1-benzylpyridinium-4-aldoxime chloride | 7375-29-3

• 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: 1-benzylpyridinium-4-aldoxime chloride
• 英文别名: N-benzylpyridinium-4-aldoxime chloride；BPA4-Cl；1-Benzyl-4-(nitrosomethylidene)-1,4-dihydropyridine--hydrogen chloride (1/1)；1-benzyl-4-(nitrosomethylidene)pyridine;hydrochloride
• CAS: 7375-29-3
• 化学式: C₁₃H₁₃N₂O*Cl
• mdl: MFCD01741600
• 分子量: 248.712
• InChiKey: MZIWPBVMHLZHLT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.74
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.076
• 拓扑面积：
  36.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  sodium amminepentacyanoferrate(II) trihydrate 、 1-benzylpyridinium-4-aldoxime chloride 以 乙醇 、 水 为溶剂， 生成 [Fe(CN)₅(N-benzylpyridinium-4-aldoxime)]^-2
  参考文献：
  名称：

  Spectroscopic and structural insights into N-substituted pyridinium-4-aldoximes and their pentacyanoferrate(II) complexes

  摘要：

  Comparative kinetic and equilibrium studies on the formation and dissociation of three mono- and one bis-pyridinium-4-aldoxime pentacyanoferrate(II) complexes have been carried out in aqueous solutions at 25 degrees C and I = 0.1 M. The synthesis, spectroscopic and thermal characterization of a new N-methylpyridinium-4-aldoxime pentacyanoferrate(II) complex is presented. The obtained values for the equilibrium constants, identified as apparent formation constants (beta(f)/M-1) along with kinetic parameters, the formation (k(f)/M-1 s(-1)) and dissociation (k(d)/s(-1)) rate constants indicated the behaving of all protonated pyridinium-4-aldoximes as weak pi-acceptors. The pH-dependence of the dissociation rates has been analyzed in terms of ionization abilities of the coordinated ligands. The magnitude of the dissociation rates suggested that both protonated and deprotonated ligand forms are effective sigma-donors that bind to the [Fe(CN)(5)](3-) moiety through the nitrogen atom. The deprotonation of the coordinated aldoxime group leads to the reduced lability of the complexes due to increased sigma-donor capability of aldoximato nitrogen causing the strengthened of the iron(II)-nitrogen bond. The values of dissociation activation parameters, Delta H-double dagger and Delta S-double dagger, are found to be consistent with the S(N)1 dissociative type of mechanism. The spectroscopic data (FT-IR, NMR and UV-Vis) of the isolated coordinated pentacyanoferrates(II) conforms with the weak pi-acceptor properties of the pyridinium-4-aldoxime ligands. A detailed structural characterization of the iodide and chloride salt of N-methylpyridinium-4-aldoxime was also presented using NMR, FT-IR and UV-Vis spectroscopy, as well as X-ray diffraction. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2012.07.077
• 作为产物：
  描述：

  4-吡啶甲醛肟 、 氯化苄 以 乙醇 为溶剂， 反应 168.0h， 以70.4%的产率得到1-benzylpyridinium-4-aldoxime chloride
  参考文献：
  名称：

  Preparation, characterization and reactivity of 1-benzylpyridinium-4-aldoxime chloride and 1-phenacylpyridinium-4-aldoxime chloride and their complexes with the aquapentacyanoferrate(II) ion

  摘要：

  A detailed structural characterization of the biologically active 1-benzylpyridinium-4-aldoxime chloride and 1-phenacylpyridinium-4-aldoxime chloride was performed using NMR and vibrational and electronic spectroscopy, as well as X-ray diffraction. The complexes of these compounds with the aquapentacyanoferrate(II) ion were examined in solution, isolated as solids and characterized by elemental analysis, electronic, FT-IR and NMR spectral data. They were found to be mononuclear substituted pentacyanoferrates(II) containing the aldoxime group coordinated to the iron through the nitrogen atom. The complexes were also precipitated in the form of the respective zinc salts; the analysis of these complexes revealed a molar Fe/Zn ratio of 1, thus confirming the charge of the complex anions to be -2. The ionization constants of the aldoxime group in the free ligands and in the respective cyano complexes were also determined. Despite the presence of two donor sites in 1-phenacylpyridinium-4-aldoxime chloride, only the aldoxime group was found to be reactive. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2010.01.041

文献信息

• Supramolecular inter-ionic charge-transfer complexes between derivatives of pyridinium-4-oxime cations and hexacyanoferrate(<scp>ii</scp>) anions
  作者：Blaženka Foretić、Robert Vianello、Dubravka Matković-Čalogović、Dijana Jadreško、Igor Picek

  DOI：10.1039/c8nj03066a

  日期：——

  charge-transfer band in the visible spectral region whose energy is closely related to the acceptor's electron affinity, LUMO orbital energy and one-electron reduction potential. Such influence of the acceptor's electrochemical nature is revealed through varying the group attached to the N atom of the pyridinium-4-oxime moiety. The color, composition and spectroscopic analysis of the complexes in the solid state

