trimethylamine-dicyanohydroborane | 197140-57-1

• 英文名称: trimethylamine-dicyanohydroborane
• CAS: 197140-57-1
• 化学式: C₅H₁₀BN₃
• 分子量: 122.966
• InChiKey: VPZBYUYKKCBVKS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  trimethylamine-dicyanohydroborane 、 二乙胺 以 乙腈 为溶剂， 以89%的产率得到diethylamine-dicyanohydroborane
  参考文献：
  名称：

  Synthesis of Amine-dicyanohydroboranes, [Amine-bis(ethylnitrilium)hydroboron(2+)] Tetrafluoroborates, and Their Derivatives as Precursors of Amine-dicarboxyboranes

  摘要：

  Numerous amine-dicyanohydroboranes [A.BH(CN)(2), 1, A = quinuclidine (Q, c), trimethylamine (Me3N, d), 4-picoline (Pic, e), 4-(dimethylamino)pyridine (DMAP, f), N,N,N',N'-tetramethylethylenediamine (TMEDA, j), 1.4-diazabicyclo[2.2.2]octane (DABCO, k)] have been prepared by base exchange reactions from 4-cyanopyridine-dicyanohydroborane (4-CN-py.BH(CN)(2), 1a). In analogous experiments with secondary amines [piperidine (g), diethylamine (h), and morpholine (i)] 1a underwent aminodecyanation also, probably via SNAr mechanism, which demonstrates the strong electron-withdrawing effect of the >N.BHX2 moiety toward the substituents on the nitrogen. Amine-dicyanohydroboranes have been transformed into [amine-bis(C-hydroxy-N-ethylimidate)hydroboron(2+)] (3) [amine-N-ethylcarbamoyl(C-hydroxy-N-ethylimido)hydroboron(1+)] (4), [amine-bis(C-methoxy-N-ethylimidate)hydroboron(2+)] (5), [amine-bis(amidinium)hydroboron(2+)] (6), and [amine-bis(triethylamidinium)hydroboron(2+)] (7) cations, precursors of amine-dicarboxyboranes and their derivatives. These transformations were carried out in two steps. First, the otherwise nonreactive cyano groups were activated by ethylation employing Et3OBF4, yielding [amine-bis(ethylnitrilium)hydroboron(2+)] tetrafluoroborates (2), then 3-7 were obtained by nucleophilic addition to 2. The pK(a) values corresponding to the protonation of the N-ethylamide group were found to be extremely high (3.1-3.3), which demonstrates the strong electron-donating effect of >N.BHX2 moiety toward the substituents on the boron.

  DOI：

  10.1021/ic990023i
• 作为产物：
  描述：

  4-cyanopyridine-dicyanohydroborane 、 三甲胺 以 乙腈 为溶剂， 以97%的产率得到trimethylamine-dicyanohydroborane
  参考文献：
  名称：

  Synthesis of the first amine–dicarboxyboranes and their derivatives

  摘要：

  通过[胺双(乙基硝基)氢硼(2+)]四氟硼酸盐、[胺双(C-羟基-N-乙基亚氨基)氢硼(2 )]阳离子和胺双(N-乙基氨基甲酰基)硼烷，从胺双氰基硼烷合成了第一种胺双硼烷及其二甲酯；与硼相邻的 C-甲氧基-N-乙基亚氨基基团发生了不寻常的水解。

  DOI：

  10.1039/a702843a

文献信息

• Syntheses of the First Amine-dicarboxyboranes and Their Bis(methylester) and Bis(<i>N</i>-ethylamide) Derivatives
  作者：Béla Györi、Zoltán Berente

  DOI：10.1021/ic000557f

  日期：2001.4.1

  be isolated in very good yield. On the other hand, amine-bis(N-ethylcarbamoyl)boranes containing amines with sp(2)-hybridized N atoms (3f-k) undergo complete decomposition under similar conditions probably because of the increased hydridic character of the hydrogen adjacent to boron. Base exchange reactions starting from 4b resulted in the ammonium salts of 4c-e, h, i of composition [A.BH(COOH)(COO(-))][AH(+)]

  胺双（N-乙基氨基甲酰基）硼烷[A.BH（CONHEt）（2），3; 在对[胺-双（C-羟基）进行质子化处理后，制备了A =三甲胺（Me（3）N，a），奎尼丁（Q，b），吡啶（py，f），4-甲基吡啶（pic，g）] -N-乙基亚氨酸根）氢硼（2+）]阳离子（2），是通过[胺-双（乙基氮化）氢硼（2+）]四氟硼酸酯（1）水解而形成的。3的许多代表[A =二乙胺（Et（2）NH，c），哌啶（pip，d），吡咯烷（pyrr，e），4-氨基吡啶（4-NH（2）-py，h），4- （二甲基氨基）吡啶（DMAP，i），咪唑（Him，j），1-甲基咪唑（Mim，k）]是通过3a的碱交换反应制备的。3a-e在酸性或碱性水性介质中极其稳定，可能是由于可能的反应中心存在很大的空间位阻。但是，它们被转化为胺-二羧基硼烷[A. BH（COOH）（2），4a-e]在酸性条件下（100-130摄氏度）在酸性介质中。