trans-4-azido-4'-(dimethylamino)stilbene

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: trans-4-azido-4'-(dimethylamino)stilbene
• 英文别名: 4-[(E)-2-(4-azidophenyl)ethenyl]-N,N-dimethylaniline
• 化学式: C₁₆H₁₆N₄
• 分子量: 264.33
• InChiKey: MNOBENXLZGOWGI-ONEGZZNKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  17.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  对硝基苯乙酸 在 哌啶 、 盐酸 、 sodium azide 、 氨 、 iron(II) sulfate 、 sodium nitrite 作用下， 以 乙醇 、 水 为溶剂， 反应 18.0h， 生成 trans-4-azido-4'-(dimethylamino)stilbene
  参考文献：
  名称：

  Photochemical Reactions of Nitroso Oxides at Low Temperatures:  The First Experimental Evidence for Dioxaziridines

  摘要：

  Several singlet nitroso oxides (3a-e) were generated by the thermal reaction of triplet nitrenes (2a-e) with triplet oxygen at. 95 K in 2-methyltetrahydrofuran. After photolysis of the nitroso oxides at 77 K using strong light intensities, the formation of intermediates was observed for the first rime. From spectroscopic, kinetic, and chemical arguments, we postulate the formation of the following dioxaziridines: 4-(dioxaziridin-yl)stilbene (4a), 4-(dioxaziridin-yl)-4'-nitrostilbene (4b), 4'-(dioxaziridin-yl)-4-(dimethylamino)st (4c), 4'-(dioxaziridin-yl)-4-aminobiphenyl (4d), and 4-(dioxaziridin-yl)-4'-(nitrene-substituted)stilbene (4f). All dioxaziridines observed are highly reactive species. At 77 K, they react thermally to form the corresponding nitro compounds (5). The velocity of the ring opening reaction of the dioxaziridines (4 --> 5) is not significantly influenced by substituents; the rate constants at 77 K are all equal to 0.0030 +/- 0.0005 s(-1). The transients were characterized by stationary UV/vis and/or ESR spectroscopy. Ab initio calculations of the thermal reaction of the nonsubstituted dioxaziridine (6) and N-phenyldioxaziridine (9) were performed. From this, it follows that dioxaziridines are experimentally observable species which are separated from the corresponding nitro products by an orbital symmetry-forbidden barrier.

  DOI：

  10.1021/ja9803660

文献信息

• Photochemical Reactions of Nitroso Oxides at Low Temperatures:  The First Experimental Evidence for Dioxaziridines
  作者：T. Harder、P. Wessig、J. Bendig、R. Stösser

  DOI：10.1021/ja9803660

  日期：1999.7.1

  Several singlet nitroso oxides (3a-e) were generated by the thermal reaction of triplet nitrenes (2a-e) with triplet oxygen at. 95 K in 2-methyltetrahydrofuran. After photolysis of the nitroso oxides at 77 K using strong light intensities, the formation of intermediates was observed for the first rime. From spectroscopic, kinetic, and chemical arguments, we postulate the formation of the following dioxaziridines: 4-(dioxaziridin-yl)stilbene (4a), 4-(dioxaziridin-yl)-4'-nitrostilbene (4b), 4'-(dioxaziridin-yl)-4-(dimethylamino)st (4c), 4'-(dioxaziridin-yl)-4-aminobiphenyl (4d), and 4-(dioxaziridin-yl)-4'-(nitrene-substituted)stilbene (4f). All dioxaziridines observed are highly reactive species. At 77 K, they react thermally to form the corresponding nitro compounds (5). The velocity of the ring opening reaction of the dioxaziridines (4 --> 5) is not significantly influenced by substituents; the rate constants at 77 K are all equal to 0.0030 +/- 0.0005 s(-1). The transients were characterized by stationary UV/vis and/or ESR spectroscopy. Ab initio calculations of the thermal reaction of the nonsubstituted dioxaziridine (6) and N-phenyldioxaziridine (9) were performed. From this, it follows that dioxaziridines are experimentally observable species which are separated from the corresponding nitro products by an orbital symmetry-forbidden barrier.