N-(diisopropylphosphino)-N-methylpyridin-2-amine | 1111241-71-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: N-(diisopropylphosphino)-N-methylpyridin-2-amine
• 英文别名: N-di(propan-2-yl)phosphanyl-N-methylpyridin-2-amine
• CAS: 1111241-71-4
• 化学式: C₁₂H₂₁N₂P
• 分子量: 224.286
• InChiKey: FKHQTTVVDGTWMF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  16.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trichlorotris(tetrahydrofuran)chromium(III) 、 N-(diisopropylphosphino)-N-methylpyridin-2-amine 以 四氢呋喃 为溶剂， 以78%的产率得到[PyN(Me)PⁱPr₂]CrCl₃(THF)
  参考文献：
  名称：

  Selective Ethylene Oligomerization with Chromium Complexes Bearing Pyridine–Phosphine Ligands: Influence of Ligand Structure on Catalytic Behavior

  摘要：

  Chromium complexes bearing a series of pyridinephosphine ligands have been synthesized and examined for their catalytic behavior in ethylene oligomerization. The choice of solvent, toluene versus methylcyclohexane, shows a pronounced influence on the catalytic activity for all these complexes. Variations of the ligand system have been introduced by modifying the phosphine substituents affecting ligand bite angles and flexibility. It has been demonstrated that minor differences in the ligand structure can result in remarkable changes not only in catalytic activity but also in selectivity toward a-olefins versus polyethylene and distribution of oligomeric products. Ligand PyCH2N(Me)(PPr2)-Pr-i, in combination with CrCl3(THF)(3) afforded selective ethylene tri- and tetramerization, giving 1-hexene and 1-octene with good overall selectivity and high purity, albeit with the presence of small amounts of PE.

  DOI：

  10.1021/om5003683
• 作为产物：
  描述：

  2-(甲氨基)吡啶 、 氯二异丙基膦 在 potassium hydride 作用下， 以 甲苯 为溶剂， 以71%的产率得到N-(diisopropylphosphino)-N-methylpyridin-2-amine
  参考文献：
  名称：

  用伯醇选择性催化铱催化（杂）芳族胺单烷基化的有效方法

  摘要：

  描述了多种P，N配体的有效克级合成规程。合成是通过两步反应完成的。首先，使胺去质子化，然后加入氯膦，得到相应的P，N配体。胺的去质子化通常是在低温下用n- BuLi实现的，但是要制备具有2,2'-二吡啶氨基氨基主链的配体和具有高空间需求的膦，必须将KH与反应温度110°结合使用C为盐复分解步骤。两当量选定的P，N配体与一当量铱络合物[IrCl（cod）] 2的反应（cod ＝ 1，5-环辛二烯）以定量收率得到P，N配体配位的铱配合物。这些配合物之一的X射线单晶结构分析揭示了固态的单体五配位结构。铱配合物用于形成氮的催化剂芳香胺与醇的烷基化。通过研究8种不同的P，N配体，9种不同的溶剂和14种不同的碱对催化剂体系进行了优化。底物与碱以及胺与醇的比例以及催化剂负载量的系统变化导致优化的催化反应条件。通过合成20种不同的胺显示了已开发的催化方案的底物范围，其中12种胺的分离收率可高于90％。已经

  DOI：

  10.1002/adsc.200700596

文献信息

• An Efficient Method for the Selective Iridium-Catalyzed Monoalkylation of (Hetero)aromatic Amines with Primary Alcohols
  作者：Benoît Blank、Martyna Madalska、Rhett Kempe

  DOI：10.1002/adsc.200700596

  日期：2008.3.25

  combination with reaction temperatures of 110 °C for the salt metathesis step. The reaction of two equivalents of a selected P,N ligand with one equivalent of the iridium complex [IrCl(cod)]2 (cod=1,5-cyclooctadiene) affords P,N ligand-coordinated iridium complexes in quantitative yield. X-Ray single crystal structure analysis of one of these complexes reveals a monomeric five-coordinated structure in

