tris(phenylethynyl)phosphine oxide | 31398-96-6

• 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: tris(phenylethynyl)phosphine oxide
• 英文别名: tri(phenylethynyl)phosphane oxide；Tris-(phenylacetylenyl)-phosphonsaeure；Tris-phenylaethinyl-phosphinoxid；Tris(phenylethynyl)phosphinoxid；tris-phenylethynyl-phosphane oxide；2-[Bis(2-phenylethynyl)phosphoryl]ethynylbenzene
• CAS: 31398-96-6
• 化学式: C₂₄H₁₅OP
• 分子量: 350.356
• InChiKey: ZNWZRZCSUFCGFD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  tris(phenylethynyl)phosphine oxide 在 ammonium acetate 作用下， 以 溶剂黄146 为溶剂， 生成 1,4-dihydro-2,6-diphenyl-4-(phenylethynyl)-1,4-azaphosphorine 4-oxide
  参考文献：
  名称：

  Organic Compounds of Phosphorus; XII¹. Ammonium Acetate/Acetic Acid, A Reagent for the Direct Heterocyclization of Bis- and Tris[1-alkynyl]-phosphine Oxides

  摘要：

  DOI：

  10.1055/s-1979-28575
• 作为产物：
  描述：

  tri(phenylethynyl)phosphine 在 双氧水 作用下， 以 二氯甲烷 为溶剂， 以90%的产率得到tris(phenylethynyl)phosphine oxide
  参考文献：
  名称：

  通过自加速 P-C 偶联反应制备超微孔有机磷聚合物：对交联环境和多孔结构的动力学影响

  摘要：

  多孔有机聚合物（POPs）在各种应用中引起了广泛关注。然而，影响持久性有机污染物非均相聚合和孔隙率的因素仍不清楚。在此，我们报告了一种构建具有高表面积（1283 m 2）的多孔有机磷聚合物（POPPs）的新策略。/g) 和超微孔结构 (0.67 nm)。该策略在三角锥体 P 中心利用有效的过渡金属催化的磷-碳 (P-C) 偶联反应，这与合成 POPs 中使用的典型碳-碳偶联反应不同。作为对 POPs 偶联反应的第一个动力学研究，我们发现了由碱和催化剂的选择控制的自加速反应特性。P-C偶联反应的自加速特性有利于POPPs的高表面积和均匀的超微孔率。P 中心的直接交联允许31 P 固态 (ss)NMR 实验明确揭示 POPP 的交联环境。利用动力学研究和31通过 P ssNMR 研究，我们能够揭示 P-C 偶联反应对 POPP 的交联环境和多孔结构的动力学影响。此外，我们的研究表明，POPPs

  DOI：

  10.1021/jacs.2c03759

文献信息

• Gold(I)‐Catalyzed Synthesis of Six‐Membered P,O‐Heterocycles <i>via</i> Hydration/Intramolecular Cyclization Cascade Reaction
  作者：Shan Zhang、Haiyang Cheng、Sheng Mo、Shiwei Yin、Zunting Zhang、Tao Wang

  DOI：10.1002/adsc.201900605

  日期：2019.9.17

  Herein, we report the synthesis of six‐membered P,O‐heterocycles from dialkynylphosphine oxides. By using gold(I) complexes, the chemoselectivity of the reaction was switched from literature‐reported double hydration to a hydration/intramolecular cyclization cascade. Control experiments indicated that the first alkyne hydration product is an intermediate of the reaction. In addition, a density functional

  本文中，我们报道了由二炔基膦氧化物合成六元P，O-杂环。通过使用金（I）配合物，反应的化学选择性从文献报道的双重水合转变为水合/分子内环化级联反应。对照实验表明，第一炔烃水合产物是反应的中间体。此外，密度泛函理论（DFT）计算允许合理化所观察到的化学选择性。
• Triaryl-Like MONO-, BIS-, and TRISKITPHOS Phosphines: Synthesis, Solution NMR Studies, and a Comparison in Gold-Catalyzed Carbon–Heteroatom Bond Forming 5-<i>exo</i>-dig and 6-<i>endo</i>-dig Cyclizations
  作者：Simon Doherty、Julian G. Knight、Daniel O. Perry、Nicholas A. B. Ward、Dror M. Bittner、William McFarlane、Corinne Wills、Michael R. Probert

  DOI：10.1021/acs.organomet.6b00146

  日期：2016.5.9

  A homologous series of triaryl-like KITPHOS-type monophosphines containing one, two, or three bulky 12-phenyl-9,10-dihydro-9,10-ethenoanthracene (KITPHOS) units have been developed, and the influence of increasing steric bulk on their efficacy as ligands in gold(I)-catalyzed carbon-heteroatom bond-forming cyclizations has been investigated. Detailed solution NMR studies on Ph-TRISKITPHOS, its oxide, and the corresponding gold(I) chloride adduct identified a conformational exchange process involving a concerted librational motion of the individual anthracene-derived organic substituents about their P-C bonds. The cessation of this motion at reduced temperatures lowers the molecular symmetry such that the two C6H4 rings in each of the KITPHOS units become inequivalent; a lower energy process involving restricted rotation of the biaryl-like phenyl ring has also been identified. Electrophilic gold(I) complexes of these triaryl-like KITPHOS monophosphines catalyze the 5-exo-dig cycloisomerization of propargyl amides to afford the corresponding methylene oxazolines, which were used in a subsequent tandem carbonyl-ene reaction to afford functionalized 2 -substituted oxazolines. A comparative survey revealed that catalyst efficiency for cycloisomerization decreases in the order MONOKITPHOS = BISKITPHOS > PPh3 > TRISKITPHOS. The optimum system also catalyzes the selective 6-endo-dig cyclization of 2-alkynylbenzyl alcohols, 2-alkynylbenzoic acid, and 2-phenylethynyl benzamides; gratifyingly, in several cases the yields obtained are markedly higher and/or reaction times significantly shorter than those previously reported for related gold catalysts. Moreover, these are the first examples of gold(I)-catalyzed 6-endo-dig cycloisomerizations involving 2-phenylethynyl benzamides and, reassuringly, the optimum gold(I)/MONOKITPHOS systems either rivaled or outperformed existing silver or palladium based catalysts. The steric parameters of this homologous series of phosphines have been quantified and compared with selected triarylphosphines using a combination of Solid -G calculations, to determine the percentage of the metal coordination sphere shielded by the phosphine (the G parameter), and Salerno molecular buried volume calculations (SambVca) to determine the percent buried volume (%V-bur); the corresponding Tolman cone angles have also been determined from correlations.
• Hydratation d'une serie d'oxydes de phosphines acetyleniques acces aux oxo-4, oxa-1, P5 phosphorinnes-4
  作者：Michel Simalty、Le Van Chau

  DOI：10.1016/s0040-4039(00)89434-4

  日期：1970.1
• SKOLIMOWSKI J.; SIMALTY M., SYNTHESIS, 1979, NO 2, 109-110
  作者：SKOLIMOWSKI J.、 SIMALTY M.

  DOI：——

  日期：——
• Organic Compounds of Phosphorus; XII¹. Ammonium Acetate/Acetic Acid, A Reagent for the Direct Heterocyclization of Bis- and Tris[1-alkynyl]-phosphine Oxides
  作者：Janusz Skolimowski、Michel Simalty

  DOI：10.1055/s-1979-28575

  日期：——