K[(2,6-iPr2C6H3)N-C(C5H4N)(=CH2)] | 724425-50-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: K[(2,6-iPr2C6H3)N-C(C5H4N)(=CH2)]
• 英文别名: Potassium;[2,6-di(propan-2-yl)phenyl]-(1-pyridin-2-ylethenyl)azanide
• CAS: 724425-50-7
• 化学式: C₁₉H₂₃N₂*K
• 分子量: 318.503
• InChiKey: UEPUDRHUCJRMQT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.01
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  13.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  K[(2,6-iPr2C6H3)N-C(C5H4N)(=CH2)] 以 四氢呋喃 、 苯 为溶剂， 反应 48.0h， 生成
  参考文献：
  名称：

  第一行过渡金属和锂吡啶-烯-酰胺络合物，具有N-和C-异构体以及基于苄基CH键的配体活化

  摘要：

  Ene-amines Z-3-(2-pyridyl)-1-aza(2,6-Pr-i(2)-Ph)propene, (pynac)H, and 2-(2-pyridy1)-1-aza(2,6-R,R'-Ph)propene, (pyEA-ArRR')H, were synthesized by condensation procedures; corresponding lithium or potassium ene-amides were prepared via standard deprotonation protocols. Addition of 2 equiv of (pynac)H to {(Me3Si)(2)N}(2)Fe(THF) or 2 Li(pynac) to FeBr2(THF)(2) afforded (pynac)(2)Fe (1), while treatment of CrCl2(THE)(2), MnCl2, FeBr2(THF)(2), and CoCl(2)py(4) with 2 equiv of (pyEA-(ArPr2)-Pr-i)K afforded pseudotetrahedral (pyEA-(ArPr2)-Pr-i)(2)M (2-M, M = Cr, Mn, Fe) and (pyEA-(ArPr2)-Pr-i)(2)Co-py (2-Co-py). Diamagnetic (kappa-C,N-pyEA-(ArPr2)-Pr-i)(3)Co (3) was prepared in low yield (similar to 7%) from CoCl2, and its Co-C(sp(3)) linkages are unusually low in field strength. Reactivity studies yielded little clean reactivity, but thermolysis of 2-Co-py afforded the bis-indolamide derivative -{kappa-N,N-N(C6H3(2-Pr-i)CMe2C(Me)(2-py)}(2)Co (5-Co), and related thermolyses of 2-M (M = Cr, Mn, Fe), conducted on NMA. tube scales, generated related 5-M (M = Cr, Mn, Fe) at roughly the same rates. This observation prompted thermolyses of (pyEA-ArRR')Li, which rearrange to their corresponding indolamides in >90% yields. Rate studies, accompanied by KLE and EIE observations, revealed that an initial hydrogen transfer is reversible and is likely to correspond to an anionic rearrangement, whereas C-C bond formation is rate-determining, as suggested by accompanying calculations. X-ray structure determinations of 1, 2-Fe, 2-Co-py, 3, and 5-Co were conducted.

  DOI：

  10.1021/acs.organomet.5b00385
• 作为产物：
  描述：

  2,6-diisopropyl-N-(1-(pyridin-2-yl)ethylidene)aniline 在 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 50.0h， 以99%的产率得到K[(2,6-iPr2C6H3)N-C(C5H4N)(=CH2)]
  参考文献：
  名称：

