diethyl 3,3,3-trifluoropropenylphosphonate | 153650-91-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: diethyl 3,3,3-trifluoropropenylphosphonate
• 英文别名: 1-diethoxyphosphoryl-3,3,3-trifluoroprop-1-ene
• CAS: 153650-91-0
• 化学式: C₇H₁₂F₃O₃P
• 分子量: 232.139
• InChiKey: YHWLDJBMOFBQTR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.33
• 重原子数：
  14.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  diethyl 3,3,3-trifluoropropenylphosphonate 在 吡啶 、 四氧化锇 作用下， 反应 24.0h， 以54%的产率得到diethyl 1,2-dihydroxy-3,3,3-trifluoropropanephosphonate
  参考文献：
  名称：

  A convenient synthesis of perfluoroalkylated hydroxy- and dihydroxy-phosphonates

  摘要：

  Perfluoroalkylated 1-hydroxyphosphonates may be easily synthesized in good yield by the reaction of the corresponding perfluoroalkyl aldehydes with dimethyl phosphite. Perfluoroalkylcarboxylic esters react with the phosphonate anion to give (perfluoroacyl)methylphosphonates, their tautomeric isomers (2-perfluoroalkyl-2-hydroxy)vinylphosphonates and their hydrates (2-perfluoroalkyl-2,2-dihydroxy)ethylphosphonates, which are reduced with sodium borohydride affording perfluoroalkylated 2-hydroxyphosphonates in 61-68% yield. Perfluoroalkylated dihydroxyphosphonates may be obtained by the reaction of the bisphosphonate anion with perfluoroalkyl aldehydes followed by oxidation with osmium tetraoxide in 54-68% yield.

  DOI：

  10.1016/s0022-1139(00)80472-8
• 作为产物：
  描述：

  2,2,2-三氟乙醛 、 亚甲基二磷酸四乙酯 在 叔丁基锂 作用下， 生成 diethyl 3,3,3-trifluoropropenylphosphonate
  参考文献：
  名称：

  氟化2-氨基膦酸酯的新合成

  摘要：

  全氟烷基化的α，β-不饱和磷酸酯与饱和甲醇氨溶液反应，得到2-氨基-2-全氟烷基乙基膦酸酯，与苄基胺得到2-苄基氨基-2-全氟烷基乙基膦酸酯，氢化后得到2-氨基-2-全氟烷基乙基膦酸酯。

  DOI：

  10.1016/0022-1139(94)03194-5

文献信息

• Rhodium(<scp>i</scp>)-catalyzed 1,4-conjugate arylation toward β-fluoroalkylated electron-deficient alkenes: a new entry to a construction of a tertiary carbon center possessing a fluoroalkyl group
  作者：Atsunori Morigaki、Tomoo Tanaka、Tomotsugu Miyabe、Takashi Ishihara、Tsutomu Konno

  DOI：10.1039/c2ob26708j

  日期：——

  Treatment of β-fluoroalkylated-α,β-unsaturated ketones with 1.2 equiv. of various arylboronic acids in the presence of 5 mol% of [Rh(COD)2]BF4 and 6 mol% of (S)-BINAP in toluene/H2O (v/v = 4/1) at the reflux temperature for 3 h gave the corresponding Michael adducts in high yields with over 90% enantioselectivity. Though other electron-deficient alkenes, such as vinylsulfone and vinylphosphonate, were found to be much less reactive in the rhodium-catalyzed conjugate addition with arylboronic acids, the reaction of various arylstannanes toward such electron-deficient alkenes took place very smoothly to afford the corresponding adducts in high yields.

  在甲苯/H2O（v/v = 4/1）溶液中，加入 5 摩尔的[Rh(COD)2]BF4 和 6 摩尔的(S)-BINAP，在回流温度下，用 1.2 等份的各种芳基硼酸处理δ-氟烷基化-δ,δ-不饱和酮 3 小时，可得到相应的迈克尔加合物，产率高，对映选择性超过 90%。虽然其他缺电子烯类，如乙烯基砜和乙烯基膦酸，在铑催化的芳基硼酸共轭加成反应中反应性要差得多，但各种芳基锡烷与这些缺电子烯类的反应非常顺利，能以高产率得到相应的加合物。