5-bromo-2-methoxy-1,3-phenylenebis[N-tert-butyl-N-(tert-butyldimethylsilyloxy)amine] | 151799-70-1

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 5-bromo-2-methoxy-1,3-phenylenebis[N-tert-butyl-N-(tert-butyldimethylsilyloxy)amine]
• CAS: 151799-70-1
• 化学式: C₂₇H₅₃BrN₂O₃Si₂
• 分子量: 589.804
• InChiKey: JGHITUOTJCASFJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.54
• 重原子数：
  35.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  34.17
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  5-bromo-2-methoxy-1,3-phenylenebis[N-tert-butyl-N-(tert-butyldimethylsilyloxy)amine] 在 正丁基锂 、 亚硝酸正戊酯 作用下， 以 四氢呋喃 为溶剂， 以7.7%的产率得到
  参考文献：
  名称：

  Molecular structure and magnetic properties of N,N-bis{4-methoxy-3,5-bis(N-tert-butyl-N-oxyamino)phenyl)}aminoxyl. An approach to a stable and high-spin pentaradical

  摘要：

  制备了稳定的五元基团N,N-双{4-甲氧基-3,5-双(N-叔丁基-N-氧基氨基)苯基}氨基氧基，并通过在聚氯乙烯基质中稀释的五元基团的SQUID磁化测量确定其基态为六重态（S = 5/2）。

  DOI：

  10.1039/a704160h
• 作为产物：
  描述：

  2,4,6-三溴苯甲醚 在 咪唑 、 亚硝基叔丁烷 作用下， 以 乙醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 10.0h， 生成 5-bromo-2-methoxy-1,3-phenylenebis[N-tert-butyl-N-(tert-butyldimethylsilyloxy)amine]
  参考文献：
  名称：

  Persistent 1,3,5-benzenetriyltris(N-tert-butyl nitroxide) and its analogs with quartet ground states. Intramolecular triangular exchange coupling among three nitroxide radical centers

  摘要：

  1,3,5-Benzenetriyltris(N-tert-butyl nitroxide (3), its 2-methoxy derivative (4), and 1,3,5-tris{ip-(N-oxy-N-tert-butylamino)phenyl}benzene (5) were prepared and studied by EPR and magnetic susceptibility/magnetization measurements. Trinitroxides 3 and 4 showed EPR fine structures characteristic of quartet states: 3: g = 2.0062, \D/hc\ = 0.009 32 cm-1 and \E/hc\ = 0.000 15 cm-1; 4: g = 2.0063, \D/hc\ = 0.009 66 cm-1 and \E/hc\ = 0.000 32 cm-1. The changes in the signal intensity vs reciprocal temperature obeyed Curie's law in the range 10-100 K, suggesting that the quartets are their ground states. Magnetization data for 3 and 4 at 1.8, 3.0, and 4.0 K in the field range 0-7 T obeyed the Brillouin function in which S = 3/2. The effective magnetic moment of a crystalline sample of 4 obtained on a SQUID susceptometer was 3.21 mu(B) at 240 K, increased gradually, reached a maximum (mu(eff)/mu(B) = 3.73) at 32 K, and decreased steeply as the temperature was decreased. The results were interpreted in terms of an isosceles-triangular exchange interaction among the three nitroxide radicals within a molecule (J1/k(B) = 68.4 and J2/k(B) = 5.0 K) and antiferromagnetic intermolecular interaction (theta = -1.7 K). A methoxy group on the m-phenylene ring was found to weaken the through-ring exchange coupling among the attached nitroxide radicals by an order of magnitude. An X-ray structure analysis of a clear red block cubic single crystal of 5, Pa3BAR (No. 205), a = 18.786(2) angstrom, V = 6631(2) angstrom3, Z = 8, D(calc) = 1.301 g cm-3, revealed the molecular structure with three nitroxide groups 37.5-degrees out of the peripheral p-phenylene rings which am tilted out of the central benzenetriyl unit by 19.5-degrees in a propeller conformation. Temperature dependences of the mu(eff) values observed for crystalline and matrix-isolated 5 in the range 5-300 K gave J/k(B) values of +6.8 K (theta = -2.1 K) and +5.3 K, respectively, when analyzed in terms of a regular-triangular exchange coupling model. Lower spin polarization on the 1,3,5-triphenylbenzene chromophore is concluded to be responsible for the reduced J value in 5.

  DOI：

  10.1021/j100152a034