diethyl-(1E)-1-fluoro-2-phenylethenophosphonate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: diethyl-(1E)-1-fluoro-2-phenylethenophosphonate
• 英文别名: [(E)-2-diethoxyphosphoryl-2-fluoroethenyl]benzene
• 化学式: C₁₂H₁₆FO₃P
• 分子量: 258.229
• InChiKey: VUAMDAUEABLOIX-ZRDIBKRKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  二乙基[二溴(氟)甲基]膦酸酯 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 生成 diethyl-(1E)-1-fluoro-2-phenylethenophosphonate
  参考文献：
  名称：

  An efficient synthesis of tetraethyl fluoromethylenediphosphonate and derivatives from diethyl dibromofluoromethylphosphonate

  摘要：

  Treatment of diethyl I,1-dibromo-1-fluoromethylphosphonate with n-BuLi (1:1) at low temperature affords by self-trapping in quantitative yield the lithiated derivative of tetraethyl fluoromethylenediphosphonate which is reacted with alkylating and halogenating agents or converted with high selectivity into (E) diethyl fluorovinylphosphonates by reaction with carbonyl compounds. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)00821-1

文献信息

• A new route to α-fluorovinylphosphonates utilizing Peterson olefination methodology
  作者：Rachel Waschbüsch、John Carran、Philippe Savignac

  DOI：10.1016/0040-4020(96)00859-9

  日期：1996.11

  Several α-fluorovinylphosphonates (6) have been synthesised from the Peterson olefination reaction applied to both aldehydes and ketones in conjunction with α-lithiated-α-fluoro-α-trimethylsilylmethylphosphonate (2). The reaction with aldehydes gives mainly the E-isomer whereas reaction with ketones gives mainly the Z-isomer. We propose a closed transition state to explain the results of our study

  几个α-fluorovinylphosphonates（6）已经从施加到两个醛和酮结合α-锂化-α氟-α-trimethylsilylmethylphosphonate（Peterson烯反应，合成2）。与醛的反应主要产生E-异构体，而与酮的反应主要产生Z-异构体。我们提出了一个封闭的过渡状态来解释我们的研究结果。
• The synthesis of α-monofluorovinylphosphonates by a Peterson type olefination reaction
  作者：Angela Keeney、Jens Nieschalk、David O'Hagan

  DOI：10.1016/s0022-1139(96)03460-4

  日期：1996.9

  The reaction of α-lithium-α-fluoro-α-trimethylsilyl-methylphosphonate 2 with aldehydes 3a-f leads to α-fluorovinylphosphonates 4a-f by a Peterson type olefination reaction.

  α-锂-α-氟-α-三甲基甲硅烷基-甲基膦酸酯2与醛3a-f的反应通过彼得森型烯烃化反应产生α-氟乙烯基膦酸酯4a-f。
• A kinetic separation method for the stereoselective preparation of 1-fluorovinylphosphonates from E/Z mixtures of 1-bromo-1-fluoroolefins
  作者：Xin Zhang、Donald J. Burton

  DOI：10.1016/s0022-1139(01)00482-1

  日期：2001.11

  Reaction of E/Z mixtures of 1-bromo-1-fluoroolefins with diethylphosphite and catalytic Pd(PPh3)4 in triethylamine at 30–40°C gave predominately the (E)-isomer of the 1-fluorovinylphosphonate (E/Z≥95:5) in good yields. Pure (E)-1-fluorovinylphosphonate could be readily obtained by chromatographic separation of the 95:5 E/Z mixture. Pure (Z)-1-bromo-1-fluoroolefin could be recovered and phosphorylated

  的反应Ë / ž 1-溴-1-氟烯烃与亚磷酸二乙酯和催化的Pd（PPh混合物3）4在30-40在三乙胺℃下，得到主要在（ë）1- fluorovinylphosphonate（ -异构体Ë / ž ≥ 95：5）。通过色谱分离95：5 E / Z混合物可轻松获得纯净的（E）-1-氟乙烯基膦酸酯。可以回收纯的（Z）-1-溴-1-氟烯烃，并在70°C进行磷酸化，以51-60％的收率得到纯的（Z）-1-氟乙烯基膦酸酯。因此，E / Z1-溴-1-氟烯烃的混合物可以动力学分离成纯的（E）-和（Z）-1-氟乙烯基膦酸酯。该方法学提供了从容易获得的1-溴-1-氟烯烃到异构纯的（E）-和（Z）-1-氟乙烯基膦酸酯的明确途径。
• Stereoselective Synthesis of (E)-α-Fluorovinylphosphonates from α,α-Difluorophosphonates
  作者：Petr Beier、Prabhakar Cherkupally、Anton Slazhnev

  DOI：10.1055/s-0030-1259294

  日期：2011.2

  α,α-Difluorophosphonates, which are readilyavailable from alkyl halides and diethyl difluoromethylphosphonate,undergo elimination of hydrogen fluoride using alkali metal alkoxidesto provide α-fluorovinylphosphonates in high yields and E/ Z selectivities.

  α,α-二氟膦酸酯很容易从卤代烷和二氟甲基膦酸二乙酯中获得，使用碱金属醇盐消除氟化氢，以高产率和 E/Z 选择性提供 α-氟乙烯基膦酸酯。
• Ru-Catalyzed Hydrogen Atom Transfer/C–F Bond Cleavage of Difluoroalkyl Diazos with Hantzsch Ester via a Photocatalytic Radical Process
  作者：Qian Wang、Jiang Liu、Haibo Mei、Romana Pajkert、Mira Kessler、Gerd-Volker Röschenthaler、Jianlin Han

  DOI：10.1021/acs.orglett.2c03268

  日期：2022.11.4

  reaction of difluoroalkyl diazo compounds with Hantzsch ester under visible light to achieve the formation of α-fluorovinylphosphonates via a radical process has been developed. Mechanistic experiments and density functional theory calculations reveal that the generation of a carbon radical is directly through the hydrogen atom transfer (HAT) by Hantzsch ester. This system represents the first example of

  已经开发了在可见光下二氟烷基重氮化合物与 Hantzsch 酯的 Ru 催化反应，以通过自由基过程实现 α-氟乙烯基膦酸酯的形成。机械实验和密度泛函理论计算表明，碳自由基的产生是直接通过 Hantzsch 酯的氢原子转移 (HAT) 产生的。该系统代表了通过 Hantzsch 酯辅助 HAT 从重氮化合物生成碳自由基的第一个示例，并且还展示了二氟烷基重氮化合物的新自由基参与途径。