  描述了多种P，N配体的有效克级合成规程。合成是通过两步反应完成的。首先，使胺去质子化，然后加入氯膦，得到相应的P，N配体。胺的去质子化通常是在低温下用n- BuLi实现的，但是要制备具有2,2'-二吡啶氨基氨基主链的配体和具有高空间需求的膦，必须将KH与反应温度110°结合使用C为盐复分解步骤。两当量选定的P，N配体与一当量铱络合物[IrCl（cod）] 2的反应（cod ＝ 1，5-环辛二烯）以定量收率得到P，N配体配位的铱配合物。这些配合物之一的X射线单晶结构分析揭示了固态的单体五配位结构。铱配合物用于形成氮的催化剂芳香胺与醇的烷基化。通过研究8种不同的P，N配体，9种不同的溶剂和14种不同的碱对催化剂体系进行了优化。底物与碱以及胺与醇的比例以及催化剂负载量的系统变化导致优化的催化反应条件。通过合成20种不同的胺显示了已开发的催化方案的底物范围，其中12种胺的分离收率可高于90％。已经
• Proton-detected fast-magic-angle spinning NMR of paramagnetic inorganic solids
  作者：Jan Blahut、Ladislav Benda、Arthur L. Lejeune、Kevin J. Sanders、Benjamin Burcher、Erwann Jeanneau、David Proriol、Leonor Catita、Pierre-Alain R. Breuil、Anne-Agathe Quoineaud、Andrew J. Pell、Guido Pintacuda

  DOI：10.1039/d1ra04110j

  日期：——

  Fast (60 kHz) magic angle spinning solid-state NMR allows very sensitive proton detection in highly paramagnetic organometallic powders. We showcase this technique with the complete assignment of 1H and 13C resonances in a high-spin Fe(ii) polymerisation catalyst with less than 2 mg of sample at natural abundance.

  快速 (60 kHz) 魔角旋转固态 NMR 可以在高顺磁性有机金属粉末中进行非常灵敏的质子检测。我们展示了这项技术，在高自旋 Fe(ii) 聚合催化剂中完整分配 1H 和 13C 共振，自然丰度下的样品少于 2 mg。
• Straightforward Access to Stable, 16-Valence-Electron Phosphine-Stabilized Fe⁰ Olefin Complexes and Their Reactivity
  作者：Benjamin Burcher、Kevin J. Sanders、Ladislav Benda、Guido Pintacuda、Erwann Jeanneau、Andreas A. Danopoulos、Pierre Braunstein、Hélène Olivier-Bourbigou、Pierre-Alain R. Breuil

  DOI：10.1021/acs.organomet.6b00803

  日期：2017.2.13

  The use of the dialkene divinyltetramethyldisiloxane (dvtms) allows easy access to the reactive 16-valence-electron complexes [Fe-0 (L-L(dvtms)] (L-L = dppe (1,2-bis-(diphenylphosphino)ethane; 1), dppp (1,2-bis(diphenylphOsphino)-propane; 2), pyNMe:P('Pr)(2) (N-(diisopropylphosphino)-N-methylpyridin-2-amine; 4), dipe (1,2-bis(diisopropylphosphino)ethane; 5)) and [Fe-0(L)(2)(dvtms)] (L = PMe3; 3) by a mild reductive route using AlEt2(OEt) as reducing agent. In contrast, by the "same methodology, the 18-valence-electron complexes [Fe-0(L-L)2(ethylene)] (L-L = dppin (1,2-bis(diphenylphosphino)methane; 6),.dppa (1,2-bis-(diphenylphosphino)amine; 7), dppe (8)) were obtained, Which do not contain dvtms. In addition, a combined DFT and solid-state paramagnetic NMR methodology is introduced for the structure determination of 5. A comparative study of the reactivity of 1, 2, 4-6, and 8 with 3-hexyne highlights emerging mechanistic implications for C C coupling reactions using these complexes as catalysts.
• Selective Ethylene Oligomerization with Chromium Complexes Bearing Pyridine–Phosphine Ligands: Influence of Ligand Structure on Catalytic Behavior
  作者：Yun Yang、Joanna Gurnham、Boping Liu、Robbert Duchateau、Sandro Gambarotta、Ilia Korobkov

  DOI：10.1021/om5003683

  日期：2014.10.27

  Chromium complexes bearing a series of pyridinephosphine ligands have been synthesized and examined for their catalytic behavior in ethylene oligomerization. The choice of solvent, toluene versus methylcyclohexane, shows a pronounced influence on the catalytic activity for all these complexes. Variations of the ligand system have been introduced by modifying the phosphine substituents affecting ligand bite angles and flexibility. It has been demonstrated that minor differences in the ligand structure can result in remarkable changes not only in catalytic activity but also in selectivity toward a-olefins versus polyethylene and distribution of oligomeric products. Ligand PyCH2N(Me)(PPr2)-Pr-i, in combination with CrCl3(THF)(3) afforded selective ethylene tri- and tetramerization, giving 1-hexene and 1-octene with good overall selectivity and high purity, albeit with the presence of small amounts of PE.