3,9-Dioxido-3,9-diphenyl-25,29,33,37-tetrakis(2-phenylethyl)-2,4,8,10,14,16,20,22-octaoxa-3,9-diphosphonianonacyclo[21.15.1.124,38.05,36.07,34.011,32.013,30.017,28.019,26]tetraconta-1(38),5,7(34),11(32),12,17(28),18,23(39),24(40),26,30,35-dodecaene | 1254578-52-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: 3,9-Dioxido-3,9-diphenyl-25,29,33,37-tetrakis(2-phenylethyl)-2,4,8,10,14,16,20,22-octaoxa-3,9-diphosphonianonacyclo[21.15.1.124,38.05,36.07,34.011,32.013,30.017,28.019,26]tetraconta-1(38),5,7(34),11(32),12,17(28),18,23(39),24(40),26,30,35-dodecaene
• 英文别名: 3,9-dioxido-3,9-diphenyl-25,29,33,37-tetrakis(2-phenylethyl)-2,4,8,10,14,16,20,22-octaoxa-3,9-diphosphonianonacyclo[21.15.1.124,38.05,36.07,34.011,32.013,30.017,28.019,26]tetraconta-1(38),5,7(34),11(32),12,17(28),18,23(39),24(40),26,30,35-dodecaene
• CAS: 1254578-52-3
• 化学式: C₇₄H₆₂O₁₀P₂
• 分子量: 1173.25
• InChiKey: UVQSYABFMSUYCB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  18.1
• 重原子数：
  86
• 可旋转键数：
  14
• 环数：
  15.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  120
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为产物：
  描述：

  氯碘甲烷 、 6,12-Dioxido-6,12-diphenyl-20,24,27,33-tetrakis(2-phenylethyl)-5,7,11,13-tetraoxa-6,12-diphosphoniaheptacyclo[15.9.7.128,32.04,25.08,23.010,21.014,19]tetratriaconta-1(26),2,4(25),8,10(21),14(19),15,17,22,28(34),29,31-dodecaene-2,16,29,31-tetrol 在 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 4.0h， 以65%的产率得到3,9-Dioxido-3,9-diphenyl-25,29,33,37-tetrakis(2-phenylethyl)-2,4,8,10,14,16,20,22-octaoxa-3,9-diphosphonianonacyclo[21.15.1.124,38.05,36.07,34.011,32.013,30.017,28.019,26]tetraconta-1(38),5,7(34),11(32),12,17(28),18,23(39),24(40),26,30,35-dodecaene
  参考文献：
  名称：

  Restricted Guest Tumbling in Phosphorylated Self-Assembled Capsules

  摘要：

  ABii diphosphonatocavitands self-assemble in chloroform solution to form dimeric molecular capsules. The molecular capsules can incarcerate an N-methylpyridinium or N-methylpicolinium guest. We have demonstrated that the supramolecular assembly acts as a molecular rotor as a result of the restricted motion of the guest inside the molecular cavity. In the solid state, X-ray diffraction analysis of the free host showed that two cavitands interact through strong hydrogen bonds to give the supramolecular self-assembled capsule. The solid-state structure of the N-methylpicolinium complex is comparable to that of the free host and indicates that the guest is not a prerequisite for the formation of the capsule. DOSY NMR studies provided a definitive argument for the formation of the free and complexed supramolecular capsule in CDCl3 solution. In solution, the tumbling of the N-methylpyridinium and N-methylpicolinium guests about the equatorial axes of the host can be frozen and differs by the respective energy barriers, with the larger picolinium substrate having a larger value (Delta G(double dagger) = 69.7 kJ mol(-1)) than the shorter pyridinium guest (Delta G(double dagger) = 44.8 kJ mol(-1)). This behavior corresponds to the restricted rotation of a rotator in a supramolecular rotor.

  DOI：

  10.1021/ja104388t

文献信息

• Restricted Guest Tumbling in Phosphorylated Self-Assembled Capsules
  作者：Steven Harthong、Béatrice Dubessy、Jérôme Vachon、Christophe Aronica、Jean-Christophe Mulatier、Jean-Pierre Dutasta

  DOI：10.1021/ja104388t

  日期：2010.11.10

  ABii diphosphonatocavitands self-assemble in chloroform solution to form dimeric molecular capsules. The molecular capsules can incarcerate an N-methylpyridinium or N-methylpicolinium guest. We have demonstrated that the supramolecular assembly acts as a molecular rotor as a result of the restricted motion of the guest inside the molecular cavity. In the solid state, X-ray diffraction analysis of the free host showed that two cavitands interact through strong hydrogen bonds to give the supramolecular self-assembled capsule. The solid-state structure of the N-methylpicolinium complex is comparable to that of the free host and indicates that the guest is not a prerequisite for the formation of the capsule. DOSY NMR studies provided a definitive argument for the formation of the free and complexed supramolecular capsule in CDCl3 solution. In solution, the tumbling of the N-methylpyridinium and N-methylpicolinium guests about the equatorial axes of the host can be frozen and differs by the respective energy barriers, with the larger picolinium substrate having a larger value (Delta G(double dagger) = 69.7 kJ mol(-1)) than the shorter pyridinium guest (Delta G(double dagger) = 44.8 kJ mol(-1)). This behavior corresponds to the restricted rotation of a rotator in a supramolecular rotor.