isopropyl(phenyl)phosphine oxide | 63762-20-9

• 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: isopropyl(phenyl)phosphine oxide
• 英文别名: phenyl isopropyl phosphine oxide；Propan-2-ylphosphonoylbenzene
• CAS: 63762-20-9
• 化学式: C₉H₁₃OP
• 分子量: 168.175
• InChiKey: QAVNOWGBUASIPS-UHFFFAOYSA-N

物化性质

• 沸点：
  251.0±23.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  isopropyl(phenyl)phosphine oxide 在 sodium 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 28.03h， 生成 1-hydroxymethyl(isopropyl)phenylphosphine-borane
  参考文献：
  名称：

  Reduction of Functionalized Tertiary Phosphine Oxides with BH₃

  摘要：

  A direct stereoselective conversion of tertiary hydroxyalkylphosphine oxides to the corresponding tertiary hydroxyalkylphosphineboranes involving facile reduction of the P=O bond by BH3 under mild conditions has been developed. The unprecedented facility of reduction of the strong P=O bond by BH3, a mild reducing agent, has been achieved through an intramolecular P=O center dot center dot center dot B complexation directed by proximal alpha- or beta-hydroxy groups present in the phosphine oxide structures. As established by two chemical correlations, the developed transformation of hydroxyalkylphosphine oxides into hydroxyalkylphosphine-boranes takes place with complete inversion of configuration at P.

  DOI：

  10.1021/jo502623g
• 作为产物：
  描述：

  苯基二氯化磷 在 air 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 4.58h， 生成 isopropyl(phenyl)phosphine oxide
  参考文献：
  名称：

  通过 Pd 催化的不对称烯丙基烷基化使次膦酸去对称化——快速获得对手性次膦酸盐

  摘要：

  P-手性化合物的合成是一项具有挑战性的任务，特别是因为制备此类分子的有用催化方法很少。在此，我们公开了一种去对称化，它在 Pd 催化的不对称烯丙基烷基化反应中使用次膦酸作为动态前手性亲核试剂，以高度对映选择性和非对映选择性方式提供次膦酸盐。这种新方法具有广泛的应用范围，适用于对映体富集的叔氧化膦的合成。

  DOI：

  10.1021/jacs.9b07340

文献信息

• A Superior Method for the Reduction of Secondary Phosphine Oxides
  作者：Carl A. Busacca、Jon C. Lorenz、Nelu Grinberg、Nizar Haddad、Matt Hrapchak、Bachir Latli、Heewon Lee、Paul Sabila、Anjan Saha、Max Sarvestani、Sherry Shen、Richard Varsolona、Xudong Wei、Chris H. Senanayake

  DOI：10.1021/ol0517832

  日期：2005.9.1

  to be outstanding reductants for secondary phosphine oxides (SPOs). All classes of SPOs can be readily reduced, including diaryl, arylalkyl, and dialkyl members. Many SPOs can now be reduced at cryogenic temperatures, and conditions for preservation of reducible functional groups have been found. Even the most electron-rich and sterically hindered phosphine oxides can be reduced in a few hours at 50-70

  [反应：见正文]已发现氢化二异丁基铝（DIBAL-H）和三异丁基铝是仲氧化膦（SPO）的杰出还原剂。所有类别的SPO都可以轻松还原，包括二芳基，芳基烷基和二烷基成员。现在可以在低温下还原许多SPO，并发现了保存可还原官能团的条件。即使是最富电子和位阻的膦氧化物，也可以在50-70摄氏度的温度下在几小时内还原。这种新的还原方法与现有技术相比具有明显的优势。
• [EN] A METHOD FOR GENERATING SECONDARY PHOSPHINES<br/>[FR] PROCEDE DE PRODUCTION DE PHOSPHINES SECONDAIRES
  申请人：BOEHRINGER INGELHEIM PHARMA

  公开号：WO2005068479A1

  公开（公告）日：2005-07-28

  This invention provides a method for generating secondary phosphines from secondary phosphine oxides in the presence of a reducing agent, such as diisobutylaluminum hydride (DIBAL-H), triisobutyldialuminoxane, triisobutylaluminum, tetraisobutyldialuminoxane, or another reducing agent comprising: (i) an R1R2AIH moiety, wherein R1 and R2 are each an alkyl species or oxygen, and wherein at least one of R1 or R2 comprises at least 2 carbon atoms, or (ii) an R1R2R3AI moiety, wherein R1, R2, and R3 are not hydrogen, and wherein at least one of R1, R2, and R3 is an alkyl species comprising a β-hydrogen, not including triethylaluminum. Preferred reducing agents for the present invention include: diisobutylaluminum hydride, triisobutyldialiuminoxane, triisobutylaluminum, tetraisobutyldialuminoxane, and combinations thereof.

