diethyl (1,1,2,3,3-pentafluoroprop-2-en-1-yl)phosphonate | 132485-71-3

• 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 (1,1,2,3,3-pentafluoroprop-2-en-1-yl)phosphonate
• 英文别名: Diethyl (1,1,2,3,3-pentafluoroprop-2-en-1-yl)phosphonate；3-diethoxyphosphoryl-1,1,2,3,3-pentafluoroprop-1-ene
• CAS: 132485-71-3
• 化学式: C₇H₁₀F₅O₃P
• 分子量: 268.12
• InChiKey: WBIOEOBRVVLAKY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  三甲基溴硅烷 、 diethyl (1,1,2,3,3-pentafluoroprop-2-en-1-yl)phosphonate 以 四氢呋喃 为溶剂， 以99 %的产率得到bis(trimethylsilyl) (1,1,2,3,3-pentafluoroprop-2-en-1-yl)phosphonate
  参考文献：
  名称：

  O-和P-亲核试剂与全氟烯烃的相互作用：氟化含磷单体的新合成路线

  摘要：

  提出了一种制备部分氟化不饱和膦酸二乙酯和膦酸的新合成方法，该方法涉及用强碱对起始α-羟甲基二乙基膦酸酯或二乙基亚磷酸酯进行去质子化，然后原位添加O-或P-全氟化烯烃的末端双键的亲核体。随后消除相应的离去基团并恢复双键​​，得到目标双官能全氟化烯烃。膦酸二乙酯基团与三甲基溴硅烷（TMS-Br）反应，随后水解/甲醇分解，得到相应的不饱和膦酸。在使用α-羟甲基二乙基膦酸酯的情况下，反应可以伴随添加第二当量的O-亲核试剂以形成双官能内烯烃。还讨论了反应条件、影响反应活性的因素、过程的立体和区域选择性、试剂的选择以及竞争反应的过程。

  DOI：

  10.1016/j.jfluchem.2023.110152
• 作为产物：
  描述：

  在 三甲基乙酸 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 生成 diethyl (1,1,2,3,3-pentafluoroprop-2-en-1-yl)phosphonate
  参考文献：
  名称：

  Facile Synthesis of Fluorinated Phosphonates via Photochemical and Thermal Reactions

  摘要：

  Under UV irradiation (254 nm) at ambient temperature, a degassed mixture of (EtO)(2)POP(OEt)(2) and RfI {R-f=CF3, C2F5, C4F9, C6F13, (CF3)(2)CF, CF2CF=CF2, ClCF2CF2, BrCF2CF2, C6F5, ClCF2CFClCF2CF2, I(CF2)(3), I(CF2)(4), FO2S(CF2)(4), FO2S(CF2)(2)O(CF2)(2)} affords the fluorinated phosphonite, [RfP(OEt)(2)]. Oxidation of the phosphonites, [RfP(OEt)(2)], with Me3COOH gave the corresponding fluorinated phosphonates, (EtO)(2)P(O)R-f(1-14), in 35-80% isolated yields. CF3CCl2I reacts with (EtO)(2)POP(OEt)(2) at room temperature in the absence of UV irradiation to afford [CF3CCl2P(OEt)(2)] which upon oxidation gave a 52% yield of CF3CCl2P(O)(OEt)(2) (15). The reaction of (EtO)(2)POP(OEt)(2) and RfI (R-f=ClCF2CF2, BrCF2CF2, C2F5) at 125 degrees C in the presence of Me3COOCMe3 and subsequent oxidation of the resultant phosphonites afforded phosphonates (2, 7, and 8) albeit in lower yields (49-62%) compared to those of the photochemical reaction (58-80%). (RO)(2)P(O)CF2CF2I (R=Et, i-Pr) (16 and 17) was obtained (42-48%) when a degassed mixture of (RO)(3)P and BrCF2CF2I was subjected to UV irradiation (254 nm) at ambient temperature via a unique photochemical transformation.

  DOI：

  10.1021/ja971345t

文献信息

• WO2023/79414
  申请人：——

  公开号：——

  公开（公告）日：——
• Facile Synthesis of Fluorinated Phosphonates <i>via</i> Photochemical and Thermal Reactions
  作者：Haridasan K. Nair、Donald J. Burton

  DOI：10.1021/ja971345t

  日期：1997.10.1

  Under UV irradiation (254 nm) at ambient temperature, a degassed mixture of (EtO)(2)POP(OEt)(2) and RfI R-f=CF3, C2F5, C4F9, C6F13, (CF3)(2)CF, CF2CF=CF2, ClCF2CF2, BrCF2CF2, C6F5, ClCF2CFClCF2CF2, I(CF2)(3), I(CF2)(4), FO2S(CF2)(4), FO2S(CF2)(2)O(CF2)(2)} affords the fluorinated phosphonite, [RfP(OEt)(2)]. Oxidation of the phosphonites, [RfP(OEt)(2)], with Me3COOH gave the corresponding fluorinated phosphonates, (EtO)(2)P(O)R-f(1-14), in 35-80% isolated yields. CF3CCl2I reacts with (EtO)(2)POP(OEt)(2) at room temperature in the absence of UV irradiation to afford [CF3CCl2P(OEt)(2)] which upon oxidation gave a 52% yield of CF3CCl2P(O)(OEt)(2) (15). The reaction of (EtO)(2)POP(OEt)(2) and RfI (R-f=ClCF2CF2, BrCF2CF2, C2F5) at 125 degrees C in the presence of Me3COOCMe3 and subsequent oxidation of the resultant phosphonites afforded phosphonates (2, 7, and 8) albeit in lower yields (49-62%) compared to those of the photochemical reaction (58-80%). (RO)(2)P(O)CF2CF2I (R=Et, i-Pr) (16 and 17) was obtained (42-48%) when a degassed mixture of (RO)(3)P and BrCF2CF2I was subjected to UV irradiation (254 nm) at ambient temperature via a unique photochemical transformation.
• Interaction of O- and P- nucleophiles with perfluorinated olefins: Novel synthetic route to fluorinated phosphorus-containing monomers
  作者：Sergey N. Tverdomed、Markus E. Hirschberg、Romana Pajkert、Katja Vlasov、Gerd-Volker Röschenthaler

  DOI：10.1016/j.jfluchem.2023.110152

  日期：2023.7

  situ addition of an O- or P-nucleophile to the terminal double bond of the perfluorinated olefin. Subsequent elimination of the corresponding leaving groups and restoring of the double bond leads to the target bifunctional perfluorinated olefins. Reaction of the diethyl phosphonate group with trimethylsilyl bromide (TMS-Br) and subsequent hydrolysis/methanolysis gave the corresponding unsaturated phosphonic

  提出了一种制备部分氟化不饱和膦酸二乙酯和膦酸的新合成方法，该方法涉及用强碱对起始α-羟甲基二乙基膦酸酯或二乙基亚磷酸酯进行去质子化，然后原位添加O-或P-全氟化烯烃的末端双键的亲核体。随后消除相应的离去基团并恢复双键​​，得到目标双官能全氟化烯烃。膦酸二乙酯基团与三甲基溴硅烷（TMS-Br）反应，随后水解/甲醇分解，得到相应的不饱和膦酸。在使用α-羟甲基二乙基膦酸酯的情况下，反应可以伴随添加第二当量的O-亲核试剂以形成双官能内烯烃。还讨论了反应条件、影响反应活性的因素、过程的立体和区域选择性、试剂的选择以及竞争反应的过程。