N,N-diisopropylaminomethyllithium | 845778-43-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N,N-diisopropylaminomethyllithium
• 英文别名: N,N-diisopropylaminomethyllithum；LiCH2N(i)Pr2
• CAS: 845778-43-0
• 化学式: C₇H₁₆LiN
• 分子量: 121.152
• InChiKey: XLWUZNHKJQTZHM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.52
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 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：

  N,N-diisopropylaminomethyllithium 、 二甲基镓氯化物 以 正己烷 为溶剂， 以69%的产率得到N,N-diisopropylaminomethyldimethylgallium
  参考文献：
  名称：

  N,N-Diisopropylaminomethyllithium:  Synthesis, Oxidative Degradation, and Organoaluminum and -gallium Derivatives

  摘要：

  N,N-Diisopropylaminomethyllithium (1) was prepared by transmetalation from (Me3SnCH2NPr2)-Pr-i and n-BuLi. It was characterized by NMR spectroscopy (H-1, C-13, Li-7). Compound 1 crystallizes as a hexamer ((LiCH2NPr2)-Pr-i)(6) and allowed the determination of the first solvent-free structure of an alpha-lithiated amine. It contains a Li-6 core (distorted octahedron) 6-fold capped by (CH2NPr2)-Pr-i units. 1 is very sensitive to air-oxidation. A partially [(LiCH2NiPr2)(4)-(LiOCH2NiPr2)(2) (2)] and a completely oxidized [((LiOCH2NPr2)-Pr-i)(6) (3)] cluster compound could be isolated. 2 and 3 were characterized by multinuclear NMR spectroscopy and by single-crystal X-ray diffraction. The results show that the hexameric structure is retained upon partial or complete oxidation. 1 was used as aminomethylating agent and reacted with Me2AlCl and Me2GaCl to give the aminomethylaluminum and -gallium compounds ((Me2MCH2NPr2)-Pr-i)(2) (M = Al, Ga), which are dimers containing six-membered rings. They were characterized by elemental analyses, NMR spectroscopy, and crystal structure determinations. They are present as dimers containing six-membered M2C2N2 rings in solution and in the solid state.

  DOI：

  10.1021/om049631i

文献信息

• Organoaluminium and -gallium compounds with N,N-diisopropylaminomethyl groups
  作者：Xin Tian、Roland Fröhlich、Norbert W. Mitzel

  DOI：10.1039/b415585h

  日期：——

  The N,N-diisopropylaminomethyl aluminium compound [tBu2AlCH2NiPr2·LiCl]2 (1) and the gallium compounds Li[tBu2Ga(CH2NiPr2)2] (2) and [tBu2GaCH2N(H)iPr2]Cl·tBu3Ga (3) were prepared by transmetallation of N,N-diisopropylaminomethyllithium LiCH2NiPr2 with di-tert-butylaluminium or -gallium chloride, and characterised by elemental analyses, multinuclear NMR spectroscopy (1H, 13C, 27Al, 7Li) and IR spectroscopy. The crystal structures have been determined by single crystal X-ray diffraction. Compound 1 aggregates as a centrosymmetric dimer, with two Al–C–N units connected by a frame of two LiCl molecules [Al–Cl 2.367(1), Cl–Li 2.339(4) and 2.374(4), Li–N 1.977(4) Å]. Compound 2 is a lithium organogallate with two weak Li⋯N bonds [1.965(7) and 1.937(7) Å]. Compound 3 contains two different moieties: tBu3Ga and a [tBu2GaCH2N(H)iPr2]+ cation, which are bridged by a Cl− anion [Ga–Cl 2.445(1) and 2.579(1), H⋯Cl 2.362(3) Å].

  N,N-二异丙基氨基甲基铝化合物[tBu2AlCH2NiPr2·LiCl]2 (1) 镓化合物Li[tBu2Ga(CH2NiPr2)2] (2)和[tBu2GaCH2N(H)iPr2]Cl·tBu3Ga(3)是通过N,N-二异丙基氨基甲基锂LiCH2NiPr2与二叔丁基铝或氯化镓进行金属转移反应制备的，并通过元素分析、多核NMR谱(1H , 13C, 27Al, 7Li) 和红外光谱。晶体结构已通过单晶X射线衍射测定。化合物 1 聚集为中心对称二聚体，两个 Al-C-N 单元通过两个 LiCl 分子框架连接 [Al-Cl 2.367(1)、Cl-Li 2.339(4) 和 2.374(4)、Li-N 1.977 (4) 一个]。化合物 2 是一种有机没食子酸锂，具有两个弱 Li⋯N 键 [1.965(7) 和 1.937(7) 一个]。化合物 3 包含两个不同的部分：tBu3Ga 和 [tBu2GaCH2N(H)iPr2]+ 阳离子，它们通过 Cl− 阴离子桥联 [Ga–Cl 2.445(1) 和 2.579(1), H⋯Cl 2.362(3) 一个]。
• <i>N,N</i>-Diisopropylaminomethyllithium:  Synthesis, Oxidative Degradation, and Organoaluminum and -gallium Derivatives
  作者：Xin Tian、Markus Woski、Christian Lustig、Tania Pape、Roland Fröhlich、Duc Le Van、Klaus Bergander、Norbert W. Mitzel

  DOI：10.1021/om049631i

  日期：2005.1.1

  N,N-Diisopropylaminomethyllithium (1) was prepared by transmetalation from (Me3SnCH2NPr2)-Pr-i and n-BuLi. It was characterized by NMR spectroscopy (H-1, C-13, Li-7). Compound 1 crystallizes as a hexamer ((LiCH2NPr2)-Pr-i)(6) and allowed the determination of the first solvent-free structure of an alpha-lithiated amine. It contains a Li-6 core (distorted octahedron) 6-fold capped by (CH2NPr2)-Pr-i units. 1 is very sensitive to air-oxidation. A partially [(LiCH2NiPr2)(4)-(LiOCH2NiPr2)(2) (2)] and a completely oxidized [((LiOCH2NPr2)-Pr-i)(6) (3)] cluster compound could be isolated. 2 and 3 were characterized by multinuclear NMR spectroscopy and by single-crystal X-ray diffraction. The results show that the hexameric structure is retained upon partial or complete oxidation. 1 was used as aminomethylating agent and reacted with Me2AlCl and Me2GaCl to give the aminomethylaluminum and -gallium compounds ((Me2MCH2NPr2)-Pr-i)(2) (M = Al, Ga), which are dimers containing six-membered rings. They were characterized by elemental analyses, NMR spectroscopy, and crystal structure determinations. They are present as dimers containing six-membered M2C2N2 rings in solution and in the solid state.