3-(3,5-dimethylpyrazol-1-yl)-6-(piperidin-1-yl)-1,2,4,5-tetrazine

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 3-(3,5-dimethylpyrazol-1-yl)-6-(piperidin-1-yl)-1,2,4,5-tetrazine
• 英文别名: 3-(3,5-Dimethyl-pyrazol-1-yl)-6-(piperidin-1-yl)-1,2,4,5-tetrazine；3-(3,5-dimethylpyrazol-1-yl)-6-piperidin-1-yl-1,2,4,5-tetrazine
• 化学式: C₁₂H₁₇N₇
• 分子量: 259.314
• InChiKey: CMKSNYNBTZCIDW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  72.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3-(3,5-dimethylpyrazol-1-yl)-6-(piperidin-1-yl)-1,2,4,5-tetrazine 在 potassium tert-butylate 作用下， 以 异丙醇 为溶剂， 反应 0.75h， 以82%的产率得到
  参考文献：
  名称：

  Replacement of dimethylpyrazolyl group in 1,2,4,5-tetrazines by aliphatic alcohols and water

  摘要：

  Reactions of 3,6-bis(4-R-3,5-dimethyl-1H-pyrazol-1-yl)-1,2,4,5-tetrazines and 3-amino-6-(3,5-dimethyl-1H-pyrazol-1-yl)-1,2,4,5-tetrazines with aliphatic alcohols and water in the presence of a base involved replacement of the dimethylpyrazolyl group and resulted in the formation of mono- and dialkoxy-1,2,4,5-tetrazines and 6-substituted 3-hydroxy-1,2,4,5-tetrazines. Dissociation constants of the latter were determined by potentiometric titration.

  DOI：

  10.1134/s1070428009070197
• 作为产物：
  描述：

  在 dinitrogen tetraoxide 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 4.0h， 生成 3-(3,5-dimethylpyrazol-1-yl)-6-(piperidin-1-yl)-1,2,4,5-tetrazine
  参考文献：
  名称：

  The ‘inverse electron-demand' Diels–Alder reaction in polymer synthesis. Part 4.1 The preparation and crystal structures of some bis(1,2,4,5-tetrazines)

  摘要：

  3,6-双(3,5-二甲基吡唑基)-1,2,4,5-四嗪与 单胺和二胺会产生一个或多个亲核取代 两个吡唑基取代基，并在下与二胺反应 适当的条件可以产生双(3-氨基-1,2,4,5-四嗪)， 例如12a、12b和13。其中两个的晶体结构 (12a和13)显示了四嗪环和 氨基，但四嗪环和吡唑环之间没有。在 12a 有广泛的网络 N·H····· N个氢键。

  DOI：

  10.1039/a607646g

文献信息

• Synthesis, structures, and magnetic properties of crystals of dinuclear copper(II) and cobalt(II) complexes with 3-(3,5-dimethylpyrazol-1-yl)-6-R-1,2,4,5-tetrazines
  作者：E. V. Cherdantseva、D. V. Starichenko、P. A. Slepukhin、R. I. Ishmetova、Yu. N. Shvachko、A. V. Korolev、G. L. Rusinov、V. V. Ustinov、A. I. Matern、V. N. Charushin

  DOI：10.1007/s11172-010-0152-x

  日期：2010.4

  Dinuclear complexes of CuII with 3-(3,5-dimethylpyrazol-1-yl)-6-(2-hydroxyethylami-no)-1,2,4,5-tetrazine (1) and CoII with 3-(3,5-dimethylpyrazol-1-yl)-6-(piperidin-1-yl)-1,2,4,5- tetrazine (2) were synthesized and structurally characterized, and the magnetic (SQUID) and resonance (EPR) properties of van der Waals crystals based on these complexes were studied. Unusual behavior of the effective magnetic moment μeff(T) is observed at T < 60 K. A nonmonotonic increase in μeff(?) for 1 (s~6 %) and a 20% reduction of μeff(?) for 2 have a common origin and are due to the influence of spin-orbital coupling on the character of the splitting between the t2g and eg levels of the central ion. Distortions of the coordination site “switch on” a positive (1) or negative (2) contribution of the orbital magnetic moment near 6 K. Irreversible temperature behavior of μeff(T) in the heating and cooling regimes in the vicinity of 60 K suggests that the character of structural distortions and the magnetic properties are related to ligand geometry. This factor plays a significant role in crystal engineering of magnetoactive structures with polynitrogen ligands.

