triethyl 2-fluoro-3-oxo-2-phosphono-3-phenylpropanoate | 171916-53-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: triethyl 2-fluoro-3-oxo-2-phosphono-3-phenylpropanoate
• 英文别名: Ethyl 2-diethoxyphosphoryl-2-fluoro-3-oxo-3-phenylpropanoate
• CAS: 171916-53-3
• 化学式: C₁₅H₂₀FO₆P
• 分子量: 346.292
• InChiKey: YRNSSHXFTPGTAG-UHFFFAOYSA-N

物化性质

• 沸点：
  433.4±45.0 °C(Predicted)
• 密度：
  1.226±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  23
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  triethyl 2-fluoro-3-oxo-2-phosphono-3-phenylpropanoate 在 sodium tetrahydroborate 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 ethyl (E)-2-fluoro-3-phenylacrylate
  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：

  在 正丁基锂 、 air 、 二叔丁基过氧化物 作用下， 生成 triethyl 2-fluoro-3-oxo-2-phosphono-3-phenylpropanoate
  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

• Tandem reduction–olefination of triethyl 2-acyl-2-fluoro-2-phosphonoacetates and a synthetic approach to Cbz-Gly-Ψ[(Z)-CFC]-Gly dipeptide isostere
  作者：Shigeki Sano、Yoko Kuroda、Katsuyuki Saito、Yukiko Ose、Yoshimitsu Nagao

  DOI：10.1016/j.tet.2006.09.096

  日期：2006.12

  (Z)-alpha-Fluoro-alpha,beta-unsaturated esters (Z)-7a-f were stereoselectively prepared by a tandem reduction-olefination of triethyl 2-acyl-2-fluoro-2-phosphonoacetates 6a-f with NaBH4 in EtOH. A concise synthesis of Cbz-Gly-Psi[(Z)-CF=C]-Gly (26) as a dipeptide isostere was achieved via the tandem reduction-olefination of the corresponding 2-acyl-2-fluoro-2-phosphonoacetate 20. (c) 2006 Elsevier Ltd. All rights reserved.
• Acylation of α-fluorophosphonoacetate derivatives using magnesium chloride-triethylamine
  作者：Dae Young Kim、Yong Mi Lee、Young Jae Choi

  DOI：10.1016/s0040-4020(99)00807-8

  日期：1999.11

  Acylation of alpha-fluorophosphonoacetate derivatives in the presence of magnesium chloride-triethylamine has been described. Acylations of triethyl alpha-fluorophosphonoacetate 1 and diethyl alpha-fluorophosphonoacetic acid 7 were proceeded under mild conditions to provide alpha-fluoro-beta-keto esters 3 and alpha-fluoro-beta-keto phosphonates 9, respectively, in high yields. (C) 1999 Elsevier Science Ltd. All rights reserved.
• A Facile P-C Bond Cleavage of 2-Fluoro-2-Phosphonyl-1,3-Dicarbonyl Compounds on Silica Gel
  作者：Dae Young Kim

  DOI：10.1080/00397910008087140

  日期：2000.4

  alpha-Fluoro-beta-keto esters and alpha-fluoromalonates were prepared by the P-C bond cleavage of 2-fluoro-2-phosphonyl-1,3-dicarbonyl compounds on wet silica gel.
• P-C Bond Cleavage of Triethyl 2-Fluoro-3-oxo-2-phosphonoacetates with Magnesium Chloride: A Synthesis of α-Fluoro-β-keto Esters
  作者：Dae Young Kim、Jin Seok Choi、Dae Yong Rhie

  DOI：10.1080/00397919708003055

  日期：1997.3

  P-C bond cleavage of triethyl 2-fluoro-3-oxo-2-phosphonoacetates in the presence of magnesium chloride provides a synthetic route to alpha-fluoro-beta-keto esters.
• Tsai, Hou-Jen; Thenappan, Alagappan; Burton, Donald J., Phosphorus, Sulfur and Silicon and the Related Elements, 1995, vol. 105, # 1-4, p. 205 - 212
  作者：Tsai, Hou-Jen、Thenappan, Alagappan、Burton, Donald J.

  DOI：——

  日期：——