2,3,7,8-Tetramethyl-5,10-diphenylphosphanthrene | 1309381-72-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,3,7,8-Tetramethyl-5,10-diphenylphosphanthrene
• 英文别名: 2,3,7,8-tetramethyl-5,10-diphenylphosphanthrene
• CAS: 1309381-72-3；1309381-76-7
• 化学式: C₂₈H₂₆P₂
• 分子量: 424.462
• InChiKey: PAVLRAWMGKJLTE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  30
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2,3,7,8-Tetramethyl-5,10-diphenylphosphanthrene 在 air 作用下， 生成 2,3,7,8-tetramethyl-5,10-diphenyl-5,10-dihydrophosphanthrene dioxide 、 2,3,7,8-tetramethyl-5,10-diphenyl-5,10-dihydrophosphanthrene dioxide
  参考文献：
  名称：

  Synthesis, Isolation, and Skeletal Inversion of 5,10-Dihydrophosphanthrenes

  摘要：

  Two stereoisomers, the trans form 1a and the cis form 1b, of 2,3,7,8-tetramethyl-5,10-diphenyl-5,10-dihydrophosphanthrene dioxide (1) were formed by spontaneous oxidation in air of the corresponding 5,10-dihydrophosphanthrenes 2 and were separated by recrystallization. Both 1a and 1b were characterized by X-ray crystallographic analysis, which revealed configurations at the phosphorus and conformations of the central tricyclic system. The P-31 NMR of the reaction mixture showed at first two signals at - 15.3 and - 15.1 ppm, which shifted to 9.11 and 10.3 ppm after purification of the reaction mixture under aerobic conditions by oxidation of phosphorus atoms. The reaction of 1b with HSiCl3 in toluene-d(8) at 100 degrees C gave no change, whereas 1a reacted with HSiCl3 to give reduced compounds 2a and 2b under the same conditions. The trans-cis isomerization of 2 occurred via vertex inversion at phosphorus atom. VT-NMR, X-ray analysis, and density functional theory (DFT) calculation showed that the conformational exchange of the cis form 1b proceeded via skeletal inversion of the tricyclic ring.

  DOI：

  10.1080/10426507.2010.515957
• 作为产物：
  描述：

  1,2-二溴-4,5-二甲苯 、 苯基二氯化磷 在 叔丁基锂 作用下， 以 四氢呋喃 为溶剂， 生成 2,3,7,8-Tetramethyl-5,10-diphenylphosphanthrene
  参考文献：
  名称：

  Synthesis, Isolation, and Skeletal Inversion of 5,10-Dihydrophosphanthrenes

  摘要：

  Two stereoisomers, the trans form 1a and the cis form 1b, of 2,3,7,8-tetramethyl-5,10-diphenyl-5,10-dihydrophosphanthrene dioxide (1) were formed by spontaneous oxidation in air of the corresponding 5,10-dihydrophosphanthrenes 2 and were separated by recrystallization. Both 1a and 1b were characterized by X-ray crystallographic analysis, which revealed configurations at the phosphorus and conformations of the central tricyclic system. The P-31 NMR of the reaction mixture showed at first two signals at - 15.3 and - 15.1 ppm, which shifted to 9.11 and 10.3 ppm after purification of the reaction mixture under aerobic conditions by oxidation of phosphorus atoms. The reaction of 1b with HSiCl3 in toluene-d(8) at 100 degrees C gave no change, whereas 1a reacted with HSiCl3 to give reduced compounds 2a and 2b under the same conditions. The trans-cis isomerization of 2 occurred via vertex inversion at phosphorus atom. VT-NMR, X-ray analysis, and density functional theory (DFT) calculation showed that the conformational exchange of the cis form 1b proceeded via skeletal inversion of the tricyclic ring.

  DOI：

  10.1080/10426507.2010.515957

文献信息

• Synthesis, Isolation, and Skeletal Inversion of 5,10-Dihydrophosphanthrenes
  作者：Yosuke Uchiyama、Yasuhiro Mazaki

  DOI：10.1080/10426507.2010.515957

  日期：2011.3.31

  Two stereoisomers, the trans form 1a and the cis form 1b, of 2,3,7,8-tetramethyl-5,10-diphenyl-5,10-dihydrophosphanthrene dioxide (1) were formed by spontaneous oxidation in air of the corresponding 5,10-dihydrophosphanthrenes 2 and were separated by recrystallization. Both 1a and 1b were characterized by X-ray crystallographic analysis, which revealed configurations at the phosphorus and conformations of the central tricyclic system. The P-31 NMR of the reaction mixture showed at first two signals at - 15.3 and - 15.1 ppm, which shifted to 9.11 and 10.3 ppm after purification of the reaction mixture under aerobic conditions by oxidation of phosphorus atoms. The reaction of 1b with HSiCl3 in toluene-d(8) at 100 degrees C gave no change, whereas 1a reacted with HSiCl3 to give reduced compounds 2a and 2b under the same conditions. The trans-cis isomerization of 2 occurred via vertex inversion at phosphorus atom. VT-NMR, X-ray analysis, and density functional theory (DFT) calculation showed that the conformational exchange of the cis form 1b proceeded via skeletal inversion of the tricyclic ring.