2,2′-(2,9-dioxo-1,2,3,5,6,8,9,10-octahydrobenzo-[b][1,4,7,10]tetra-azacyclododecine-4,7-diyl)diacetic acid | 167777-85-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2,2′-(2,9-dioxo-1,2,3,5,6,8,9,10-octahydrobenzo-[b][1,4,7,10]tetra-azacyclododecine-4,7-diyl)diacetic acid
• 英文别名: 2,9-dioxo-1,4,7,10-tetraazabicyclo[1.10.1]hexadeca-1(11),13,15-triene-4,7-diacetic acid；2-[8-(Carboxymethyl)-3,10-dioxo-2,5,8,11-tetrazabicyclo[10.4.0]hexadeca-1(16),12,14-trien-5-yl]acetic acid
• CAS: 167777-85-7
• 化学式: C₁₆H₂₀N₄O₆
• 分子量: 364.358
• InChiKey: HTDYSSCSSSOTLF-UHFFFAOYSA-N

物化性质

• 沸点：
  722.4±60.0 °C(Predicted)
• 密度：
  1.328±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -5.2
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  139
• 氢给体数：
  4
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  copper(II) choride dihydrate 、 2,2′-(2,9-dioxo-1,2,3,5,6,8,9,10-octahydrobenzo-[b][1,4,7,10]tetra-azacyclododecine-4,7-diyl)diacetic acid 在 Li₂CO₃ 作用下， 以 水 为溶剂， 生成
  参考文献：
  名称：

  Metal–ligand interactions in benzodioxotetraaza-macrocyclic metal chelates

  摘要：

  Reactions of ethylenediaminetetraacetic (edta) dianhydride with o-phenylenediamine (od) and 9,10-diaminophenanthrene (phn) gave (edtaod)H-2 and (edtaphn)H-2, respectively, in which a chelating edta unit and an aromatic diamine unit are linked by two amide bonds. The complexation of these new 12-membered macrocycles with transition metal ions was studied by X-ray crystallography, potentiometric titrations, UV-Vis absorption spectroscopy and fluorescence spectroscopy. The absorption spectra are sensitively changed by metal complexation. The spectral changes are the most significant for the Cu2+ complexes, and are well correlated with the species distribution diagram. The X-ray study of the Cu2+ complex, [Cu(edtaod)](o), has shown that a square plane is formed around the central metal ion by an amide oxygen atom, a carboxylate oxygen atom and an amino nitrogen atom from a ligand molecule and a carboxylate oxygen atom from the adjacent chelate molecule. The amide nitrogen atoms in [Cu(edtaod)](o) are readily deprotonated and result in the formation of [Cu(edtaodH(-1))](-) and [Cu(edtaodH(-2))](2-) in neutral and basic media. The coordination of deprotonated amide nitrogen atoms to a Cu2+ ion leads to a strong metal-ligand interaction, which causes an intense charge-transfer band in [Cu(edtaodH(-1))](-), new UV absorption bands in [Cu(edtaodH(-2))](2-) and the effective quenching of emission in the Cu2+ complex of (edtaphn)H-2. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(01)00536-9
• 作为产物：
  描述：

  乙二胺四乙酸二酐 、 邻苯二胺 以 四氢呋喃 为溶剂， 反应 20.0h， 以95%的产率得到2,2′-(2,9-dioxo-1,2,3,5,6,8,9,10-octahydrobenzo-[b][1,4,7,10]tetra-azacyclododecine-4,7-diyl)diacetic acid
  参考文献：
  名称：

  具有侧链酸性功能的大环双内酰胺可作为镧系离子的识别剂

  摘要：

  N，N'-双（羧甲基）大环二内酰胺是由二胺和二酐以高收率合成的。通过电位法在水溶液中测量它们的配体质子化和镧系元素络合物的稳定常数。通过EDTA和EGTA的稳定性常数测量，从EDTA和EGTA衍生的12和18元大环双内酰胺的镧系元素识别能力与其他大环化合物（如二氨基冠醚和双内酯）进行了比较。在双内酰胺系列中，发现Eu 3+络合物对于衍生自邻苯二胺和EGTA二酐的配体最稳定。

  DOI：

  10.1016/0040-4020(94)00994-6

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
• Antibiofilm properties of copper (II) and iron (III) complexes with an EDTA-based phenylene macrocycle and its acyclic analogue against food and clinical related pathogens
  作者：F.J. Vázquez-Armenta、M. Beltrán-Torres、J.F. Ayala-Zavala、E.F. Velázquez-Contreras、F. Rocha-Alonzo、G.A. González-Aguilar、R. Sugich-Miranda

  DOI：10.1016/j.poly.2021.115076

  日期：2021.4
• A N,N′-diacetate benzodioxotetraazamacrocycle and its transition metal complexes
  作者：Sara Lacerda、Maria Paula Campello、Isabel C. Santos、Isabel Santos、Rita Delgado

  DOI：10.1016/j.poly.2004.12.008

  日期：2005.2

  Reaction of 2,9-dioxo-1,4,7,10-tetraazabicyclo[1.10.1]hexadeca-1(11), 13,15-triene-4,7-diacetic acid (H(2)L1) with CuCl2 . 2H(2)O in ethanol at pH 6 led to the monomeric benzodioxochlorocomplex [Cu(L'1)Cl] (1) (HL'1 = monoethylesther of H2LI). X-ray structural analysis has shown that in complex 1 the Cu is five-coordinated by two nitrogen and two oxygen atoms of the macrocycle and by a chloride, displaying a square pyramidal coordination geometry. One of the acetate arms does not coordinate to the Cu and has suffered an in situ ethanolic esterification reaction. The protonation constants of H2L1 and the stability constants of its complexes with Cu2+, Ni2+, Zn2+, Cd2+ and Pb2+ were determined by potentiometric methods and in some cases by H-1 NMR spectroscopy. The stability constants of the complexes follow the trend [Ni(H(-1)L1)](-) > [Cu(H(-1)L1)](-) much greater than [Pb(H(-1)Ll)](-) > [Zn(H(-1)L1)](-) > [Cd(H(-1)L1)](-), probably due to steric requirements. Spectroscopic measurements (absorption and EPR) at different pH values have shown the effect of the pH on the coordination sphere of the Cu complexes. (C) 2005 Elsevier Ltd. All rights reserved.