3,6-bis-(1,2-pyrazol-1-yl)-1,2,4,5-tetrazine | 1612764-64-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 3,6-bis-(1,2-pyrazol-1-yl)-1,2,4,5-tetrazine
• 英文别名: bis-3,6-(pyrazol-1-yl)-1,2,4,5-tetrazine；bis-3,6-(pyrazolyl)1,2,4,5-tetrazine；3,6-bis(pyrazol-1-yl)-1,2,4,5-tetrazine；3,6-bis(pyrazolyl)-1,2,4,5-tetrazine；3,6-bis(1H-pyrazol-1-yl)-1,2,4,5-tetrazine；3,6-di(1H-pyrazol-1-yl)-1,2,4,5-tetrazine；3,6-Di(pyrazol-1-yl)-1,2,4,5-tetrazine
• CAS: 1612764-64-3
• 化学式: C₈H₆N₈
• 分子量: 214.189
• InChiKey: FXDUPTJKQSCLHD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.8
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  87.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,6-bis-(1,2-pyrazol-1-yl)-1,2,4,5-tetrazine 在 氨 作用下， 以 乙腈 为溶剂， 反应 0.25h， 生成 [iron(II)(3-amino-6-(pyrazol-1-yl)-1,2,4,5-tetrazine)₃](perchlorate)₂ acetonitrile monosolvate
  参考文献：
  名称：

  Energetic Chromophores: Low-Energy Laser Initiation in Explosive Fe(II) Tetrazine Complexes

  摘要：

  The synthesis and characterization of air stable Fe(II) coordination complexes with tetrazine and triazolo-tetrazine ligands and perchlorate counteranions have been achieved. Time-dependent density functional theory (TD-DFT) was used to model the structural, electrochemical, and optical properties of these materials. These compounds are secondary explosives that can be initiated with Nd:YAG laser light at lower energy thresholds than those of PETN. Furthermore, these Fe(II) tetrazine complexes have significantly lower sensitivity than PETN toward mechanical stimuli such as impact and friction. The lower threshold for laser initiation was achieved by altering the electronic properties of the ligand scaffold to tune the metal ligand charge transfer (MLCT) bands of these materials from the visible into the near-infrared region of the electromagnetic spectrum. Unprecedented decrease in both the laser initiation threshold and the mechanical sensitivity makes these materials the first explosives that are both safer to handle and easier to initiate than PETN with NIR lasers.

  DOI：

  10.1021/jacs.6b02155
• 作为产物：
  描述：

  吡唑 、 3,6-二(3,5-二甲基-1H-吡唑-1-基)-1,2,4,5-四嗪 以 乙腈 为溶剂， 反应 2.0h， 以50%的产率得到3,6-bis-(1,2-pyrazol-1-yl)-1,2,4,5-tetrazine
  参考文献：
  名称：

  Thermally Stable 3,6-Disubstituted 1,2,4,5-Tetrazines

  摘要：

  以 3,6-双-(3,5-二甲基吡唑-1-基)-1,2,4,5-四嗪和 3,6-二氯-1,2,4,5-四嗪为亲电体，通过亲核取代反应合成了几种 3,6-二取代的 1,2,4,5-四嗪。所有新化合物都通过 1H NMR、13C NMR 和振动光谱、质谱和元素分析（C、H、N）进行了表征。为了分析热稳定性，使用了差示扫描量热法（DSC）。尤其是对称的双-3,5-二氨基-1,2,4-三唑基取代衍生物显示出极高的热稳定性，最高温度可达 370 ℃。因此，我们测定了它的能量特性，并将其与己酮二苯乙烯（HNS）的能量特性进行了比较。低温 X 射线衍射测定了 3,6-双肼基-1,2,4,5-四嗪、3,6-二氯-1,2,4,5-四嗪和 3-氨基-6-(3,5-二氨基-1,2,4-三唑-1-基)-1,2,4,5-四嗪二水合物的晶体结构。

