2-(Diethoxy-phosphoryl)-2-fluoro-3-oxo-succinic acid diethyl ester | 2796-37-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-(Diethoxy-phosphoryl)-2-fluoro-3-oxo-succinic acid diethyl ester
• 英文别名: Diethyl 2-diethoxyphosphoryl-2-fluoro-3-oxobutanedioate
• CAS: 2796-37-4
• 化学式: C₁₂H₂₀FO₈P
• 分子量: 342.258
• InChiKey: PAIXYPCEUJSJPM-UHFFFAOYSA-N

物化性质

• 沸点：
  398.2±42.0 °C(Predicted)
• 密度：
  1.253±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  22
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  105
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  甲基碘化镁 、 2-(Diethoxy-phosphoryl)-2-fluoro-3-oxo-succinic acid diethyl ester 以 四氢呋喃 、 乙醚 为溶剂， 生成 (E)-diethyl 2-fluoro-3-methyl fumarate
  参考文献：
  名称：

  An expedient synthesis of α-fluoro-α,β-unsaturated diesters

  摘要：

  Acylation of [(EtO)2P(O)CFCO2Et]-Li+ (2) with alkyloxalyl chlorides followed by subsequent reaction of the acylated phosphonates with Grignard reagents provides the title compounds in moderate to good yields with high E-stereoselectivity.

  DOI：

  10.1016/s0040-4039(00)60990-5
• 作为产物：
  描述：

  溴氟乙酸乙酯 、 草酰氯单乙酯 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 2-(Diethoxy-phosphoryl)-2-fluoro-3-oxo-succinic acid diethyl ester
  参考文献：
  名称：

  A Novel Intramolecular Horner-Wadsworth-Emmons Reaction: A Simple and General Route to .alpha.-Fluoro-.alpha.,.beta.-unsaturated Diesters

  摘要：

  Diethyl (fluorocarbethoxymethyl)phosphonate (1), prepared from triethyl phosphite and ethyl bbromofluoroacetate, reacts with n-butyllithium in THF to give the phosphonate carbanion 2. Addition of the pregenerated carbanion 2 to a THF solution of methyl or ethyl oxalyl chloride at -78 degrees C forms the acylated phosphonate (EtO)(2)P(O)CF(COCO(2)R)CO(2)Et (3). In situ reaction of 3 with Grignard reagents affords alpha-fluoro-alpha,beta-unsaturated diesters R'(CO(2)R)C=CFCO(2)Et in moderate to good yields with high E-stereoselectivity. The reaction is applicable to primary, secondary, and tertiary alkyl, alkenyl, alkynyl, aryl, cyclohexyl, and perfluorinated Grignard reagents. The assignment of E and Z configuration is based on NOE experiment. The E/Z ratio of unsaturated diesters formed in the reaction varies with the metal ion and cosolvent. However, solvents and bases have little influence on the stereoselectivity.

  DOI：

  10.1021/jo00102a038

文献信息

• Isolation and Characterization of intermediate in the Synthesis of α-Fluorodiesters
  作者：Hou-Jen Tsai

  DOI：10.1002/jccs.199800082

  日期：1998.8

  AbstractThe anion [(EtO)2P(O)CFCO2Et]−Li+, pregenerated from its precursor diethyl (carboethoxyfluoromethyl)phosphonate (EtO)2P(O)CFHCO2Et and n‐butyllithium, was added via syringe to a THF solution of ethyl oxaiyl chloride to yield an acylated phosphonate (EtO)2P(O)CF(COCO2Et)CO2Et. In situ reaction with Grignard reagents RMgX produces the α‐fluorodiesters (E,Z)‐R(CO2Et)C=CFCO2Et in good yields. In contrast, addition of ethyl oxalyl chloride to a THF solution of diethyl (carboethoxyfluoromethyl)phosphonate anion gives an isolated intermediate (EtO)2P(O)CFCO2Et(CO2Et)C=CFCO2Et. Subsequent reaction of this isolated intermediate with Grignard reagents also affords a one‐pot synthesis of the α‐fluorodiesters with high E‐stereoselectivity. The E‐stereoselectivity increases when HMPT or DMPU is used as a cosolvent in the preparation of diethyl 2‐fluoro‐3‐phenylfumarate (E,Z)‐Ph(CO2Et)C=CFCO2Et.