diphenyl(2-oxobutyl)phosphine oxide | 73270-33-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: diphenyl(2-oxobutyl)phosphine oxide
• 英文别名: 1-(diphenylphosphinoyl)butan-2-one；1-diphenylphosphinoyl-butan-2-one；1-(Diphenylphosphoryl)butan-2-one；1-diphenylphosphorylbutan-2-one
• CAS: 73270-33-4
• 化学式: C₁₆H₁₇O₂P
• 分子量: 272.284
• InChiKey: VRXQSWAYHDCBOZ-UHFFFAOYSA-N

物化性质

• 熔点：
  104-105 °C(Solv: ethyl acetate (141-78-6); methanol (67-56-1); hexane (110-54-3))
• 沸点：
  386.0±25.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  diphenyl(2-oxobutyl)phosphine oxide 在 正丁基锂 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 75.5h， 生成 (4RS,6RS)-(E)-diphenylphosphinoyl-4-methyl-1-phenyl-nona-1,8-dien-5-one
  参考文献：
  名称：

  Diphenylphosphinoyl-mediated synthesis of ketones

  摘要：

  α-二苯基膦酰基酮在α位上选择性且顺序性地进行烷基化。双锂化和选择性烷基化发生在较不稳定的γ位。脱膦酰化得到的烷基化产物是酮。单烷基化具有选择性，形成的中间体晶体高度结晶，且可以进行一步完成的方法。该方法非常适合制备酸敏感的酮。

  DOI：

  10.1039/b606873a
• 作为产物：
  描述：

  buta-1,2-dien-1-yl diphenyl phosphine oxide 在 potassium hydride 作用下， 以 四氢呋喃 、 二甲基亚砜 为溶剂， 反应 1.25h， 生成 diphenyl(2-oxobutyl)phosphine oxide
  参考文献：
  名称：

  Carbanion-accelerated Claisen rearrangements. 7. Phosphine oxide and phosphonate anion stabilizing groups

  摘要：

  The utility of phosphine oxide and phosphonate groups has been examined in the context of the carbanion-accelerated Claisen rearrangement (CACR). Both of the groups permit the construction of substituted allyl vinyl ethers by allyl oxide addition to phosphorus-substituted allenes. Extensive optimization was required to suppress isomerization of both the allenes and the vinyl ethers. Using potassium dimsylate and lithium chloride as the base, both the phosphine oxides and phosphonates rearranged readily at room temperature with complete regioselectivity in good yield (62-93%). The phosphonates also showed a high level of diastereoselectivity (92% de). The characteristic features of the CACR were compared with the original arylsulfone version.

  DOI：

  10.1021/jo00003a021

文献信息

• Torr, Richard S.; Warren, Stuart, Journal of the Chemical Society. Perkin transactions I, 1983, p. 1173 - 1180
  作者：Torr, Richard S.、Warren, Stuart

  DOI：——

  日期：——
• TORR, R. S.;WARREN, S., J. CHEM. SOC. PERKIN TRANS., 1983, N 6, 1173-1179
  作者：TORR, R. S.、WARREN, S.

  DOI：——

  日期：——
• Diphenylphosphinoyl-mediated synthesis of ketones
  作者：David J. Fox、Daniel Sejer Pedersen、Stuart Warren

  DOI：10.1039/b606873a

  日期：——

  α-Diphenylphosphinoyl ketones are selectively and sequentially alkylated at the α-position. Double lithiation and selective alkylation occurs at the less stabilised γ-position. Dephosphinoylation of the alkylation products gives ketones. Mono-alkylation is selective, highly crystalline intermediates are formed and a one-pot strategy is possible. The method is ideally suited for the preparation of acid-sensitive ketones.

  α-二苯基膦酰基酮在α位上选择性且顺序性地进行烷基化。双锂化和选择性烷基化发生在较不稳定的γ位。脱膦酰化得到的烷基化产物是酮。单烷基化具有选择性，形成的中间体晶体高度结晶，且可以进行一步完成的方法。该方法非常适合制备酸敏感的酮。
• Carbanion-accelerated Claisen rearrangements. 7. Phosphine oxide and phosphonate anion stabilizing groups
  作者：Scott E. Denmark、John E. Marlin

  DOI：10.1021/jo00003a021

  日期：1991.2

  The utility of phosphine oxide and phosphonate groups has been examined in the context of the carbanion-accelerated Claisen rearrangement (CACR). Both of the groups permit the construction of substituted allyl vinyl ethers by allyl oxide addition to phosphorus-substituted allenes. Extensive optimization was required to suppress isomerization of both the allenes and the vinyl ethers. Using potassium dimsylate and lithium chloride as the base, both the phosphine oxides and phosphonates rearranged readily at room temperature with complete regioselectivity in good yield (62-93%). The phosphonates also showed a high level of diastereoselectivity (92% de). The characteristic features of the CACR were compared with the original arylsulfone version.