1-[2'-(4-methoxyphenylsulfonylamino)ethyl]-4,7,10-tris(carboxymethyl)-1,4,7,10-tetraazacyclododecane

• 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: 1-[2'-(4-methoxyphenylsulfonylamino)ethyl]-4,7,10-tris(carboxymethyl)-1,4,7,10-tetraazacyclododecane
• 英文别名: 2-[4,7-Bis(carboxymethyl)-10-[2-[(4-methoxyphenyl)sulfonylamino]ethyl]-1,4,7,10-tetrazacyclododec-1-yl]acetic acid；2-[4,7-bis(carboxymethyl)-10-[2-[(4-methoxyphenyl)sulfonylamino]ethyl]-1,4,7,10-tetrazacyclododec-1-yl]acetic acid
• 化学式: C₂₃H₃₇N₅O₉S
• 分子量: 559.641
• InChiKey: DDSJDRKCIDFJTH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -7.3
• 重原子数：
  38
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  189
• 氢给体数：
  4
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  cerium(III) chloride 、 1-[2'-(4-methoxyphenylsulfonylamino)ethyl]-4,7,10-tris(carboxymethyl)-1,4,7,10-tetraazacyclododecane 生成
  参考文献：
  名称：

  Solution Structures, Stabilities, Kinetics, and Dynamics of DO3A and DO3A–Sulphonamide Complexes

  摘要：

  The Gd3+-DO3A arylsulphonamide (DO3A-SA) complex is a promising pH-sensitive MRI agent. The stability constants of the DO3A-SA and DO3A complexes formed with Mg2+, Ca2+, Mn2+, Zn2+, and Cu2+ ions are similar, whereas the logicK(LnL) values of Ln(DO3A-SA) complexes are 2 orders of magnitude higher than those of the Ln(DO3A) complexes. The protonation constant (log K-MHL) of the sulphonamide nitrogen in the Mg2+, Ca2+, Mn2+, Zn2+, and Cu2+ complexes is very similar to that of the free ligand, whereas the logK(LnHL) values of the Ln(DO3A-SA) complexes are lower by about 4 logK units, indicating a strong interaction between the Ln(3+) ions and the sulphonamide N atom. The Ln(HDO3A-SA) complexes are formed via triprotonated *Ln(H(3)DO3A-SA) intermediates which rearrange to the final complex in an OH--assisted deprotonation process. The transmetalation reaction of Gd(HDO3A-SA) with Cu2+ is very slow (t(1/2) = 5.6 X 10(3) h at pH = 7.4), and it mainly occurs through proton-assisted dissociation of the complex. The H-1 and C-13 NMR spectra of the La-, Eu-, and Lu(DO3A-SA) complexes have been assigned using 2D correlation spectroscopy (COSY, EXSY, HSQC). Two sets of signals are observed for Eu-, Y-, and Lu(DO3A, SA), showing two coordination isomers in solution, that is, square antiprismatic (SAP) and twisted square antiprismatic (TSAP) geometries with ratios of 86-14, 93 7, and 94-6%, respectively. Line shape analysis of the C-13 NMR spectra of La-, Y-, and Lu(DO3A-SA) gives higher rates and lower activation entropy values compared to Ln(DOTA) for the arm rotation, which indicates that the Ln(DO3A-SA) complexes are less rigid due to the larger flexibility of the ethylene group in the sulphonamide pendant arm. The fast isomerization and the lower activation parameters of Ln(DO3A-SA) have been confirmed by theoretical calculations in vacuo and by using the polarizable continuum model. The solid state X-ray structure of Cu(H(2)DO3A-SA) shows distorted octahedral coordination. The coordination sites of Cu2+ are occupied by two ring N- and two carboxylate O-atoms in equatorial position. The other two ring N-atoms complete the coordination sphere in axial positions. The solid state structure also indicates that a carboxylate O atom and the sulphonamide nitrogen are protonated and noncoordinated.

