12H-Benzophenoxazine-6,11-dione | 75197-84-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并恶嗪类
• 英文名称: 12H-Benzophenoxazine-6,11-dione
• 英文别名: 12H-benzo[b]phenoxazine-6,11-dione；12H-Benzo[b]phenoxazin-6,11-dion；12H-benzo[b]phenoxazine-6,11-dione
• CAS: 75197-84-1
• 化学式: C₁₆H₉NO₃
• 分子量: 263.252
• InChiKey: KUCAOPIGRFYVJV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  N-Tosylbenzophenoxazine-6,11-dione 在 硫酸 作用下， 反应 0.5h， 以95%的产率得到12H-Benzophenoxazine-6,11-dione
  参考文献：
  名称：

  Synthesis and Characterization of Novel Donor-Acceptor Naphthoquinone Derivatives with Photoinduced Charge-Transfer Properties. A Joint Experimental and Theoretical Study

  摘要：

  The synthesis of substituted benzo[b]phenoxazine-6,11-diones (7a-d) and their precursor N-tosyl derivatives (6a-d) is reported. The N-methylbenzo[b]phenoxazine-6,11-dione (8) and the analogous benzo[b]phenothiazine-6,11-dione (9) are also prepared. The UV-vis spectra of compounds 6, 7, and 9 show the existence of an intramolecular electronic transfer from the respective benzoxazine or benzothiazine donor fragments to the acceptor p-benzoquinone moiety. In agreement with this donor-acceptor character, the cyclic voltammograms of 7-9 exhibit two one-electron reduction waves to the corresponding radical-anion and dianion and two quasireversible oxidation peaks; however, the tosyl group in compounds 6 results in only one quasireversible oxidation wave at higher positive values. This causes a strong hypsochromic shift of the low-energy charge-transfer band. The molecular and electronic structures of compounds 6-8 are investigated using the semiempirical PM3 method and the nonempirical VEH approach, respectively. PM3 calculations predict that both the neutral and the reduced/oxidized compounds are nonplanar, the largest distortions from planarity being found for the most hindered N-tosylated derivatives 6. VEH calculations are used to rationalize the redox potentials and justify the low oxidation potentials measured for compounds 7 and 8. They also show the charge-transfer nature of the lowest-energy HOMO --> LUMO electronic transition, thus supporting the experimental UV-vis results. The higher oxidation potentials and blue-shifted absorption bands observed for compounds 6 are due to their highly distorted geometries which lead to a stabilization of the HOMO and a destabilization of the resulting cation-radical.

  DOI：

  10.1021/jo00122a054

文献信息

• Ullmann; Ettisch, Chemische Berichte, 1921, vol. 54, p. 271
  作者：Ullmann、Ettisch

  DOI：——

  日期：——
• Quinone chemistry. Reaction of 2,3-dichloro-1,4-naphthoquinone with 2-aminophenols in pyridine
  作者：Nand L. Agarwal、Wolfram Schaefer

  DOI：10.1021/jo01313a024

  日期：1980.12
• Synthesis and Characterization of Novel Donor-Acceptor Naphthoquinone Derivatives with Photoinduced Charge-Transfer Properties. A Joint Experimental and Theoretical Study
  作者：Beatriz Illescas、Nazario Martin、Jose L. Segura、C. Seoane、Enrique Orti、Pedro M. Viruela、Rafael Viruela

  DOI：10.1021/jo00122a054

  日期：1995.9

  The synthesis of substituted benzo[b]phenoxazine-6,11-diones (7a-d) and their precursor N-tosyl derivatives (6a-d) is reported. The N-methylbenzo[b]phenoxazine-6,11-dione (8) and the analogous benzo[b]phenothiazine-6,11-dione (9) are also prepared. The UV-vis spectra of compounds 6, 7, and 9 show the existence of an intramolecular electronic transfer from the respective benzoxazine or benzothiazine donor fragments to the acceptor p-benzoquinone moiety. In agreement with this donor-acceptor character, the cyclic voltammograms of 7-9 exhibit two one-electron reduction waves to the corresponding radical-anion and dianion and two quasireversible oxidation peaks; however, the tosyl group in compounds 6 results in only one quasireversible oxidation wave at higher positive values. This causes a strong hypsochromic shift of the low-energy charge-transfer band. The molecular and electronic structures of compounds 6-8 are investigated using the semiempirical PM3 method and the nonempirical VEH approach, respectively. PM3 calculations predict that both the neutral and the reduced/oxidized compounds are nonplanar, the largest distortions from planarity being found for the most hindered N-tosylated derivatives 6. VEH calculations are used to rationalize the redox potentials and justify the low oxidation potentials measured for compounds 7 and 8. They also show the charge-transfer nature of the lowest-energy HOMO --> LUMO electronic transition, thus supporting the experimental UV-vis results. The higher oxidation potentials and blue-shifted absorption bands observed for compounds 6 are due to their highly distorted geometries which lead to a stabilization of the HOMO and a destabilization of the resulting cation-radical.