Biphenylyl-2-dimethyl-phosphinoxid | 16546-80-8

• 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: Biphenylyl-2-dimethyl-phosphinoxid
• CAS: 16546-80-8
• 化学式: C₁₄H₁₅OP
• 分子量: 230.246
• InChiKey: TXQQVCSYAOAVIV-UHFFFAOYSA-N

物化性质

• 沸点：
  429.5±28.0 °C(Predicted)
• 密度：
  1.10±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  16.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  Biphenylyl-2-dimethyl-phosphinoxid 在 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 反应 12.0h， 以84%的产率得到[1,1′-biphenyl]-2-yldimethylphosphine
  参考文献：
  名称：

  将膦酸酯直接转化为膦氧化物：包括第一个甲基JohnPhos合成的改进的合成膦路线

  摘要：

  使用化学计量的烷基或芳基格氏试剂和三氟甲烷磺酸钠（NaOTf），可以可靠地实现由膦酸酯合成叔膦氧化物，并以优异的收率获得良好的收率。在没有NaOTf添加剂的情况下，镁和磷物种的共价配位低聚物占主导地位，产生了非常低的氧化膦收率，但是膦酸酯原料的转化率很高。机理研究表明，五配位的磷物质（不是次膦酸盐）是反应的中间体。使用多种用于直接碳-磷官能化的格氏试剂，将各种各样的膦酸酯转化为氧化膦。这种新方法特别简化了二甲基膦基（RPMe 2）型膦通过使用对空气，水和二氧化硅稳定的中间体。为了突出该反应，以优异的产率合成了新的布赫瓦尔德型配体（[1,1'-联苯] -2-基二甲基膦或甲基JohnPhos）和经典的双齿膦双（二苯基膦基）丙烷（dppp）。

  DOI：

  10.1021/om500854u
• 作为产物：
  描述：

  [1,1′-biphenyl]-2-yldimethylphosphine 在 氧气 作用下， 以 氘代苯 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 85.0h， 生成 Biphenylyl-2-dimethyl-phosphinoxid
  参考文献：
  名称：

  Steric and Electronic Influences of Buchwald-Type Alkyl-JohnPhos Ligands

  摘要：

  The electron-donating and steric properties of Buchwald-type ligands ([1,1'-biphenyl-2-yl]dialkylphosphine; R-JohnPhos, where R = Me, Et, Pr-i, Cy, Bu-t) were determined. The pi-acidity and sigma-donating properties of the R-JohnPhos ligands were quantified using a Cotton-Kraihanzel analysis of the Cr-0(CO)(5)(R-JohnPhos) complexes. Somewhat surprisingly, the sigma-donating abilities of the R-JohnPhos ligands follow the trend Bu-t-JohnPhos < Et-JohnPhos < Pr-i-JohnPhos < Cy-JohnPhos << Me-JohnPhos. This ordering is proposed to arise from competition between the intrinsic electron-donating ability of the R groups (Me < Et < Pr-i approximate to Cy < Bu-t) and steric interactions (front and back strain) that decrease the electron-donating ability of the phosphine. X-ray crystallographic data of 22 metal complexes (general forms: trans-Cr-0(CO)(4)(PR3)(2), Pd-0(PR3)(2)(eta(2)-dba), and trans-Pd-II(Cl)(2)(PR3)(2)) were also analyzed to help explain the electronic trends measured for the R-JohnPhos ligands. The R-JohnPhos ligands are exceptionally sensitive to back strain in comparison to typical phosphines, and the strong sigma-donating ability of the Methyl-JohnPhos ligand is attributed to its ability to avoid both front strain and back strain. Consequently, the -PMe2 moiety allows for very short phosphorus-metal bond distances. Because of the sterically dominating o-biphenyl and close phosphorus-metal bond distances, MeJPhos maintains a large overall steric profile that is actually larger than that of CyJPhos as measured by percent buried volume (%V-bur). Overall, the -PMe2 moiety is a powerful way to incorporate strong sigma-donation into designer phosphines while retaining other advantageous structural and reactivity properties.

  DOI：

  10.1021/acs.inorgchem.5b02996

文献信息

• Synthesis and reactions of 2,2′-biphenylylenebisdiethylphosphine. Formation of cyclic diquaternary dibromides with alkylene dibromides, and the nature and probable mechanism of their thermal decomposition
  作者：David W. Allen、Ian T. Millar、F. G. Mann

  DOI：10.1039/j39670001869

  日期：——

  9-alkyl-9-arsafluorenes, but the other members lose alkyl bromide with retention of the heterocyclic ring as a ditertiary arsine. The strictly analogous tetraethyl diarsonium dibromides undergo thermal decomposition with degradation of the heterocyclic ring. It is suggested that the ring contraction reactions shown by all these series of salts when heated are examples of a general internal nucleophilic displacement

  描述了上述二膦的合成。它通过与亚烷基二溴化物Br·[CH 2 ] n ·Br（其中n = 1-4）和与邻二甲苯基二溴化物的类似盐结合形成环状二季二溴化物。这些盐和二膦的二甲基碘化物在加热时会发生新的降解，从而生成9-烷基-9-磷芴。将这些反应与类似的环状四甲基二亚砷酸二溴化物显示的反应进行了比较，其中二溴化物由Br·[CH 2 ] n ·Br形成，其中n= 2–4经历类似的降解，得到9-烷基-9-ar杂芴，但其他成员失去烷基溴化物并保留杂环作为二叔a。严格相似的四乙基二砷二溴化物经历热分解，杂环降解。建议所有这些系列的盐在加热时显示的环收缩反应是一般内部亲核取代机理的一个例子。讨论了其他示例。
• Radical Arylation of Triphenyl Phosphite Catalyzed by Salicylic Acid: Mechanistic Investigations and Synthetic Applications
  作者：Manel Estruch-Blasco、Diego Felipe-Blanco、Irene Bosque、Jose C. Gonzalez-Gomez

  DOI：10.1021/acs.joc.0c00795

  日期：2020.11.20

  arylphosphonates at 20 °C within 1–2 h is reported using inexpensive SA as the catalytic promoter of the reaction. Mechanistic investigations suggest that the reaction proceeds via radical–radical coupling, consistent with the so-called persistent radical effect. The reaction tolerated a wide range of functional groups and heteroaromatic moieties. The synthetic usefulness and the unique reactivity of the

  据报道，使用廉价的SA作为反应的催化促进剂，可在20°C下1-2小时内合成一种简单且可扩展的方法，以合成二苯基芳基膦酸酯。机理研究表明，该反应通过自由基与自由基的耦合进行，这与所谓的持久自由基效应相一致。该反应耐受各种官能团和杂芳族部分。在不同的一步转化中证明了所得膦酸酯的合成有用性和独特的反应性。