1,4,5,6,7,8,9,11-octahydro-2H-benzo[e][1,4,7,10]tetraazacyclotridecine-2,10(3H)-dione | 935762-92-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酰胺类
• 英文名称: 1,4,5,6,7,8,9,11-octahydro-2H-benzo[e][1,4,7,10]tetraazacyclotridecine-2,10(3H)-dione
• 英文别名: 2,10-dioxo-1,4,8,11-tetraazabicyclo[11.4.0]-1,12-heptadeca-1(12),14,16-triene；2,5,9,12-Tetrazabicyclo[11.4.0]heptadeca-1(17),13,15-triene-3,11-dione；2,5,9,12-tetrazabicyclo[11.4.0]heptadeca-1(17),13,15-triene-3,11-dione
• CAS: 935762-92-8
• 化学式: C₁₃H₁₈N₄O₂
• 分子量: 262.312
• InChiKey: BFZFOBXRQMKKNN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  82.3
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,4,5,6,7,8,9,11-octahydro-2H-benzo[e][1,4,7,10]tetraazacyclotridecine-2,10(3H)-dione 、 氯化镓 在 sodium methoxide 作用下， 以 甲醇 为溶剂， 以53.2%的产率得到
  参考文献：
  名称：

  Macrocyclic Diamide Ligand Systems: Potential Chelators for ⁶⁴Cu- and ⁶⁸Ga-Based Positron Emission Tomography Imaging Agents

  摘要：

  The N-4-macrocyclic ligand 2,10-dioxo-1,4,8,11-tetraazabicyclo[11,4.0]1,12-heptadeca-1(12),14,16-triene H2L has been synthesized by the [1 + 1]condensation reactionbetween N,N'-bis(chloroacetyl)-1,2-phenylenediamine and 1,3-propylenediamine. The coordination chemistry of this ligand has been investigated with the metal ions Cu (II), Ni(II), Zn(II), and Ga(III) (complexes 1, 2, 3 and 4, respectively). H2L and its metal complexes have been fully characterized by the use of NMR, UV/vis, electron paramagnetic resonance, and elemental analysis where appropriate. The four metal complexes 1-4 have been structurally characterized by X-ray crystallography which confirmed that in all cases the amide nitrogen atoms are deprotonated and coordinated to the metal center. Complexes 3 and 4 are five-coordinate with a water molecule and chloride ion occupying the apical site, respectively. Cyclic voltammetric measurements on complex 1 show that this complex is oxidized reversibly with a half-wave potential, E-1/2 = 0.47 V, and reduced irreversibly at E-P = - 1.84 V. Density functional theory calculations reproduce the geometries of the four complexes. The one-electron reduction and oxidation potentials for 1 were calculated by using two solvent models, DMF and H2O. The calculations indicated that the one electron oxidation of 1 may involve removal of an electron from the ligand as opposed to the metal center, producing a diradical. The diamide macrocyle is of interest for the development of new positron emission tomography (PET) and single photon emission computed tomography (SPECT) imaging agents, and a radiolabeled complex has been synthesized with the positron emitting isotope (CU)-C-64. In vivo biodistribution studies for the Cu-64 labeled complex, C-64-1, in male Lewis rats, showed that the activity is cleared rapidly from the blood within 1-2 h post-administration.

  DOI：

  10.1021/ic900307f
• 作为产物：
  描述：

  邻苯二胺 在 potassium carbonate 、 potassium iodide 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 0.5h， 生成 1,4,5,6,7,8,9,11-octahydro-2H-benzo[e][1,4,7,10]tetraazacyclotridecine-2,10(3H)-dione
  参考文献：
  名称：

  由合成镍超氧化物介导的黄酮醇双加氧酶化学

  摘要：

  大自然利用过渡金属中心来增强和调节 O 2和 H 2 O 2等天然氧化剂的氧化能力. 设计和研究与金属蛋白具有相似反应性的合成金属复合物提供了一种策略，可用于深入了解氧化酶、加氧酶和双加氧酶（如镍槲皮素酶 (Ni-QueD)）等氧活化酶的机制基础。Ni-QueD 催化多酚槲皮素的氧化开环，这是一种具有抗氧化特性的天然产物。在此，我们报告了 Ni(13-DOB) 的合成和表征，Ni(II) 物种由 N4-大环化合物络合，已通过单晶 X 射线晶体学表征。Ni(13-DOB)在用 H 2 O 2和 Et 3处理后形成 Ni-超氧化物中间体 (Ni(13-DOB)O 2 •- )N，通过共振拉曼光谱验证。我们通过 UV/vis 和 LCMS 证明 Ni(13-DOB)O 2 •-能够对黄酮醇进行单电子氧化，包括 3-羟基黄酮（3-HF，最简单的黄酮醇）和槲皮素本身。通过来自 Ni(13-DOB)O

  DOI：

  10.1016/j.jinorgbio.2022.112021

文献信息

• Mn(II) complexes of phenylenediamine based macrocyclic ligands as T1-MRI contrast agents
  作者：Thavasilingam Nagendraraj、S. Senthil Kumaran、Ramasamy Mayilmurugan

  DOI：10.1016/j.jinorgbio.2021.111684

  日期：2022.3

  The Mn(II) complexes are emerging as alternative T1-MRI contrast agents (CAs) to the currently available Gd-based CAs. The complexes [Mn(L1)] 1 and [Mn(L2)] 2 of o-phenylenediamine based macrocyclic ligands are reported as T1-CAs for MRI applications. The high spin state of the Mn(II) complexes (S = 5/2) is confirmed by EPR spectra. The complexes showed an irreversible Mn(II)/Mn(III) redox potential