  DOI：

  10.5560/znb.2013-3237
• 作为试剂：
  描述：

  1,3,5-三甲氧基苯 、 tert-butyl (1-(ethylthio)-3-phenylpropyl)carbamate 在 2,2,2-三氟乙醇 、 3,6-bis-(1,2-pyrazol-1-yl)-1,2,4,5-tetrazine 、 氧气 作用下， 以 乙腈 为溶剂， 反应 20.0h， 以90%的产率得到tert-butyl (3-phenyl-1-(2,4,6-trimethoxyphenyl)propyl)carbamate
  参考文献：
  名称：

  s-四嗪染料：一种用于常规氧化的轻质氧化还原有机催化剂的产生。

  摘要：

  合成了一系列从s-四嗪衍生的有机染料，并对其光物理和电化学性质进行了系统的研究。在硫醚的模型氧化CS键裂解中测试这些化合物作为光氧化还原催化剂，已使我们发现了新型的活性s-四嗪类。而且，它们中的一些可以由市售的3，6-二氯四嗪原位形成，从而使得该光催化的CS键官能化简单且高度实用。

  DOI：

  10.1021/acs.joc.9b02454

文献信息

• Photoactive energetic materials
  申请人：LOS ALAMOS NATIONAL SECURITY, LLC.

  公开号：US09902748B2

  公开（公告）日：2018-02-27

  Energetic materials that are photoactive or believed to be photoactive may include a conventional explosive (e.g. PETN, nitroglycerine) derivatized with an energetic UV-absorbing and/or VIS-absorbing chromophore such as 1,2,4,5-tetrazine or 1,3,5-triazine. Absorption of laser light having a suitably chosen wavelength may result in photodissociation, decomposition, and explosive release of energy. These materials may be used as ligands to form complexes. Coordination compounds include such complexes with counterions. Some having the formula M(L)n2+ were synthesized, wherein M is a transition metal and L is a ligand and n is 2 or 3. These may be photoactive upon exposure to a laser light beam having an appropriate wavelength of UV light, near-IR and/or visible light. Photoactive materials also include coordination compounds bearing non-energetic ligands; in this case, the counterion may be an oxidant such as perchlorate.

  具有光活性或被认为具有光活性的活性材料可能包括与能量吸收紫外线和/或可见光色团（如1,2,4,5-四唑或1,3,5-三唑）衍生的传统爆炸物（例如PETN，硝化甘油）。吸收具有适当选择波长的激光光线可能导致光解、分解和爆炸释放能量。这些材料可以用作配体形成配合物。配位化合物包括具有对离子的这些配合物。一些具有M(L)n2+公式的化合物已经合成，其中M是过渡金属，L是配体，n为2或3。这些化合物在暴露于具有适当波长的紫外线、近红外和/或可见光的激光光束时可能具有光活性。光活性材料还包括携带非活性配体的配位化合物；在这种情况下，对离子可能是诸如高氯酸盐之类的氧化剂。
• Correlating the Structural, Electronic, and Explosive Sensitivity Properties of CuII Tetrazine Complexes
  作者：Thomas W. Myers、Kathryn E. Brown、David E. Chavez、R. Jason Scharff、Jacqueline M. Veauthier

  DOI：10.1002/ejic.201600344

  日期：2016.7

  tetrazine ligands and nitrate counter-anions have been achieved. The complexes adopt a variety of coordination geometries including monomeric and dimeric architectures with five and six coordinate CuII centers. The thermal stabilities of the complexes correlate to the strength of the Cu–nitrate interaction such that more strongly bound nitrates exhibit higher thermal stability. Exchanging amine groups

  已经实现了CuII与富氮四嗪配体和硝酸盐抗衡阴离子的爆炸性配位配合物的合成和表征。这些配合物采用多种配位几何结构，包括具有五个和六个坐标 CuII 中心的单体和二聚体结构。配合物的热稳定性与 Cu-硝酸盐相互作用的强度相关，因此结合力更强的硝酸盐表现出更高的热稳定性。将配位体上的胺基与 3,3'-二硝基氮杂环丁烷基团交换导致固态结构发生变化，并增加了所得配合物相对于相应胺衍生物的冲击敏感性。
• New green energetic materials based on unsymmetrically substituted pyrazole-tetrazines and their hydroperchlorates
  作者：Zhen-Li Yang、Zhen Wang、Wen-li Cao、Tong Li、Jun-Qing Yang、Jian-Guo Zhang