  单吡啶和双吡啶-4-肟化合物被引入作为新的电子受体，与六氰合铁酸酯形成有色，超分子，离子间电荷转移络合物（II）作为捐赠者。形成的复合物的结构和性质通过实验研究和计算研究相结合来表征。在水中，电子给体/受体二重体在可见光谱区域显示出特征性的电荷转移带，其能量与受体的电子亲和力，LUMO轨道能和单电子还原电势密切相关。通过改变连接到吡啶鎓-4-肟部分的N原子上的基团，揭示了受体的电化学性质的这种影响。固态配合物的颜色，组成和光谱分析为洞悉阳离子和阴离子对应物的结合以及晶格水的作用提供了见识。报道了两种4-吡啶肟/六氰基高铁酸盐的晶体结构（II）配合物，其溶液通过UV / Vis和1 H-NMR光谱表征。固态结构和水相二元化合物的比较揭示了涉及共轭吡啶鎓-4-肟作为电子受体的电荷转移相互作用的性质。
• Burger, N.; Hankonyi, V.; Smeric, Z., Zeitschrift fur Physikalische Chemie (Leipzig), 1990, vol. 271, # 4, p. 787 - 791
  作者：Burger, N.、Hankonyi, V.、Smeric, Z.

  DOI：——

  日期：——
• Preparation, characterization and reactivity of 1-benzylpyridinium-4-aldoxime chloride and 1-phenacylpyridinium-4-aldoxime chloride and their complexes with the aquapentacyanoferrate(II) ion
  作者：Blaženka Foretić、Igor Picek、Ivica Đilović、Nicoletta Burger

  DOI：10.1016/j.ica.2010.01.041

  日期：2010.4

  A detailed structural characterization of the biologically active 1-benzylpyridinium-4-aldoxime chloride and 1-phenacylpyridinium-4-aldoxime chloride was performed using NMR and vibrational and electronic spectroscopy, as well as X-ray diffraction. The complexes of these compounds with the aquapentacyanoferrate(II) ion were examined in solution, isolated as solids and characterized by elemental analysis, electronic, FT-IR and NMR spectral data. They were found to be mononuclear substituted pentacyanoferrates(II) containing the aldoxime group coordinated to the iron through the nitrogen atom. The complexes were also precipitated in the form of the respective zinc salts; the analysis of these complexes revealed a molar Fe/Zn ratio of 1, thus confirming the charge of the complex anions to be -2. The ionization constants of the aldoxime group in the free ligands and in the respective cyano complexes were also determined. Despite the presence of two donor sites in 1-phenacylpyridinium-4-aldoxime chloride, only the aldoxime group was found to be reactive. (C) 2010 Elsevier B.V. All rights reserved.
• Spectroscopic and structural insights into N-substituted pyridinium-4-aldoximes and their pentacyanoferrate(II) complexes
  作者：Blaženka Foretić、Igor Picek、Vladimir Damjanović、Danijela Cvijanović、Ivana Pulić、Boris-Marko Kukovec、Dubravka Matković-Čalogović

  DOI：10.1016/j.poly.2012.07.077

  日期：2013.3

  Comparative kinetic and equilibrium studies on the formation and dissociation of three mono- and one bis-pyridinium-4-aldoxime pentacyanoferrate(II) complexes have been carried out in aqueous solutions at 25 degrees C and I = 0.1 M. The synthesis, spectroscopic and thermal characterization of a new N-methylpyridinium-4-aldoxime pentacyanoferrate(II) complex is presented. The obtained values for the equilibrium constants, identified as apparent formation constants (beta(f)/M-1) along with kinetic parameters, the formation (k(f)/M-1 s(-1)) and dissociation (k(d)/s(-1)) rate constants indicated the behaving of all protonated pyridinium-4-aldoximes as weak pi-acceptors. The pH-dependence of the dissociation rates has been analyzed in terms of ionization abilities of the coordinated ligands. The magnitude of the dissociation rates suggested that both protonated and deprotonated ligand forms are effective sigma-donors that bind to the [Fe(CN)(5)](3-) moiety through the nitrogen atom. The deprotonation of the coordinated aldoxime group leads to the reduced lability of the complexes due to increased sigma-donor capability of aldoximato nitrogen causing the strengthened of the iron(II)-nitrogen bond. The values of dissociation activation parameters, Delta H-double dagger and Delta S-double dagger, are found to be consistent with the S(N)1 dissociative type of mechanism. The spectroscopic data (FT-IR, NMR and UV-Vis) of the isolated coordinated pentacyanoferrates(II) conforms with the weak pi-acceptor properties of the pyridinium-4-aldoxime ligands. A detailed structural characterization of the iodide and chloride salt of N-methylpyridinium-4-aldoxime was also presented using NMR, FT-IR and UV-Vis spectroscopy, as well as X-ray diffraction. (C) 2012 Elsevier Ltd. All rights reserved.