1,8-bis[di(4-methylphenyl)phosphino]-10-n-octyltriptycene | 1296194-86-9

• 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: 1,8-bis[di(4-methylphenyl)phosphino]-10-n-octyltriptycene
• 英文别名: [13-Bis(4-methylphenyl)phosphanyl-8-octyl-3-pentacyclo[6.6.6.02,7.09,14.015,20]icosa-2(7),3,5,9(14),10,12,15,17,19-nonaenyl]-bis(4-methylphenyl)phosphane；[13-bis(4-methylphenyl)phosphanyl-8-octyl-3-pentacyclo[6.6.6.02,7.09,14.015,20]icosa-2(7),3,5,9(14),10,12,15,17,19-nonaenyl]-bis(4-methylphenyl)phosphane
• CAS: 1296194-86-9
• 化学式: C₅₆H₅₆P₂
• 分子量: 791.008
• InChiKey: PJBINWNPWBPYEM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16
• 重原子数：
  58
• 可旋转键数：
  13
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  bis(1,5-cyclooctadiene)nickel (0) 、 1,8-bis[di(4-methylphenyl)phosphino]-10-n-octyltriptycene 以 氘代苯 为溶剂， 生成 (1,8-bis[di(4-methylphenyl)phosphino]-10-n-octyltriptycene)Ni(η2-1,5-cyclooctadiene)
  参考文献：
  名称：

  Highly Efficient Nickel-Catalyzed 2-Methyl-3-butenenitrile Isomerization: Applications and Mechanistic Studies Employing the TTP Ligand Family

  摘要：

  A series of sterically and electronically fine-tuned, chelating diphosphine ligands were synthesized. The ligands are analogues of Triptyphos (TTP, 1), all based upon a variably 9,10-two-carbon-bridged 9,10-dihydroanthracene scaffold. These new TTP-type ligands were employed in the Ni(0)-catalyzed isomerization of 2-methyl-3-butenenitrile (2M3BN), one of the key steps of industrial adiponitrile production by the DuPont process. The reaction showed a surprising preference for ligands bearing electron-donating substituents, such as methoxy or methyl groups, in the phenyl para position of the Ni-ligating PPh2 units. Octyltriptyphos (3) afforded the highest 2M3BN-isomerization turnover rate yet reported. A series of deuterium-labeling experiments was performed to investigate the possibility of an isomerization mechanism consisting of a cascade of de- and rehydrocyanation steps, which could be excluded. Using the ethano-bridged ligand 4, complex 16a (4-kappa P:kappa P')Ni(eta(3)-C4H7)CN (supposedly an intermediate of the 2M3BN-isomerization reaction) was isolated, and its solid-state structure was determined by X-ray diffraction analysis. The complete catalytic cycle of 2M3BN isomerization with ligand 4, as suggested by the available experimental evidence, was modeled using DFT methods.

  DOI：

  10.1021/om200164f
• 作为产物：
  描述：

  1,8-dichloro-10-n-octyltriptycene 、 P,P-双(4-甲基苯基)-氯化膦 氯二对甲苯基膦 在 sodium 、 lithium 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 以22%的产率得到1,8-bis[di(4-methylphenyl)phosphino]-10-n-octyltriptycene
  参考文献：
  名称：

  Highly Efficient Nickel-Catalyzed 2-Methyl-3-butenenitrile Isomerization: Applications and Mechanistic Studies Employing the TTP Ligand Family

  摘要：

  A series of sterically and electronically fine-tuned, chelating diphosphine ligands were synthesized. The ligands are analogues of Triptyphos (TTP, 1), all based upon a variably 9,10-two-carbon-bridged 9,10-dihydroanthracene scaffold. These new TTP-type ligands were employed in the Ni(0)-catalyzed isomerization of 2-methyl-3-butenenitrile (2M3BN), one of the key steps of industrial adiponitrile production by the DuPont process. The reaction showed a surprising preference for ligands bearing electron-donating substituents, such as methoxy or methyl groups, in the phenyl para position of the Ni-ligating PPh2 units. Octyltriptyphos (3) afforded the highest 2M3BN-isomerization turnover rate yet reported. A series of deuterium-labeling experiments was performed to investigate the possibility of an isomerization mechanism consisting of a cascade of de- and rehydrocyanation steps, which could be excluded. Using the ethano-bridged ligand 4, complex 16a (4-kappa P:kappa P')Ni(eta(3)-C4H7)CN (supposedly an intermediate of the 2M3BN-isomerization reaction) was isolated, and its solid-state structure was determined by X-ray diffraction analysis. The complete catalytic cycle of 2M3BN isomerization with ligand 4, as suggested by the available experimental evidence, was modeled using DFT methods.

  DOI：

  10.1021/om200164f