4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-(pyridin-2-yl)-6-methylpyrimidine | 1428770-01-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: 4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-(pyridin-2-yl)-6-methylpyrimidine
• 英文别名: 4-(3,5-Dimethyl-1h-pyrazol-1-yl)-6-methyl-2-(pyridin-2-yl)pyrimidine；4-(3,5-dimethylpyrazol-1-yl)-6-methyl-2-pyridin-2-ylpyrimidine
• CAS: 1428770-01-7
• 化学式: C₁₅H₁₅N₅
• 分子量: 265.318
• InChiKey: RGTNLKYJERQZOR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  56.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  copper(II) choride dihydrate 、 4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-(pyridin-2-yl)-6-methylpyrimidine 以 乙醇 为溶剂， 以56%的产率得到[Cu(4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-(pyridin-2-yl)-6-methylpyrimidine)Cl2]
  参考文献：
  名称：

  Mono-, di-, tetra- and heptanuclear copper(II) complexes with 4-(3,5-di-R-1H-pyrazol-1-yl)-6-methyl-2-(pyridin-2-yl)pyrimidines (R=H, Me): Syntheses, crystal structures and electrospray ionization mass spectrometry

  摘要：

  A series of mono- and oligonuclear copper(II) complexes with new hybrid NNN-tridentate 4-(1H-pyrazol-1-yl)-2-(pyridin-2-yl)pyrimidine ligands, 4-(1H-pyrazol-1-yl)-2-(pyridin-2-yl)-6-methylpyrimidine (L-1) and 4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-(pyridin-2-yl)-6-methylpyrimidine (L-2), have been synthesized. The reaction of CuCl2 with L-1 in EtOH in the 1: 1 metal-to-ligand molar ratio affords the mononuclear complex [(CuLCl2)-Cl-1]center dot 0.5H(2)O (1). An increase of the metal-to-ligand molar ratio up to 4: 1 as well as the use of less polar mixed solvent, EtOH/CHCl3, leads to mononuclear complex [(CuLCl2)-Cl-1] (2). Attempts to crystallize di- or oligonuclear copper(II) complex with L-1 (the 8:1 metal-to-ligand molar ratio, EtOH/CHCl3) resulted in the formation of ionic halocuprate compound, [(CuL14Cl12)-L-7][Cu2Cl6] (3), containing unique heptanuclear cation, [(CuL4Cl12)-L-7-Cl-1](2+), and dinuclear anion [Cu2Cl6](2) . The reaction of CuCl2 with L-2 in EtOH in the 1:1 metal-to-ligand molar ratio affords mononuclear complex [CuL2Cl2] (4). Di- and tetranuclear complexes, [Cu2L2Cl4] (5) and [(Cu4L2Cl8)-Cl-2] (6), can be crystallized from ethanolic solution when the 2: 1 metal-to-ligand molar ratio is used. The former is the product of kinetic control, while the latter is that of thermodynamic one. Being coordinated, the molecules of L-1 and L-2 adopt tridentate chelating coordination mode binding copper atoms through pyrazolyl N-2, pyrimidine N-3 and pyridinyl N atoms and forming thus two five-membered chelate rings (CuN3C and CuN2C2). Depending on the metal-to-ligand molar ratio in the solution, electrospray ionization mass spectrometry (ESI-MS) evidenced the presence of mono- and oligonuclear copper species in the CuCl2-L-1 and CuCl2-L-2 solutions. The isolation of oligonuclear species in the solid state seems to be related with the absence of hydrogen-bond donor groups in the molecules of 4-(1H-pyrazol-1-yl)-2-(pyridin-2-yl) pyrimidine ligands. (C) 2012 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.ica.2012.10.018
• 作为产物：
  描述：

  3,5-二甲基吡唑 、 4-氯-6-甲基-2-(2-吡啶)嘧啶 在 caesium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 15.0h， 以34%的产率得到4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-(pyridin-2-yl)-6-methylpyrimidine
  参考文献：
  名称：

  Mono-, di-, tetra- and heptanuclear copper(II) complexes with 4-(3,5-di-R-1H-pyrazol-1-yl)-6-methyl-2-(pyridin-2-yl)pyrimidines (R=H, Me): Syntheses, crystal structures and electrospray ionization mass spectrometry

