tri{3,5-bis[(dimethylamino)methyl]phenyl}phosphane | 587874-34-8

• 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: tri{3,5-bis[(dimethylamino)methyl]phenyl}phosphane
• 英文别名: tris(3,5-bis[(dimethylamino)methyl]phenyl)phosphine；1-[3-bis[3,5-bis[(dimethylamino)methyl]phenyl]phosphanyl-5-[(dimethylamino)methyl]phenyl]-N,N-dimethylmethanamine
• CAS: 587874-34-8
• 化学式: C₃₆H₅₇N₆P
• 分子量: 604.863
• InChiKey: YUZCNMBZKJDPGD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  43
• 可旋转键数：
  15
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  19.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  tri{3,5-bis[(dimethylamino)methyl]phenyl}phosphane 在 双氧水 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以1.21 g的产率得到tris{3,5-bis[(dimethylamino)methyl]phenyl}phosphane oxide
  参考文献：
  名称：

  Design and synthesis of tris[bis(benzylammonium)aryl]phosphines with bulky meta-substituents

  摘要：

  A novel 3,5,3',5,3",5"-hexakis(dimethylamino)methyl substituted triphenylphosphine analogue has been prepared. The six amine functionalities of the corresponding phosphine oxide and sulfide were alkylated quantitatively with methyl iodide and benzyl bromide, as well as with G I and G2 Frechet dendrons to afford the respective hexa-ammonium triarylphosphine oxides and sulfides. The phosphine sulfide derivatives were deprotected with P(n-Bu)3 to afford a series of hexa-ammonium triarylphosphines that range from small molecules to first and second generation dendrimers (MW up to 5451.44). Upon formation of the hexa-ammonium salt a clear shift in P-31 NMR is observed, indicative for opening of the C-P-C angle of the triaryl phosphine. Calculations on the hexacationic phosphines show an increased barrier of rotation around the P-C(aryl) bond with increasing size of the N-substituents. The calculated structure of the G2-dendron alkylated hexa-ammonium triarylphosphine shows that this dendritic phosphine has a disc-like rather than a cone-like structure, with an estimated cone angle of approximately 180degrees (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(03)00467-8
• 作为产物：
  描述：

  tris{3,5-bis[(dimethylamino)methyl]phenyl}phosphane oxide 在 三氯硅烷 、 三乙胺 作用下， 以 苯 为溶剂， 反应 2.0h， 以64%的产率得到tri{3,5-bis[(dimethylamino)methyl]phenyl}phosphane
  参考文献：
  名称：

  Synthesis, coordination chemistry, and metal complex reactivity of (dimethylamino)methyl-substituted triarylphosphanes; X-ray study on [AuCl(PPh3−nArn)] (Ar=1-C6H3(CH2NMe2)2-3,5, n=1, 3; Ar=1-C6H4(CH2NMe2)-4, n=3)

  摘要：

  The synthesis of the first series of 4-mono and 3,5-bis(dimethylamino)methyl-functionalized triarylphosphanes of the general formula PPh3-nArn (Ar = 1-C6H3(CH2NMe2)(2)-3,5 (NC(H)N), n = 1 (ligand 2) or n = 3 (ligand 4); Ar = 1 -C6H4(CH2NMe2)-4 (NC(H)), n = 3 (ligand 7)) is described. These phosphanes were used for the construction of complexes of the form [AuCl(P)] and [PtCl2(P)(2)]. In these complexes selective coordination of phosphorus to the metal ion is observed. The P-31 NMR data show the formation of cis-Pt complexes, even in the case of triarylphosphane 4, which features a tris{3,5-bis(dimethylamino)methyl} substitution pattern. The structure of the gold complex of mono-3,5-functionalized triarylphosphane 2 in the solid state shows a striking resemblance to the structure of the corresponding complex [AuCl(PPh3)]. The solid-state structure of the AuCl complex of tris-4-functionalized ligand 7 differs from that of [AuCl(PPh3)] in the sign of the torsion angles. The amine functionalities in this class of gold compounds could be reacted selectively with either acid (HCl, H3PO4) to generate ammonium salts or with an alkylating agent (benzyl bromide) to afford benzyl ammonium salts, without the violation of the Au-P bond. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2005.09.009

文献信息

• Fast Suzuki–Miyaura Cross-Coupling Reaction with Hexacationic Triarylphosphine Bn-Dendriphos as Ligand
  作者：Dennis J. M. Snelders、Robert Kreiter、Judith J. Firet、Gerard van Koten、Robertus J. M. Klein Gebbink

  DOI：10.1002/adsc.200700366

  日期：2008.1.25

  The application of hexa[(dimethylamino)methyl]-functionalized triphenylphosphine (1) and its benzylammonium salt, Bn-Dendriphos (2), in the Suzuki–Miyaura cross-coupling of aryl bromides with arylboronic acids is described. The 3,5-bis[(benzyldimethylammonio)methyl] substitution pattern in 2 leads to a rate enhancement compared to both the non-ionic parent compound 1 and triphenylphospine (PPh3) itself

  描述了六[（二甲基氨基）甲基]官能化的三苯基膦（1）及其苄基铵盐Bn- Dendrisphos（2）在芳烃溴化物与芳基硼酸的Suzuki-Miyaura交叉偶联中的应用。的3,5-双[（benzyldimethylammonio）甲基]取代在图案2所导致相比，无论所述非离子母体化合物的速率增强1和三苯基膦（PPH 3）本身。同时，即使在膦/钯比为1时，所得的催化物质也对钯黑形成稳定。这些观察结果归因于膦配体的骨架中总共存在六个铵基，据推测导致不饱和膦-钯络合物。