O,O-diethyl (difluoromethyl)phosphononothioate | 873957-67-6

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机硫代磷化合物
• 英文名称: O,O-diethyl (difluoromethyl)phosphononothioate
• 英文别名: (Difluoromethyl)phosphonothioic acid diethyl ester；difluoromethyl-diethoxy-sulfanylidene-λ5-phosphane
• CAS: 873957-67-6
• 化学式: C₅H₁₁F₂O₂PS
• 分子量: 204.178
• InChiKey: RLFSBODQKUBCKR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  O,O-diethyl (difluoromethyl)phosphononothioate 在 偶氮二异丁腈 、 三(三甲基硅基)硅烷 、 四丁基氟化铵 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 水 、 甲苯 为溶剂， 反应 1.25h， 生成 O,O-diethyl 1,1-difluoroprop-2-enylphosphonothioate
  参考文献：
  名称：

  Phosphonodifluoromethyl and Phosphonothiodifluoromethyl Radicals. Generation and Addition onto Alkenes and Alkynes

  摘要：

  Selanylated difluorornethylphosphonates and difluoromethylphosphonothioates are good precursors to phosphonodifluoromethyl and phosphonothiodifluoromethyl radicals, respectively. When generated in the presence of alkenes and a hydrogen donor, the corresponding alpha,alpha-difluorinated alkylphosphonates C, ID. or alkylphosphonothioates are produced in fair to good yields. The use of alkynes results in the formation of alpha,alpha-difluorinated allyl derivatives in useful yields. The presence of the sulfur atom in phosphono-thiodifluoromethyl radicals usually translates into higher isolated yields.

  DOI：

  10.1021/jo051511c
• 作为产物：
  描述：

  二氟甲基膦酸二乙酯 在 劳森试剂 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以74%的产率得到O,O-diethyl (difluoromethyl)phosphononothioate
  参考文献：
  名称：

  Phosphonodifluoromethyl and Phosphonothiodifluoromethyl Radicals. Generation and Addition onto Alkenes and Alkynes

  摘要：

  Selanylated difluorornethylphosphonates and difluoromethylphosphonothioates are good precursors to phosphonodifluoromethyl and phosphonothiodifluoromethyl radicals, respectively. When generated in the presence of alkenes and a hydrogen donor, the corresponding alpha,alpha-difluorinated alkylphosphonates C, ID. or alkylphosphonothioates are produced in fair to good yields. The use of alkynes results in the formation of alpha,alpha-difluorinated allyl derivatives in useful yields. The presence of the sulfur atom in phosphono-thiodifluoromethyl radicals usually translates into higher isolated yields.

  DOI：

  10.1021/jo051511c

文献信息

• First and Efficient Synthesis of Phosphonodifluoromethylene Analogues of Nucleoside 3‘-Phosphates:  Crucial Role Played by Sulfur in Construction of the Target Molecules
  作者：Chrystel Lopin、Arnaud Gautier、Géraldine Gouhier、Serge R. Piettre

  DOI：10.1021/ja027850u

  日期：2002.12.1

  corresponding difluoromethylene phosphonates as isopolar mimics, a single example of such an analogue featuring this particular substitution pattern has so far been reported in the literature, due to synthetic problems associated with their preparation. The lithium salt of diethyl difluoromethylphosphonothioate 28d provides a solution to this problem, as demonstrated by an 8-step synthesis of all five fully protected

  仲醇的磷酸酯在生物系统中无处不在。然而，尽管相应的二氟亚甲基膦酸酯作为等极模拟物的明显兴趣，由于与它们的制备相关的合成问题，迄今为止文献中已经报道了具有这种特殊取代模式的这种类似物的一个例子。二氟甲基硫代膦酸二乙酯 28d 的锂盐为这个问题提供了解决方案，正如所有五个完全保护的核苷 3'-磷酸类似物的 8 步合成所证明的那样，总产率为 9-18%，来自容易获得的酮。硫被证明在将磷取代的二氟亚甲基单元引入呋喃糖环中起着至关重要的作用。在需要立体控制的过程的三个步骤中观察到完全的非对映选择性。P=S 键向其含氧类似物的关键转化是通过使用间氯过氧苯甲酸简单实现的。值得注意的是，该合成可以大规模进行：已经制备了31-g批次的化合物26b。脱保护的核苷 3'-磷酸类似物可以从它们的前体中释放出来，例如将 7b、8b 和 9b 转化为相应的二氟膦酸，以二钠盐的形式分离。