(E)-3-diphenylphosphinoyl-4-phenyl-butane-2-one | 172420-63-2

• 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: (E)-3-diphenylphosphinoyl-4-phenyl-butane-2-one
• 英文别名: 3-Diphenylphosphoryl-4-phenylbutan-2-one；3-diphenylphosphoryl-4-phenylbutan-2-one
• CAS: 172420-63-2
• 化学式: C₂₂H₂₁O₂P
• 分子量: 348.381
• InChiKey: XSWFYVQMWOSTLL-UHFFFAOYSA-N

物化性质

• 熔点：
  189-192 °C(Solv: ethyl acetate (141-78-6); methanol (67-56-1); hexane (110-54-3))
• 沸点：
  481.7±38.0 °C(Predicted)
• 密度：
  1.16±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  (E)-3-diphenylphosphinoyl-4-phenyl-butane-2-one 在 sodium hydroxide 作用下， 以 乙醇 为溶剂， 反应 1.5h， 以86%的产率得到苄基丙酮
  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：

  甲基二苯基氧化膦 在 正丁基锂 、 sodium methylate 作用下， 以 四氢呋喃 为溶剂， 反应 31.0h， 生成 (E)-3-diphenylphosphinoyl-4-phenyl-butane-2-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

文献信息

• TiCl4 Mediated LiBH4 reduction of β-ketophosphine oxides: a high stereoselective route to the synthesis of anti-β-hydroxyphosphine oxides
  作者：Giuseppe Bartoli、Marcella Bosco、Letizia Sambri、Enrico Marcantoni

  DOI：10.1016/0040-4039(96)01601-2

  日期：1996.10

  The reduction of an α-alkyl-β-ketophosphine oxide with LiBH4 in presence of a strong chelating agent, such as TiCl4, gives the corresponding β-hydroxyphosphine oxide in high yields and with high anti-diastereoselectivity independently from the size of both the α- and β-alkyl chains.

  在强螯合剂（例如TiCl 4）存在下，用LiBH 4还原α-烷基-β-酮膦氧化物，可以独立于两者的大小，以高收率和高抗-非对映选择性生成相应的β-羟基膦氧化物。α-和β-烷基链。
• Opposite Stereochemical Effects Exerted by CeCl3 and TiCl4 on the Lewis Acid Mediated Reduction of α-Alkyl-β-ketophosphine Oxides with Metallic Hydrides: A Highly Stereoselective Protocol for the Synthesis of syn and anti α-alkyl-β-Hydroxyphosphine Oxides
  作者：Giuseppe Bartoli、Marcella Bosco、Letizia Sambri、Renato Dalpozzo、Enrico Marcantoni

  DOI：10.1002/chem.19970031209

  日期：1997.12

  AbstractA general, highly efficient methodology for obtaining both syn and anti β‐hydroxyphosphine oxides by reduction of the corresponding β‐ketophosphine oxides is described. The nature of the Lewis acid was found to be pivotal in determining the outcome of these reactions. Strongly chelating TiCl4 led to the anti isomer in high diastereoisomeric excess in noncoordinating solvents (CH2Cl2) at ‐78°C with BH3/py as reducing agent, while nonchelating CeCl3 gave a high excess of the syn isomer in coordinating solvents (THF) at the same temperature with LiBH4 as reducing agent. In the latter case, CeCl3 is essential in achieving high yields and stereoselectivity, since it allows the reaction to be performed at low temperatures. Otherwise, higher temperatures (0°C) are required, which lower both yields and selectivities. Moreover, each step of the protocol for the synthesis of stereodefined disubstituted olefins from alkylphosphine oxides (Warren's modification of the Horner procedure) has been optimized, and the optimized procedure has been applied to the synthesis of muscalure, the pheromone of the domestic fly.
• Bartoli, Giuseppe; Marcantoni, Enrico; Sambri, Letizia, Angewandte Chemie, 1995, vol. 107, # 18, p. 2163 - 2164
  作者：Bartoli, Giuseppe、Marcantoni, Enrico、Sambri, Letizia、Tamburini, Monica

  DOI：——

  日期：——