N-methyl-N-tri(propan-2-yl)germylmethanamine | 1031401-84-9

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: N-methyl-N-tri(propan-2-yl)germylmethanamine
• CAS: 1031401-84-9
• 化学式: C₁₁H₂₇GeN
• 分子量: 245.932
• InChiKey: KWLZDYDVNYSIOL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.72
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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-methyl-N-tri(propan-2-yl)germylmethanamine 、 H(GePh2)4H 以 乙腈 为溶剂， 反应 72.0h， 以53%的产率得到Prⁱ₃Ge(GePh₂)₄GePrⁱ₃
  参考文献：
  名称：

  Synthesis, structure, and properties of the hexagermane Prⁱ₃Ge(GePh₂)₄GePrⁱ₃

  摘要：

  合成了六锗烷Prⁱ₃Ge(GePh₂)₄GePrⁱ_{3>，起始物为环四锗烷(Ph2Ge)4。将(Ph2Ge)4与Br2开环得到Br(GePh2)4Br，再转化为H(GePh2)4H，然后用两等当量的Prⁱ3GeNMe2处理，通过水合锗烷反应得到Prⁱ3Ge(GePh2)4GePrⁱ3。确定了(Ph2Ge)4、Br(GePh2)4Br和Prⁱ3Ge(GePh2)4GePrⁱ3的X射线晶体结构。这种六锗烷Prⁱ3Ge(GePh2)4GePrⁱ3是迄今为止报道的结构最长的线性寡锗烷，具有类似于更大多锗烷系统的物理性质。这种六锗烷是发光的，与偏振光相互作用，在一个偏振光方向下呈淡黄色，在另一个方向下呈深蓝色。还探讨了Prⁱ3Ge(GePh2)4GePrⁱ3的电化学性质，该物种表现出预期的五个不可逆氧化波。}

  DOI：

  10.1139/cjc-2013-0485
• 作为产物：
  描述：

  ethoxy-tri(propan-2-yl)germane 以 乙醚 、 正己烷 、 苯 为溶剂， 反应 19.5h， 生成 N-methyl-N-tri(propan-2-yl)germylmethanamine
  参考文献：
  名称：

  A Series of Isopropyl-Substituted Oligogermanes Prⁱ₃Ge(GePh₂)_nGePrⁱ₃ (n = 0–3) Featuring a Luminescent and Dichroic Pentagermane Prⁱ₃Ge(GePh₂)₃GePrⁱ₃

  摘要：

  The series of oligogermanes (Pr3Ge)-Ge-i(GePh2)(n)GePr3i (n = 0, 2; n = 1, 3; n = 2, 4; n = 3, 5) were prepared by the hydrogermolysis reaction. All four species were characterized by NMR (H-1 and C-13) and UV/visible spectroscopy as well by cyclic voltammetry and differential pulse voltammetry. The oligogermanes exhibited a successive red shift in their absorbance maxima as the length of the Ge-Ge chain was increased, and these molecules also became easier to oxidize as the chain length was increased. The X-ray crystal structures of 4 and 5 as well as the trigermane HPh2GeGePh2GePh2H (6) were determined. The pentagermane 5 was shown to be dichroic in the solid state due to the packing of the individual molecules in a columnar fashion in the crystal. Pentagermane 5 is also luminescent in solution, exhibiting an emission maximum at 380 nm. The physical properties of 5, like the hexagermane (Pr3Ge)-Ge-i(GePh)(4)GePr3i, mimic the properties of the larger polygermane systems.

  DOI：

  10.1021/acs.organomet.6b00596

文献信息

• A luminescent and dichroic hexagermane
  作者：Kimberly D. Roewe、Arnold L. Rheingold、Charles S. Weinert

  DOI：10.1039/c3cc45450a

  日期：——

  The hexagermane Pri3Ge(GePh2)4GePri3 has been synthesized and is not only the first such linear oligogermane to be structurally characterized but also is the first such compound to exhibit fluorescence and dichroic properties when observed under different orientations of plane polarized visible light.

