4-cyanopyridine-dicyanohydroborane | 88503-50-8

• 英文名称: 4-cyanopyridine-dicyanohydroborane
• CAS: 88503-50-8
• 化学式: C₈H₅BN₄
• 分子量: 167.965
• InChiKey: CQRHXFIZYXDBQN-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：

  吗啉 、 4-cyanopyridine-dicyanohydroborane 以 乙腈 为溶剂， 以87%的产率得到morpholine-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-氰基吡啶 、 lithium dicyanodihydroborate 在 溴 作用下， 以 乙腈 为溶剂， 以88%的产率得到4-cyanopyridine-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

文献信息

• Synthesis of the first amine–dicarboxyboranes and their derivatives
  作者：Zoltán Berente、Béla Györi

  DOI：10.1039/a702843a

  日期：——

  The first amine–dicarboxyboranes and their dimethyl esters are synthesized from amine–dicyanoboranes via [amine–bis(ethylnitrilium)hydroboron(2+)] tetrafluoroborates, [amine–bis(C-hydroxy-N-ethyliminium)hydroboron(2 )] cations and amine–bis(N-ethylcarbamoyl)boranes; C-methoxy-N-ethyliminium groups adjacent to boron undergo unusual hydrolysis.

  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。
• Pyridine Adducts of Tricyano‐ and Dicyanoboranes
  作者：Jarno Riefer、Ludwig Zapf、Raphael Wirthensohn、Philipp T. Hennig、Tatjana Ribbeck、Jan A. P. Sprenger、Nikolai V. Ignat'ev、Maik Finze

  DOI：10.1002/ejoc.202300031

  日期：——

  Efficient syntheses for pyridine and 4-cyanopyridine adducts of the strong Lewis acids BH(CN)2, B(CN)3, and BF(CN)2 starting from readily available hydridoborates are described. The different Lewis acidities of the three boranes have been assessed by the Gutmann-Becket method and by calculated fluoride ion affinities (FIA). In addition, the electrochemical properties of the borane adducts have been studied

  描述了从容易获得的氢化硼酸盐开始，高效合成强路易斯酸 BH(CN) 2、B(CN) 3和 BF(CN) 2的吡啶和 4-氰基吡啶加合物。三种硼烷的不同路易斯酸度已通过 Gutmann-Becket 方法和计算的氟离子亲和力 (FIA) 进行了评估。此外，通过循环伏安法研究了硼烷加合物的电化学性质。