3-bromo<3>staffane | 145143-28-8

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机溴化物
• 英文名称: 3-bromo<3>staffane
• 英文别名: 1,1a(2):3a(2),1a(2)a(2)-Terbicyclo[1.1.1]pentane, 3-bromo-；1-(1-bicyclo[1.1.1]pentanyl)-3-(3-bromo-1-bicyclo[1.1.1]pentanyl)bicyclo[1.1.1]pentane
• CAS: 145143-28-8
• 化学式: C₁₅H₁₉Br
• 分子量: 279.22
• InChiKey: BEUILQVDJQXLKL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  9.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  <3>staffane-3-carboxylic acid chloride 在 1-溴-1-氯-2,2,2-三氟乙烷 、 2-mercaptopyridine-1-oxide sodium salt 作用下， 反应 3.0h， 以60%的产率得到3-bromo<3>staffane
  参考文献：
  名称：

  Long-range spin density propagation in saturated hydrocarbons: 3-[n]staffyl radicals

  摘要：

  The bridgehead radicals derived from the first three [n]staffanes (n = 1-3), oligomers of [1.1.1]propellane, have been generated from the corresponding bromides, and their solution EPR spectra have been recorded. Remarkably long-range hyperfine coupling has been found to epsilon, zeta, and even iota hydrogens, in qualitative agreement with ab initio UHF calculations. The coupling to the bridgehead hydrogen is attenuated by a factor of about 25 per added bicyclo[1.1.1]pentane cage. The long-range propagation of spin density can be attributed to strong interaction between the orbitals used to make the exocyclic bonds in the 1 and 3 positions of each bicyclo[1.1.1]pentane cage. The situation can be understood simply in terms of a linear sigma-hyperconjugated chain of orbitals interacting through resonance integrals whose effective magnitude alternates in an about 1:5 ratio. A more detailed analysis is provided by considering the effect on the spin density of the various types of off-diagonal elements in the UHF Hartree-Fock matrix expressed in terms of maximally spin-paired natural bond orbitals (MSP-NBO). This permits a clean separation of through-space and through-bond interactions as well as further separation of each of these into contributions due to bond delocalization and those due to bond spin polarization.

  DOI：

  10.1021/ja00052a070