diphenyl((trimethylsilyl)methyl)phosphine oxide | 4920-02-9

• 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: diphenyl((trimethylsilyl)methyl)phosphine oxide
• 英文别名: (trimethylsilylmethyl)diphenylphosphine oxide；diphenyltrimethylsilylmethylphosphane oxide；Trimethylsilylmethyl-diphenylphosphinoxyd；Diphenylphosphorylmethyl(trimethyl)silane
• CAS: 4920-02-9
• 化学式: C₁₆H₂₁OPSi
• 分子量: 288.401
• InChiKey: QRVSSWJGUPIKRB-UHFFFAOYSA-N

物化性质

• 熔点：
  107.5-108.5 °C
• 沸点：
  357.4±25.0 °C(Predicted)
• 密度：
  1.03±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.88
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  diphenyl((trimethylsilyl)methyl)phosphine oxide 在 正丁基锂 、 2,2,6,6-tetramethylpiperidinyl-lithium 作用下， 以 四氢呋喃 为溶剂， 反应 48.5h， 生成 (E)-2-diphenylphosphoryl-1-phenylhept-2-ene-1,7-diol
  参考文献：
  名称：

  Tandem Peterson-Michael Reaction Using a-Silylalkylphosphine Chalcogenides and Horner-Emmons Reaction of in situ Generated a-Carbanions of Its Products

  摘要：

  Title tandem reaction was achieved by using alpha-(trimethylsilyl)alkylphosphine chalcogenides and the lithio derivative of 2-hydroxytetrahydropyran. The Horner-Emmons reaction of the tandem products was accomplished to give the corresponding 2-(beta-styryl)tetrahydropyran derivatives by in situ generation and trapping of alpha-lithio derivatives, followed by Warren's method of olefination.

  DOI：

  10.3987/com-96-s49
• 作为产物：
  描述：

  二苯基乙氧基膦 、 氯甲基三甲基硅烷 生成 diphenyl((trimethylsilyl)methyl)phosphine oxide
  参考文献：
  名称：

  Synthesis of compounds containing phosphorus and silicon

  摘要：

  DOI：

  10.1007/bf00845591

文献信息

• Synthesis of Phosphane Oxides and Phosphonates by Cerium-Mediated Addition of Organolithium Compounds to Chloro-Phosphorus Compounds
  作者：Renato Dalpozzo、Antonio De Nino、Daniela Miele、Antonio Tagarelli、Giuseppe Bartoli

  DOI：10.1002/(sici)1099-0690(199909)1999:9<2299::aid-ejoc2299>3.0.co;2-y

  日期：1999.9

  phosphinoyl chloride 1a or chlorophosphates 1b leads to the synthesis of phosphane oxides 3aa–ag and phosphonates 3bb, be in good to high yield. The reaction can be extended to cerium enolates 4 (of ketones) and 6 (of nitriles) except when a benzyl group bound to the carbonyl moiety should be metallated. The latter reaction is the first reported synthesis of β-oxophosphane oxides by a simple reaction between

  将有机铈试剂 2a-g 添加到膦酰氯 1a 或氯磷酸盐 1b 中，合成了氧化膦 3aa-ag 和膦酸酯 3bb，收率良好。该反应可以扩展到铈烯醇化物 4（酮）和 6（腈），除非与羰基部分结合的苄基应该被金属化。后一个反应是首次报道通过烯醇化物和磷（V）卤化物之间的简单反应合成 β-氧代磷烷氧化物。
• Aryl group – a leaving group in arylphosphine oxides
  作者：Marek Stankevič、Jolanta Pisklak、Katarzyna Włodarczyk

  DOI：10.1016/j.tet.2015.12.043

  日期：2016.2

  The treatment of triphenylphosphine oxide with organometallic reagents leads to the substitution of up to three phenyl substituents with the incoming carbon nucleophile. The replacement of the phenyl/aryl group in tertiary diarylalkylphosphine oxides or even aryldialkylphosphine oxides was also observed. Naphthyl-substituted phosphine oxides undergo Michael-type addition at the naphthyl group when

  用有机金属试剂处理三苯基氧化膦会导致最多三个苯基取代基被传入的碳亲核试剂取代。还观察到叔二芳基烷基膦氧化物或什至芳基二烷基膦氧化物中苯基/芳基的取代。当用有机锂试剂处理时，萘基取代的氧化膦在萘基上经历迈克尔型加成。
• The reactions of tris(trimethylsilyl)methyl-lithium with some carbon electrophiles
  作者：Ian Fleming、Christopher D. Floyd

  DOI：10.1039/p19810000969

  日期：——

  non-enolisable aldehydes, ketones, and acid chlorides, and with some epoxides, with the formation of carbon–carbon bonds. This method of preparing functionalized silanes is limited by the readiness with which (1) abstracts a proton, if one is available, rather than attacks at carbon. In the reaction with epoxides, the product alkoxide can transfer a silyl group from carbon to oxygen, and in one case the

  三（三甲基甲硅烷基）甲基锂（1）与不可烯化的醛，酮，酰氯和某些环氧化物发生反应，形成碳-碳键。这种制备官能化硅烷的方法受到准备工作的限制，准备工作是：（1）提取质子（如果有的话）而不是提取碳。在与环氧化物的反应中，产物醇盐可以将甲硅烷基基团从碳转移至氧，并且在一种情况下，如此形成的中间体反应生成环丙烷（32），其为彼得森反应的同系物。当所得的碳负离子通过苯硫基和二苯基膦酰基等基团稳定时，在其他系统中会发生甲硅烷基的1，4-转移。
• The Lithiation Reactivity and Selectivity of Differentially Branched Alkyldiphenylphosphine Oxides - A Simple and Versatile Approach to<i>ortho-</i>Functionalized Arylphosphine Oxides
  作者：Shraddha G. Mahamulkar、Ivana Císařová、Ullrich Jahn

  DOI：10.1002/adsc.201400861

  日期：2015.3.9

  alkyllithium reagents. Here, the lithiation of differentially branched alkyldiphenylphosphine oxides was investigated and a diverse, but predictable reactivity was found. γ‐Branched derivatives undergo selective directed ortho‐metalation (DoM) using butyllithium and TMEDA as an additive. With decreasing degree of γ‐branching α‐lithiation becomes predominant. The ortho‐phosphinoyllithium intermediates

  烷基二苯基膦氧化物通常用烷基锂试剂进行α-去质子化。在此，对差异支化的烷基二苯基膦氧化物的锂化进行了研究，发现了多种多样但可预测的反应性。γ-支链衍生物离岗选择性定向邻-metalation使用（DOM）丁基锂和TMEDA作为添加剂。随着γ支化度的降低，α锂化变得占主导地位。的邻-phosphinoyllithium中间体受官能化和C  C键形成反应，从而提供了一种方便的方法，以新的氧化膦和膦-硼烷复合物，其具有用于一种方法来用于催化新配体的潜力。
• Preparation and reactions of sulfoxides and phosphine oxides containing silicon and germanium
  作者：A. G. Brook、D. G. Anderson

  DOI：10.1139/v68-345

  日期：1968.6.15

  The preparation of several sulfoxides containing silicon or germanium is reported. The thermal rearrangement of the silicon-containing sulfoxides has been observed but neither germanium-containing sulfoxides nor silicon-containing phosphine oxides were found to rearrange thermally at a detectable rate.

  报道了几种含硅或锗的亚砜的制备。观察到了含硅亚砜的热重排，但未发现含锗亚砜或含硅膦氧化物以可检测速率进行热重排。