘要：

  {4-[双（2-二乙氨基乙基）氨基甲基]二苯基}膦，N3P，一种具有两亲性的三苯基膦（TPP）类似物，已被合成并表征。制备了其金属配合物[Rh(CO)(N3P)(acac)]和顺式[PtCl2(N3P)2]，并确定了前者的晶体结构。此外，还证明了[Rh(CO)2(acac)]和 N3P 原位形成的催化剂在均相和双相条件下对 1-己烯进行加氢甲酰化反应的可行性。

  DOI：

  10.1039/a908077e

文献信息

• Regioselectivity in aqueous palladium catalysed hydroxycarbonylation of styrene: a catalytic and mechanistic study
  作者：Adriana Ionescu、G?bor Laurenczy、Ola F. Wendt

  DOI：10.1039/b607331j

  日期：——

  Regioselectivity control was studied in palladium catalysed hydroxycarbonylation of styrene in neat water with water-soluble phosphines, mostly trisulfonated triphenylphosphine, TPPTS, but also N-bis(N′,N′-diethyl-2-aminoethyl)-4-aminomethylphenyl-diphenylphosphine, N3P. The factor giving the highest changes in regioselectivity in the TPPTS system, under similar reaction conditions, is the temperature. In the N3P case, only a minor variation in the n/i ratio as a function of temperature is observed. Insitu normal- and high-pressure NMR experiments were performed to obtain further information about the catalytic cycle and the reaction intermediates. Two palladium hydride intermediates, a palladium η3-benzylic complex and both the branched and linear palladium acyl complexes were identified in the HP NMR experiments. The hydroxycarbonylation in water using styrene as a substrate operates using a hydride mechanism for pathways leading to both linear and branched product. Insertion of styrene in the palladium–hydride bond gives an η3-benzyl compound. A high CO pressure gives a kinetic preference for the iso-acyl in the next step. In the TPPTS system, at moderate temperatures, the hydrolysis of the iso-acyl is faster than its conversion to the thermodynamically more stable n-acyl. A low n/i therefore requires high pressures and reasonably low temperatures. The N3P ligand always favours the linear product since isomerisation of the iso-acyl to the n-acyl in this system is fast under all conditions investigated.

  研究了钯催化苯乙烯在纯水中与水溶性膦（主要是三硫化三苯基膦，TPPTS）发生羟基羰基化反应的区域选择性控制，也包括 N-双（N′,N′-二乙基-2-氨基乙基）-4-氨基甲基苯基-二苯基膦，N3P。在类似的反应条件下，TPPTS 系统中区域选择性变化最大的因素是温度。在 N3P 的情况下，只观察到 n/i 比率随温度的微小变化。为了进一步了解催化循环和反应中间产物，我们进行了现场常压和高压核磁共振实验。高压核磁共振实验确定了两种钯氢化物中间体、一种钯 η3-苄基络合物以及支链和线性钯酰基络合物。以苯乙烯为底物在水中进行的羟基羰基化反应是通过氢化物机制进行的，这种机制可产生线性和支化产物。苯乙烯插入钯氢键后会产生一种 η3-苄基化合物。在下一步中，高 CO 压力会使异酰基产生动力学偏好。在 TPPTS 体系中，在中等温度下，异酰基的水解快于其向热力学上更稳定的正酰基的转化。因此，低 n/i 需要高压和合理的低温。N3P 配体总是有利于线性产物，因为在所有研究条件下，该体系中异酰基向正酰基的异构化速度都很快。
• Hydroformylation of propene and 1-hexene catalysed by a α-zirconium phosphate supported rhodium-phosphine complex
  作者：Magnus Karlsson、Carlaxel Andersson、Jes Hjortkjaer

  DOI：10.1016/s1381-1169(00)00480-5

  日期：2001.2

  The reaction of the amphiphilic ligand 4-[bis(diethylaminoethyl)aminomethyl]diphenyl}phosphine with alpha -zirconium phosphate, of intermediate surface area (24m(2) g(-1)), provided a phosphine functionalised support in which electrostatic interaction between ammonium groups on the ligand and de-protonated surface hydroxyl groups on the support provided the binding force. The X-ray powder diffractogram of the material showed that the binding lowers the crystallinity of the carrier and that the ligand is not intercalated but bound at the outer surface and at the entrances to the interlamellar space. Reaction of the phosphine functionalised support with Rh(CO)(2)(acac) led to CO-phosphine exchange and formation of an immobilised complex of the composition LRh(CO)(acac) (L = surface bound phosphine). When applied as catalyst in continuous gas-phase hydroformylation of propene and in liquid phase hydroformylation of 1-hexene the immobilised complex showed intermediate activity and regioselectivity, (C) 2001 Elsevier Science B.V. All rights reserved.
• 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
• Synthesis, characterisation and ligand properties of a new amphiphilic triphenylphosphine analogue †
  作者：Magnus Karlsson、Maria Johansson、Carlaxel Andersson

  DOI：10.1039/a908077e

  日期：——

  4-[Bis(2-diethylaminoethyl)aminomethyl]diphenyl}phosphine, N3P, an analogue of triphenylphosphine (TPP) with amphiphilic character, was synthesized and characterised. Its metal complexes [Rh(CO)(N3P)(acac)] and cis-[PtCl2(N3P)2] have been prepared and the crystal structure of the former determined. The feasibility of catalysts formed in situ from [Rh(CO)2(acac)] and N3P in the hydroformylation of 1-hexene under homogeneous and biphasic conditions is also demonstrated.

  4-[双（2-二乙氨基乙基）氨基甲基]二苯基}膦，N3P，一种具有两亲性的三苯基膦（TPP）类似物，已被合成并表征。制备了其金属配合物[Rh(CO)(N3P)(acac)]和顺式[PtCl2(N3P)2]，并确定了前者的晶体结构。此外，还证明了[Rh(CO)2(acac)]和 N3P 原位形成的催化剂在均相和双相条件下对 1-己烯进行加氢甲酰化反应的可行性。