  研究人员合成了 CuII 与 3-(3,5-二甲基吡唑-1-基)-6-(2-羟乙基氨基)-1,2,4,5-四嗪 (1) 的双核配合物，以及 CoII 与 3-(3,5-二甲基吡唑-1-基)-6-(哌啶-1-基)-1,2,4,5-四嗪 (2) 的双核配合物、5- tetrazine (2) 进行了合成和结构表征，并研究了基于这些配合物的范德华晶体的磁性（SQUID）和共振（EPR）特性。1的μeff(?)非单调增加（s~6%）和2的μeff(?)减少20%有着共同的原因，都是由于自旋轨道耦合对中心离子的t2g和eg电平之间分裂特性的影响。配位位点的畸变在 6 K 附近 "开启 "了轨道磁矩的正（1）或负（2）贡献。μeff(T) 在 60 K 附近的加热和冷却状态下的不可逆温度行为表明，结构畸变的特征和磁性与配体的几何形状有关。这一因素在多氮配体磁活性结构的晶体工程中发挥着重要作用。
• Latosh; Rusinov; Ganebnykh, Russian Journal of Organic Chemistry, 1999, vol. 35, # 9, p. 1363 - 1371
  作者：Latosh、Rusinov、Ganebnykh、Chupakhin

  DOI：——

  日期：——
• On the composition of copper(II), cobalt(II), and nickel(II) complexes with some 3,6-disubstituted 1,2,4,5-tetrazines
  作者：E. V. Cherdantseva、A. V. Nesterova、A. I. Matern、L. Yu. Buldakova、M. Yu. Yanchenko、R. I. Ishmetova、G. L. Rusinov

  DOI：10.1134/s1070363210090240

  日期：2010.9

  Complex formation in the systems containing copper(II), cobalt(II) and nickel(II) ions (M) and 3(3,5-dimethylpyrazol-1-yl)-6-R-1,2,4,5-tetrazines (R = 2-hydroxyethylamino, piperidino) (L) was studied by voltammetry and spectrophotometry. Cu(II), Co(II) and Ni(II) were found to form complex compounds with derivatives of 1,2,4,5-tetrazine with the ratio of the components M:L = 1:1. The complex stability constants
• Replacement of dimethylpyrazolyl group in 1,2,4,5-tetrazines by aliphatic alcohols and water
  作者：R. I. Ishmetova、N. I. Latosh、I. N. Ganebnykh、N. K. Ignatenko、S. G. Tolshchina、G. L. Rusinov

  DOI：10.1134/s1070428009070197

  日期：2009.7

  Reactions of 3,6-bis(4-R-3,5-dimethyl-1H-pyrazol-1-yl)-1,2,4,5-tetrazines and 3-amino-6-(3,5-dimethyl-1H-pyrazol-1-yl)-1,2,4,5-tetrazines with aliphatic alcohols and water in the presence of a base involved replacement of the dimethylpyrazolyl group and resulted in the formation of mono- and dialkoxy-1,2,4,5-tetrazines and 6-substituted 3-hydroxy-1,2,4,5-tetrazines. Dissociation constants of the latter were determined by potentiometric titration.
• The ‘inverse electron-demand' Diels–Alder reaction in polymer synthesis. Part 4.1 The preparation and crystal structures of some bis(1,2,4,5-tetrazines)
  作者：Christopher Glidewell、Philip Lightfoot、Brodyck J. L. Royles、David M. Smith

  DOI：10.1039/a607646g

  日期：——

  Reaction of 3,6-bis(3,5-dimethylpyrazolyl)-1,2,4,5-tetrazine with mono- and di-amines gives rise to nucleophilic substitution of one or both of the pyrazolyl substituents, and reaction with diamines under appropriate conditions can lead to bis(3-amino-1,2,4,5-tetrazines), e.g. 12a, 12b and 13. The crystal structures of two of these (12a and 13) show electronic interaction between the tetrazine rings and the amino groups, but none between the tetrazine and pyrazole rings. In 12a there is an extensive network of N–H · · · N hydrogen bonds.

  3,6-双(3,5-二甲基吡唑基)-1,2,4,5-四嗪与 单胺和二胺会产生一个或多个亲核取代 两个吡唑基取代基，并在下与二胺反应 适当的条件可以产生双(3-氨基-1,2,4,5-四嗪)， 例如12a、12b和13。其中两个的晶体结构 (12a和13)显示了四嗪环和 氨基，但四嗪环和吡唑环之间没有。在 12a 有广泛的网络 N·H····· N个氢键。