bis[(diphenylphosphanyl)ethyl]methylamine | 200885-37-6

• 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: bis[(diphenylphosphanyl)ethyl]methylamine
• 英文别名: bis[(2-diphenylphosphino)ethyl]methylamine；N-methyl (bis(2-(diphenylphosphanyl)ethyl))amine；2-(diphenylphosphaneyl)-N-(2-(diphenylphosphaneyl)ethyl)-N-methylethan-1-amine；PNMeP；Methylamine, N,N-bis(2-diphenylphosphinoethyl)-；2-diphenylphosphanyl-N-(2-diphenylphosphanylethyl)-N-methylethanamine
• CAS: 200885-37-6
• 化学式: C₂₉H₃₁NP₂
• 分子量: 455.519
• InChiKey: MSTFNLRJWKVMMA-UHFFFAOYSA-N

物化性质

• 沸点：
  559.2±35.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  32
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  bis[(diphenylphosphanyl)ethyl]methylamine 以 乙醚 为溶剂， 生成
  参考文献：
  名称：

  Unrealized concepts of masked alkylidenes in (PNP)FeXY systems and alternative approaches to LnXmFe(IV)=CHR

  摘要：

  Treatment of PNP ligands with iron(II) halides yielded pseudo tetrahedral {(Ph2PCH2)(2)NR}FeX2 (R '' = Bu-t, 1a-X; Me, 1b-X) and {((Bu2PCH2)-Bu-i)(2)NR ''}FeX2 (R '' = Bu-t, 2a-X; Me, 2b-X) complexes, which could be mono- and dialkylated to afford various {(Ph2PCH2)(2)NR ''}FeCl(R) (R '' = Bu-t, 3a-R; Me, 3b-R), {((Bu2PCH2)-Bu-i)(2)NR ''}FeCl (R) (R '' = Bu-t, 4a-R; Me, 4b-R), {(Ph2PCH2)(2)(NBu)-Bu-t}Fe((neo)Pe)(2) (5a-(neo)Pe) and {((Bu2PCH2)-Bu-i)(2)(NBu)-Bu-t}Fe(1-nor)(2) (6a-nor). All of the complexes were high spin (S = 2), and structural studies of {(Ph2PCH2)(2)NMe}FeCl2 (1b-Cl), {((Bu2PCH2)-Bu-i)(2)(NBu)-Bu-t}FeCl2 (2a-Cl), and {((Bu2PCH2)-Bu-i)(2)(NBu)-Bu-t}FeCl(1-nor) (4a-nor), revealed chair conformations for the PNP ligands, which were calculated to have modest barriers to boat configurations via twist-boats as calculational minima. Attempts to convert these complexes to zwitterionic NCRR'Fe-containing species as "masked alkylidenes" failed to materialize. Alternative approaches involving structurally characterized diamagnetic {((Bu2PCH2)-Bu-i)(2)(NBu)-Bu-t}(CO)(2)FeCl(CO(neo)Pe) (8), the carbonylation product of 4a-neoPe, and low-valent {(Ph2PCH2CH2)(2)(NBu)-Bu-t}Fe((H2C=CHSiMe2)(2)O) (9) also failed. An analysis of orbital energies and overlap is given for alkylidenes. Covalence is identified as a crucial feature necessary for the alkylidene to metalacyclobutane transformation in metathesis. (C) 2020 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2020.114460
• 作为产物：
  描述：

  恩比兴 、 二苯基膦 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 4.0h， 以0.6538 g的产率得到bis[(diphenylphosphanyl)ethyl]methylamine
  参考文献：
  名称：

  钴夹钳配合物催化还原羧酸酯

  摘要：

  在将羧酸酯催化还原为醇的过程中，测试了具有不同取代方式的钴（I）和钴（II）钳型复合物的选择。钴钳型配合物4适用于芳族以及脂族和环状酯的氢化。机理研究表明金属配体协同反应途径。

  DOI：

  10.1002/chem.201705201

文献信息

• Ruthenium-Pincer-Catalyzed Hydrogenation of Lactams to Amino Alcohols
  作者：Jiangbo Chen、Jiaquan Wang、Tao Tu

  DOI：10.1002/asia.201800759

  日期：2018.9.4

  available ruthenium pincer complex (Ru‐MACHO‐BH) as a catalyst, the challenging direct hydrogenation of lactams and analogues has been successfully accomplished to deliver corresponding value‐added amino alcohols in good‐to‐excellent yields under mild reaction conditions. Remarkably, in addition to N‐protected lactams, unprotected ones could also be readily reduced in the presence of a catalytic amount

  通过使用市售的钌夹钳络合物（Ru‐MACHO‐BH）作为催化剂，成功完成了具有挑战性的内酰胺和类似物的直接氢化反应，以在温和的反应条件下以良好或优异的产率提供相应的增值氨基醇。值得注意的是，除了N保护的内酰胺外，在催化量的弱碱存在下甚至在中性反应条件下，未保护的内酰胺也可以轻松还原，这进一步突出了广泛的底物范围和操作效率。
• Hydrogenation or Dehydrogenation of N-Containing Heterocycles Catalyzed by a Single Manganese Complex
  作者：Viktoriia Zubar、Jannik C. Borghs、Magnus Rueping

