| 1193731-94-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• CAS: 1193731-94-0；1327160-19-9
• 化学式: C₈H₂₀N*C₁₈H₁₀F₁₂O₂P
• 分子量: 647.484
• InChiKey: VDFNTPQFXXGSMW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.07
• 重原子数：
  42.0
• 可旋转键数：
  4.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  在 重水 作用下， 以 氘代二甲亚砜 为溶剂， 反应 0.5h， 以96%的产率得到
  参考文献：
  名称：

  Isolation of a Metastable Geometrical Isomer of a Hexacoordinated Dihydrophosphate: Elucidation of Its Enhanced Reactivity in Umpolung of a Hydrogen Atom of Water

  摘要：

  Two of five conceivable geometrical isomers of a hexacoordinated dihydrophosphate bearing two sets of a bidentate ligand were investigated. X-ray crystallographic analysis of both of isomers, 1a-TPP and 1b-TEA, revealed their octahedral geometries of C-2 and C-1 symmetry, respectively, which were consistent with the NMR spectra. The isomer 1b-TEA underwent both hydride reduction of an aldehyde and proton exchange with water at room temperature in DMSO without any additive. A one-pot reaction of both of the reactions of 1b-TEA with D2O and an aldehyde or a ketone under the above conditions proceeded successfully to give the deuterated alcohol. Thus, umpolung of a hydrogen atom of water with 1b-TEA was achieved under much milder conditions than those used in the reaction with another isomer, la-TEA. Quantitative isomerization of 1b-TEA to la-TEA occurred in methanol at room temperature. Calculations on the five conceivable geometrical isomers of the anionic part of the dihydrophosphate revealed their relative stability, which reasonably explained the isomerization, and the larger negative charge at the atoms located at the trans positions of the oxygen atoms. The smaller coupling constants of the P H and P C bonds located at the rear of an oxygen atom in the NMR spectra resulted in the smaller s character of these bonds. The differences in both hydride-donation and proton-exchange reactivities between la-TEA and 1b-TEA could be explained by the differences in the atomic charge of the hydrogen atom and the stability difference of the initially formed phosphorane intermediates, respectively.

  DOI：

  10.1021/ic2012765
• 作为产物：
  描述：

  四乙基溴化铵 、 (S)-3,3,3',3'-tetrakis(trifluoromethyl)-1,1'-spirobi<3H,2,1λ⁵-benzoxaphosphole> 在 lithium aluminium tetrahydride 作用下， 以 乙醚 、 二甲基亚砜 为溶剂， 反应 1.0h， 以43%的产率得到
  参考文献：
  名称：

  Isolation of a Metastable Geometrical Isomer of a Hexacoordinated Dihydrophosphate: Elucidation of Its Enhanced Reactivity in Umpolung of a Hydrogen Atom of Water

  摘要：

  Two of five conceivable geometrical isomers of a hexacoordinated dihydrophosphate bearing two sets of a bidentate ligand were investigated. X-ray crystallographic analysis of both of isomers, 1a-TPP and 1b-TEA, revealed their octahedral geometries of C-2 and C-1 symmetry, respectively, which were consistent with the NMR spectra. The isomer 1b-TEA underwent both hydride reduction of an aldehyde and proton exchange with water at room temperature in DMSO without any additive. A one-pot reaction of both of the reactions of 1b-TEA with D2O and an aldehyde or a ketone under the above conditions proceeded successfully to give the deuterated alcohol. Thus, umpolung of a hydrogen atom of water with 1b-TEA was achieved under much milder conditions than those used in the reaction with another isomer, la-TEA. Quantitative isomerization of 1b-TEA to la-TEA occurred in methanol at room temperature. Calculations on the five conceivable geometrical isomers of the anionic part of the dihydrophosphate revealed their relative stability, which reasonably explained the isomerization, and the larger negative charge at the atoms located at the trans positions of the oxygen atoms. The smaller coupling constants of the P H and P C bonds located at the rear of an oxygen atom in the NMR spectra resulted in the smaller s character of these bonds. The differences in both hydride-donation and proton-exchange reactivities between la-TEA and 1b-TEA could be explained by the differences in the atomic charge of the hydrogen atom and the stability difference of the initially formed phosphorane intermediates, respectively.

  DOI：

  10.1021/ic2012765
• 作为试剂：
  描述：

  肉桂醛 在 C₈H₂₀N⁽¹⁺⁾*C₁₈H₁₀F₁₂O₂P^(1-) 、 溶剂黄146 作用下， 反应 1.0h， 以12%的产率得到3-苯丙醇
  参考文献：
  名称：

  Umpolung of a Hydrogen Atom of Water by Using a Hexacoordinated Phosphate and Its Application to Deuteride Reduction Reactions of Carbonyl Compounds

  摘要：

  The polarity of a chemical bond is an important factor that determines the reactivity because a reaction of a positively charged atom with a negatively charged atom easily occurs. We report here a method for reversing the polarity of a hydrogen atom of water, which meant conversion of a protic hydrogen (H(delta+)) to a hydridic hydrogen (H(delta-)), by using a hexacoordinated phosphorus species. The method enables a reductive deuteration of carbonyl compounds utilizing inexpensive and easily usable D2O under mild conditions. The umpolung of a hydrogen atom was achieved by utilizing tautomerization of phosphorus compounds. Classical metal hydrides never have this function, and these results demonstrated the potential utility of nonmetallic compounds for umpolung of a hydrogen atom.

  DOI：

  10.1021/ja906875d