1,2,8,9-Tetramethyl-2,5,8,9-tetraaza-1-phosphonia-bicyclo[3.3.3]undecane | 138800-22-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1,2,8,9-Tetramethyl-2,5,8,9-tetraaza-1-phosphonia-bicyclo[3.3.3]undecane
• 英文别名: 1,2,8,9-Tetramethyl-2,5,8,9-tetraza-1-phosphoniabicyclo[3.3.3]undecane；1,2,8,9-tetramethyl-2,5,8,9-tetraza-1-phosphoniabicyclo[3.3.3]undecane
• CAS: 138800-22-3
• 化学式: C₁₀H₂₄N₄P
• 分子量: 231.301
• InChiKey: JRJFZCOGEDAQTP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  13
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,2,8,9-Tetramethyl-2,5,8,9-tetraaza-1-phosphonia-bicyclo[3.3.3]undecane 在 sodium 作用下， 以 氨 为溶剂， 反应 1.0h， 以40%的产率得到2,8,9-Trimethyl-1-methylene-2,5,8,9-tetraaza-1λ⁵-phospha-bicyclo[3.3.3]undecane
  参考文献：
  名称：

  Synthesis and Photoelectron Spectroscopic Studies of N(CH₂CH₂NMe)₃PE (E = O, S, NH, CH₂)

  摘要：

  The synthesis and the crystal and molecular structure of N(CH2CH2NMe)(3)P=CH2 is reported. The P-N-ax distance is rather long in N(CH2CH2NMe)(3)P=CH2. The ylide N(CH2CH2NMe)(3)P=CH2 proved to be a stronger proton acceptor than proazaphosphatrane N(CH2CH2NMe)(3)P, since it was shown to deprotonate N(CH2CH2NMe)(3)PH+. The extremely strong basicity of the ylide is in accordance with its low ionization energy (6.3 eV), which is the lowest in the presently investigated series N(CH2CH2NMe)(3)P=E (E: CH2, NH, lone pair, O and S), and to the best of our knowledge it is the smallest value observed for a non-conjugated phosphorus ylide. Computations reveal the existence of two bond strech isomers, and the stabilization of the phosphorus centered cation by electron donation from the equatorial and the axial nitrogens. Similar stabilizing effects operate in the case of protonation of E. A fine balance of these different interactions determines the P-N-ax distance, which is thus very sensitive to the level of the theory applied. According to the quantum mechanical calculations, methyl substitution at the equatorial nitrogens flattens the pyramidality of this atom, increasing its electron donor capability. As a consequence, the PNax distance in the short-transannular bonded protonated systems and the radical cations is longer by about 0.5 angstrom in the N-eq(Me) than in the N-eq(H) systems. Accordingly, isodesmic reaction energies show that a stabilization of about 25 and 10 kcal/mol is attributable to the formation of the transannular bond in case of N-eq(H) and the experimentally realizable N-eq(Me) species, respectively.

  DOI：

  10.1021/ja0547533
• 作为产物：
  描述：

  三[2-(甲基氨基)乙基]胺 以 xylene 为溶剂， 生成 1,2,8,9-Tetramethyl-2,5,8,9-tetraaza-1-phosphonia-bicyclo[3.3.3]undecane
  参考文献：
  名称：

  Gudat, D.; Lensink, C.; Schmidt, H., Phosphorus, Sulfur and Silicon and the Related Elements, 1989, vol. 41, p. 21 - 30

  摘要：

  DOI：

文献信息

• Gudat, D.; Lensink, C.; Schmidt, H., Phosphorus, Sulfur and Silicon and the Related Elements, 1989, vol. 41, p. 21 - 30
  作者：Gudat, D.、Lensink, C.、Schmidt, H.、Xi, S.-K.、Verkade, J. G.

  DOI：——

  日期：——
• Synthesis and Photoelectron Spectroscopic Studies of N(CH₂CH₂NMe)₃PE (E = O, S, NH, CH₂)
  作者：Tamás Kárpáti、Tamás Veszprémi、Natesan Thirupathi、Xiaodong Liu、Zhigang Wang、Arkady Ellern、László Nyulászi、John G. Verkade

  DOI：10.1021/ja0547533

  日期：2006.2.1

  The synthesis and the crystal and molecular structure of N(CH2CH2NMe)(3)P=CH2 is reported. The P-N-ax distance is rather long in N(CH2CH2NMe)(3)P=CH2. The ylide N(CH2CH2NMe)(3)P=CH2 proved to be a stronger proton acceptor than proazaphosphatrane N(CH2CH2NMe)(3)P, since it was shown to deprotonate N(CH2CH2NMe)(3)PH+. The extremely strong basicity of the ylide is in accordance with its low ionization energy (6.3 eV), which is the lowest in the presently investigated series N(CH2CH2NMe)(3)P=E (E: CH2, NH, lone pair, O and S), and to the best of our knowledge it is the smallest value observed for a non-conjugated phosphorus ylide. Computations reveal the existence of two bond strech isomers, and the stabilization of the phosphorus centered cation by electron donation from the equatorial and the axial nitrogens. Similar stabilizing effects operate in the case of protonation of E. A fine balance of these different interactions determines the P-N-ax distance, which is thus very sensitive to the level of the theory applied. According to the quantum mechanical calculations, methyl substitution at the equatorial nitrogens flattens the pyramidality of this atom, increasing its electron donor capability. As a consequence, the PNax distance in the short-transannular bonded protonated systems and the radical cations is longer by about 0.5 angstrom in the N-eq(Me) than in the N-eq(H) systems. Accordingly, isodesmic reaction energies show that a stabilization of about 25 and 10 kcal/mol is attributable to the formation of the transannular bond in case of N-eq(H) and the experimentally realizable N-eq(Me) species, respectively.