  摘要：

  A series of mono- and oligonuclear copper(II) complexes with new hybrid NNN-tridentate 4-(1H-pyrazol-1-yl)-2-(pyridin-2-yl)pyrimidine ligands, 4-(1H-pyrazol-1-yl)-2-(pyridin-2-yl)-6-methylpyrimidine (L-1) and 4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-(pyridin-2-yl)-6-methylpyrimidine (L-2), have been synthesized. The reaction of CuCl2 with L-1 in EtOH in the 1: 1 metal-to-ligand molar ratio affords the mononuclear complex [(CuLCl2)-Cl-1]center dot 0.5H(2)O (1). An increase of the metal-to-ligand molar ratio up to 4: 1 as well as the use of less polar mixed solvent, EtOH/CHCl3, leads to mononuclear complex [(CuLCl2)-Cl-1] (2). Attempts to crystallize di- or oligonuclear copper(II) complex with L-1 (the 8:1 metal-to-ligand molar ratio, EtOH/CHCl3) resulted in the formation of ionic halocuprate compound, [(CuL14Cl12)-L-7][Cu2Cl6] (3), containing unique heptanuclear cation, [(CuL4Cl12)-L-7-Cl-1](2+), and dinuclear anion [Cu2Cl6](2) . The reaction of CuCl2 with L-2 in EtOH in the 1:1 metal-to-ligand molar ratio affords mononuclear complex [CuL2Cl2] (4). Di- and tetranuclear complexes, [Cu2L2Cl4] (5) and [(Cu4L2Cl8)-Cl-2] (6), can be crystallized from ethanolic solution when the 2: 1 metal-to-ligand molar ratio is used. The former is the product of kinetic control, while the latter is that of thermodynamic one. Being coordinated, the molecules of L-1 and L-2 adopt tridentate chelating coordination mode binding copper atoms through pyrazolyl N-2, pyrimidine N-3 and pyridinyl N atoms and forming thus two five-membered chelate rings (CuN3C and CuN2C2). Depending on the metal-to-ligand molar ratio in the solution, electrospray ionization mass spectrometry (ESI-MS) evidenced the presence of mono- and oligonuclear copper species in the CuCl2-L-1 and CuCl2-L-2 solutions. The isolation of oligonuclear species in the solid state seems to be related with the absence of hydrogen-bond donor groups in the molecules of 4-(1H-pyrazol-1-yl)-2-(pyridin-2-yl) pyrimidine ligands. (C) 2012 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.ica.2012.10.018

文献信息

• Hysteretic spin crossover in isomeric iron(<scp>ii</scp>) complexes
  作者：Mark B. Bushuev、Viktor P. Krivopalov、Elena B. Nikolaenkova、Katerina A. Vinogradova、Yuri V. Gatilov

  DOI：10.1039/c8dt02223b

  日期：——

  Two mononuclear iron(II) complexes with isomeric N,N,N-tridentate pyrimidine-based ligands were synthesized. Both complexes show reproducible hysteretic spin crossover. Low spin state to high spin state switching is cooperative due to autocatalysis.

  合成了具有同分异构的N，N，N-三齿嘧啶基配体的两个单核铁（II）配合物。两种配合物均显示出可重现的滞后自旋交叉。低自旋状态到高自旋状态的切换由于自身催化而协同进行。
• A mononuclear iron(<scp>ii</scp>) complex: cooperativity, kinetics and activation energy of the solvent-dependent spin transition
  作者：Mark B. Bushuev、Denis P. Pishchur、Vladimir A. Logvinenko、Yuri V. Gatilov、Ilya V. Korolkov、Inna K. Shundrina、Elena B. Nikolaenkova、Viktor P. Krivopalov

  DOI：10.1039/c5dt03750f

  日期：——

  K up to 145 K. The reproducible hysteresis loop of 145 K is the widest ever reported one for a spin crossover complex. The phase 1A/LS combines the outstanding spin crossover properties with thermal robustness allowing for multiple cycling in sealed ampoules without degradation. The kinetics of the 1A/LS → 1A/HS transition is sigmoidal which is indicative of strong cooperative interactions. The cooperativity

