diethyl α,α-difluoromethyl-α-(phenylseleno)phosphonate | 327156-99-0

• 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 α,α-difluoromethyl-α-(phenylseleno)phosphonate
• 英文别名: diethyl α,α-difluoro-α-(phenylseleno)phosphonate；O,O-diethyl (phenylselanyl)(difluoromethyl)phosphonate；diethyl phenylselanyldifluoromethylphosphonate；Phosphonic acid, [difluoro(phenylseleno)methyl]-, diethyl ester；[diethoxyphosphoryl(difluoro)methyl]selanylbenzene
• CAS: 327156-99-0
• 化学式: C₁₁H₁₅F₂O₃PSe
• 分子量: 343.169
• InChiKey: IDQJXKJIFZIKAX-UHFFFAOYSA-N

物化性质

• 沸点：
  336.7±42.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.83
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  diethyl α,α-difluoromethyl-α-(phenylseleno)phosphonate 在 劳森试剂 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以55%的产率得到O,O-diethyl (phenylselanyl)(difluoromethyl)phosphonothioate
  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：

  苯基氯化硒 、 二氟甲基膦酸二乙酯 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.25h， 以71%的产率得到diethyl α,α-difluoromethyl-α-(phenylseleno)phosphonate
  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

• Aromatic Substitution with Photochemically Generated Difluoromethyl ­Radicals Bearing Electron-Withdrawing Group
  作者：Toshio Fuchigami、Satoru Murakami、Shokaku Kim、Hideki Ishii

  DOI：10.1055/s-2004-820026

  日期：——

  Novel and facile aromatic and heteroaromatic substitutions with difluoromethyl radicals bearing electron-withdrawing group generated by the photo-initiated Se-CF 2 bond cleavage of ethyl α,α-difluoro-α-(phenylseleno)acetate and diethyl α,α-difluoromethyl-α-(phenylseleno)phosphonate were successfully carried out to provide the corresponding a-aryl-α,α-difluoroacetates and α-aryl-α,α-difluoromethylphosphonates

  通过光引发 Se-CF 2 键裂解 α,α-二氟-α-（苯基硒基）乙酸乙酯和二乙基 α,α-二氟甲基-α 产生带有吸电子基团的二氟甲基自由基的新型和简便的芳族和杂芳族取代-(苯基硒基)膦酸酯被成功地进行以良好到中等的产率提供相应的α-芳基-α,α-二氟乙酸酯和α-芳基-α,α-二氟甲基膦酸酯。
• Photochemical substitution of olefins and aromatic compounds with difluoromethyl radicals bearing ester and phosphonate groups
  作者：Satoru Murakami、Hideki Ishii、Toshiki Tajima、Toshio Fuchigami

  DOI：10.1016/j.tet.2005.12.057

  日期：2006.4

  transfer at an early stage followed by elimination of phenylselenol from the adducts once formed to provide the unsaturated difluoromethylene adducts selectively. This novel photochemical method was successfully extended to aromatic and heteroaromatic substitutions to provide the corresponding α-aryl-α,α-difluoroacetates and α-aryl-α,α-difluoromethylphosphonates in good to moderate yields.

  在2,4,6-三甲基吡啶和二苯基二硒化物的存在下，成功地进行了光生的带有酯基和膦酸酯基团的二氟甲基基团对环状和无环乙烯基醚的高效选择性取代，从而选择性地提供了相应的区域选择性不饱和二氟亚甲基加合物。该反应涉及在早期阶段进行苯基硒烯基转移，随后一旦形成就选择性地提供不饱和二氟亚甲基加合物而从加合物中消除苯基硒醇。这种新颖的光化学方法已成功地扩展到芳族和杂芳族取代，从而以良好至中等的产率提供了相应的α-芳基-α，α-二氟乙酸酯和α-芳基-α，α-二氟甲基膦酸酯。
• Sulfanyl- and Selanyldifluoromethylphosphonates as a Source of Phosphonodifluoromethyl Radicals and Their Addition onto Alkenes
  作者：Thierry Lequeux、Fanny Lebouc、Chrystel Lopin、Hongli Yang、Géraldine Gouhier、Serge R. Piettre

  DOI：10.1021/ol006746j

  日期：2001.1.1

  [GRAPHICS]Two different strategies are shown to produce sulfanyl and selanyldifluoromethylphosphonates, Thus, treatment of sulfanyldichloromethylphosphonates by 3HF . NEt3 in the presence of zinc bromide produces the corresponding sulfanyldifluoromethylphosphonates. In addition, lithiation of difluoromethylphosphonates followed by quenching with phenylsulfanyl chloride, phenylselanyl chloride, or diphenyl diselenide yields the corresponding sulfanyl- and selanyldifluorophosphonates. Generation of phosphonodifluoromethyl radicals from such precursors in the presence of alkenes produces the expected adducts.
• Phosphonodifluoromethyl and Phosphonothiodifluoromethyl Radicals. Generation and Addition onto Alkenes and Alkynes
  作者：Sébastien Pignard、Chrystel Lopin、Géraldine Gouhier、Serge R. Piettre

  DOI：10.1021/jo051511c

  日期：2006.1.1

  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.