2,2,4,4,6,6,8,8-octamethyl-4H,6H-benzo[1,2-d;5,4-d']bis[1,3]oxazine-1,9-diyldioxyl | 36884-22-7

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 2,2,4,4,6,6,8,8-octamethyl-4H,6H-benzo[1,2-d;5,4-d']bis[1,3]oxazine-1,9-diyldioxyl
• 英文别名: 2,2,4,4,6,6,8,8-Octamethyl-9-oxido-[1,3]oxazino[5,4-g][3,1]benzoxazin-1-ium 1-oxide
• CAS: 36884-22-7
• 化学式: C₁₈H₂₆N₂O₄
• 分子量: 334.415
• InChiKey: GNQUZEDAAFDMTF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  24
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  64.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  cobalt bis(1,1,1,5,5,5-hexafluoroacetylacetonato) dihydrate 、 二氯甲烷 、 2,2,4,4,6,6,8,8-octamethyl-4H,6H-benzo[1,2-d;5,4-d']bis[1,3]oxazine-1,9-diyldioxyl 、 丙酮 生成 ((CH3)16C20H3N4O5(O)2(OH))Co(hfac)2(water)*0.75CH2Cl2*1.25(CH3)2CO
  参考文献：
  名称：

  Conformationally Constrained, Stable, Triplet Ground State (S = 1) Nitroxide Diradicals. Antiferromagnetic Chains of S = 1 Diradicals

  摘要：

  Nitroxide diradicals, in which nitroxides are annelated to m-phenylene forming tricyclic benzobisoxazine-like structures, have been synthesized and characterized by X-ray crystallography, magnetic resonance (EPR and H-1 NMR) spectroscopy, as well as magnetic studies in solution and in solid state. For the octamethyl derivative of benzobisoxazine nitroxide diradical, the conformationally constrained nitroxide moieties are coplanar with the m-phenylene, leading to large values of 2J (2J/k > 200 K in solution and 2J/k > 300 K in the solid state). For the diradical, in which all ortho and para positions of the m-phenylene are sterically shielded, distortion of the nitroxide moieties from coplanarity is moderate, such that the singlet-triplet gaps remain large in both solution (2J/k > 200 K) and the solid state (2J/k approximate to 400-800 K), though an onset of thermal depopulation of the triplet ground state is detectable near room temperature. These diradicals have robust triplet ground states with strong ferromagnetic coupling and good stability at ambient conditions. Magnetic behavior of the nitroxide diradicals at low temperature is best fit to the model of one-dimensional S = 1 Heisenberg chains with intrachain antiferromagnetic coupling. The antiferromagnetic coupling between the S = 1 diradicals may be associated with the methyl nitroxide C-H- - -O contacts, including nonclassical hydrogen bonds. These unprecedented organic S = 1 antiferromagnetic chains are highly isotropic, compared to those of the extensively studied Ni(II)-based chains.

  DOI：

  10.1021/ja0712017
• 作为产物：
  描述：

  2,2,4,4,6,6,8,8-octamethyl-1,4,8,9-tetrahydro-2H,6H-benzo[1,2-d;5,4-d']bis[1,3]oxazine 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以90.0 mg的产率得到2,2,4,4,6,6,8,8-octamethyl-4H,6H-benzo[1,2-d;5,4-d']bis[1,3]oxazine-1,9-diyldioxyl
  参考文献：
  名称：

  Conformationally Constrained, Stable, Triplet Ground State (S = 1) Nitroxide Diradicals. Antiferromagnetic Chains of S = 1 Diradicals

  摘要：

  Nitroxide diradicals, in which nitroxides are annelated to m-phenylene forming tricyclic benzobisoxazine-like structures, have been synthesized and characterized by X-ray crystallography, magnetic resonance (EPR and H-1 NMR) spectroscopy, as well as magnetic studies in solution and in solid state. For the octamethyl derivative of benzobisoxazine nitroxide diradical, the conformationally constrained nitroxide moieties are coplanar with the m-phenylene, leading to large values of 2J (2J/k > 200 K in solution and 2J/k > 300 K in the solid state). For the diradical, in which all ortho and para positions of the m-phenylene are sterically shielded, distortion of the nitroxide moieties from coplanarity is moderate, such that the singlet-triplet gaps remain large in both solution (2J/k > 200 K) and the solid state (2J/k approximate to 400-800 K), though an onset of thermal depopulation of the triplet ground state is detectable near room temperature. These diradicals have robust triplet ground states with strong ferromagnetic coupling and good stability at ambient conditions. Magnetic behavior of the nitroxide diradicals at low temperature is best fit to the model of one-dimensional S = 1 Heisenberg chains with intrachain antiferromagnetic coupling. The antiferromagnetic coupling between the S = 1 diradicals may be associated with the methyl nitroxide C-H- - -O contacts, including nonclassical hydrogen bonds. These unprecedented organic S = 1 antiferromagnetic chains are highly isotropic, compared to those of the extensively studied Ni(II)-based chains.

  DOI：

  10.1021/ja0712017

文献信息

• Conformationally Constrained, Stable, Triplet Ground State (<i>S</i> = 1) Nitroxide Diradicals. Antiferromagnetic Chains of <i>S</i> = 1 Diradicals
  作者：Andrzej Rajca、Masahiro Takahashi、Maren Pink、Gaëlle Spagnol、Suchada Rajca

  DOI：10.1021/ja0712017

  日期：2007.8.1

  Nitroxide diradicals, in which nitroxides are annelated to m-phenylene forming tricyclic benzobisoxazine-like structures, have been synthesized and characterized by X-ray crystallography, magnetic resonance (EPR and H-1 NMR) spectroscopy, as well as magnetic studies in solution and in solid state. For the octamethyl derivative of benzobisoxazine nitroxide diradical, the conformationally constrained nitroxide moieties are coplanar with the m-phenylene, leading to large values of 2J (2J/k > 200 K in solution and 2J/k > 300 K in the solid state). For the diradical, in which all ortho and para positions of the m-phenylene are sterically shielded, distortion of the nitroxide moieties from coplanarity is moderate, such that the singlet-triplet gaps remain large in both solution (2J/k > 200 K) and the solid state (2J/k approximate to 400-800 K), though an onset of thermal depopulation of the triplet ground state is detectable near room temperature. These diradicals have robust triplet ground states with strong ferromagnetic coupling and good stability at ambient conditions. Magnetic behavior of the nitroxide diradicals at low temperature is best fit to the model of one-dimensional S = 1 Heisenberg chains with intrachain antiferromagnetic coupling. The antiferromagnetic coupling between the S = 1 diradicals may be associated with the methyl nitroxide C-H- - -O contacts, including nonclassical hydrogen bonds. These unprecedented organic S = 1 antiferromagnetic chains are highly isotropic, compared to those of the extensively studied Ni(II)-based chains.