  六锗烷 Pri3Ge(GePh2)4GePri3 已被合成，它不仅是第一个进行结构表征的线性低锗烷，而且是第一个在平面偏振可见光的不同方向下观察时表现出荧光和二向色性的化合物。
• Exploring the Versatility of the Amidation of Aryl Acid Fluorides using the Germylamines R₃GeNMe₂
  作者：Vanessa A. Fortney、Julia K. Murphy、Thad R. Stancil、Milan Gembicky、Arnold L. Rheingold、Charles S. Weinert

  DOI：10.1002/asia.202300788

  日期：2023.12.14

  The formation of amide bonds is an important process since this linkage is an essential component in proteins, pharmaceuticals, and other medicinally and biologically significant molecules. Recently, it was demonstrated that germylamines R₃GeNR’₂ were useful reagents for the conversion of acid fluorides to amides. This transformation occurs readily at room temperature and has a low activation energy. In the present study, the versatility of this amidation reaction with aryl acid fluorides is investigated. A series of thirteen acid fluorides with various substituents on the aromatic ring were reacted with the germylamine Ph₃GeNMe₂ and twelve of these were converted to the corresponding amides in high yields, the exception being 1,4‐benzenedicarbonyl difluoride. The germylamines Buⁿ₃GeNMe₂ and Prⁱ₃GeNMe₂ also could be used for this interconversion, and both of these species successfully converted 1,4‐benzenedicarbonyl difluoride to the corresponding amide. In addition, the crystal structure of Ph₃GeNMe₂ is reported. This represents one of only three crystallographically characterized germylamines. The synthesis and ¹⁹F NMR characterization of three fluorogermanes R₃GeF (R=Buⁿ, Prⁱ, and Mes) are also reported herein.

  摘要酰胺键的形成是一个重要的过程，因为这种连接是蛋白质、药物和其他具有药物和生物意义的分子的重要组成部分。最近的研究表明，胚芽胺 R3GeNR'2 是将酸性氟化物转化为酰胺的有用试剂。这种转化在室温下很容易发生，而且活化能很低。本研究探讨了这种与芳基酸性氟化物的酰胺化反应的多功能性。一系列在芳香环上具有不同取代基的 13 种酸氟化物与胚芽胺 Ph3GeNMe2 发生了反应，其中 12 种以高产率转化为相应的酰胺，1,4-苯二羰基二氟化物除外。胚芽胺 Bun3GeNMe2 和 Pri3GeNMe2 也可用于这种相互转化，它们都成功地将 1,4-苯二羰基二氟化物转化为相应的酰胺。此外，还报告了 Ph3GeNMe2 的晶体结构。这是仅有的三种具有晶体学特征的胚芽胺之一。本文还报道了三种氟锗（R3GeF，R=Bun、Pri 和 Mes）的合成和 19F NMR 表征。
• Hydrogermolysis reactions involving the α-germylated nitriles R3GeCH2CN (R=Ph, Pri, But) and germanium amides R3GeNMe2 (R=Pri, But) with Ph3GeH: Substituent-dependent reactivity and crystal structures of Pri3GeGePh3 and But3Ge[NHC(CH3)CHCN]
  作者：Monika L. Amadoruge、Antonio G. DiPasquale、Arnold L. Rheingold、Charles S. Weinert

  DOI：10.1016/j.jorganchem.2008.01.045

  日期：2008.5

  The alpha-germylated nitriles R(3)GeCH(2)CN ( R = Ph, Pr(i), Bu(t)) and germanium amides R(3)GeNMe(2) (R = Pr(i) and Bu(t)) have been prepared and characterized and their reactivity with Ph(3)GeH in CH(3)CN has been explored to investigate their utility for the construction of Ge-Ge bonds. In each case the phenyl and iso-propyl derivatives furnish the corresponding digermanes R(3)GeGePh(3) (R = Ph, Pr(i)) where the amide reagents are converted to R(3)GeCH(2)CN in situ which subsequently react with Ph(3)GeH. The rate of the Ge-C bond cleavage reactions was found to depend on the steric and electronic properties of the organic substituents. Attempted synthesis of Bu(3)(t)GeGePh(3) by these methods did not result in the desired product but rather in isolation of the 3-amidocrotononitrile species Bu(3)(t)Ge[NHC(CH(3))CHCN]. The crystal structures of Pr(3)(i)GeGePh(3) and Bu(3)(t)Ge[NHC(CH(3))CHCN] have been determined. (C) 2008 Elsevier B. V. All rights reserved.
• Synthesis, structure, and properties of the hexagermane Pr^<i>i</i>₃Ge(GePh₂)₄GePr^<i>i</i>₃
  作者：Kimberly D. Roewe、James A. Golen、Arnold L. Rheingold、Charles S. Weinert

