6-bromobenzo-1,2,3,4-tetrazine 1,3-dioxide | 474658-14-5

• 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-bromobenzo-1,2,3,4-tetrazine 1,3-dioxide
• 英文别名: 6-Bromo-1,3-dioxido-1,2,3,4-benzotetrazine-1,3-diium
• CAS: 474658-14-5
• 化学式: C₆H₃BrN₄O₂
• 分子量: 243.019
• InChiKey: JHNFTYYAQXXJLN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  13
• 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-bromobenzo-1,2,3,4-tetrazine 1,3-dioxide 在 sodium azide 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.3h， 以88%的产率得到6-azido-benzotetrazine 1,3-dioxide
  参考文献：
  名称：

  摘要：

  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.

  DOI：

  10.1023/a:1021396317258
• 作为产物：
  描述：

  5-bromo-2-(tert-butyl-NNO-azoxy)phenyldiazonium tetrafluoroborate 在 过氧化氢苯甲酰 、 sodium acetate 作用下， 以 乙腈 为溶剂， 生成 6-bromobenzo-1,2,3,4-tetrazine 1,3-dioxide
  参考文献：
  名称：

  Benzo-1,2,3,4-tetrazine 1,3-Dioxides: Synthesis and NMR Study

  摘要：

  DOI：

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

文献信息

• New syntheses of [1,2,5]oxadiazolo[3,4-e][1,2,3,4]tetrazine 4,6-dioxide
  作者：V. P. Zelenov、A. A. Lobanova、S. V. Sysolyatin、N. V. Sevodina

  DOI：10.1134/s107042801303024x

  日期：2013.3

  New methods were developed for the synthesis of [1,2,5]oxadiazolo[3,4-e][1,2,3,4]tetrazine 4,6-dioxide from 4-(tert-butyl-NNO-azoxy)-N-nitro-1,2,5-oxadiazol-3-amine or its alkali metal salts and acid anhydrides (or chlorides) in the presence of strong acids. The yield of [1,2,5]oxadiazolo[3,4-e][1,2,3,4]tetrazine 4,6-dioxide in acetic anhydride in the presence of sulfuric acid or sulfuric anhydride

  新方法被用于合成开发[1,2,5]恶二唑并[3,4- ë ] [1,2,3,4]四嗪从4- 4,6-二氧化物（叔丁基- NNO -azoxy） -在强酸存在下的N-硝基-1,2,5-恶二唑-3-胺或其碱金属盐和酸酐（或氯化物）。在硫酸或硫酸酐存在下，于20°C，在乙酸酐中，[1,2,5]恶二唑并[3,4- e ] [1,2,3,4]四嗪4,6-二氧化物在乙酸酐中的产率20分钟达到83％。提出了研究反应的一般机理。在合成1,2,3,4-四嗪1,3-二氧化物和[1,2,5]恶二唑[3,4- e ]中，乙酰基首次作为离去基团从[ N- [4-（乙酰基-NNO - az氧基）-1，2，5-恶二唑-3-基]乙酰胺中以47％的收率获得] [1,2,3,4]四嗪4，6-二氧化物。
• Generation of oxodiazonium ions 2. Synthesis of benzotetrazine-1,3-dioxides from 2-(tert-butyl-NNO-azoxy)-N-nitroanilines
  作者：M. S. Klenov、V. P. Zelenov、A. M. Churakov、Yu. A. Strelenko、V. A. Tartakovsky

  DOI：10.1007/s11172-011-0310-9

  日期：2011.10

  A new method for the synthesis of benzotetrazine-1,3-dioxides was developed, which involves the reaction of 2-(tert-butyl-NNO-azoxy)-N-nitroanilines with the Ac2O/H2SO4 system. This method was also used for the synthesis of [1,2,5]oxadiazolo[3,4-c]cinnoline-5-oxide from 3-nitramino-4-phenylfurazan. The suggested mechanism of these reactions involves the formation of the intermediate oxodiazonium ion, resulting from acetylation of the oxygen atom of the nitramine group, followed by protonation and ionic dissociation. Then the oxodiazonium ion enters the intramolecular reaction with the neighboring tert-butyl-NNO-azoxy or phenyl group to form the corresponding heterocyclic systems.

  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。
• 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 annulated with tetraazapentalenes
  作者：A. Yu. Tyurin、A. M. Churakov、Yu. A. Strelenko、V. A. Tartakovsky

  DOI：10.1007/s11172-008-0028-5

  日期：2008.1

  New heterocyclic system, viz., 8,12-dehydro-8H,12H-[1,2,3]triazolo[2′,1′:1,2][1,2,3]triazolo-[4,5-f][1,2,3,4]benzotetrazine 2,4-dioxide, has been synthesized by thermolysis of 5-azido-6-(1,2,3-triazol-2-yl)benzotetrazine 1,3-dioxide, and its thermal stability and spectral properties have been studied.

  新的杂环系统，即8,12-dehydro-8H,12H-[1,2,3]triazolo[2′,1′:通过热解 5-叠氮-6-(1,2,3-三唑-2-基)苯并四嗪 1,3-二氧化物合成了 8,12-脱氢-8H,12H-[1,2,3]三唑并[2′,1′: 1,2,3]三唑并[4,5-f][1,2,3,4]苯并四嗪 2,4-二氧化物，并对其热稳定性和光谱特性进行了研究。
• ——
  作者：O. Yu. Smirnov、A. M. Churakov、Yu. A. Strelenko、S. L. Ioffe、V. A. Tartakovsky

  DOI：10.1023/a:1021344300420

  日期：——

  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.