(2-Anilino-2-phenylethyl)diphenylphosphine | 125295-03-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (2-Anilino-2-phenylethyl)diphenylphosphine
• 英文别名: Ph2PCH2CH(Ph)NHPh；N-(2-diphenylphosphanyl-1-phenylethyl)aniline
• CAS: 125295-03-6
• 化学式: C₂₆H₂₄NP
• 分子量: 381.457
• InChiKey: PLPVUMDAWFUFAG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  bis(η3-allyl-μ-chloropalladium(II)) 、 (2-Anilino-2-phenylethyl)diphenylphosphine 以 二氯甲烷 为溶剂， 以71%的产率得到(PdCl(η3-C3H5)(Ph2PCH2CH(Ph)NHPh-κP))
  参考文献：
  名称：

  Synthesis of β-P,N Aminophosphines and Coordination Chemistry to Pd^II. X-ray Structures of [PdCl₂(Ph₂PCH₂CH(Ph)NHPh-κP,κN)] and [PdCl(η³-C₃H₅)(Ph₂PCH₂CH(Ph)NHPh-κP)]

  摘要：

  The reaction of the C=N bond in PhCH=NPh with the carbanionic species Ph2PCH2-, leading to the N-phenyl beta -aminsphosphine Ph2PCH2CH(Ph)NHPh, L-1, is described. This molecule reacts with different organic electrophiles to afford related compounds Ph2PCH2CH(Ph)NPhX (X = SiMe3, L-2; COPh, L-4), [Ph2MePCH2CH(Ph)NHPh](+)(I-), L-3, and [Ph2PCH2CH(Ph)N(Ph)CO](2), L-5, containing two amido and two phosphino functions. The coordination properties of L-1, L-2, and L-4 have been studied in palladium chemistry. The X-ray structure of [PdCl2(Ph2PCH2-CH(Ph)NHPh-kappaP,kappaN)I shows the bidentate coordination mode for the L-1 Ligand with equatorial C-Ph-N-Ph phenyl groups. [PdCl2(Ph2PCH2CH(Ph)NHPh-kappaP,kappaN)] crystallizes at 298 K in the space group P2(1)/n with cell parameters a = 10.689(2) Angstrom, b = 21.345(3) Angstrom, c = 12.282(2) Angstrom, beta = 90.294(1.2)degrees Z = 4, D-calcd = 1.526. The reaction between 2 equiv of L-1 and [PdCl(eta (3)-C3H5)](2) affords the [PdCl(eta (3)-C3H5)(Ph2PCH2CH(Ph)NHPh-kappaP)] complex in which an unexpected N-H . . . Cl intramolecular interaction has been observed by an X-ray diffraction analysis. [PdCl(eta (3)-C3H5)(Ph2PCH2CH(Ph)NHPh-kappaP)] crystallizes at 298 K in the monoclinic space group Cc with cell parameters a = 10.912(1) Angstrom, b = 17.194(2) Angstrom, c = 14.169(2) Angstrom, beta = 100.651(9)degrees Z = 4, D-calcd = 1.435. Neutral and cationic alkyl or allyl palladium chloride complexes containing L-1 are also reported as well as a neutral allyl palladium chloride complex containing L-4. Variable-temperature P-31{H-1} NMR studies on the allyl complexes show that the eta (3)/eta (1) allyl interconversion is enhanced by a positive charge and also by a N-H . . . Cl intramolecular interaction.

  DOI：

  10.1021/ic000867y
• 作为产物：
  描述：

  N-phenyl methyldiphenyl-λ⁵-phosphazene 在 lithium aluminium tetrahydride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 7.0h， 生成 (2-Anilino-2-phenylethyl)diphenylphosphine
  参考文献：
  名称：

  Diastereofacial Selectivity in the Reaction of (C-1)-Metalated Alkyldiphenylphosphine Imides with Schiff Bases

  摘要：

  erythro-2-Anilinoalkyldiphenyphosphine phenylimides are obtained by reaction of (C-1)-metalated alkyldiphenylphosphine imides with aldimines in a diastereoselective fashion. Reaction of the products with carbon dioxide or with lithium aluminum hydride leads to 2-anilinoalkyldiphenylphosphine oxides or 2-anilinoalkyldiphenylphosphines, respectively.