  Mn(II) 配合物正在成为目前可用的基于 Gd 的 CA 的替代 T 1 -MRI 造影剂 (CA)。基于邻苯二胺的大环配体的配合物[Mn(L1)] 1和[Mn(L2)] 2被报道为用于MRI应用的T 1 -CA。EPR 光谱证实了 Mn(II) 配合物 (S = 5/2) 的高自旋状态。配合物在 pH 7.28 时显示出不可逆的 Mn(II)/Mn(III) 氧化还原电位，在酸性和碱性 pH 值下分别变得越来越少。物质 [MnL]、[Mn(LH - 1 ) 和 [Mn(LH - 2 ) 持续存在于溶液中。复合体1对 Ca(II)、Mg(II) 和 Zn(II) 呈惰性，而络合物2对 Ca(II) 和 Mg(II) 呈惰性，在 Zn(II) 和 Cu(II) 离子下不稳定。配合物1通过内球水弛豫在 1.41 T、25 和 37 °C 下分别显示出3.27 和 2.32 mM -1  s -1的
• Macrocyclic Diamide Ligand Systems: Potential Chelators for ⁶⁴Cu- and ⁶⁸Ga-Based Positron Emission Tomography Imaging Agents
  作者：Peter J. Barnard、Jason P. Holland、Simon R. Bayly、Thaddeus J. Wadas、Carolyn J. Anderson、Jonathan R. Dilworth

  DOI：10.1021/ic900307f

  日期：2009.8.3

  The N-4-macrocyclic ligand 2,10-dioxo-1,4,8,11-tetraazabicyclo[11,4.0]1,12-heptadeca-1(12),14,16-triene H2L has been synthesized by the [1 + 1]condensation reactionbetween N,N'-bis(chloroacetyl)-1,2-phenylenediamine and 1,3-propylenediamine. The coordination chemistry of this ligand has been investigated with the metal ions Cu (II), Ni(II), Zn(II), and Ga(III) (complexes 1, 2, 3 and 4, respectively). H2L and its metal complexes have been fully characterized by the use of NMR, UV/vis, electron paramagnetic resonance, and elemental analysis where appropriate. The four metal complexes 1-4 have been structurally characterized by X-ray crystallography which confirmed that in all cases the amide nitrogen atoms are deprotonated and coordinated to the metal center. Complexes 3 and 4 are five-coordinate with a water molecule and chloride ion occupying the apical site, respectively. Cyclic voltammetric measurements on complex 1 show that this complex is oxidized reversibly with a half-wave potential, E-1/2 = 0.47 V, and reduced irreversibly at E-P = - 1.84 V. Density functional theory calculations reproduce the geometries of the four complexes. The one-electron reduction and oxidation potentials for 1 were calculated by using two solvent models, DMF and H2O. The calculations indicated that the one electron oxidation of 1 may involve removal of an electron from the ligand as opposed to the metal center, producing a diradical. The diamide macrocyle is of interest for the development of new positron emission tomography (PET) and single photon emission computed tomography (SPECT) imaging agents, and a radiolabeled complex has been synthesized with the positron emitting isotope (CU)-C-64. In vivo biodistribution studies for the Cu-64 labeled complex, C-64-1, in male Lewis rats, showed that the activity is cleared rapidly from the blood within 1-2 h post-administration.
• Flavonol dioxygenase chemistry mediated by a synthetic nickel superoxide
  作者：F. Khamespanah、N.M. Patel、A.K. Forney、D.R. Heitger、C.M. Amarasekarage、L.E. Springer、K. Belecki、H.R. Lucas

  DOI：10.1016/j.jinorgbio.2022.112021

  日期：2023.1

  natural product with antioxidant properties. Herein, we report the synthesis and characterization of Ni(13-DOB), a Ni(II) species complexed by an N4-macrocycle that has been characterized by single crystal X-ray crystallography. Ni(13-DOB) forms a Ni-superoxide intermediate (Ni(13-DOB)O2•-) upon treatment with H2O2 and Et3N, as verified by resonance Raman spectroscopy. We demonstrate through UV/vis and

  大自然利用过渡金属中心来增强和调节 O 2和 H 2 O 2等天然氧化剂的氧化能力. 设计和研究与金属蛋白具有相似反应性的合成金属复合物提供了一种策略，可用于深入了解氧化酶、加氧酶和双加氧酶（如镍槲皮素酶 (Ni-QueD)）等氧活化酶的机制基础。Ni-QueD 催化多酚槲皮素的氧化开环，这是一种具有抗氧化特性的天然产物。在此，我们报告了 Ni(13-DOB) 的合成和表征，Ni(II) 物种由 N4-大环化合物络合，已通过单晶 X 射线晶体学表征。Ni(13-DOB)在用 H 2 O 2和 Et 3处理后形成 Ni-超氧化物中间体 (Ni(13-DOB)O 2 •- )N，通过共振拉曼光谱验证。我们通过 UV/vis 和 LCMS 证明 Ni(13-DOB)O 2 •-能够对黄酮醇进行单电子氧化，包括 3-羟基黄酮（3-HF，最简单的黄酮醇）和槲皮素本身。通过来自 Ni(13-DOB)O