1,8-bis(diphenylphosphino)-9,10-ethano-9,10-dihydroanthracene | 832673-32-2

• 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(diphenylphosphino)-9,10-ethano-9,10-dihydroanthracene
• 英文别名: Rucaphos；1,8-Bis(diphenylphosphino)-9,10-dihydro-9,10-ethanoanthracene；(13-diphenylphosphanyl-3-tetracyclo[6.6.2.02,7.09,14]hexadeca-2(7),3,5,9(14),10,12-hexaenyl)-diphenylphosphane
• CAS: 832673-32-2
• 化学式: C₄₀H₃₂P₂
• 分子量: 574.642
• InChiKey: OGPMTQBIWRYJNE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.7
• 重原子数：
  42
• 可旋转键数：
  6
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.1
• 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：

  1,8-bis(diphenylphosphino)-9,10-ethano-9,10-dihydroanthracene 以 四氢呋喃 为溶剂， 生成 (1,8-bis(diphenylphosphino)-9,10-ethano-9,10-dihydroanthracene)Ni(η3-methallyl)BF4
  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-9,10-ethano-9,10-dihydroanthracene 、 二苯基氯化膦 在 sodium 、 lithium 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 以69%的产率得到1,8-bis(diphenylphosphino)-9,10-ethano-9,10-dihydroanthracene
  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

文献信息

• Method for the production of 1,7-octadiene and use thereof
  申请人：Bohm Volker

  公开号：US20070083066A1

  公开（公告）日：2007-04-12

  The invention relates to a method for the production of 1,7 octadiene by reacting metathesis of cyclohexene with ethylene. The invention also relates to the production of 1,10-decandiol by hydroformulating 1,7 octadiene produced according to said method. The invention further relates to a method for the production of muscone or olefinically unsaturated analogs thereof using 1,10 decandiol which is obtainable in said manner.

  该发明涉及一种通过环己烯与乙烯进行交换反应生产1,7-辛二烯的方法。该发明还涉及通过对按照该方法生产的1,7-辛二烯进行氢甲酰化制备1,10-癸二醇的方法。该发明还涉及一种利用以该方式获得的1,10-癸二醇生产麝香酮或其烯烃不饱和类似物的方法。
• Phospor, arsenic and antimony compounds based upon diaryl-anellated diaryl-anellated bicyclo'2.2.n! parent substances and catalysts containing same
  申请人：——

  公开号：US20030055253A1

  公开（公告）日：2003-03-20

  Novel compounds of phosphorus, of arsenic and of antimony can be used as ligands to form complexes of metals of transition group VIII which can be used in catalysts for hydroformylation, hydrocyanation, carbonylation, hydrogenations, oligomerization and polymerization of olefins and for metathesis.

  磷、砷和锑的新化合物可以用作配体，形成过渡金属VIII族金属的配合物，可以用于羰基化、氢化、寡聚和聚合烯烃以及交换反应的催化剂中。
• VERBINDUNGEN DES PHOSPHORS, ARSENS UND DES ANTIMONS BASIEREND AUF DIARYLANELLIERTEN BICYCLO[2.2.N]-GRUNDKÖRPERN UND DIESE ENTHALTENDE KATALYSATOREN
  申请人：BASF AKTIENGESELLSCHAFT

  公开号：EP1257361B1

  公开（公告）日：2003-11-26
• US6977312B2
  申请人：——

  公开号：US6977312B2

  公开（公告）日：2005-12-20
• Highly Efficient Nickel-Catalyzed 2-Methyl-3-butenenitrile Isomerization: Applications and Mechanistic Studies Employing the TTP Ligand Family
  作者：Michael E. Tauchert、Daniel C. M. Warth、Sebastian M. Braun、Irene Gruber、Alexandra Ziesak、Frank Rominger、Peter Hofmann

  DOI：10.1021/om200164f

  日期：2011.5.23

  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.