  DOI：

  10.1055/s-1989-27230

文献信息

• Amino‐phosphanes in Rh ^I ‐Catalyzed Hydroformylation: Hemilabile Behavior of P,N Ligands under High CO Pressure and Catalytic Properties
  作者：Jacques Andrieu、Jean‐Michel Camus、Philippe Richard、Rinaldo Poli、Luca Gonsalvi、Francesco Vizza、Maurizio Peruzzini

  DOI：10.1002/ejic.200500432

  日期：2006.1

  the number of backbone carbon atoms linking P and N decreases from 3 to 1. IR and 31P HPNMR studies in solution show that all P,N ligands adopt exclusively a κ1-P coordination mode in rhodium chloride carbonyl complexes under high CO pressure. In the solid state a κ1-P-α-amino-phosphane coordination has been ascertained by X-ray methods in trans-[RhCl(CO)(γ-P,N-1)2]. In contrast, an equilibrium between

  含有 α-、β- 或 γ-氨基磷烷配体 Ph2PCH2NEt2 (α-P,N-1)、Ph2PCH(Ar)NHPh [α-P,N-2; Ar = η6(o-C6H4Cl)Cr(CO)3], Ph2PCH2NPh2 (α-P,N-3), Ph2PCH2CH(Ph)NHPh (β-P,N), Ph2PCH2(o-C6H4–NMe2) (γ- P,N-1)、Ph2PCH(o-C6H4–CH2NHPh) (γ-P,N-2) 和 α,β-二氨基磷烷配体 Et2NCH2P(Ph)CH2CH(Ph)NHPh (α,β-N ,P,N), 在苯乙烯加氢甲酰化中进行了研究。结果表明，当连接 P 和 N 的骨架碳原子数从 3 减少到 1 时，活性增加。 溶液中的 IR 和 31P HPNMR 研究表明，所有 P，N 配体在氯化铑羰基中仅采用 κ1-P 配位模式在高 CO 压力下形成复合物。在固态中，κ1-P-α-氨基-磷烷配位已通过
• Resolution of β-aminophosphines with chiral cyclopalladated complexes
  作者：Jean-Michel Camus、Patricia Roy Garcı́a、Jacques Andrieu、Philippe Richard、Rinaldo Poli

  DOI：10.1016/j.jorganchem.2005.01.023

  日期：2005.3

  1:1 ratio. After successive crystallizations from ethanol, a d.e. of 98% was achieved for one aminophosphine palladium complex, while no significant d.e. was obtained after crystallizations from chlorinated solvents. The X-ray structure analysis has pointed out intermolecular hydrogen interactions N–H⋯Cl between the P,N ligand and the chloride ion, which are responsible for the formation and stabilization

  的分辨率外消旋手性β-氨基膦博士2 PCH 2 CH（PH）NH（AR）（大号1作为Ar = C 6 H ^ 5和大号2在Ar = 2,6-C 6 H ^ 3我镨2已通过使用不同的环palpalated配合物作为手性剂进行了研究。所得的复合物以1：1的比例提供非对映异构体加合物。从乙醇中连续结晶后，一种氨基膦钯配合物的de达到98％，而从氯化溶剂中结晶后没有获得明显的de。X射线结构分析指出了P，N配体与氯离子之间的分子间氢相互作用N–H⋯Cl，这是非对映异构体加合物的形成和稳定的原因。因此，使用含氧溶剂可通过其更强的供体特性消除此类氢相互作用，并使非对映异构体分离成为可能，从而分离出光学纯的（R）-Ph 2 PCH2 CH（Ph）NH（Ph）L 1，其绝对构型已从相关的二氯化钯配合物的X射线结构分析中确定。
• Allylpalladium( <scp>II</scp> ) Complexes with Aminophosphane Ligands: Solution Behaviour and X‐ray Structure of <i>cis</i> ‐[Pd(η ³ ‐CH ₂ CHCHPh){Ph ₂ PCH ₂ CHPhNH(2,6‐C ₆ H ₃ <i>i</i> Pr ₂ )}][PF ₆ ]
  作者：Jean‐Michel Camus、Jacques Andrieu、Philippe Richard、Rinaldo Poli

