Phosphocrypt

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: Phosphocrypt
• 英文别名: 2,5,8,11,13,16,19,22,23,26,29,32-Dodecaoxa-1lambda5,12lambda5-diphosphabicyclo[10.10.10]dotriacontane 1,12-dioxide；2,5,8,11,13,16,19,22,23,26,29,32-dodecaoxa-1λ5,12λ5-diphosphabicyclo[10.10.10]dotriacontane 1,12-dioxide
• 化学式: C₁₈H₃₆O₁₄P₂
• 分子量: 538.423
• InChiKey: FUQFNHKUYNSFPS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.5
• 重原子数：
  34
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  145
• 氢给体数：
  0
• 氢受体数：
  14

反应信息

• 作为产物：
  描述：

  三乙二醇 在 palladium on activated charcoal 吡啶 、 氢气 、 sodium hydride 、 三氯氧磷 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 为溶剂， 8.0 ℃ 、275.79 kPa 条件下， 反应 22.5h， 生成 Phosphocrypt
  参考文献：
  名称：

  Synthesis, Characterization, and Alkali Metal Stability Constants of a New Bis(phosphotriester) Macrobicyclic Polyether Cryptand

  摘要：

  The synthesis of a new bis(phosphotriester) macrobicyclic polyether cryptand, O=P[O(CH2)(2)O(CH2)(2)O(CH2)(2)O]P-3=O (9), called phosphocrypt, and its acyclic tripodal precursor O=P[O(CH2)(2)O(CH2)(2)O(CH2)(2)OH](3) (8) are described. The new cryptand 9 was synthesized by condensation of 8 and phosphoryl chloride which were simultaneously added under high dilution conditions in the presence of pyridine. The highest yield of 9 (30%) was obtained with a final concentration of 3 mM in vigorously stirred methylene chloride. Both 8 and 9 form stable complexes with K+ and Rb+ in water. Log K-s values measured with a cation selective electrode for 8 are 3.6 and 3.0 and 3.7 and 3.6 for 9, respectively. The K-s values for phosphocrypt are 1000-fold greater than those of comparably sized nitrogen bridgehead cryptands. H-1 and C-13 NMR indicate 9 is flexible at 20 degrees C. Molecular dynamics and mechanics calculations indicate that phosphocrypt has more cation-dipole interactions and more favorable conformational changes associated with complexation than comparably sized nitrogen bridgehead cryptands.

  DOI：

  10.1021/jo00104a026

文献信息

• Allan Christian B., Spreer Larry O., J. Org. Chem, 59 (1994) N 25, S 7695-7700
  作者：Allan Christian B., Spreer Larry O.

  DOI：——

  日期：——
• Synthesis, Characterization, and Alkali Metal Stability Constants of a New Bis(phosphotriester) Macrobicyclic Polyether Cryptand
  作者：Christian B. Allan、Larry O. Spreer

  DOI：10.1021/jo00104a026

  日期：1994.12

  The synthesis of a new bis(phosphotriester) macrobicyclic polyether cryptand, O=P[O(CH2)(2)O(CH2)(2)O(CH2)(2)O]P-3=O (9), called phosphocrypt, and its acyclic tripodal precursor O=P[O(CH2)(2)O(CH2)(2)O(CH2)(2)OH](3) (8) are described. The new cryptand 9 was synthesized by condensation of 8 and phosphoryl chloride which were simultaneously added under high dilution conditions in the presence of pyridine. The highest yield of 9 (30%) was obtained with a final concentration of 3 mM in vigorously stirred methylene chloride. Both 8 and 9 form stable complexes with K+ and Rb+ in water. Log K-s values measured with a cation selective electrode for 8 are 3.6 and 3.0 and 3.7 and 3.6 for 9, respectively. The K-s values for phosphocrypt are 1000-fold greater than those of comparably sized nitrogen bridgehead cryptands. H-1 and C-13 NMR indicate 9 is flexible at 20 degrees C. Molecular dynamics and mechanics calculations indicate that phosphocrypt has more cation-dipole interactions and more favorable conformational changes associated with complexation than comparably sized nitrogen bridgehead cryptands.