6,8-dibromobenzo-1,2,3,4-tetrazine 1,3-dioxide | 478189-82-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四嗪
• 英文名称: 6,8-dibromobenzo-1,2,3,4-tetrazine 1,3-dioxide
• 英文别名: 5,7-Dibromo-2,4-dioxido-1,2,3,4-benzotetrazine-2,4-diium
• CAS: 478189-82-1
• 化学式: C₆H₂Br₂N₄O₂
• 分子量: 321.915
• InChiKey: SWLIOPJKJFXTBM-UHFFFAOYSA-N

物化性质

• 沸点：
  501.7±46.0 °C(Predicted)
• 密度：
  2.61±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  76.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  6,8-dibromobenzo-1,2,3,4-tetrazine 1,3-dioxide 在 硫酸 、 1,3-二溴-1,3,5-三嗪-2,4,6-三酮 、 三氟乙酸 作用下， 反应 0.33h， 以80%的产率得到5,6,8-tribromobenzo-1,2,3,4-tetrazine 1,3-dioxide
  参考文献：
  名称：

  摘要：

  Benzo-1,2,3,4-tetrazine 1,3-dioxide (BTDO) and its derivatives were nitrated with HNO3/H2SO4 or HNO3/oleum and brominated with dibromoisocyanuric acid in CF3CO2H/H2SO4 (5 : 1) or H2SO4. The reactivity of positions in the benzene ring of this heterocyclic system as regards electrophilic substitution was found to change in the following order: 5 approximate to 7 > 8 > 6. Mono- and dinitro-BTDOs and mono- and polybromo-BTDOs were synthesized. Their structures were confirmed by H-1, C-13, and N-14 NMR spectra.

  DOI：

  10.1023/a:1021344300420
• 作为产物：
  描述：

  3,5-dibromo-2-(tert-butyl-NNO-azoxy)aniline 在 nitronium tetrafluoborate 、 硫酸 、 乙酸酐 作用下， 以 乙腈 为溶剂， 反应 0.58h， 生成 6,8-dibromobenzo-1,2,3,4-tetrazine 1,3-dioxide
  参考文献：
  名称：

  Generation of oxodiazonium ions 2. Synthesis of benzotetrazine-1,3-dioxides from 2-(tert-butyl-NNO-azoxy)-N-nitroanilines

  摘要：

  开发了一种合成苯并四嗪-1,3-二氧化物的新方法，该方法涉及 2-（叔丁基-NNO-氮氧）-N-硝基苯胺与 Ac2O/H2SO4 系统的反应。这种方法还被用于从 3-硝基氨基-4-苯基呋咱合成 [1,2,5]噁二唑并[3,4-c]噌啉-5-氧化物。这些反应的机理是，硝胺基团的氧原子乙酰化后形成中间体氧二氮离子，然后质子化和离子解离。然后，氧二氮离子与邻近的叔丁基-NNO-氮氧基或苯基发生分子内反应，形成相应的杂环系统。

  DOI：

  10.1007/s11172-011-0310-9

文献信息

• Annulated benzotetrazine 1,3-dioxides 2.* [1,2,5]Oxadiazolo[3,4-f ][1,2,3,4]benzotetrazine 1,3,7-trioxide
  作者：A. Yu. Tyurin、O. Yu. Smirnov、A. M. Churakov、Yu. A. Strelenko、V. A. Tartakovsky

  DOI：10.1007/s11172-006-0259-2

  日期：2006.2

  Thermolysis of 8-azido-7-nitrobenzotetrazine 1,3-dioxide led to benzotetrazine 1,3-dioxide annulated with the furoxan ring at the C(7)—C(8) bond. Complete assignment of the signals in the 13C NMR spectrum of the compound obtained was performed. Attempted syntheses of benzotetrazine 1,3-dioxides annulated with a furoxan ring at the C(6)—C(7) bond or two furoxan rings at the C(5)—C(6) and C(7)—C(8) bonds were unsuccessful.

  8-叠氮-7-硝基苯并四氮杂环1,3-二氧化物的热裂解导致了在C(7)—C(8)键处与呋喃环相连的苯并四氮杂环1,3-二氧化物的生成。对所获得化合物的13C NMR光谱信号进行了完整的归属。对在C(6)—C(7)键处与呋喃环相连或在C(5)—C(6)和C(7)—C(8)键处与两个呋喃环相连的苯并四氮杂环1,3-二氧化物的合成尝试均未成功。
• Generation of oxodiazonium ions 4. Nitramine O-alkyl derivatives in the synthesis of benzotetrazine-1,3-dioxides
  作者：M. S. Klenov、A. M. Churakov、Yu. A. Strelenko、V. A. Tartakovsky

  DOI：10.1007/s11172-011-0312-7

  日期：2011.10

  A new method for the synthesis of benzotetrazine-1,3-dioxides was developed from the 2-(tert-butyl-NNO-azoxy)-N-nitroaniline O-alkyl derivatives upon the action of strong acids (H2SO4, MeSO3H, CF3CO2H) or BF3·Et2O. A mechanism suggested for these reactions includes transformation of the N=N(O)OR group (R = Me, Pri) to the oxodiazonium ion (N=N=O)+, which intramolecularly reacts with the neighboring tert-butyl-NNO-azoxy group, furnishing the tetrazine-1,3-dioxide ring.

  在强酸（H2SO4、MeSO3H、CF3CO2H）或 BF3-Et2O 的作用下，从 2-（叔丁基-NNO-氮氧）-N-硝基苯胺 O-烷基衍生物中开发出一种合成苯并四嗪-1,3-二氧 化物的新方法。这些反应的机理包括：N=N(O)OR 基团（R=Me，Pri）转变成氧二氮离子（N=N=O）+，后者与邻近的叔丁基-NNO-氮氧基团发生分子内反应，生成四嗪-1,3-二氧化物环。
• Benzo-1,2,3,4-tetrazine 1,3-Dioxides: Synthesis and NMR Study
  作者：Aleksandr M. Churakov、Oleg Yu. Smirnov、Sema L. Ioffe、Yuri A. Strelenko、Vladimir A. Tartakovsky

  DOI：10.1002/1099-0690(200207)2002:14<2342::aid-ejoc2342>3.0.co;2-h

  日期：2002.7
• ——
  作者：O. Yu. Smirnov、A. M. Churakov、A. Yu. Tyurin、Yu. A. Strelenko、S. L. Ioffe、V. A. Tartakovsky

  DOI：10.1023/a:1021396317258

  日期：——

  Nucleophilic substitution in nitro- and bromobenzo-1,2,3,4-tetrazine 1,3-dioxides (BTDOs) was studied. In most cases, the bromo and nitro groups are replaced by methylamino, dimethylamino, azido, and methoxy groups without opening of the tetrazine ring. It was illustrated with the reactions of dibromo-BTDOs with sodium methoxide that the reactivity of positions 5 to 8 in their benzene ring as regards nucleophilic substitution changes in the following order: 6 > 8 > 7 > 5. The structures of the BTDOs obtained were confirmed by H-1, C-13, and N-14 NMR data.