4-[(8-carboxy-2,2,6,6-tetramethyl-[1,3]dithiolo[4,5-f][1,3]benzodithiol-4-yl)-[4-[C-hydroxy-N-[5-hydroxy-5-(2,2,6,6-tetramethyl-1-oxidopiperidin-4-yl)iminopentyl]carbonimidoyl]-2,2,6,6-tetramethyl-[1,3]dithiolo[4,5-f][1,3]benzodithiol-1-ium-8-ylidene]methyl]-2,2,6,6-tetramethyl-[1,3]dithiolo[4,5-f][1,3]benzodithiole-8-carboxylic acid | 1417914-81-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: 4-[(8-carboxy-2,2,6,6-tetramethyl-[1,3]dithiolo[4,5-f][1,3]benzodithiol-4-yl)-[4-[C-hydroxy-N-[5-hydroxy-5-(2,2,6,6-tetramethyl-1-oxidopiperidin-4-yl)iminopentyl]carbonimidoyl]-2,2,6,6-tetramethyl-[1,3]dithiolo[4,5-f][1,3]benzodithiol-1-ium-8-ylidene]methyl]-2,2,6,6-tetramethyl-[1,3]dithiolo[4,5-f][1,3]benzodithiole-8-carboxylic acid
• CAS: 1417914-81-8
• 化学式: C₅₄H₆₅N₃O₇S₁₂
• 分子量: 1252.92
• InChiKey: VMMVMSVCPUZPRU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.3
• 重原子数：
  76
• 可旋转键数：
  11
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  445
• 氢给体数：
  4
• 氢受体数：
  21

反应信息

• 作为反应物：
  描述：

  4-[(8-carboxy-2,2,6,6-tetramethyl-[1,3]dithiolo[4,5-f][1,3]benzodithiol-4-yl)-[4-[C-hydroxy-N-[5-hydroxy-5-(2,2,6,6-tetramethyl-1-oxidopiperidin-4-yl)iminopentyl]carbonimidoyl]-2,2,6,6-tetramethyl-[1,3]dithiolo[4,5-f][1,3]benzodithiol-1-ium-8-ylidene]methyl]-2,2,6,6-tetramethyl-[1,3]dithiolo[4,5-f][1,3]benzodithiole-8-carboxylic acid 在 维生素 C 作用下， 以 aq. phosphate buffer 为溶剂， 反应 2.5h， 生成
  参考文献：
  名称：

  三苯甲基-氮杂双自由基与环糊精的超分子宿主-客体相互作用：自旋-自旋相互作用和氧化还原敏感性的调节†

  摘要：

  三苯甲基-硝基氧根（TN）双自由基CT02-VT，CT02-AT和CT02-GT与甲基-β-环糊精（M-β-CD），羟丙基-β-环糊精（H-β-CD）的超分子宿主-客体相互作用通过EPR光谱法研究了γ-环糊精和γ-环糊精（γ-CD）。在存在环糊精（即γ-CD，M-β-CD和H-β-CD）的情况下，会形成CT02-VT的宿主-客体复合物，其中的氮氧化物和连接基可能与环糊精的腔相互作用。与环糊精的络合可抑制CT02-VT中分子内贯穿空间的自旋-自旋交换耦合，因此可确定通过EPR模拟计算为1.6 G的贯穿键自旋-自旋交换耦合。不同类型的环糊精与CT02-VT的结合亲和力呈γ-CD顺序（95 M-1）>M-β-CD（70 M -1）>H-β-CD（32 M -1）。此外，还研究了TN双基中的连接基对宿主-客体相互作用的影响。在研究的三个TN双自由基中，CT02-VT与一种指定的环糊精衍生物具有最高

  DOI：

  10.1039/c5ob02450a
• 作为产物：
  描述：

  4-(5-amino-pentaneamido)-2,2,6,6-tetramethyl-piperidynyl-1-oxyl 、 tris(8-carboxy-2,2,6,6-tetramethylbenzo[1,2-d;4,5-d']bis[1,3]dithiol-4-yl)methyl 在 (benzotriazo-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate 、 1-羟基苯并三唑 、 N,N-二异丙基乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以4.1 mg的产率得到4-[(8-carboxy-2,2,6,6-tetramethyl-[1,3]dithiolo[4,5-f][1,3]benzodithiol-4-yl)-[4-[C-hydroxy-N-[5-hydroxy-5-(2,2,6,6-tetramethyl-1-oxidopiperidin-4-yl)iminopentyl]carbonimidoyl]-2,2,6,6-tetramethyl-[1,3]dithiolo[4,5-f][1,3]benzodithiol-1-ium-8-ylidene]methyl]-2,2,6,6-tetramethyl-[1,3]dithiolo[4,5-f][1,3]benzodithiole-8-carboxylic acid
  参考文献：
  名称：

  Structural Factors Controlling the Spin–Spin Exchange Coupling: EPR Spectroscopic Studies of Highly Asymmetric Trityl–Nitroxide Biradicals

  摘要：

  Highly asymmetric exchange-coupled biradicals, e.g., the trityl-nitroxides (TNs), possess particular magnetic properties that have opened new possibilities for their application in biophysical, physicochemical, and biological studies. In the present work, we investigated the effect of the linker length on the spin-spin coupling interaction (J) in TN biradicals using the newly synthesized biradicals CT02-GT, CT02-AT, CT02-VT, and CT02-PPT as well as the previously reported biradicals TNN14 and TN1. The results show that the magnitude of J can be easily tuned from similar to 4 G (conformer 1 in CT02-PPT) to >1200 G (in TNN14) by varying the linker separating the two radical moieties and changing the temperature. Computer simulations of EPR spectra were carried out to estimate J values of the TN biradicals directly. In addition to the spin-spin coupling interaction of TN biradicals, their g, hyperfine-splitting, and zero-field-splitting interactions were explored at low temperature (220 K). Our present study clearly shows that varying the spin-spin interaction as a function of linker distance and temperature provides an effective strategy for the development of new TN biradicals that can find wide applications in relevant fields.

  DOI：

  10.1021/ja311571v