  第一行过渡金属和锂吡啶-烯-酰胺络合物，具有N-和C-异构体以及基于苄基CH键的配体活化

  摘要：

  Ene-amines Z-3-(2-pyridyl)-1-aza(2,6-Pr-i(2)-Ph)propene, (pynac)H, and 2-(2-pyridy1)-1-aza(2,6-R,R'-Ph)propene, (pyEA-ArRR')H, were synthesized by condensation procedures; corresponding lithium or potassium ene-amides were prepared via standard deprotonation protocols. Addition of 2 equiv of (pynac)H to {(Me3Si)(2)N}(2)Fe(THF) or 2 Li(pynac) to FeBr2(THF)(2) afforded (pynac)(2)Fe (1), while treatment of CrCl2(THE)(2), MnCl2, FeBr2(THF)(2), and CoCl(2)py(4) with 2 equiv of (pyEA-(ArPr2)-Pr-i)K afforded pseudotetrahedral (pyEA-(ArPr2)-Pr-i)(2)M (2-M, M = Cr, Mn, Fe) and (pyEA-(ArPr2)-Pr-i)(2)Co-py (2-Co-py). Diamagnetic (kappa-C,N-pyEA-(ArPr2)-Pr-i)(3)Co (3) was prepared in low yield (similar to 7%) from CoCl2, and its Co-C(sp(3)) linkages are unusually low in field strength. Reactivity studies yielded little clean reactivity, but thermolysis of 2-Co-py afforded the bis-indolamide derivative -{kappa-N,N-N(C6H3(2-Pr-i)CMe2C(Me)(2-py)}(2)Co (5-Co), and related thermolyses of 2-M (M = Cr, Mn, Fe), conducted on NMA. tube scales, generated related 5-M (M = Cr, Mn, Fe) at roughly the same rates. This observation prompted thermolyses of (pyEA-ArRR')Li, which rearrange to their corresponding indolamides in >90% yields. Rate studies, accompanied by KLE and EIE observations, revealed that an initial hydrogen transfer is reversible and is likely to correspond to an anionic rearrangement, whereas C-C bond formation is rate-determining, as suggested by accompanying calculations. X-ray structure determinations of 1, 2-Fe, 2-Co-py, 3, and 5-Co were conducted.

  DOI：

  10.1021/acs.organomet.5b00385

文献信息

• Pyridineenolato and pyridineenamido complexes of zirconium, titanium and aluminum
  作者：Ui Gab Joung、Tae Ho Kim、Dae June Joe、Bun Yeoul Lee、Dong Mok Shin、Young Keun Chung

  DOI：10.1016/j.poly.2004.03.009

  日期：2004.5

  Deprotonation of 2-acetylpyridine with KH in THF afford a potassium enolate compound (2) which reacts with Zr(NEt2)(2)Cl-2(THF)(2) and Ti(NMe2)(2)Cl-2 to yield [CH2 = C(C5H4N)O-kappa(2)N,O](2)M(NR2)(2) (M = Zr, R = Et, 3; M = Ti, R = Me, 4) in 84% and 76% yield, respectively. Deprotonation of imines derived from 2-acetylpyridine, (2,6-Me2C6H3)N = C(C5H4N)(CH3) (5) and (2,6-iPr(2)C(6)H(3))N = C(C5H4N)(CH3) (6), affords potassium enamides, K[(2,6-Me2C6H3)N-C(C5H4N)( = CH2)] (7) and K[(2,6-iPr(2)C(6)H(3))N-(C5H4N)( = CH2)] (8). Reactions of the potassium salt 7 with Zr(NEt2)(2)Cl-2(THF)(2) and Ti(NMe2)(2)Cl-2 afford pyridineenamido complexes, [(2,6-Me2C6H3)NC(C5H4N)( = CH2)-kappa(2)N,N](2)M(NR2)(2) (M = Zr, R = Et, 9; M = Ti, R = Me, 10). Reaction of 8 with Zr(NEt2)(2)Cl-2(THF)(2) affords [(2,6-iPr(2)C(6)H(3))NC(C5H4N)( = CH2)](2)Zr(NEt2)(2) (11) but the reaction of 8 with Ti(NMe2)(2)Cl-2 yields [(2,6-iPrC(6)H(3))NC(C5H4N)( = CH2)]TiCl(NMe2)(2) (12). Addition of excess AlMe3 to 3 or 4 results in transmetallation of Zr or Ti to Al to afford an aluminum enolate complex, [CH2 = C(C5H4N)(OAlMe3)-kappa(2)N,O]AlMe2 (13). Addition of AlMe3 to 12 results in the formation of a transmetallated complex, [(2,6-iPr(2)C(6)H(3))NC(C5H4N)( = CH2)]AlMe2 (14). The solid structures of 4, 11, 13 and 14 were determined by X-ray crystallography. (C) 2004 Elsevier Ltd. All rights reserved.