26,27-Dimethoxy-3,7,24-trimethyl-3-sulfanylidene-11,14,17,20-tetraoxa-2,4-diaza-3lambda5-phosphatricyclo[20.3.1.15,9]heptacosa-1(25),5,7,9(27),22(26),23-hexaene | 185062-94-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 26,27-Dimethoxy-3,7,24-trimethyl-3-sulfanylidene-11,14,17,20-tetraoxa-2,4-diaza-3lambda5-phosphatricyclo[20.3.1.15,9]heptacosa-1(25),5,7,9(27),22(26),23-hexaene
• 英文别名: 26,27-dimethoxy-3,7,24-trimethyl-3-sulfanylidene-11,14,17,20-tetraoxa-2,4-diaza-3λ5-phosphatricyclo[20.3.1.15,9]heptacosa-1(25),5,7,9(27),22(26),23-hexaene
• CAS: 185062-94-6
• 化学式: C₂₅H₃₇N₂O₆PS
• 分子量: 524.618
• InChiKey: JKHFHCRRQONLGS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  35
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  112
• 氢给体数：
  2
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  26,27-Dimethoxy-3,7,24-trimethyl-3-sulfanylidene-11,14,17,20-tetraoxa-2,4-diaza-3lambda5-phosphatricyclo[20.3.1.15,9]heptacosa-1(25),5,7,9(27),22(26),23-hexaene 在 sodium hydride 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 4,21,28-trimethyl-29,30-dimethoxy-8,11,14,17-tetraoxa-1,24,28-diazaphosphatetracyclo[22,3,1,1^2,6,1^19,23]triaconta-2,4,6(29),19,21,23(30)-hexaene-28-oxide
  参考文献：
  名称：

  Synthesis, Molecular Structure, and Binding Properties of a Hemispherand Incorporating a Phosphoryl Hard Donor Group

  摘要：

  Phosphahemispherand 3 was synthesized in 63 % yield from its macrocyclic precursor 2 and 1,3-propanediol ditosylate in the presence of NaH in THF. Host 3 exhibited temperature-dependent H-1, Cl-13 and P-31 NMR spectra owing to conformational exchange throughout the molecular framework. Exo and endo conformers are in equilibrium in solution, and the energy barrier between the two forms is 61 kJ mol(-1). Two exo conformers, with the P=O bond directed away from the macrocyclic cavity, were predominant at low temperature. The major form was assigned to the C-s symmetry exo conformation, The minor exo form was assigned to the asymmetric conformation that has one methoxy group on each face of the macroring. The energy barrier for interconversion between the two exo forms is 56 kJ mol(-1). The binding energies of alkali metal and ammonium cations to 2 and 3 wore measured by the picrate extraction technique, The highest K-a values were obtained for the complexes of 3 with K+ and Rb+. The conformational changes observed upon complexation were examined by NMR spectroscopy and X-ray analysis and are discussed in terms of pre organization, The formation of 1:1 complexes was only observed with the endo conformer.

  DOI：

  10.1002/(sici)1521-3765(199801)4:1<100::aid-chem100>3.0.co;2-5
• 作为产物：
  描述：

  二(二甲基氨基)甲基膦 、 1,12-bis(2-methoxy-5-methyl-3-aminophenyl)-2,5,8,11-tetraoxadodecane 在 sulfur 作用下， 生成 26,27-Dimethoxy-3,7,24-trimethyl-3-sulfanylidene-11,14,17,20-tetraoxa-2,4-diaza-3lambda5-phosphatricyclo[20.3.1.15,9]heptacosa-1(25),5,7,9(27),22(26),23-hexaene 、
  参考文献：
  名称：

  Synthesis and molecular structure of new phosphorous-crown compounds containing the thiophosphoryl group

  摘要：

  报告了四种磷大环（1-4）的合成和表征。化合物 1-4 和溶质 1-H2O 的 X 射线晶体结构显示，分子呈不对称构象，苯氧基取代基中至少有一个甲基朝向大环空腔的中心。变温 1H NMR 实验表明，在溶液中，分子主要以快速相互转化的构象存在。在 18 元环 1 中，动态过程导致了不对称构象的对映体转化，转化障碍为 8 kcal mol-1。

  DOI：

  10.1039/p29960002471

文献信息

• Synthesis and molecular structure of new phosphorous-crown compounds containing the thiophosphoryl group
  作者：Jean-Paul Declercq、Pascale Delangle、Jean-Pierre Dutasta、Luc Van Oostenryck、Pascal Simon、Bernard Tinant

  DOI：10.1039/p29960002471

  日期：——

  The synthesis and characterization of four phosphorus macrocycles (1–4) are reported. The X-ray crystal structures of compounds 1–4 and solvate 1·H2O show the molecules in asymmetric conformations with at least one methyl group of the phenoxy substituents oriented toward the centre of the macrocyclic cavity. Variable-temperature 1H NMR experiments show that in solution the molecules exist mainly as rapidly interconverting conformers. In the 18-membered ring 1, the dynamic process results in the enantiomerization of asymmetric conformers with a barrier of 8 kcal mol–1.‡ The 21-membered ring 3 is more flexible and exists in several conformations.

  报告了四种磷大环（1-4）的合成和表征。化合物 1-4 和溶质 1-H2O 的 X 射线晶体结构显示，分子呈不对称构象，苯氧基取代基中至少有一个甲基朝向大环空腔的中心。变温 1H NMR 实验表明，在溶液中，分子主要以快速相互转化的构象存在。在 18 元环 1 中，动态过程导致了不对称构象的对映体转化，转化障碍为 8 kcal mol-1。
• Synthesis, Molecular Structure, and Binding Properties of a Hemispherand Incorporating a Phosphoryl Hard Donor Group
  作者：Pascale Delangle、Jean-Pierre Dutasta、Jean-Paul Declercq、Bernard Tinant

  DOI：10.1002/(sici)1521-3765(199801)4:1<100::aid-chem100>3.0.co;2-5

  日期：1998.1

  Phosphahemispherand 3 was synthesized in 63 % yield from its macrocyclic precursor 2 and 1,3-propanediol ditosylate in the presence of NaH in THF. Host 3 exhibited temperature-dependent H-1, Cl-13 and P-31 NMR spectra owing to conformational exchange throughout the molecular framework. Exo and endo conformers are in equilibrium in solution, and the energy barrier between the two forms is 61 kJ mol(-1). Two exo conformers, with the P=O bond directed away from the macrocyclic cavity, were predominant at low temperature. The major form was assigned to the C-s symmetry exo conformation, The minor exo form was assigned to the asymmetric conformation that has one methoxy group on each face of the macroring. The energy barrier for interconversion between the two exo forms is 56 kJ mol(-1). The binding energies of alkali metal and ammonium cations to 2 and 3 wore measured by the picrate extraction technique, The highest K-a values were obtained for the complexes of 3 with K+ and Rb+. The conformational changes observed upon complexation were examined by NMR spectroscopy and X-ray analysis and are discussed in terms of pre organization, The formation of 1:1 complexes was only observed with the endo conformer.