1,8-diphenylphosphinotriptycene | 354152-92-4

• 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-diphenylphosphinotriptycene
• 英文别名: 1,8-bis(diisopropylphosphino)triptycene；1,8-(bis-diphenylphosphino)triptycene；(13-Diphenylphosphanyl-3-pentacyclo[6.6.6.02,7.09,14.015,20]icosa-2(7),3,5,9(14),10,12,15,17,19-nonaenyl)-diphenylphosphane
• CAS: 354152-92-4
• 化学式: C₄₄H₃₂P₂
• 分子量: 622.686
• InChiKey: APMSPWALESAGFL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.2
• 重原子数：
  46
• 可旋转键数：
  6
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.05
• 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-diphenylphosphinotriptycene 、 dichloro( 1,5-cyclooctadiene)platinum(ll) 以 not given 为溶剂， 生成
  参考文献：
  名称：

  Highly Selective Hydrocyanation of Butadiene toward 3-Pentenenitrile

  摘要：

  A triptycene-based diphosphine ligand was synthesized in good yield following a new route. The corresponding Pt(II)- and Ni(0)complexes were characterized. In butadiene hydrocyanation the tript-PPh2Ni(cod) catalyst leads to exceptionally high selectivities for the linear product 3-pentenenitrile, combining high activity for both hydrocyanation and isomerization. This one-step procedure could be the key toward process intensification.

  DOI：

  10.1021/ja074922e
• 作为产物：
  描述：

  2,10-Dichlorotriptycen 、 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80%的产率得到1,8-diphenylphosphinotriptycene
  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
• 作为试剂：
  描述：

  2-甲基-3-丁烯腈 在 1,8-diphenylphosphinotriptycene 、 bis(1,5-cyclooctadiene)nickel (0) 作用下， 以 1,4-二氧六环 为溶剂， 反应 4.0h， 生成 3-戊烯腈
  参考文献：
  名称：

  Nickel-catalyzed isomerization of 2-methyl-3-butenenitrile to 3-pentenenitrile: A kinetic study using in situ FTIR-ATR spectroscopy

  摘要：

  The isomerization of 2-methyl-3-butenenitrile (2M3BN) to 3-pentenenitrile (3PN) was followed using operando FTIR spectroscopy. The spectra were analyzed comprehensively to obtain kinetic profiles from the different band dynamics. Several spectral regions were transformed to their second derivative in order to improve the peak resolution. The dynamics in the spectra were calculated and normalized to the end conversion towards 3PN determined by GC. Similar kinetic profiles were obtained from the dynamics of different bands. Furthermore, calculations on the DFT level were performed for 2M3BN and trans- and cis-3PN in order to help identifying the corresponding bands in the spectra of the reaction mixture. An average conversion profile was calculated from different bands of the substrate and the product, applying a "quasi-multivariate analysis'' technique to correlate different band dynamics. This approach was validated using advanced chemometrics. These profiles obtained by IR spectroscopic analysis for the formation of 3PN and the consumption of 2M3BN showed a zero order kinetic. (C) 2009 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.cattod.2009.08.017

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。
• Conformational Flexibility of Dibenzobarrelene-Based PC(sp³)P Pincer Iridium Hydride Complexes: The Role of Hemilabile Functional Groups and External Coordinating Solvents
  作者：Gleb A. Silantyev、Oleg A. Filippov、Sanaa Musa、Dmitri Gelman、Natalia V. Belkova、Klaus Weisz、Lina M. Epstein、Elena S. Shubina

  DOI：10.1021/om500308g

  日期：2014.11.10

  Bifunctional dibenzobarrelene-based PC(sp3)P pincer iridium complex 1 is known as an efficient catalyst in acceptorless dehydrogenation of alcohols and hydrogenation/hydroformylation of alkenes. In order to shed light on the mechanism of the hydrogen formation/activation, we performed variable-temperature IR and NMR (1H, 31P) analysis of intra- and intermolecular interactions involving a hydride ligand

  双官能的基于二苯并barrelene的PC（sp 3）P夹钳铱配合物1是已知的醇类无受体脱氢和烯烃加氢/加氢甲酰化的有效催化剂。为了在所述氢气生成/激活的机制阐明，我们进行了变温IR和NMR（1 H，31 P）分子内和分子间相互作用的分析涉及氢化物配位体和在羟甲基配合1及其类似物。将在不同介质（二氯甲烷，甲苯，DMSO和混合溶剂）中的光谱测量结果与量子化学计算（DFT / M06和B3PW91）进行了比较。所获得的数据暗示了基于二苯并barrelene的支架的灵活性，这对于常规的夹钳配体而言是空前的。CH 2 OH取代的配合物1及其COOEt类似物3均偏爱PCP配体的面部构型，其P–Ir–P角约为ca。100°。这种几何形状通过与悬挂官能团的Ir··O相互作用而稳定，并且由于H和Cl配体的相互排列而不同。配合物显示出两个最稳定的表面活性剂之间的动态平衡-异构体，可以在配位添加剂（CH 3 CN，DMSO或CO，但不包括Et