diethyl α,α-difluorooctanephosphonate | 141642-60-6

• 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-difluorooctanephosphonate
• 英文别名: diethyl 1,1-difluorooctylphosphonate；1-Diethoxyphosphoryl-1,1-difluorooctane
• CAS: 141642-60-6
• 化学式: C₁₂H₂₅F₂O₃P
• 分子量: 286.299
• InChiKey: WEERBHBQVYJTGI-UHFFFAOYSA-N

物化性质

• 沸点：
  308.4±37.0 °C(Predicted)
• 密度：
  1.043±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  18
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  1-庚烯 在 四(三苯基膦)钯 、 nickel dichloride 、 锌 作用下， 以 四氢呋喃 为溶剂， 反应 8.33h， 生成 diethyl α,α-difluorooctanephosphonate
  参考文献：
  名称：

  A novel, general method for the preparation of α,gad̄ifluoro functionalized phosphonates

  摘要：

  The addition reaction of diethyl iododifluoromethylphosphonate to alkenes catalyzed by palladium in the absence of solvent gives the corresponding adducts in good yields at room temperature. A variety of functional groups in the alkenes, including alkyl, trimethylsilyl, hydroxy, epoxy, ketone and ester, are tolerated under the reaction conditions. The reduction of the adducts with nickel chloride and zinc in moist THF provides the title compounds.

  DOI：

  10.1016/s0040-4039(00)74476-5

文献信息

• Photochemical generation of difluoromethyl radicals having various functional groups and their highly regioselective addition to olefins and aromatic substitution
  作者：Hirokatsu Nagura、Satoru Murakami、Toshio Fuchigami

  DOI：10.1016/j.tet.2007.07.081

  日期：2007.10

  Difluoromethyl radicals bearing ester, phosphonate, nitrile, cyclic carbonate, and carbamate groups were generated by the photoinitiated S–CF2 bond cleavage of electrosynthesized α,α-difluorosulfides, and their addition to olefins and aromatic substitution were successfully carried out to provide the regioselective adducts and substitution products in moderate yields. The yields of substitution products

  电合成的α，α-二氟硫化物通过光引发的S–CF 2键裂解生成带有酯基，膦酸酯基，腈基，环状碳酸酯基和氨基甲酸酯基团的二氟甲基自由基，并成功地将其添加到烯烃中并进行了芳族取代，从而提供了区域选择性加合物和替代产品的收率中等。通过加入二苯基二硒化物和2,4,6-三甲基吡啶，取代产物的产率提高。
• A novel and practical preparation of .alpha.,.alpha.-difluoro functionalized phosphonates from iododifluoromethylphosphonate
  作者：Zhen Yu Yang、Donald J. Burton

  DOI：10.1021/jo00043a027

  日期：1992.8

  The addition reaction of iododifluoromethylphosphonate 1 with alkenes is catalyzed by tetrakis(triphenylphosphine)palladium or copper metal under mild conditions. A variety of functional groups, including alkyl, trimethylsilyl, hydroxy, epoxy, acetoxy, ketone, and ester, in the alkenes could be tolerated under the reaction conditions. Reaction of 2 equiv of 1 with dienes gives the corresponding bisphosphonates. Although the palladium complex fails to induce addition of 1 to cyclohexene, the addition reaction proceeds readily with copper at 85-degrees-C. With diallyl ether, a tetrahydrofuran derivative is obtained. Electron scavenger and radical inhibitors suppressed the addition reaction completely. A single electron transfer initiated radical mechanism is proposed. Treatment of the adducts with zinc in the presence of nickel chloride in moist THF at room temperature provides the corresponding alpha,alpha-difluoro-functionalized phosphonates in good yields.
• A general method for the synthesis of 1,1-difluoroalkylphosphonates
  作者：Stephen F. Martin、Daniel W. Dean、Allan S. Wagman

  DOI：10.1016/s0040-4039(00)74156-6

  日期：1992.3

  A facile method for preparing 1,1-difluoroalkylphosphonates has been developed that features radical deoxygenation of thionocarbonates derived from the adducts formed upon addition of 9 to aldehydes.