RRRS(+/-)-1,4,7,10-tetrakis[(3'-carboxyl)-1'-carboxypropyl]-1,4,7,10-tetraazacyclododecane

• 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: RRRS(+/-)-1,4,7,10-tetrakis[(3'-carboxyl)-1'-carboxypropyl]-1,4,7,10-tetraazacyclododecane
• 英文别名: RRRS/SSSR-1,4,7,10-tetrakis[(3-carboxyl)-1'-carboxypropyl]-1,4,7,10-tetraazacyclododecane；(2R)-2-[4,10-bis[(1R)-1,3-dicarboxypropyl]-7-[(1S)-1,3-dicarboxypropyl]-1,4,7,10-tetrazacyclododec-1-yl]pentanedioic acid
• 化学式: C₂₈H₄₄N₄O₁₆
• 分子量: 692.675
• InChiKey: AFQGVJQUGCIFLZ-WTGUMLROSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -11
• 重原子数：
  48
• 可旋转键数：
  20
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  311
• 氢给体数：
  8
• 氢受体数：
  20

反应信息

• 作为反应物：
  描述：

  europium(III) nitrate hexahydrate 、 RRRS(+/-)-1,4,7,10-tetrakis[(3'-carboxyl)-1'-carboxypropyl]-1,4,7,10-tetraazacyclododecane 在 sodium hydroxide 作用下， 以 水 为溶剂， 生成 (H3O)[Eu(RRRS/SSSR-1,4,7,10-tetrakis[(3-carboxyl)-1'-carboxypropyl]-1,4,7,10-tetraazacyclododecane)(H2O)]*2H2O
  参考文献：
  名称：

  Correlation of Water Exchange Rate with Isomeric Composition in Diastereoisomeric Gadolinium Complexes of Tetra(carboxyethyl)dota and Related Macrocyclic Ligands

  摘要：

  The solution structure and dynamics of metal-bound water exchange have been studied in a series of diastereoisomeric gadolinium complexes of tetra(carboxyethyl) derivatives of 1,4,7,10-tetraazacyclodecane. The structures of the (RRRS), (RSRS), and (RRSS) ligands and the Eu, Gd, and Tb complexes of the (RRRR) isomer have been determined by X-ray crystallography. Luminescence measurements on the Eu and Tb complexes revealed an integral hydration state (q = 1) in each case for the Eu isomers, whereas nonintegral values were measured for the (RRRR) and (RRRS) Tb isomers (e.g., [(RRRR)-Tb .1](-), q = 0.60). The ratio of the twisted and regular monocapped square antiprismatic isomers has been measured in solution by H-1 NMR for the Eu and Tb complexes and followed the order, (RRRR) > (RRRS) > (RSRS) > (RRSS). Water exchange rates in the gadolinium complexe have been determined by O-17 NMR and were fastest for the (RRRR) isomer [tau (m) = 68 ns (298 K)] and correlated very well with the proportion of the twisted square anti-prismatic isomer. The rate of water exchange in the (RRRR) Gd complexes is likely to be sufficiently fast so as not to limit the overall relaxivity in higher MW conjugates.

  DOI：

  10.1021/ja994492v
• 作为产物：
  描述：

  2-溴戊二酸二甲酯 、 轮环藤宁 在 potassium carbonate 、 sodium hydroxide 作用下， 以 乙腈 、 甲醇 为溶剂， 反应 66.0h， 生成 RRRS(+/-)-1,4,7,10-tetrakis[(3'-carboxyl)-1'-carboxypropyl]-1,4,7,10-tetraazacyclododecane 、 RRSS-1,4,7,10-tetrakis[(3'-carboxyl)-1'-carboxypropyl]-1,4,7,10-tetraazacyclododecane 、 RSRS-1,4,7,10-tetrakis[(3'-carboxyl)-1'-carboxypropyl]-1,4,7,10-tetraazacyclododecane 、 RRRR(SSSS)-1,4,7,10-tetrakis[(3'-carboxyl)-1'-carboxypropyl]-1,4,7,10-tetraazacyclododecane
  参考文献：
  名称：

  Correlation of Water Exchange Rate with Isomeric Composition in Diastereoisomeric Gadolinium Complexes of Tetra(carboxyethyl)dota and Related Macrocyclic Ligands

  摘要：

  The solution structure and dynamics of metal-bound water exchange have been studied in a series of diastereoisomeric gadolinium complexes of tetra(carboxyethyl) derivatives of 1,4,7,10-tetraazacyclodecane. The structures of the (RRRS), (RSRS), and (RRSS) ligands and the Eu, Gd, and Tb complexes of the (RRRR) isomer have been determined by X-ray crystallography. Luminescence measurements on the Eu and Tb complexes revealed an integral hydration state (q = 1) in each case for the Eu isomers, whereas nonintegral values were measured for the (RRRR) and (RRRS) Tb isomers (e.g., [(RRRR)-Tb .1](-), q = 0.60). The ratio of the twisted and regular monocapped square antiprismatic isomers has been measured in solution by H-1 NMR for the Eu and Tb complexes and followed the order, (RRRR) > (RRRS) > (RSRS) > (RRSS). Water exchange rates in the gadolinium complexe have been determined by O-17 NMR and were fastest for the (RRRR) isomer [tau (m) = 68 ns (298 K)] and correlated very well with the proportion of the twisted square anti-prismatic isomer. The rate of water exchange in the (RRRR) Gd complexes is likely to be sufficiently fast so as not to limit the overall relaxivity in higher MW conjugates.

  DOI：

  10.1021/ja994492v

文献信息

• Structure and dynamics of all of the stereoisomers of europium complexes of tetra(carboxyethyl) derivatives of dota: ring inversion is decoupled from cooperative arm rotation in the RRRR and RRRS isomers
  作者：Judith A. K. Howard、Alan M. Kenwright、Janet M. Moloney、David Parker、Mark Woods、Judith A. K. Howard、Marc Port、Michel Navet、Olivier Rousseau

  DOI：10.1039/a802847h

  日期：——

  The absolute configuration of the four stereoisomeric α-substituted derivatives of dota has been defined; in their Eu complexes, 2D-NMR methods have revealed that in solution ring inversion is independent of pendant arm rotation and the (RRRR)-[EuL1a] complex which in the solid state crystallises as a square antiprismatic structure.

  多塔的四种立体异构α-取代衍生物的绝对构型已经确定；在它们的 Eu 复合物中，二维-核磁共振方法揭示了溶液中的环反转与垂臂旋转无关，(RRRR)-[EuL1a] 复合物在固态下结晶为方形反三棱镜结构。