  DOI：10.1139/cjc-2013-0485

  日期：2014.6

  The synthesis of the hexagermane Prⁱ₃Ge(GePh₂)₄GePrⁱ₃ was achieved starting from the cyclotetragermane (Ph₂Ge)₄. Ring-opening of (Ph₂Ge)₄ with Br₂ yielded Br(GePh₂)₄Br that was converted to H(GePh₂)₄H, and this material was treated with two equiv. of Prⁱ₃GeNMe₂ to furnish Prⁱ₃Ge(GePh₂)₄GePrⁱ₃ via the hydrogermolysis reaction. The X-ray crystal structures of (Ph₂Ge)₄, Br(GePh₂)₄Br and Prⁱ₃Ge(GePh₂)₄GePrⁱ₃ were determined. The hexagermane Prⁱ₃Ge(GePh₂)₄GePrⁱ₃ represents the longest structurally characterized linear oligogermane reported to date and exhibits physical properties that resemble those of the larger polygermane systems. The hexagermane is luminescent and interacts with polarized light, appearing pale yellow under one orientation of polarized light and deep blue under the opposite orientation. The electrochemistry of Prⁱ₃Ge(GePh₂)₄GePrⁱ₃ was also explored, and this species exhibits the expected five irreversible oxidation waves.

  合成了六锗烷Prⁱ₃Ge(GePh₂)₄GePrⁱ_{3>，起始物为环四锗烷(Ph2Ge)4。将(Ph2Ge)4与Br2开环得到Br(GePh2)4Br，再转化为H(GePh2)4H，然后用两等当量的Prⁱ3GeNMe2处理，通过水合锗烷反应得到Prⁱ3Ge(GePh2)4GePrⁱ3。确定了(Ph2Ge)4、Br(GePh2)4Br和Prⁱ3Ge(GePh2)4GePrⁱ3的X射线晶体结构。这种六锗烷Prⁱ3Ge(GePh2)4GePrⁱ3是迄今为止报道的结构最长的线性寡锗烷，具有类似于更大多锗烷系统的物理性质。这种六锗烷是发光的，与偏振光相互作用，在一个偏振光方向下呈淡黄色，在另一个方向下呈深蓝色。还探讨了Prⁱ3Ge(GePh2)4GePrⁱ3的电化学性质，该物种表现出预期的五个不可逆氧化波。}
• A Series of Isopropyl-Substituted Oligogermanes Pr^<i>i</i>₃Ge(GePh₂)_<i>n</i>GePr^<i>i</i>₃ (<i>n</i> = 0–3) Featuring a Luminescent and Dichroic Pentagermane Pr^<i>i</i>₃Ge(GePh₂)₃GePr^<i>i</i>₃
  作者：Sangeetha P. Komanduri、F. Alexander Shumaker、Kimberly D. Roewe、Melanie Wolf、Frank Uhlig、Curtis E. Moore、Arnold L. Rheingold、Charles S. Weinert

  DOI：10.1021/acs.organomet.6b00596

  日期：2016.9.26

  The series of oligogermanes (Pr3Ge)-Ge-i(GePh2)(n)GePr3i (n = 0, 2; n = 1, 3; n = 2, 4; n = 3, 5) were prepared by the hydrogermolysis reaction. All four species were characterized by NMR (H-1 and C-13) and UV/visible spectroscopy as well by cyclic voltammetry and differential pulse voltammetry. The oligogermanes exhibited a successive red shift in their absorbance maxima as the length of the Ge-Ge chain was increased, and these molecules also became easier to oxidize as the chain length was increased. The X-ray crystal structures of 4 and 5 as well as the trigermane HPh2GeGePh2GePh2H (6) were determined. The pentagermane 5 was shown to be dichroic in the solid state due to the packing of the individual molecules in a columnar fashion in the crystal. Pentagermane 5 is also luminescent in solution, exhibiting an emission maximum at 380 nm. The physical properties of 5, like the hexagermane (Pr3Ge)-Ge-i(GePh)(4)GePr3i, mimic the properties of the larger polygermane systems.