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 | 36884-24-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 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
• 英文别名: 2,2,4,4,6,6,8,8-Octamethyl-1,9-dihydro-[1,3]oxazino[5,4-g][3,1]benzoxazine
• CAS: 36884-24-9
• 化学式: C₁₈H₂₈N₂O₂
• 分子量: 304.433
• InChiKey: CWZJFJFNUONQLB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  22
• 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：
  42.5
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  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 N-溴代丁二酰亚胺(NBS) 、 碳酸氢钠 、 sodium sulfate 作用下， 以 氯仿 为溶剂， 反应 1.2h， 以59.1 mg的产率得到
  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'-(4,6-diamino-m-phenylene)-bis-propan-2-ol 、 丙酮 在 silica gel 作用下， 以 正戊烷 为溶剂， 反应 8.0h， 以75%的产率得到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
  参考文献：
  名称：

  硅胶催化高效合成三环苯并二恶嗪

  摘要：

  报道了一种新的合成三环苯并双恶嗪的方法，该方法基于硅胶催化的两个3,1-恶嗪环的形成。形成恶嗪环的缩合反应的可逆性允许在苯并双恶嗪中进行硅胶催化的酮交换，因此能够获得苯并双恶嗪的非对称衍生物。

  DOI：

  10.1021/jo062670e

文献信息

• Rassat,A.; Sieveking,H.U., Angewandte Chemie, 1972, vol. 84, p. 353 - 354
  作者：Rassat,A.、Sieveking,H.U.

  DOI：——

  日期：——
• 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.
• Efficient Synthesis of Tricyclic Benzobisoxazines by Silica Gel Catalysis
  作者：Gaëlle Spagnol、Andrzej Rajca、Suchada Rajca

  DOI：10.1021/jo062670e

  日期：2007.3.1

  method for the synthesis of tricyclic benzobisoxazines, based upon silica gel-catalyzed formation of two 3,1-oxazine rings, is reported. The reversibility of the condensation reaction, forming an oxazine ring, allows for implementation of silica gel catalyzed ketone exchange in benzobisoxazine, thus enabling access to nonsymmetric derivatives of benzobisoxazines.

  报道了一种新的合成三环苯并双恶嗪的方法，该方法基于硅胶催化的两个3,1-恶嗪环的形成。形成恶嗪环的缩合反应的可逆性允许在苯并双恶嗪中进行硅胶催化的酮交换，因此能够获得苯并双恶嗪的非对称衍生物。