  DOI：10.1002/ejic.200300627

  日期：2004.3

  AbstractA new β‐aminophosphane L2 [Ph2PCH2CH(Ph)NH(2,6‐C6H3iPr2)], bearing an asymmetric carbon atom and a vicinal prochiral nitrogen centre and (η3‐allyl)palladium complexes of general formula [Pd(η3‐C3H4R)η2‐Ph2PCH2CH(Ph)NHAr}][PF6] (1−6) (R = H, Me or Ph and Ar = Ph or 2,6‐C6H3iPr2) have been synthesised. NMR spectroscopic studies and a crystal structure analysis of complex 6 (R = Ph, Ar = 2,6‐C6H3iPr2) confirmed the highly diastereoselective coordination of the nitrogen atom. Because of the allyl fluxionality and the presence of asymmetric centres, all the complexes exist in solution as mixtures of up to four diastereomers. For the monosubstituted allyl complexes [Pd(η3‐C3H4R)Ph2PCH2CH(Ph)NHAr}][PF6] (3−6, R = Me or Ph) only cis/trans‐P and endo/exo isomers with syn‐oriented allyl substituents have been observed in solution. The diastereomeric distribution is subject to a steric control since a modification of the steric bulk of the allyl substituents and/or N‐aryl groups strongly affect the isomers ratio. An X‐ray diffraction study of compound 6 reveals a mixture of endo and exo cis‐P syn isomers and corresponds to the first cis‐P isomer crystal structure for an N,P‐ligand allyl complex. A phase‐sensitive 2‐D NOESY NMR analysis showed that complex 1 undergoes a selective syn‐anti exchange isomerisation, involving exclusively a trans‐P opening of the η3‐allyl moiety. Therefore, η3‐η1‐η3 rearrangements in allylic complexes 1−6 were assumed to occur via the regioselective formation of a σ‐allyl intermediate. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• BARLUENGA, JOSE;LOPEZ, FERNANDO;PALACIOS, FRANCISCO, SYNTHESIS,(1989) N, C. 298-300
  作者：BARLUENGA, JOSE、LOPEZ, FERNANDO、PALACIOS, FRANCISCO

  DOI：——

  日期：——
• Diastereofacial Selectivity in the Reaction of (<i>C</i>-1)-Metalated Alkyldiphenylphosphine Imides with Schiff Bases
  作者：José Barluenga、Fernando López、Francisco Palacios

  DOI：10.1055/s-1989-27230

  日期：——

  erythro-2-Anilinoalkyldiphenyphosphine phenylimides are obtained by reaction of (C-1)-metalated alkyldiphenylphosphine imides with aldimines in a diastereoselective fashion. Reaction of the products with carbon dioxide or with lithium aluminum hydride leads to 2-anilinoalkyldiphenylphosphine oxides or 2-anilinoalkyldiphenylphosphines, respectively.

  erythro-2-Anilinoalkyldiphenyphosphine phenylimides are obtained by reaction of (C-1)-metalated alkyldiphenylphosphine imides with aldimines in a diastereoselective fashion. Reaction of the products with carbon dioxide or with lithium aluminum hydride leads to 2-anilinoalkyldiphenylphosphine oxides or 2-anilinoalkyldiphenylphosphines, respectively.