  DOI：10.1039/c9nj04519h

  日期：——

  Five novel nitrogen-rich energetic materials were synthesized using 3,6-bis(3,5-dimethyl-pyrazole-1-yl)-1,2,4,5-tetrazine (BT) and 3,6-bis(pyrazole-1-yl)-1,2,4,5-tetrazine as raw materials. The materials were comprehensively characterized by single-crystal X-ray diffraction, FT-IR, mass spectra and elemental analysis. The synthesized compounds show good experimental densities, ranging from 1.59 to

  使用3,6-双（3,5-二甲基-吡唑-1-基）-1,2,4,5-四嗪（BT）和3,6-双（吡唑-以1-yl）-1,2,4,5-四嗪为原料。通过单晶X射线衍射，FT-IR，质谱和元素分析对材料进行了全面表征。合成的化合物显示出良好的实验密度，范围为1.59至1.70 g cm -3。DSC技术用于分析热稳定性。五种高能材料的分解温度范围为204.0至276.5°C。计算了非等温动力学参数和地层焓值。另外，根据BAM方法进行了摩擦敏感性测量，结果表明这五种化合物可以归类为不敏感的高能材料。为了更好地理解电子结构特征，进一步计算了化合物1和2的静电势（ESP）和自然键轨道（NBO）。爆轰参数是通过EXPLO5 V6.04获得的。发现五种高能材料的爆炸速度在6436 ms的范围内-1至7759 ms -1，它们的爆炸压力在15.8 GPa和24.6 GPa之间。它们中的大多数表现出比TNT好得多的爆炸性能。
• Synthesis and Electrochemical Behavior of Electron‐Rich s‐Tetrazine and Triazolo‐tetrazine Nitrate Esters
  作者：Thomas W. Myers、Christopher J. Snyder、David E. Chavez、R Jason Scharff、Jacqueline M. Veauthier

  DOI：10.1002/chem.201601422

  日期：2016.7.18

  tetrazine explosives. At these potentials, electron‐rich tetrazines with either covalently bound or co‐dissolved nitrate ester groups are irreversibly reduced. Effectively, changes in the electronic structure of tetrazines affect their electrochemical response to the presence of nitrate ester groups. Thus, it may be possible to develop tetrazine‐based electrochemical sensors for the detection of specific

  我们已经制备了1,2,4,5-四嗪和1,2,4-三唑[4,3- b]的高能硝酸酯衍生物]-[1,2,4,5]-四嗪环系统作为模型化合物，用于研究在存在爆炸基团的情况下四嗪的电化学行为。相对于PETN（季戊四醇四硝酸酯），模型化合物显示出较低的热稳定性，但机械敏感性略有提高。富电子胺供体的存在导致四嗪氧化还原电势相对于先前报道的四嗪炸药发生阴极移动。在这些电势下，带有共价键合或共溶解的硝酸酯基团的富电子四嗪被不可逆地还原。有效地，四嗪的电子结构的变化会影响它们对硝酸酯基团存在的电化学反应。因此，
• PHOTOACTIVE ENERGETIC MATERIALS
  申请人：LOS ALAMOS NATIONAL SECURITY, LLC.

  公开号：US20160031767A1

  公开（公告）日：2016-02-04

  Energetic materials that are photoactive or believed to be photoactive may include a conventional explosive (e.g. PETN, nitroglycerine) derivatized with an energetic UV-absorbing and/or VIS-absorbing chromophore such as 1,2,4,5-tetrazine or 1,3,5-triazine. Absorption of laser light having a suitably chosen wavelength may result in photodissociation, decomposition, and explosive release of energy. These materials may be used as ligands to form complexes. Coordination compounds include such complexes with counterions. Some having the formula M(L) n 2+ were synthesized, wherein M is a transition metal and L is a ligand and n is 2 or 3. These may be photoactive upon exposure to a laser light beam having an appropriate wavelength of UV light, near-IR and/or visible light. Photoactive materials also include coordination compounds bearing non-energetic ligands; in this case, the counterion may be an oxidant such as perchlorate.