1,3,5-benzenetriyltris(N-tert-butyl-N-hydroxyamine) | 151799-68-7

• 分子结构分类: 有机化合物 - 苯类化合物 - N-苯基羟胺
• 英文名称: 1,3,5-benzenetriyltris(N-tert-butyl-N-hydroxyamine)
• 英文别名: N-[3,5-bis[tert-butyl(hydroxy)amino]phenyl]-N-tert-butylhydroxylamine
• CAS: 151799-68-7
• 化学式: C₁₈H₃₃N₃O₃
• 分子量: 339.478
• InChiKey: YVOOHLDGRPHOBH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  70.4
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,3,5-benzenetriyltris(N-tert-butyl-N-hydroxyamine) 在 silver(l) oxide 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以16.5%的产率得到1,3,5-benzenetriyltris(N-tert-butyl nitroxide)
  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
• 作为产物：
  描述：

  5-bromo-1,3-phenylenebis(N-tert-butyl-N-(tert-butyldimethylsilyloxy)amine) 在 亚硝基叔丁烷 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 22.0h， 生成 1,3,5-benzenetriyltris(N-tert-butyl-N-hydroxyamine)
  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

文献信息

• 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
  作者：Fumio Kanno、Katsuya Inoue、Noboru Koga、Hiizu Iwamura

  DOI：10.1021/j100152a034

  日期：1993.12

  1,3,5-Benzenetriyltris(N-tert-butyl nitroxide (3), its 2-methoxy derivative (4), and 1,3,5-trisip-(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.