diethyl (2-(3-nitrophenyl)-2-oxoethyl)phosphonate | 54109-31-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: diethyl (2-(3-nitrophenyl)-2-oxoethyl)phosphonate
• 英文别名: 2-Diethoxyphosphoryl-1-(3-nitrophenyl)ethanone
• CAS: 54109-31-8
• 化学式: C₁₂H₁₆NO₆P
• 分子量: 301.236
• InChiKey: BFGJVRYUXHAFJP-UHFFFAOYSA-N

物化性质

• 熔点：
  126 °C
• 沸点：
  413.5±25.0 °C(Predicted)
• 密度：
  1.277±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  98.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  聚合甲醛 、 diethyl (2-(3-nitrophenyl)-2-oxoethyl)phosphonate 在 potassium carbonate 作用下， 以 水 为溶剂， 以65%的产率得到2-(Hydroxymethyl)-1-(3-nitrophenyl)prop-2-en-1-one
  参考文献：
  名称：

  A Synthetic and Computational Investigation into the Direct Synthesis of ?-Hydroxymethylated Enones from ?-Keto Phosphonates

  摘要：

  通过对 Horner-Wadsworth-Emmons (HWE) 反应进行 Villiéras 改良，合成了一系列 α-羟甲基化烯酮。研究人员结合合成和计算研究，对这一反应的范围、局限性和机理方面进行了调查。这些研究支持 Schlosser-Corey 型反应机理，该机理在两种途径之间保持平衡，其结果受底物立体环境的影响。

  DOI：

  10.1071/ch09301
• 作为产物：
  描述：

  在 水 作用下， 以 N-甲基吡咯烷酮 为溶剂， 反应 6.0h， 以244 mg的产率得到diethyl (2-(3-nitrophenyl)-2-oxoethyl)phosphonate
  参考文献：
  名称：

  Mn III催化的Mn叠氮化物的磷酸化：β-酮膦氧化物的合成

  摘要：

  开发了Mn III通过磷酸化催化的叠氮化乙烯基官能团，以高产率合成各种β-酮膦氧化物。该转化在温和条件下进行，并能耐受多种官能团。对照反应表明，反应机理可能通过膦化亚胺基自由基中间体的产生而进行。

  DOI：

  10.1016/j.tetlet.2017.04.069

文献信息

• Redox Reorganization: Aluminium Promoted 1,5‐Hydride Shifts Allow the Controlled Synthesis of Multisubstituted Cyclohexenes
  作者：Lewis B. Smith、Roly J. Armstrong、Jingyan Hou、Edward Smith、Ming Sze、Alistair J. Sterling、Alex Smith、Fernanda Duarte、Timothy J. Donohoe

  DOI：10.1002/anie.202307424

  日期：2023.9.4

  An efficient synthesis of cyclohexenes has been achieved from easily accessible tetrahydropyrans via a tandem 1,5‐hydride shift–aldol condensation. We discovered that readily available aluminium reagents, e.g. Al₂O₃ or Al(O^tBu)₃ are essential for this process, promoting the 1,5‐hydride shift with complete regio‐ and enantiospecificity (in stark contrast to results obtained under basic conditions). The mild conditions, coupled with multiple methods available to access the tetrahydropyran starting materials makes this a versatile method with exceptional functional group tolerance. A wide range of cyclohexenes (>40 examples) have been prepared, many in enantiopure form, showing our ability to selectively install a substituent at each position around the newly forged cyclohexene ring. Experimental and computational studies revealed that aluminium serves a dual role in facilitating the hydride shift, activating both the alkoxide nucleophile and the electrophilic carbonyl group.

  摘要 通过串联 1,5-酸酐转移-醛醇缩合，从容易获得的四氢吡喃中高效合成了环己烯。我们发现，铝试剂（如 Al2O3 或 Al(OtBu)3）在这一过程中非常重要，可促进 1,5-酸酐转移，并具有完全的区域特异性和对映体特异性（与在碱性条件下获得的结果形成鲜明对比）。温和的条件加上多种获得四氢吡喃起始材料的方法，使该方法成为一种具有特殊官能团耐受性的多功能方法。我们已经制备出了多种环己烯（40 个实例），其中许多是对映体，这表明我们有能力在新形成的环己烯环周围的每个位置选择性地安装一个取代基。实验和计算研究表明，铝在促进氢化物转移方面起着双重作用，既能激活亲氧化烷基的亲核体，又能激活亲电羰基。
• An Efficient Separation Method for Enol Phosphate and Corresponding β-Ketophosphonate from Their Mixtures Under Aqueous Conditions
  作者：Cornelis M. Moorhoff

  DOI：10.1081/scc-120021033

  日期：2003.7

  Separation of a mixture beta-ketophosphonate 3 and their corresponding enol phosphate 4 is efficiently carried out in aqueous alkaline solutions. Enol phosphate 4 is first extracted with hexanes:dichloromethane (19:1). Acidification of the aqueous layer followed by extraction of the beta-ketophosphonate 3 with dichloromethane completes the separation. Thus, when 1-bromo-2,4-pentadione 1a reacted with triethyl phosphite to give diethyl (2,4-dioxopentyl)phosphonate 3a (Arbuzov-product) and the corresponding enol phosphate 4a (Perkow-product), separation of the two compounds was carried out using this method.
• Copper ferrite nanoparticles catalyzed formation of β-Ketophosphonates via oxyphosphorylation of styrenes with H-phosphonates: A DFT study on UV–vis absorption spectra
  作者：Firouz Matloubi Moghaddam、Maryam Daneshfar、Reza Azaryan、Jean-Luc Pirat

  DOI：10.1016/j.catcom.2020.106015

  日期：2020.6

  Typical copper ferrite nanoparticles (CuFe2O4) were used as a catalyst for one-pot synthesis of beta-ketophosphonates via the reaction of alkenes with H-phosphonates under conventional heating conditions. The catalyst was prepared by using the coprecipitation method and was analyzed by physiochemical techniques. By using this catalyst system, several types of useful and new beta-ketophosphonate products were obtained in very good to excellent yields under optimized reaction conditions in a novel way. Furthermore, the catalyst is recyclable and reusable from the reaction.
• Baboulene,M.; Sturtz,G., Bulletin de la Societe Chimique de France, 1974, p. 1585 - 1590
  作者：Baboulene,M.、Sturtz,G.

  DOI：——

  日期：——