  DOI：

  10.1021/ic4025958

文献信息

• pH-Dependent Modulation of Relaxivity and Luminescence in Macrocyclic Gadolinium and Europium Complexes Based on Reversible Intramolecular Sulfonamide Ligation
  作者：Mark P. Lowe、David Parker、Ofer Reany、Silvio Aime、Mauro Botta、Giancarlo Castellano、Eliana Gianolio、Roberto Pagliarin

  DOI：10.1021/ja0103647

  日期：2001.8.1

  A series of macrocyclic Eu, Gd, and Tb complexes has been prepared in which the intramolecular ligation of a beta-arylsulfonamide nitrogen is rendered pH-dependent, giving rise to changes in the hydration state, q, at the lanthanide center. In complexes based on DO3A, variation of the p-substituent in the arylsulfonamide moiety determines the apparent protonation constant log K(MLH) with values of

  已经制备了一系列大环 Eu、Gd 和 Tb 复合物，其中 β-芳基磺酰胺氮的分子内连接呈现 pH 依赖性，导致镧系元素中心的水合状态 q 发生变化。在基于 DO3A 的复合物中，芳基磺酰胺部分中 p 取代基的变化决定了表观质子化常数 log K(MLH)，-CF(3)、-Me 和 -OMe 取代基的值为 5.7、6.4 和 6.7 ， 分别。引入三个 β-羧基烷基取代基、α 到三个环氮，可抑制添加蛋白质对结合水的置换，并抑制内源性阴离子（乳酸、HCO(3)(-)）的分子间结合。对 Eu 配合物形式和强度的 pH 依赖性的测量表明，分子内羧酸盐配位是竞争性发生的。这可以通过提高磺酰胺氮上的电子密度或通过将螯合环从 7--8 扩大来减少。pH 范围 8--5 中弛豫度变化的放大发生在蛋白质结合上，并且在 pH 值 7.4--6.8 范围内，[Gd.3a]（298 K，65.6 MHz）在 50
• Solution Structures, Stabilities, Kinetics, and Dynamics of DO3A and DO3A–Sulphonamide Complexes
  作者：Anett Takács、Roberta Napolitano、Mihály Purgel、Attila Csaba Bényei、László Zékány、Ernő Brücher、Imre Tóth、Zsolt Baranyai、Silvio Aime

  DOI：10.1021/ic4025958

  日期：2014.3.17

  The Gd3+-DO3A arylsulphonamide (DO3A-SA) complex is a promising pH-sensitive MRI agent. The stability constants of the DO3A-SA and DO3A complexes formed with Mg2+, Ca2+, Mn2+, Zn2+, and Cu2+ ions are similar, whereas the logicK(LnL) values of Ln(DO3A-SA) complexes are 2 orders of magnitude higher than those of the Ln(DO3A) complexes. The protonation constant (log K-MHL) of the sulphonamide nitrogen in the Mg2+, Ca2+, Mn2+, Zn2+, and Cu2+ complexes is very similar to that of the free ligand, whereas the logK(LnHL) values of the Ln(DO3A-SA) complexes are lower by about 4 logK units, indicating a strong interaction between the Ln(3+) ions and the sulphonamide N atom. The Ln(HDO3A-SA) complexes are formed via triprotonated *Ln(H(3)DO3A-SA) intermediates which rearrange to the final complex in an OH--assisted deprotonation process. The transmetalation reaction of Gd(HDO3A-SA) with Cu2+ is very slow (t(1/2) = 5.6 X 10(3) h at pH = 7.4), and it mainly occurs through proton-assisted dissociation of the complex. The H-1 and C-13 NMR spectra of the La-, Eu-, and Lu(DO3A-SA) complexes have been assigned using 2D correlation spectroscopy (COSY, EXSY, HSQC). Two sets of signals are observed for Eu-, Y-, and Lu(DO3A, SA), showing two coordination isomers in solution, that is, square antiprismatic (SAP) and twisted square antiprismatic (TSAP) geometries with ratios of 86-14, 93 7, and 94-6%, respectively. Line shape analysis of the C-13 NMR spectra of La-, Y-, and Lu(DO3A-SA) gives higher rates and lower activation entropy values compared to Ln(DOTA) for the arm rotation, which indicates that the Ln(DO3A-SA) complexes are less rigid due to the larger flexibility of the ethylene group in the sulphonamide pendant arm. The fast isomerization and the lower activation parameters of Ln(DO3A-SA) have been confirmed by theoretical calculations in vacuo and by using the polarizable continuum model. The solid state X-ray structure of Cu(H(2)DO3A-SA) shows distorted octahedral coordination. The coordination sites of Cu2+ are occupied by two ring N- and two carboxylate O-atoms in equatorial position. The other two ring N-atoms complete the coordination sphere in axial positions. The solid state structure also indicates that a carboxylate O atom and the sulphonamide nitrogen are protonated and noncoordinated.