1-methyl-4,7-bis(2-cyanoethyl)-1,4,7-triazacyclononane | 309955-06-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪烷类
• 英文名称: 1-methyl-4,7-bis(2-cyanoethyl)-1,4,7-triazacyclononane
• 英文别名: 1,4-bis(2-cyanoethyl)-7-methyl-1,4,7-triazacyclononane；3-[4-(2-Cyanoethyl)-7-methyl-1,4,7-triazonan-1-yl]propanenitrile
• CAS: 309955-06-4
• 化学式: C₁₃H₂₃N₅
• 分子量: 249.359
• InChiKey: SZPPBWSTVMGTAM-UHFFFAOYSA-N

物化性质

• 沸点：
  442.1±45.0 °C(Predicted)
• 密度：
  1.006±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  57.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-methyl-4,7-bis(2-cyanoethyl)-1,4,7-triazacyclononane 在 硼烷四氢呋喃络合物 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 以97%的产率得到1-methyl-4,7-bis(3-aminopropyl)-1,4,7-triazacyclononane
  参考文献：
  名称：

  Blake, Alexander J.; Danks, Jonathan P.; Li, Wan-Sheung, Journal of the Chemical Society, Dalton Transactions, 2000, # 17, p. 3034 - 3040

  摘要：

  DOI：
• 作为产物：
  描述：

  1,4-di(tosyl)-1,4,7-triazacyclononane 在 甲酸 、 硫酸 作用下， 以 水 为溶剂， 反应 96.0h， 生成 1-methyl-4,7-bis(2-cyanoethyl)-1,4,7-triazacyclononane
  参考文献：
  名称：

  Blake, Alexander J.; Danks, Jonathan P.; Li, Wan-Sheung, Journal of the Chemical Society, Dalton Transactions, 2000, # 17, p. 3034 - 3040

  摘要：

  DOI：

文献信息

• Methanolysis of nitrile-functionalised pendant arm derivatives of 1,4,7-triazacyclononane upon coordination to CuIIElectronic supplementary information (ESI) available: frozen solution EPR (77 K) spectra for [Cu(1)](BF4)2 and [Cu(2)](BF4)2·H2O (Fig. S1) and [Cu(L2)Cl2] (Fig. S2) in CH3CN–DMF (9 ∶ 1) solutions. Modelling of the disorder in [Cu(1)](BF4)2 and [Cu(2)](BF4)2·H2O. See http://www.rsc.org/suppdata/dt/b2/b209091k/
  作者：Lorenzo Tei、Alexander J. Blake、Vito Lippolis、Claire Wilson、Martin Schröder

  DOI：10.1039/b209091k

  日期：2003.1.29

  The three ligands 1,4,7-tris(cyanomethyl)-1,4,7-triazacyclononane (L1), 1,4,7-tris(2-cyanoethyl)-1,4,7-triazacyclononane (L2) and 1,4-bis(2-cyanoethyl)-7-methyl-1,4,7-triazacyclononane (L3) have been treated with Cu(BF4)2·4H2O in refluxing MeOH to afford complexes [Cu(1)](BF4)2, [Cu(2)](BF4)2·H2O and [Cu(3)](BF4)2, respectively, where 1, 2 and 3 have two nitrile groups of each starting L1, L2 and L3 ligand transformed into imino-ether groups via nucleophilic attack of MeOH at the the CN triple bond. [Cu(1)](BF4)2 and [Cu(2)](BF4)2 have been structurally characterised and show distorted square-based pyramidal coordination at CuII with the N-donors from the imino-ether groups occupying two basal positions. Interestingly, one nitrile group does not undergo methanolysis and remains unbound to the metal centre in [Cu(1)]2+ and [Cu(2)]2+. L2 and L3 have also been treated with CuCl2·2H2O in CH3CN at room temperature to give the 1 ∶ 1 complexes [Cu(L2)Cl2] and [Cu(L3)Cl2]·½MeNO2. X-Ray diffraction studies confirm that in each case the two chloride anions and the three N-donors from the [9]aneN3 framework coordinate to the metal centre in a distorted square-based pyramidal geometry. All the complexes have been characterised by electronic and EPR spectroscopy. The reaction of L2 with CuCl2·2H2O has also been carried out in refluxing MeOH and followed by electronic spectroscopy in order to investigate whether the methanolysis of the two nitrile groups is effected by the presence of more strongly coordinating anions such as chloride. The complex [Cu(4)Cl](BF4) where 4 is derived from L2 by methanolysis of only one nitrile group, has been isolated after addition of an excess of Me4NBF4.

  三种配体 1,4,7-三(氰甲基)-1,4,7-三氮杂环壬烷 (L1)、1,4,7-三(2-氰乙基)-1,4,7-三氮杂环壬烷 (L2) 和 1、[其中 1、2 和 3 配体 L1、L2 和 L3 的两个腈基通过 MeOH 对 CN 三键的亲核作用转化为亚氨基醚基。[Cu(1)](BF4)2和[Cu(2)]( )2已经过结构表征，在CuII上显示出扭曲的方基金字塔配位，来自亚氨基醚基团的N-供体占据了两个基底位置。有趣的是，[Cu(1)]2+ 和 [Cu(2)]2+ 中的一个腈基没有发生甲醇分解，仍未与金属中心结合。L2 和 L3 还在室温下用 CH3CN 中的 CuCL2-2H2O 处理，得到 1 ∶ 1 复合物 [Cu(L2)CL2] 和 [Cu(L3)CL2]-½MeNO2。X 射线衍射研究证实，在每种情况下，[9]aneN3 框架中的两个氯阴离子和三个 N-给体都以扭曲的方基金字塔几何形状与金属中心配位。所有复合物都通过电子和 EPR 光谱进行了表征。L2 与 CuCL2-2H2O 的反应也是在回流的 MeOH 中进行的，随后进行了电子能谱分析，以研究两个腈基的甲醇分解是否会受到更强配位阴离子（如氯离子）的影响。在加入过量的 Me4N 后，分离出了[Cu(4)Cl]( )复合物，其中 4 来自 L2，而 L2 只由一个腈基甲醇分解而来。
• Effective Methods for the Biotinylation of Azamacrocycles
  作者：Sara J. Krivickas、Emiliano Tamanini、Matthew H. Todd、Michael Watkinson

  DOI：10.1021/jo071175v

  日期：2007.10.1

  The biotin-(strept)avidin interaction remains a gold standard of model biological recognition events. The biotinylation of azarnacrocycles permits the investigation of signal transduction between this recognition event and the metal center of an azamacrocycle complex, of wide potential interest in biosensing. There are no generally applicable procedures in the literature for such functionalizations. We report here a comprehensive investigation into the attachment of biotin to TACN, cyclen, and cyclam.. Effective methods have been found for each ring. The efficacy of the functionalization is critically dependent on the nature of the azarnacrocycle.