N-lithio-2,4,6-trimethylborazine

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硼酸衍生物
• 英文名称: N-lithio-2,4,6-trimethylborazine
• 英文别名: 1-lithio-2,4,6-trimethylborazine；Me3(B3N3H2Li)；Lithium;2,4,6-trimethyl-1,3-diaza-5-azanida-2,4,6-triboracyclohexane；lithium;2,4,6-trimethyl-1,3-diaza-5-azanida-2,4,6-triboracyclohexane
• 化学式: C₃H₁₁B₃LiN₃
• 分子量: 128.514
• InChiKey: PBKIFOBDDHTTKM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -3.09
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  25.1
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-lithio-2,4,6-trimethylborazine 在 三溴化磷 作用下， 以 乙醚 、 正己烷 为溶剂， 以80%的产率得到bromobis(2,4,6-trimethylborazinyl)phosphane
  参考文献：
  名称：

  N ‐(2,4,6‐Trimethylborazinyl)‐Substituted Phosphanes, Arsanes, and Stibanes

  摘要：

  AbstractReaction of the N‐lithioborazine LiH2N3B3Me3·OEt2 (2) in diethyl ether with PCl3 or PBr3 leads to the borazinylphosphanes (Me3B3N3H2)PX2, (Me3B3N3H2)2PX (X = Cl, Br), and (Me3B3N3H2)3P, depending on the initial stoichiometry. The analogous arsane and stibane derivatives were obtained in a similar manner. While (Me3B3N3H2)2PBr is reduced byLiAlH4 in diethyl ether/hexane to give the monophosphane (Me3B3N3H2)2PH (13), the reaction of (Me3B3N3H2)PBr2 (5) with LiAlH4 in diethyl ether/hexane produces the zwitterionic compound [Me3B3N2(HN)]–P+H2Et (14). Dehalogenation of (Me3B3N3H2)2PBr (6) with Na yields the diphosphane (Me3B3N3H2)2PP(H2N3B3Me3)2 (18), while the mixed diphosphane (Me3B3N3H)2PPmes2 (17) is obtained from 6 and LiPmes2. Dehalogenation of Me3B3N3H2PBr2 with Na results in the exclusive formation of (Me3B3N3H2)4P4 (19), while the reaction of 5 with Li2Pmes leads to a mixture of cyclotetraphosphanes (mes)4–n(Me3B3N3H2)nP4 (A–F) along with bicyclic P4mes2. The new compounds have been characterized by NMR and IR spectroscopy and partly by mass spectrometry. X‐ray structures for compounds, 4, 5, 6, 9, 13, 14, 17, 18, 19, and E have been determined. All show different B–N bond lengths within the borazine rings, and some have borazine rings in a half‐chair conformation.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

  DOI：

  10.1002/ejic.200601001

文献信息

• N-(2,4,6-Trimethylborazinyl)-substituted Boron, Aluminum and Titanium Compounds
  作者：Birgit Gemünd、Berndt Günther、Jörg Knizek、Heinrich Nöth

  DOI：10.1515/znb-2008-0105

  日期：2008.1.1

  The N-lithioborazine LiH₂N₃B₃Me₃, 1, reacts with organoboron halides not only to the respective borazinyl organylboranes but also by Me/halogen exchange. (Me₂N)₂B-H₂N₃B₃Me₃ was obtained from 1 and (Me₂N)₂BCl. A new ten-membered B₆N₄ ring system, 5, results on treatment of Cl(Me₂N)B-B(NMe₂)Cl with 1. The B-N-borazinyl borazines 6 - 8 can be prepared from 1 and B-monohalo borazines. The synthesis of 2,4,6-trimethylborazinyl-aluminum and -titanium compounds is achieved only with mononuclear monohalides of Al(III) and Ti(IV). The 2,4,6-trimethylborazinyl- bis(piperidino)alane 9 and the tris(2,6-diisopropylphenoxo)-2,4,6-trimethylborazinyltitanium 10 were characterized by X-ray structure analysis.

  The distortion of the borazine ring by B and N substitution is discussed. In case of the N-substituted borazines YH₂N₃B₃Me₃ the B-N bonds of the YNB₂ units are elongated, e. g. for Y = PBr₂ or (RO)₃Ti, while N lithiation leads to a shortening of these B-N bond. These changes of bond lengths are also reflected by changes in the B1-N2 and B3-N3 bond lengths which become shorter in the presence of electron-withdrawing groups, but longer in case of Li substitution. Also, the bond angles B1-N2-B2 and B2-N3-B3 are affected by an increase of up to 128°.

  N-锂硼氮杂环戊烷LiH₂N₃B₃Me₃，1，不仅与有机硼卤化物反应生成相应的硼氮杂环有机硼烷，还发生Me/卤素交换反应。从1和(Me₂N)₂BCl得到了(Me₂N)₂B-H₂N₃B₃Me₃。通过用1处理Cl(Me₂N)B-B(NMe₂)Cl得到了一个新的十元环B₆N4>环系统5。硼氮硼氮杂环6-8可以通过1和B-单卤代硼氮杂环制备。只有Al(III)和Ti(IV)的单核单卤化物才能合成2,4,6-三甲基硼氮杂环铝和钛化合物。2,4,6-三甲基硼氮杂环-双(哌啶基)铝9和三(2,6-二异丙基苯氧基)-2,4,6-三甲基硼氮杂环钛10通过X射线结构分析进行了表征。

  通过B和N取代引起的硼氮杂环畸变进行了讨论。对于N取代的硼氮杂环YH₂N₃B₃Me₃，YNB₂单元的B-N键被延长，例如对于Y = PBr₂或(RO)₃Ti，而N锂化导致这些B-N键的缩短。这些键长的变化也反映在B1-N2和B3-N3键长的变化上，在电子吸引基团存在时变短，但在锂取代的情况下变长。此外，键角B1-N2-B2和B2-N3-B3受到影响，最多增加128°。