  DOI：10.1021/acs.orglett.0c01273

  日期：2020.5.15

  A highly chemoselective base-metal catalyzed hydrogenation and acceptorless dehydrogenation of N-heterocycles is presented. A well-defined Mn complex operates at low catalyst loading (as low as 2 mol %) and under mild reaction conditions. The described catalytic system tolerates various functional groups, and the corresponding reduced heterocycles can be obtained in high yields. Experimental studies

  提出了一种高度化学选择性的贱金属催化的N-杂环氢化和无受体脱氢。明确定义的Mn络合物在低催化剂负载量（低至2 mol％）和温和的反应条件下运行。所描述的催化体系可耐受各种官能团，并且可以高收率获得相应的还原杂环。实验研究表明了金属-配体协同催化机理。
• Catalytic Hydrogenation of Cyclic Carbonates: A Practical Approach from CO₂and Epoxides to Methanol and Diols
  作者：Zhaobin Han、Liangce Rong、Jiang Wu、Lei Zhang、Zheng Wang、Kuiling Ding

  DOI：10.1002/anie.201207781

  日期：2012.12.21

  Two birds with one stone: The simultaneous production of two important bulk chemicals, methanol and ethylene glycol, from CO2 and ethylene oxide has been achieved under mild conditions by the highly efficient homogeneous catalytic hydrogenation of ethylene carbonate in the presence of a (PNP)RuII catalyst (see scheme).

  两只鸟只有一块石头：在（PNP）的存在下，碳酸亚乙酯的高效均相催化加氢反应在温和的条件下实现了从CO 2和环氧乙烷同时生产两种重要的散装化学品甲醇和乙二醇钌II催化剂（参见方案）。
• New Approach to the Chemistry of Technetium(V) and Rhenium(V) Phenylimido Complexes:  Novel [M(NPh)PNP]³⁺ Metal Fragments (M = Tc, Re; PNP = Aminodiphosphine) Suitable for the Synthesis of Stable Mixed-Ligand Compounds
  作者：Marina Porchia、Francesco Tisato、Fiorenzo Refosco、Cristina Bolzati、Mario Cavazza-Ceccato、Giuliano Bandoli、Alessandro Dolmella

  DOI：10.1021/ic048486y

  日期：2005.6.1

  Ligand-exchange reactions of the aminodiphosphine ligand bis[(2-diphenylphosphino)ethyl]amine hydrochloride (PNHP x HCl) with labile M(NPh)Cl3(PPh3)2 precursors (M = Re, Tc) in the presence of triethylamine yield monocationic phenylimido mer,cis-[M(NPh)Cl2(PNHP)]Cl (M = Re, 1; Tc, 2) intermediate complexes. X-ray analyses show that in both compounds the aminodiphosphine acts as a tridentate ligand dictating

  在三乙胺存在下，氨基二膦配体双[（2-二苯基膦基）乙基]胺盐酸盐（PNHP x HCl）与不稳定的M（NPh）Cl3（PPh3）2前体（M = Re，Tc）的配体交换反应苯基亚氨基mer，cis- [M（NPh）Cl2（PNHP）] Cl（M = Re，1; Tc，2）中间体配合物。X-射线分析表明，在两种化合物中，氨基二膦都起决定齿顺式排列的三齿配体的作用。两个氯化物配体分别在赤道和轴向位置转化为线性M-NPh部分，填充了扭曲的八面体几何形状的其余位置。如mer，cis- [Re（NPh）（OEt）Cl（PNHP）] Cl 4所确定的那样，氯离子向金属-亚氨基核心的反式是不稳定的，并且被醇基取代，而没有影响原始的几何形状。 ，涉及氨基二膦酸双[（2-二苯基膦基）乙基]甲胺（PNMeP）的配体交换反应，其中的中央仲胺已被叔胺官能团取代，或其盐酸盐（PNMeP x HCl）产生三种不同的种类，取决于实验条件：fac，cis-
• Catalytic Disproportionation of Formic Acid to Methanol by using Recyclable Silylformates
  作者：Clément Chauvier、Arnaud Imberdis、Pierre Thuéry、Thibault Cantat

  DOI：10.1002/anie.202002062

  日期：2020.8.10

  A novel strategy to prepare methanol from formic acid without an external reductant is presented. The overall process described herein consists of the disproportionation of silyl formates to methoxysilanes, catalyzed by ruthenium complexes, and the production of methanol by simple hydrolysis. Aqueous solutions of MeOH (>1 mL, >70 % yield) were prepared in this manner. The sustainability of the reaction

  提出了一种无需外部还原剂即可从甲酸制备甲醇的新策略。本文所述的总体方法包括由钌络合物催化的甲硅烷基甲酸酯歧化成甲氧基硅烷，以及通过简单水解制备甲醇。以这种方式制备MeOH的水溶液（＞ 1mL，＞ 70％产率）。反应的可持续性是通过回收含硅副产物和廉价，易于获得且对环境有益的试剂而建立的。