2-(Diethoxy-phosphoryl)-2,4,4,4-tetrafluoro-3-oxo-butyric acid ethyl ester | 195833-95-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: 2-(Diethoxy-phosphoryl)-2,4,4,4-tetrafluoro-3-oxo-butyric acid ethyl ester
• CAS: 195833-95-5
• 化学式: C₁₀H₁₅F₄O₆P
• 分子量: 338.193
• InChiKey: VVBJNWYEHAVEOT-UHFFFAOYSA-N

物化性质

• 沸点：
  329.3±42.0 °C(Predicted)
• 密度：
  1.336±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.61
• 重原子数：
  21.0
• 可旋转键数：
  8.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  78.9
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  2-(Diethoxy-phosphoryl)-2,4,4,4-tetrafluoro-3-oxo-butyric acid ethyl ester 在 碳酸氢钠 作用下， 反应 6.0h， 生成 2-乙基-2,4,4,4-四氟-3-氧代丁酸酯
  参考文献：
  名称：

  Acylation of fluorocarbethoxy-substituted ylides: a simple and general route to .alpha.-fluoro .beta.-keto esters

  摘要：

  (Fluorocarbethoxymethylene)tri-n-butylphosphorane (3) reacts with acid chlorides and anhydrides to form the corresponding carbon acylated phosphonium salts 4, and hydrolysis of 4 under mild basic conditions provides RCOCFHCOOEt (8) in moderate yields. The reaction is applicable to primary, secondary, tertiary, cyclic, aromatic, and ester-substituted acid chlorides. Acylation with ethyl chloroformate and ethyl chlorothioformate leads to the diesters CFH(COOEt)2 and EtSCOCFHCOOEt. Extension of this reaction sequence to perfluorinated and partially fluorinated acid chlorides did not proceed cleanly to give the expected phosphonium salts. However, the anion derived from (EtO)2P(O)CFHC(O)OEt reacts with R(F)COCl to form the corresponding C-acylated phosphonates 10, and hydrolysis of 10 gives R(F)COCFHCOOEt.

  DOI：

  10.1021/jo00001a052
• 作为产物：
  描述：

  ethyl 2-diethoxyphosphanyl-2-diethoxyphosphoryl-2-fluoroacetate 在 正丁基锂 、 air 、 二叔丁基过氧化物 作用下， 反应 6.33h， 生成 2-(Diethoxy-phosphoryl)-2,4,4,4-tetrafluoro-3-oxo-butyric acid ethyl ester
  参考文献：
  名称：

  Acylation of fluorocarbethoxy-substituted ylides: a simple and general route to .alpha.-fluoro .beta.-keto esters

  摘要：

  (Fluorocarbethoxymethylene)tri-n-butylphosphorane (3) reacts with acid chlorides and anhydrides to form the corresponding carbon acylated phosphonium salts 4, and hydrolysis of 4 under mild basic conditions provides RCOCFHCOOEt (8) in moderate yields. The reaction is applicable to primary, secondary, tertiary, cyclic, aromatic, and ester-substituted acid chlorides. Acylation with ethyl chloroformate and ethyl chlorothioformate leads to the diesters CFH(COOEt)2 and EtSCOCFHCOOEt. Extension of this reaction sequence to perfluorinated and partially fluorinated acid chlorides did not proceed cleanly to give the expected phosphonium salts. However, the anion derived from (EtO)2P(O)CFHC(O)OEt reacts with R(F)COCl to form the corresponding C-acylated phosphonates 10, and hydrolysis of 10 gives R(F)COCFHCOOEt.

  DOI：

  10.1021/jo00001a052

文献信息

• APPLICATION OF FLUOROCARBETHOXY-SUBSTITUTED PHOSPHONATE: A FACILE ENTRY TO SUBSTITUTED 2-FLUORO-3-OXOESTERS
  作者：Hou-Jen Tsai

  DOI：10.1080/10426509708043541

  日期：1997.7.1

  Abstract Diethyl(fluorocarbethoxymethyl)phosphonate 1a or diisopropyl(fluorocarbethoxymethyl)phosphonate 1b, prepared from triethyl phosphite or triisopropyl phosphite with ethyl bromofluoroacetate, react with n-butyllithium in THF to give the corresponding phosphonate carbanions [(RO)2P(O)CFCO2Et]−Li+ 2a (R=Et) and 2b (R=i-Pr). Addition of trimethylsilyltrifluoroacetate CF3C(O)OSiMe3 to a THF solution

  摘要 由亚磷酸三乙酯或亚磷酸三异丙酯与溴氟乙酸乙酯制备的二乙基（氟碳乙氧基甲基）膦酸酯 1a 或二异丙基（氟碳乙氧基甲基）膦酸酯 1b 与正丁基锂在 THF 中反应得到相应的膦酸酯碳负离子 [(RO)2P(O)CFCO2Et]- Li+ 2a (R=Et) 和 2b (R=i-Pr)。将三甲基甲硅烷基三氟乙酸酯 CF3C(O)OSiMe3 添加到膦酸酯碳负离子的 THF 溶液中，形成三氟乙酰氟乙酸乙酯 [CF3C(O)CFCO2Et]-Li+3 的烯醇化物。随后烯醇化物的质子化、烷基化或烯丙基化得到取代的 2,4,4,4 -四氟-3-氧代酯 CF3C(O)CFR1CO2Et 10
• An expedient synthesis of α-fluoro-β-ketoesters
  作者：Alagappan Thenappan、Donald J. Burton

  DOI：10.1016/s0040-4039(01)93318-0

  日期：——