| 1313574-21-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• CAS: 1313574-21-8
• 化学式: C₄₂H₂₆ClOP
• 分子量: 613.095
• InChiKey: HSKIUOSLAHPYOM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.6
• 重原子数：
  45
• 可旋转键数：
  3
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.02
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  9-芴酮 在 正丁基锂 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  κ¹- and κ²-Complexes of Fluorenylidene–Allenyl Phosphines and Phosphine Oxides with Palladium Chloride and Iron Carbonyl: Displacement of Trimethylsilyl by Diphenylphosphino via a Stabilized Carbanion

  摘要：

  An attempt to prepare 3,3-(biphenyl-2,2'-diyl)-1-diphenylphosphino-1-(trimethylsilyl)allene, 15, by treatment of 3,3- (bipheny1-2,2'-diyl)-1-lithio-1-(trimethylsilyl)allene with chlorodiphenylphosphine led instead to 3,3-(biphenyl-2,2'-diyl)-1,1-bis(diphenylphosphino)allene, 14. The proposed mechanism invokes attack on the trimethylsilyl group in 15 by liberated chloride to form a stabilized anion that reacts with a second molecule of the chlorophosphine. The diphosphine, 14, reacts with di-iron nonacarbonyl to form monodentate 14-Fe(CO)(4) and the chelate 14-Fe(CO)(3). 9-Ethynyl-9H-fluoren-9-ol and chlorodiphenylphosphine form 3,3-(biphenyl-2,2'-diyl)-1-diphenylphosphinylallene, which is readily deprotonated by triethylamine to generate a stabilized fluorenyl anion, which reacts with a second molecule of the chlorophosphine to furnish 3,3-(biphenyl-2,2'-diyl)-1-diphenylphosphino-1-diphenylphosphinylallene, 26. This bis-phosphine-monoxide (BPMO) reacts with di-iron nonacarbonyl to form initially monodentate P-bonded 26-Fe(CO)(4), which loses a carbonyl, allowing the adjacent allene double bond in 26-Fe(CO)(3) to coordinate to iron and leave the phosphine oxide uncoordinated. In contrast, the BPMO, 26, and (PhCN)(2)PdCl2 yield the phosphine-coordinated, chlorine-bridged dimer 34 and also the chelate 35, in which the palladium is linked to both the diphenylphosphino and diphenylphosphinyl groups via phosphorus and oxygen, respectively. Surprisingly, chlorodiphenylphosphine and 1,4-bis(9-hydroxy-9H-fluorenyl)buta-1,3-diyne, 37, do not yield the expected 3,4-bis(phosphinyl)hexa-1,2,4,5-tetraene, 33, but rather the 1-chloro-2-diphenylphosphinocyclobutene, 38, bearing a spiro-bonded fluorenylidene and a fluorenylidene-allene. All new compounds were characterized by P-31 NMR spectroscopy and X-ray crystallography.

  DOI：

  10.1021/om200357v

文献信息

• κ¹- and κ²-Complexes of Fluorenylidene–Allenyl Phosphines and Phosphine Oxides with Palladium Chloride and Iron Carbonyl: Displacement of Trimethylsilyl by Diphenylphosphino via a Stabilized Carbanion
  作者：Sandra Milosevic、Emilie V. Banide、Helge Müller-Bunz、Declan G. Gilheany、Michael J. McGlinchey

  DOI：10.1021/om200357v

  日期：2011.7.25

  An attempt to prepare 3,3-(biphenyl-2,2'-diyl)-1-diphenylphosphino-1-(trimethylsilyl)allene, 15, by treatment of 3,3- (bipheny1-2,2'-diyl)-1-lithio-1-(trimethylsilyl)allene with chlorodiphenylphosphine led instead to 3,3-(biphenyl-2,2'-diyl)-1,1-bis(diphenylphosphino)allene, 14. The proposed mechanism invokes attack on the trimethylsilyl group in 15 by liberated chloride to form a stabilized anion that reacts with a second molecule of the chlorophosphine. The diphosphine, 14, reacts with di-iron nonacarbonyl to form monodentate 14-Fe(CO)(4) and the chelate 14-Fe(CO)(3). 9-Ethynyl-9H-fluoren-9-ol and chlorodiphenylphosphine form 3,3-(biphenyl-2,2'-diyl)-1-diphenylphosphinylallene, which is readily deprotonated by triethylamine to generate a stabilized fluorenyl anion, which reacts with a second molecule of the chlorophosphine to furnish 3,3-(biphenyl-2,2'-diyl)-1-diphenylphosphino-1-diphenylphosphinylallene, 26. This bis-phosphine-monoxide (BPMO) reacts with di-iron nonacarbonyl to form initially monodentate P-bonded 26-Fe(CO)(4), which loses a carbonyl, allowing the adjacent allene double bond in 26-Fe(CO)(3) to coordinate to iron and leave the phosphine oxide uncoordinated. In contrast, the BPMO, 26, and (PhCN)(2)PdCl2 yield the phosphine-coordinated, chlorine-bridged dimer 34 and also the chelate 35, in which the palladium is linked to both the diphenylphosphino and diphenylphosphinyl groups via phosphorus and oxygen, respectively. Surprisingly, chlorodiphenylphosphine and 1,4-bis(9-hydroxy-9H-fluorenyl)buta-1,3-diyne, 37, do not yield the expected 3,4-bis(phosphinyl)hexa-1,2,4,5-tetraene, 33, but rather the 1-chloro-2-diphenylphosphinocyclobutene, 38, bearing a spiro-bonded fluorenylidene and a fluorenylidene-allene. All new compounds were characterized by P-31 NMR spectroscopy and X-ray crystallography.