N,N,N',N',N'',N''-hexakis(2-pyridylmethyl)-1,3,5-tris(aminomethyl)benzene | 479420-78-5

• 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: N,N,N',N',N'',N''-hexakis(2-pyridylmethyl)-1,3,5-tris(aminomethyl)benzene
• 英文别名: N,N,N',N',N'',N''-hexa[(2-pyridyl)methyl]-1,3,5-tris(aminomethyl)benzene；benzene-1,3,5-triyltris[N,N-bis(2-picolyl)methanamine]；N-[[3,5-bis[[bis(pyridin-2-ylmethyl)amino]methyl]phenyl]methyl]-1-pyridin-2-yl-N-(pyridin-2-ylmethyl)methanamine
• CAS: 479420-78-5
• 化学式: C₄₅H₄₅N₉
• 分子量: 711.913
• InChiKey: YVTHMBKAMPQMRF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  54
• 可旋转键数：
  18
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  87.1
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  水 、 copper(II) bis(trifluoromethanesulfonate) 、 N,N,N',N',N'',N''-hexakis(2-pyridylmethyl)-1,3,5-tris(aminomethyl)benzene 以 丙酮 为溶剂， 反应 2.0h， 以28%的产率得到[Cu₃(H₂O)₆(benzene-1,3,5-triyltris[N,N-bis(2-picolyl)methanamine])](triflate)₆
  参考文献：
  名称：

  铜位点空间分布对氧还原反应选择性的影响

  摘要：

  向氢经济迈进提高了对用于氧还原反应的负担得起且高效的催化剂的需求。Cu-bmpa (bmpa = bis(2-picolyl)amine) 显示出具有中等活性，但对于将氧 4 电子还原为水的选择性较差。为了提高对水形成的选择性，研究了单个三核配合物中三个Cu-bmpa结合位点的协同作用。三核位点存在下的催化电流较低，这可能是由于结构更刚性，因此催化物质的重组能更高和/或扩散速率更慢。虽然三核配合物的氧还原活性低于单核Cu-bmpa，由于三个铜中心之间的协同效应，铜介导的氧还原对 4 电子过程的选择性显着提高。这些结果表明，仿生位点内金属离子之间的协同作用可以大大提高ORR的选择性。

  DOI：

  10.1039/d1dt03296h
• 作为产物：
  描述：

  均三甲苯 在 N-溴代丁二酰亚胺(NBS) 、 N,N-二异丙基乙胺 、 过氧化苯甲酰 作用下， 以 四氯化碳 、 乙腈 为溶剂， 反应 96.0h， 生成 N,N,N',N',N'',N''-hexakis(2-pyridylmethyl)-1,3,5-tris(aminomethyl)benzene
  参考文献：
  名称：

  Trinuclear Copper(II) Complex Showing High Selectivity for the Hydrolysis of 2‘−5‘ over 3‘−5‘ for UpU and 3‘−5‘ over 2‘−5‘ for ApA Ribonucleotides

  摘要：

  The cooperative action of multiple Cu(II) nuclear centers is shown to be effective and selective in the hydrolysis of 2'-5' and 3'-5' ribonucleotides. Reported herein is the specific catalysis by two trinuclear Cu(II) complexes of L3A and L3B. Pseudo first-order kinetic studies reveal that the L3A trinuclear Cu(II) complex effects hydrolysis of Up(2'-5')U with a rate constant of 28 x 10(-4) min(-1) and Up(3'-5')U with a rate constant of 0.5 x 10(-4) min(-1). The hydrolyses of Ap(3'-5')A and Ap(2'-5')A proceed with rate constants of 24 x 10(-4) min(-1) and 0.5 x 10(-4) min(-1) respectively. The L3A trinuclear Cu(II) complex demonstrates high specificity for Up(2'-5')U and Ap(3'-5')A. Similar studies with the more rigid L3B trinuclear Cu(II) complex shows no selectivity and yields lower rate constants for hydrolysis. The selectivity observed with the L3A ligand is attributed to the geometry of the ligand-bound diribonucleotide which ultimately dictates the proximity of the attacking hydroxyl and the phosphoester to a Cu(II) center for activation and subsequent hydrolysis.

