7-methyl-3,7,11,17-tetraazabicyclo-[11.3.1]heptadeca-1(17),13,15-triene | 106202-21-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 7-methyl-3,7,11,17-tetraazabicyclo-[11.3.1]heptadeca-1(17),13,15-triene
• 英文别名: 7-methyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),13,15-triene；7-methyl-3,7,11,17-tetraazabicyclo{11.3,1}heptadeca-1(17),13,15-triene；7-Methyl-3,7,11,17-tetrazabicyclo[11.3.1]heptadeca-1(17),13,15-triene
• CAS: 106202-21-5
• 化学式: C₁₄H₂₄N₄
• 分子量: 248.371
• InChiKey: ZWGYUOHVBRCZOX-UHFFFAOYSA-N

物化性质

• 沸点：
  379.9±42.0 °C(Predicted)
• 密度：
  0.967±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  40.2
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  7-methyl-3,7,11,17-tetraazabicyclo-[11.3.1]heptadeca-1(17),13,15-triene 在 镍 hydrogen 、 HClO₄ 作用下， 以 乙醇 、 水 为溶剂， 生成 [nickel(II)(7-methyl-3,7,11,17-tetra-azabicyclo[11.3.1]heptadecane)] perchlorate
  参考文献：
  名称：

  Alcock, Nathaniel W.; Moore, Peter; Omar, Hadi A. A., Journal of the Chemical Society, Dalton Transactions, 1986, p. 985 - 990

  摘要：

  DOI：
• 作为产物：
  描述：

  吡啶-2,6-二甲醛 在 sodium tetrahydroborate 、 copper(II) nitrate 作用下， 以 乙醇 、 水 为溶剂， 反应 7.0h， 生成 7-methyl-3,7,11,17-tetraazabicyclo-[11.3.1]heptadeca-1(17),13,15-triene
  参考文献：
  名称：

  7-Methyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),13,15-triene

  摘要：

  The title compound, C14H24N4, is known to act as a macrocyclic ligand and its conformation has been determined to facilitate future comparisons with its coordinated forms. The aliphatic macrocyclic strand is disordered with respect to a mirror plane perpendicular to the pyridine ring and contains an ordered tertiary N atom; the four donor N atoms are approximately coplanar.

  DOI：

  10.1107/s0108270198004387

文献信息

• Studies of the pyridine-containing tetra-azamacrocycle 3,7,11-trimethyl-3,7,11,17-tetra-azabicyclo[11.3.1]heptadeca-1(17),13,15-triene (L1) and its complexes with Ni2+, Cu2+, and Zn2+. Crystal structures of the unsymmetric isomer of [Ni(L1)][ClO4]2, and the five-co-ordinate complexes [Ni(L1)(dmso)][ClO4]2(dmso = dimethyl sulphoxide) and [Ni(L1)Cl]ClO4
  作者：Nathaniel W. Alcock、Peter Moore、Hadi A. A. Omar

  DOI：10.1039/dt9870001107

  日期：——

  with that at position 7 on the opposite side, readily forms five-co-ordinate complexes [Ni(L1)X][ClO4]n[X = Cl–, NCS–, or NO2–, n= 1; X = co-ordinating solvent, dimethyl sulphoxide (dmso) or H2O, n= 2]. An analogous zinc(II) complex, [Zn(L1)(dmso)][ClO4]2, has also been isolated. Crystal structures of the nickel(II) complexes, with X = Cl and dmso, show that they are square pyramidal, with the macrocycle

  制备了含吡啶的四氮杂大环3,7,11-三甲基-3,7,11,17-四氮杂双环[11.3.1] heptadeca-1（17），13,15-三烯（L 1）和分离，用通式[M（L的其金属配合物一起1）]× 2（M =镍，铜，或Zn; X = CLO 4 -或NO 3 - ）。由于大环配体平面上方和下方三个Me–N基团的可能位置，这些配合物出现了三个几何异构体。通过13 C nmr光谱对反磁性四坐标镍（II）配合物的所有三个异构体进行了表征，并通过X建立了不对称异构体的结构射线晶体学。两种对称异构体之一，在大环平面一侧的3和11位上具有Me–N基团，而在另一侧的7位上具有Me–N基团，很容易形成五坐标的配合物[Ni（L 1）X ] [ClO 4 ] n [X = Cl –，NCS –或NO 2 –，n = 1；X =配位溶剂，二甲基亚砜（dmso）或H 2 O，n = 2]。还分离了类似的锌（II）络合物[Zn（L
• Properties of a new 4-imidazolyl derivative of a 14-membered tetraazamacrocyclic chelating agent
  作者：Rute M. Nunes、Rita Delgado、M. Fátima Cabral、Judite Costa、Paula Brandão、Vítor Félix、Brian J. Goodfellow