  这项发明提供了一种从二次膦氧化物中在还原剂的存在下生成二次膦的方法，所述还原剂可以是二异丁基铝氢化物（DIBAL-H）、三异丁基二氧化铝烷、三异丁基铝、四异丁基二氧化铝烷或另一种还原剂，所述还原剂包括：（i）一个R1R2AIH基团，其中R1和R2分别是烷基物种或氧，并且R1或R2中至少有一个包含至少2个碳原子，或（ii）一个R1R2R3AI基团，其中R1、R2和R3均不是氢，且R1、R2和R3中至少有一个是包含β-氢的烷基物种，不包括三乙基铝。本发明的优选还原剂包括：二异丁基铝氢化物、三异丁基二氧化铝烷、三异丁基铝、四异丁基二氧化铝烷以及它们的组合。
• Phosphinyl Guanidine Compounds, Metal Salt Complexes, Catalyst Systems, and Their Use to Oligomerize or Polymerize Olefins
  申请人：SYDORA Orson J.

  公开号：US20130331629A1

  公开（公告）日：2013-12-12

  The present application relates to N 2 -phosphinyl guanidine metal salt complexes. The present application also relates to catalyst systems comprising N 2 -phosphinyl guanidine metal salt complexes and processes for making catalyst systems comprising N 2 -phosphinyl guanidine metal salt complexes. The present application also relates to utilizing N 2 -phosphinyl guanidine metal salt complexes in processes of oligomerizing or polymerizing olefins.

  本申请涉及N2-磷酰亚胺基胍金属盐配合物。本申请还涉及包含N2-磷酰亚胺基胍金属盐配合物的催化剂体系以及制备包含N2-磷酰亚胺基胍金属盐配合物的催化剂体系的方法。本申请还涉及在烯烃的齐聚或聚合过程中利用N2-磷酰亚胺基胍金属盐配合物。
• PROCESS FOR PRODUCTION OF OPTICALLY ACTIVE PHOSPHOROUS COMPOUND
  申请人：Han Li-Biao

  公开号：US20100174079A1

  公开（公告）日：2010-07-08

  Disclosed is a process for producing an optically active phosphorus compound having an R- or S-type absolute configuration on phosphorus in a simple manner and at high efficiency, while avoiding racemization. An optically active phosphorus compound having an R- or S-type absolute configuration on phosphorus represented by the general formula (III) can be produced by reacting an optically active phosphorus compound having an R- or S-type absolute configuration on phosphorus represented by the general formula (I) with a metal compound represented by the general formula (II) and water. (I) wherein R 1 represents a hydrogen atom, analkyl group, a cycloalkyl group, an aralkyl group or an aryl group; and R 2 represents a hydrogen, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, alkenyl group, an alkoxy group, an aryloxy group, a heterocyclic ring residue or a silyl-containing group. R 3 M (II) wherein R 3 is the same as R 2 ; and M represents a lithium or magnesium halide MgX (X═Cl, Br or I). (III) wherein R 2 and R 3 are as defined above.

  揭示了一种在简单且高效的情况下产生具有磷上的R型或S型绝对构型的光学活性磷化合物的方法，同时避免了消旋化。通过将具有磷上的R型或S型绝对构型的光学活性磷化合物（由通式（I）表示）与由通式（II）表示的金属化合物和水反应，可以生产具有磷上的R型或S型绝对构型的光学活性磷化合物（由通式（III）表示）。其中，通式（I）中R1代表氢原子、烷基、环烷基、芳基或芳基；R2代表氢、烷基、环烷基、芳基、芳基、烯基、烷氧基、芳氧基、杂环残基或含硅基团。通式（II）中R3与R2相同；M代表锂或镁卤化物MgX（X=Cl、Br或I）。通式（III）中R2和R3如上定义。
• Stereospecific Nucleophilic Substitution of Optically Pure <i>H</i>-Phosphinates: A General Way for the Preparation of Chiral P-Stereogenic Phosphine Oxides
  作者：Qing Xu、Chang-Qiu Zhao、Li-Biao Han

  DOI：10.1021/ja804412k

  日期：2008.9.24

  configurations at phosphorus to give a wide range of P-stereogenic secondary phosphine oxides and tertiary phosphine oxides, by quenching the reaction mixture with water and alkyl halides, respectively. This finding establishes a general protocol for the preparation of optically active secondary phosphine oxides and tertiary phosphine oxides from the easily accessible optically pure H-phosphinates. Mechanistic

  与普遍持有的观点相反，发现 (-)-薄荷基 (RP)-苯基次膦酸酯在碱性条件下的快速差向异构化不是由于迄今为止认为其相应阴离子的固有立体稳定性，而是由于氢的反应次膦酸酯与金属醇盐。这一发现成功地导致发现，通过在低温下将 H-次膦酸盐添加到有机锂或格氏试剂中，H-次膦酸盐的烷氧基与有机锂或格氏试剂的亲核取代立体特异性地进行，并在磷处发生构型反转通过分别用水和烷基卤化物淬灭反应混合物，得到范围广泛的 P-立体二氧化膦和叔氧化膦。这一发现建立了从容易获得的光学纯 H-次膦酸盐制备光学活性仲膦氧化物和叔膦氧化物的通用方案。机理研究表明，H-次膦酸盐与有机锂和格氏试剂的取代反应通过两条竞争反应路径进行，即两步反应路径，首先H-次膦酸盐去质子化，然后用反转取代相应的阴离子磷的构型和用 H-次膦酸盐直接取代 RM 直接产生 SPO。