5,11-Bis(chloroacetamido)-17-phthalimido-25,26,27,28-tetrapropoxycalix[4]arene | 191344-49-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: 5,11-Bis(chloroacetamido)-17-phthalimido-25,26,27,28-tetrapropoxycalix[4]arene
• CAS: 191344-49-7
• 化学式: C₅₂H₅₅Cl₂N₃O₈
• 分子量: 920.93
• InChiKey: MZCHJDITKQCBDH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.67
• 重原子数：
  65.0
• 可旋转键数：
  17.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  132.5
• 氢给体数：
  2.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  C-undecylcavitandtetrol 、 5,11-Bis(chloroacetamido)-17-phthalimido-25,26,27,28-tetrapropoxycalix[4]arene 在 caesium carbonate 、 potassium iodide 作用下， 以 乙腈 为溶剂， 反应 14.0h， 生成 41,59-Dihydroxy-19-phthalimido-14,30,62,63-tetrapropoxy-1,47,49,57-tetraundecyl-16H,21H,28H,34H-13,31:51,55-dimethano-2,46:3,45:11,15:17,21:23,27:29,33-hexametheno-1H,8H,47H,49H[1,3]benzodioxocino[9',8':4,5][1,3]benzodioxocino[9,10-d][1,3]benzo...
  参考文献：
  名称：

  Calix[4]arene-Based (Hemi)carcerands and Carceplexes: Synthesis, Functionalization, and Molecular Modeling Study

  摘要：

  AbstractThe synthesis of 11 calix[4]arene‐based carceplexes obtained by solvent or doped inclusion is reported. Carceplexes with amides, for example, DMF, NMP, and 1,5‐dimethyl‐2‐pyrrolidinone, and sulfoxides, for example, DMSO and thiolane‐1‐oxide, were obtained by solvent inclusion. In these cases the yield of the carceplex decreases with increasing guest size. Potential guests that do not form carceplexes by solvent inclusion, such as 2‐butanone and 3‐sulfolene, could be incarcerated by doped inclusion with 1,5‐dimethyl‐2‐pyrrolidinone as a solvent “doped” with 5–15 vol% of potential guest. The amide bridges of the carceplexes were converted into thioamide bridges in essentially quantitative yield by means of Lawesson's reagent in refluxing xylene. The dynamic properties of the incarcerated guests were examined by 2D NMR spectroscopy. Whereas for most guests a preference for one orientation inside the calix[4]arene‐based (thia)carcerands was observed, for DMA, NMP, and ethyl methyl sulfoxide inside calix[4]arene‐based (thia)carcerandstwo different orientationswere present. The energy barriers for interconversion between the various orientations of DMA, NMP, and ethyl methyl sulfoxide inside calix[4]arene‐based (thia)‐carcerands were determined with 2D EXSY NMR. The energy barriers are higher for the thiacarcerands than for the corresponding carcerands with amide bridges. This may be due to the stronger hydrogen‐bond‐donating character of the thioamide group. Furthermore, molecular modeling simulations indicate that in case of the thiacarcerand the cavity is smaller as a result of a smaller diametrical distance between the NHatoms. Our results demonstrate that molecular modeling can be used to estimate the energy barriers for interconversion; the calculated activation energies showed good quantitative agreement with the experimental values.

  DOI：

  10.1002/chem.19970030421
• 作为产物：
  描述：

  5,11-Dinitro-17-phthalimido-25,26,27,28-tetrapropoxycalix[4]arene 在 三乙胺 、 tin(ll) chloride 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 2.75h， 生成 5,11-Bis(chloroacetamido)-17-phthalimido-25,26,27,28-tetrapropoxycalix[4]arene
  参考文献：
  名称：

  Calix[4]arene-Based (Hemi)carcerands and Carceplexes: Synthesis, Functionalization, and Molecular Modeling Study

  摘要：

  AbstractThe synthesis of 11 calix[4]arene‐based carceplexes obtained by solvent or doped inclusion is reported. Carceplexes with amides, for example, DMF, NMP, and 1,5‐dimethyl‐2‐pyrrolidinone, and sulfoxides, for example, DMSO and thiolane‐1‐oxide, were obtained by solvent inclusion. In these cases the yield of the carceplex decreases with increasing guest size. Potential guests that do not form carceplexes by solvent inclusion, such as 2‐butanone and 3‐sulfolene, could be incarcerated by doped inclusion with 1,5‐dimethyl‐2‐pyrrolidinone as a solvent “doped” with 5–15 vol% of potential guest. The amide bridges of the carceplexes were converted into thioamide bridges in essentially quantitative yield by means of Lawesson's reagent in refluxing xylene. The dynamic properties of the incarcerated guests were examined by 2D NMR spectroscopy. Whereas for most guests a preference for one orientation inside the calix[4]arene‐based (thia)carcerands was observed, for DMA, NMP, and ethyl methyl sulfoxide inside calix[4]arene‐based (thia)carcerandstwo different orientationswere present. The energy barriers for interconversion between the various orientations of DMA, NMP, and ethyl methyl sulfoxide inside calix[4]arene‐based (thia)‐carcerands were determined with 2D EXSY NMR. The energy barriers are higher for the thiacarcerands than for the corresponding carcerands with amide bridges. This may be due to the stronger hydrogen‐bond‐donating character of the thioamide group. Furthermore, molecular modeling simulations indicate that in case of the thiacarcerand the cavity is smaller as a result of a smaller diametrical distance between the NHatoms. Our results demonstrate that molecular modeling can be used to estimate the energy barriers for interconversion; the calculated activation energies showed good quantitative agreement with the experimental values.

  DOI：

  10.1002/chem.19970030421