  DOI：10.1039/b710122h

  日期：——

  A new bis-N,N′-(5-methylimidazol-4-ylmethyl) derivative of a 14-membered tetraazamacrocycle, L1, has been synthesized. The protonation constants of this compound and the stability constants of its complexes with divalent first-row transition metal ions and Fe3+ were determined at 298.2 K in aqueous 0.10 mol dm−3 KNO3. Compound L1 exhibits high overall basicity, which is mainly conferred by the imidazolyl groups. The complexes of the divalent first row-transition metal ions of L1 follow the Irving–Williams order of stability with the maximum for Cu2+ as expected, but a steep fall of constants is verified for the Mn2+, Fe2+ and Co2+, in one side, and for the Zn2+ complexes, in the other side. Additionally, L1 shows a large affinity for Fe3+, and the relative stability constants for its Cd2+ and Pb2+ complexes indicate that L1 may be useful for the complexometric determination of these two toxic metal ions in solutions containing both metal ions. These studies together with NMR, UV-vis and EPR spectroscopic data indicated the presence of mononuclear complexes, which adopt distorted pyramidal or octahedral geometries depending on the metal centre. The X-ray crystal structure of [Cu(HL1)](PF6)2(NO3)·H2O showed that the coordination sphere of the copper centre can be described as a distorted square pyramid with the basal plane defined by three nitrogen donors of the macrocycle backbone and one nitrogen atom from one imidazolyl pendant arm. The apical position is occupied by the nitrogen atom of the macrocycle trans to the pyridine ring. To achieve this coordination environment, the macrocycle is folded along the axis defined by the two N atoms contiguous to the pyridine ring. The free methylimidazolyl arm points away from the metal centre leading to an intramolecular Cu⋯N distance of 5.155(1) Å.

  我们合成了一种新的 14 元四氮杂环的双-N,N′-（5-甲基咪唑-4-基甲基）衍生物 L1。在 298.2 K 的 0.10 mol dm-3 KNO3 水溶液中测定了该化合物的质子化常数及其与二价第一排过渡金属离子和 Fe3+ 复合物的稳定常数。化合物 L1 显示出较高的整体碱性，这主要是由咪唑基团赋予的。L1 的二价第一行过渡金属离子配合物的稳定性遵循欧文-威廉姆斯（Irving-Williams）排序，Cu2+ 的稳定性达到预期的最大值，但 Mn2+、Fe2+ 和 Co2+ 配合物的常数陡降，Zn2+ 配合物的常数陡降。此外，L1 对 Fe3+ 有很强的亲和力，其 Cd2+ 和 Pb2+ 复合物的相对稳定常数表明，L1 可用于在含有这两种金属离子的溶液中对这两种有毒金属离子进行络合测定。这些研究以及核磁共振、紫外-可见光和电致发光光谱数据表明，L1 中存在单核络合物，根据金属中心的不同，这些络合物呈扭曲的金字塔形或八面体形几何结构。[Cu(HL1)](PF6)2(NO3)-H2O的 X 射线晶体结构显示，铜中心的配位层可被描述为一个扭曲的正方体金字塔，其基面由大环骨架的三个氮供体和一个咪唑悬臂的一个氮原子确定。顶端位置由反式连接吡啶环的大环的氮原子占据。为了实现这种配位环境，大环沿着与吡啶环相邻的两个氮原子所确定的轴线进行折叠。自由的甲基咪唑基臂远离金属中心，导致分子内 Cu⋯N 距离为 5.155(1) Å。
• Studies of pendant arm macrocyclic ligands. Part 7. Synthesis of two sexidentate macrocycles based upon a pyridine-containing tetra-aza macrocycle with either two 2-pyridylmethyl or two 1-pyrazolylmethyl pendant co-ordinating arms, and characterisation of their cobalt(II), nickel(II), copper(II), and zinc(II) complexes. Crystal structure of {3,11-di(2-pyridylmethyl)-3,7,11,17-tetra-azabicyclo[11.3.1]heptadeca-1(17),13,15-triene}nickel(II) perchlorate
  作者：Karappulli P. Balakrishnan、Hadi A. A. Omar、Peter Moore、Nathaniel W. Alcock、Graham A. Pike

