bis(3-methylpyrazolyl)(5-methylpyrazolyl)methane | 255379-96-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: bis(3-methylpyrazolyl)(5-methylpyrazolyl)methane
• 英文别名: bis(3-methyl-1H-pyrazol-1-yl)(5-methyl-1H-pyrazol-1-yl)methane；bis(3-methyl-1-pyrazolyl)(5-methyl-1-pyrazolyl)methane；1-[Bis(3-methylpyrazol-1-yl)methyl]-5-methylpyrazole
• CAS: 255379-96-5
• 化学式: C₁₃H₁₆N₆
• 分子量: 256.31
• InChiKey: NIFXOKFDRVYUDH-UHFFFAOYSA-N

物化性质

• 沸点：
  421.3±45.0 °C(Predicted)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  53.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  bis(3-methylpyrazolyl)(5-methylpyrazolyl)methane 、 copper(ll) bromide 以 甲醇 为溶剂， 以72%的产率得到
  参考文献：
  名称：

  Synthesis, spectroscopic and structural characterization of Cu(II) derivatives of tris(pyrazol-1-yl)methanes

  摘要：

  The reaction between CuX2 (X = ClO4, NO3, Cl, Br and CH3COO) and excess of tris(pyrazol-1-yl)methane ligands L (L = CH(pz)(3). CH(4-Mepz)(3), CH(3,5-Me(2)pz)(3), CH(3,4,5-Me(3)pz)(3) or CH(3-Mepz)(2)(5-Mepz)) yields [CuX2(L)], [{CuX2}(3)(L-2)(2)] or [Cu(L-2)]X-2-type complexes. The ligand to metal ratio is dependent on the number and disposition of the Me substituents on the azole-type ligand and mainly on the nature of the counter-ion X. All complexes have been characterized in the solid state as well as in solution (IR and UV spectra, and conductivity determinations). The solid-state structures of [Cu{(3,5-Me(2)pz)(3)CH}(2)](NO3)(2), [Cu{(3,5-Me(2)pz)(3)CH}(2)](ClO4)(2).0.5H(2)O, [Cu{(3,4,5-Me(3)pz)(3)CH}(2)](NO3)(2).H2O, [Cu{(4-Mepz)(3)CH}(2)]Br-2.3H(2)O have been determined by single crystal X-ray studies. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(02)00772-7
• 作为产物：
  描述：

  3-甲基吡唑 、 氯仿 在 四丁基溴化铵 、 sodium carbonate 、 对甲苯磺酸 作用下， 以 水 、 甲苯 为溶剂， 反应 96.0h， 生成 bis(3-methylpyrazolyl)(5-methylpyrazolyl)methane 、 tris(3-methyl-1H-pyrazol-1-yl)methane
  参考文献：
  名称：

  Iron complexes of tris(pyrazolyl)ethane ligands methylated in the 3-, 4-, and 5-positions

  摘要：

  Four tris(pyrazolyl)ethane (tpe) ligands were synthesized from tris(pyrazolyl)methane (tpm) starting materials. The new tpe ligands differ only in the placement of methyl groups on the pyrazole rings. For each tpe ligand, the 2:1 complex with Fe(II) was readily synthesized and the structures were determined by X-ray crystallography and characterized more completely by Fe-57 Mossbauer spectroscopy, H-1 NMR, and UV-Vis spectroscopy. The complexes all contain Fe(II) in the low spin (LS) state at low temperatures, but differ in Fe-N bond lengths and spectroscopic parameters. Methyl groups in the 5-position of the pyrazoles of the tpe ligand close the bite of the ligand, strengthening the ligand field and shifting the visible absorbance band of the complex to higher energies. Methyls in the 4-position had almost no effect on the ligand, making the iron(II) complex almost indistinguishable from that of the parent tpe ligand. Methyl groups in the 3-position of the tpe ligand cause an opening of the bite of the ligand, which is evidenced by increased Fe-N bond lengths in the complex and a shift of the visible absorbance to lower energies. The complex with methyls in the 3-position also starts to display spin crossover behavior near room temperature, whereas the other tpe complexes do not. (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2014.08.046

文献信息

• An Example of Polynomial Expansion: The Reaction of 3(5)-Methyl-1H-Pyrazole with Chloroform and Characterization of the Four Isomers
  作者：Vera Silva、Artur Silva、Rosa Claramunt、Dionisia Sanz、Lourdes Infantes、Ángela Martínez-López、Felipe Reviriego、Ibon Alkorta、José Elguero

  DOI：10.3390/molecules24030568

  日期：——

  The reaction in phase-transfer catalyzed conditions of 3(5)-methyl-1H-pyrazole with chloroform affords four isomers 333, 335, 355 and 555 in proportions corresponding to the polynomial expansion (a + b)³, with a = 0.6 and b = 0.4, a and b being 3-methyl and 5-methyl proportions. The up (u) and down (d) conformation of the pyrazolyl rings with regard to the Csp³⁻H atom was established by X-ray crystallography

  在3（5）-甲基-1H-吡唑与氯仿的相转移催化条件下反应，得到四种异构体333、335、355和555，其比例对应于多项式膨胀（a + b）³，a = 0.6和b ＝ 0.4，a和b为3-甲基和5-甲基比例。吡唑基环相对于Csp³⁻H原子的上（u）和下（d）构象是通过X射线晶体学和结合溶液规和包括轨距在内的原子轨道的1 H-，13C-和15N-NMR建立的（GIAO）/ B3LYP / 6-311 ++ G（d，p）计算。进行了与三吡唑基甲烷的其他X射线结构的比较。
• Structural, Magnetic, and Mössbauer Spectral Study of the Electronic Spin-State Transition in [Fe{HC(3-Mepz)₂(5-Mepz)}₂](BF₄)₂
  作者：Daniel L. Reger、J. Derek Elgin、Elizabeth A. Foley、Mark D. Smith、Fernande Grandjean、Gary J. Long

  DOI：10.1021/ic901259e

  日期：2009.10.5

  the Fe−N bond distances average 1.99 Å, indicative of an almost fully low-spin iron(II) complex; the twist angle is only 1.3°, as expected for a complex with these Fe−N bond distances. The magnetic properties show that the complex undergoes a gradual change from low-spin iron(II) below 85 K to high-spin iron(II) at 400 K. The 4.2 to 60 K Mössbauer spectra correspond to a fully low-spin iron(II) complex

  复杂的[Fe HC（3- MePZ）2（5-MePZ）} 2 ]（BF 4）2（PZ =吡唑基环）已经准备由HC的反应（3-MePZ）2（5-MePZ）以Fe（BF 4）2 ·6H 2 O.在294和150获得的K固态结构显示一个扭曲的铁（II）八面体ñ 6螯合环施加的限制引起的偏差最大的协调环境。在294 K时，该复合物主要是高自旋的，Fe-N键的平均距离为2.14Å，该距离比纯高自旋铁（II）配合物的预期距离要短一些，因为存在高约80％的混合物自旋和20％低自旋铁（II）。在294 K时，吡唑基环从理想C 3 v处开始扭曲。对称平均仅2.2°，比以前在类似配合物中观察到的扭曲小得多。在150 K时，Fe-N键的平均距离为1.99Å，表明几乎完全为低自旋铁（II）络合物。正如对于具有这些Fe-N键距的复合物所预期的，扭曲角仅为1.3°。磁性表明复合物经历了从85 K以下的低自旋铁（II）到400