  DOI：

  10.1021/ja020877t

文献信息

• A positively charged trinuclear 3N-chelated monofunctional platinum complex with high DNA affinity and potent cytotoxicity
  作者：Yongmei Zhao、Weijiang He、Pengfei Shi、Jianhui Zhu、Lin Qiu、Liping Lin、Zijian Guo

  DOI：10.1039/b601739h

  日期：——

  3N-chelated monofunctional platinum complex, [Pt3(HPTAB)Cl3](ClO4)3 (HPTAB = N,N,N',N',N'',N''-hexakis(2-pyridylmethyl)-1,3,5-tris(aminomethyl)benzene), has been structurally characterized, which binds to DNA and demonstrates much higher potency against the murine leukemia cell line (P-388) and the human nonsmall-cell lung cancer cell line (A-549) than cisplatin.

  三核3N螯合的单官能铂络合物[Pt3（HPTAB）Cl3]（ClO4）3（HPTAB = N，N，N'，N'，N''，N''-六（2-吡啶基甲基）-1， 3,5-三（氨基甲基）苯具有结构特征，可与DNA结合并显示出对鼠白血病细胞系（P-388）和人非小细胞肺癌细胞系（A-549）更高的效能）比顺铂。
• Trinuclear Copper(II) Complex Showing High Selectivity for the Hydrolysis of 2‘−5‘ over 3‘−5‘ for UpU and 3‘−5‘ over 2‘−5‘ for ApA Ribonucleotides
  作者：Makoto Komiyama、Shinichiro Kina、Kazunari Matsumura、Jun Sumaoka、Suzanne Tobey、Vincent M. Lynch、Eric Anslyn

  DOI：10.1021/ja020877t

  日期：2002.11.1

  The cooperative action of multiple Cu(II) nuclear centers is shown to be effective and selective in the hydrolysis of 2'-5' and 3'-5' ribonucleotides. Reported herein is the specific catalysis by two trinuclear Cu(II) complexes of L3A and L3B. Pseudo first-order kinetic studies reveal that the L3A trinuclear Cu(II) complex effects hydrolysis of Up(2'-5')U with a rate constant of 28 x 10(-4) min(-1) and Up(3'-5')U with a rate constant of 0.5 x 10(-4) min(-1). The hydrolyses of Ap(3'-5')A and Ap(2'-5')A proceed with rate constants of 24 x 10(-4) min(-1) and 0.5 x 10(-4) min(-1) respectively. The L3A trinuclear Cu(II) complex demonstrates high specificity for Up(2'-5')U and Ap(3'-5')A. Similar studies with the more rigid L3B trinuclear Cu(II) complex shows no selectivity and yields lower rate constants for hydrolysis. The selectivity observed with the L3A ligand is attributed to the geometry of the ligand-bound diribonucleotide which ultimately dictates the proximity of the attacking hydroxyl and the phosphoester to a Cu(II) center for activation and subsequent hydrolysis.
• Influence of the spatial distribution of copper sites on the selectivity of the oxygen reduction reaction
  作者：N. W. G. Smits、D. Rademaker、A. I. Konovalov、M. A. Siegler、D. G. H. Hetterscheid

  DOI：10.1039/d1dt03296h

  日期：——

  species. Although the oxygen reduction activity of the trinuclear complexes is lower than that of mononuclear Cu-bmpa, the selectivity of the copper mediated oxygen reduction was significantly enhanced towards the 4-electron process due to a cooperative effect between three copper centers that have been positioned in close proximity. These results indicate that the cooperativity between metal ions within

  向氢经济迈进提高了对用于氧还原反应的负担得起且高效的催化剂的需求。Cu-bmpa (bmpa = bis(2-picolyl)amine) 显示出具有中等活性，但对于将氧 4 电子还原为水的选择性较差。为了提高对水形成的选择性，研究了单个三核配合物中三个Cu-bmpa结合位点的协同作用。三核位点存在下的催化电流较低，这可能是由于结构更刚性，因此催化物质的重组能更高和/或扩散速率更慢。虽然三核配合物的氧还原活性低于单核Cu-bmpa，由于三个铜中心之间的协同效应，铜介导的氧还原对 4 电子过程的选择性显着提高。这些结果表明，仿生位点内金属离子之间的协同作用可以大大提高ORR的选择性。