  DOI：10.1039/dt9900002965

  日期：——

  Two new sexidentate macrocycles, 3,11 -di(2-pyridylmethyl)-3,7,11,17-tetra-azabicyclo[11.3.1]heptadeca-1(17),13,15-triene(L1) and 7-methyl-3,11-di-(1-pyrazolylmethyl)-3,7,11,17-tetra-azabicyclo[11.3.1]heptadeca-1(17),13,15-triene (L2), have been prepared and characterised, together with their metal complexes of formula [M(L)][ClO4]2(M = Co, Ni, Cu, or Zn; L = L1 or L2). An X-ray crystal structure of

  两个新的六性大环化合物3,11-二（2-吡啶甲基）-3,7,11,17-四氮杂双环[11.3.1] heptadeca-1（17），13,15-三烯（L 1）和7 -甲基-3,11-二-（1-吡唑基甲基）-3,7,11,17-四氮杂双环[11.3.1] heptadeca-1（17），13,15-三烯（L 2）已被开发制备并表征了它们的分子式为[M（L）] [ClO 4 ] 2的金属配合物（M = Co，Ni，Cu或Zn； L = L 1或L 2）。[Ni（L 1）] [ClO 4 ] 2的X射线晶体结构显示镍为六坐标，大环呈折叠构型，且两个侧基2-吡啶基甲基臂占据顺式 协调站点。
• A new redox-responsive 14-membered tetraazamacrocycle with ferrocenylmethyl arms as receptor for sensing transition-metal ions
  作者：Judite Costa、Rita Delgado、Michael G. B. Drew、Vitor Félix、André Saint-Maurice

  DOI：10.1039/b000938p

  日期：——

  pyridine ring in complex 2+. To achieve the geometric arrangement described for 2+ the macrocycle folds considerably through the line defined by the two nitrogen atoms contiguous to the pyridine group. It was also found that the intramolecular distances between the ferrocene groups and transition metal receptor centres studied play an important role in the redox behaviour of these complexes.

  一种新的氧化还原反应受体3,11-双（二茂铁基甲基）-7-甲基-3,7,11,17-四氮杂双环[11.3.1] heptadeca-1（17），13,15-三烯L 1，已经合成。在25.0°C下测定该化合物的质子化常数及其与Ni 2 +，Cu 2 +，Zn 2 +，Cd 2+和Pb 2+的配合物的稳定性常数。甲醇–水（1∶1，v / v），并且在KNO 3中的离子强度为0.10mol dm -3时。L 1的质子化常数值与母体的质子化常数相似大循环，7-甲基-3,7,11,17-四氮杂双环[11.3.1] heptadeca-1（17），13,15-三烯L 2，除了K 2比L 2低1.82 log个单位。建议使用结构性原因来解释此行为。L 1的金属络合物的稳定性常数由于其较低的整体碱度而低于L 2的稳定性常数，但是Cd 2+络合物对于L 1表现出更高的稳定性。L 1与不同金属的络合物阳极移位
• Structure, Characterization, and Metal-Complexation Properties of a New Tetraazamacrocycle Containing Two Phenolic Pendant Arms
  作者：Xiuling Cui、Maria José Calhorda、Paulo J. Costa、Rita Delgado、Michael G. B. Drew、Vítor Félix

  DOI：10.1002/hlca.200490235

  日期：2004.10

  The new tetraazamacrocycle 2 (=2,2′-[[7-Methyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),13,15-triene-3,11-diyl]bis(methylene)]bis(4-bromophenol)) was synthesized and used as a ligand for different metal-ion complexes. The X-ray crystal structures of the complexes of the general formula [M(H-2)]+NO⋅MeOH (M=Ni2+, Zn2+), in which only one of the two pendant phenolic OH groups of 2 is deprotonated

  新的四氮杂大环2（= 2,2'-[[7-甲基-3,7,11,17-四氮杂双环[11.3.1] heptadeca-1（17），13,15-三烯-3,11-二基]合成了双（亚甲基）]双（4-溴苯酚），并用作不同金属离子络合物的配体。通式[M（H- 2）] + NO·MeOH（M = Ni 2 +，Zn 2+）的配合物的X射线晶体结构，其中两个侧基酚羟基只有2个被去质子化，被确定。在这两种配合物中，配位环境均为[5 + 1]型，大环骨架的四个N原子定义了围绕金属中心的正方形平面排列，相似的NiN和ZnN距离为1.961（9）至2.157 （9）Å和2.021（9）至2.284（8）Å。与此相反，MO距离是显着不同，2.060（6）和2.449（8）一种在镍II络合物，和2.027（7）和2.941（9）一种在锌II复合物。所述UV /镍的VIS光谱II和Cu II络合物具有配体2，与Cu的EP