  系统[FeL 2 ]（BF 4）2（1）–EtOH–H 2 O（L为4-（3,5-二甲基-1 H-吡唑-1-基）-2-（吡啶-2-基）-6-甲基嘧啶）在复合物[FeL 2 ]（BF 4）2的溶剂化物和多晶型的相对稳定性之间显示出复杂的平衡。新solvatomorphs，1个LS ·乙醇· ħ 2 ö和β- 1个LS · X ^ h 2 Ó，是在该系统中分离出来。他们被转换为四个子阶段，即1A / LS，1 D / LS，1 E / LS · y EtOH· z H 2 O和1 F / LS。在密封的安瓿，各相的热循环1个LS ·乙醇·ħ 2 ö和β-1个LS · X ^ h 2 ö转变成无水相位1个A / LS。对于磁滞回线宽度1个A / LS ↔1 A / HS自旋转变取决于安瓿中的水和乙醇含量，且变化范围约为 30 K到145K。可重现的145 K磁滞回线是自旋交联复合体中最广泛报道的磁滞回线。相位1
• Unprecedented bistability domain and interplay between spin crossover and polymorphism in a mononuclear iron(ii) complex
  作者：Mark B. Bushuev、Vasiliy A. Daletsky、Denis P. Pishchur、Yuri V. Gatilov、Ilya V. Korolkov、Elena B. Nikolaenkova、Viktor P. Krivopalov

  DOI：10.1039/c3dt53440e

  日期：——

  A mononuclear complex, [FeL2](BF4)2·xH2O (1LS·xH2O), where L is 4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-(pyridin-2-yl)-6-methylpyrimidine, can be converted into several phases showing different spin crossover regimes. In the first heating 1LS·xH2O loses water molecules and converts into a mixture of two high spin phases, 1A/HS and 1C/HS. Further cycling produces the low spin phase 1A/LS. The transition 1A/LS ↔ 1A/HS is accompanied by a 130 K wide hysteresis loop (Tc↑ = 490 K, Tc↓ = 360 K). Annealing the complex 1LS·xH2O at 500 K yields a high spin phase 1C/HS. The phase 1C/HS undergoes spin conversion to the corresponding low spin phase 1C/LS on cooling, T1/2 ≈ 320 K. Dehydration of 1LS·xH2O at 370 or 400 K yields a certain low spin phase, 1X/LS, which irreversibly transforms into a high spin phase 1B/HS, which, in turn, reversibly transforms to the low spin phase 1B/LS on cooling, T1/2 ≈ 320 K.

  一个单核复合物 [FeL2](BF4)2·xH2O (1LS·xH2O)，其中 L 为 4-(3,5-二甲基-1H-吡唑-1-基)-2-(吡啶-2-基)-6-甲基嘧啶，可以转变为几种不同自旋交叉状态的相。在第一次加热中，1LS·xH2O 失去水分子并转变为两种高自旋相的混合物，1A/HS 和 1C/HS。进一步的循环产生低自旋相 1A/LS。转变 1A/LS ↔ 1A/HS 伴随有一个宽度为 130 K 的滞回环（Tc↑ = 490 K, Tc↓ = 360 K）。在 500 K 下退火复合物 1LS·xH2O 可得到高自旋相 1C/HS。相 1C/HS 在冷却时经历自旋转换，变为相应的低自旋相 1C/LS，T1/2 ≈ 320 K。在 370 或 400 K 下脱水 1LS·xH2O 会得到某种低自旋相 1X/LS，该相不可逆转变为高自旋相 1B/HS，后者在冷却时又可逆转变为低自旋相 1B/LS，T1/2 ≈ 320 K。
• Spin crossover in iron(II) hexafluorophosphate complexes with 2-(pyridin-2-yl)-4-(3,5-di-R-1H-pyrazol-1-yl)-6-methylpyrimidines
  作者：Mark B. Bushuev、Katerina A. Vinogradova、Yuri V. Gatilov、Ilya V. Korolkov、Elena B. Nikolaenkova、Viktor P. Krivopalov

  DOI：10.1016/j.ica.2017.08.006

  日期：2017.10

  bonds. In the stricture of [FeL(Me,Me)2](PF6)2·nH2O the cations and anions are assembled into a 3D network via CH…F hydrogen bonds and lone pair…π interactions. Both complexes demonstrate high thermal stability. Under vacuum, the complex [FeL(Me,Me)2](PF6)2·nH2O is predominantly in the low spin state below 400 K, but at higher temperatures it shows gradual spin state switching which remains incomplete

  具有N，N，N-三齿配体，2-（吡啶-2-基）-4-（1H-吡唑-1-基）-6-甲基嘧啶（L（H，H））的六氟磷酸铁（II）配合物通过使FeCl2·4H2O（NBu4）反应合成2-（吡啶-2-基）-4-（3,5-二甲基-1H-吡唑-1-基）-6-甲基嘧啶（L（Me，Me）） PF6和L（H，H）或L（Me，Me）在酒精介质中。[FeL（H，H）2]（PF6）2·nH2O的超分子3D结构由CH…π相互作用，π…π堆积和CH…F氢键组成。在[FeL（Me，Me）2]（PF6）2·nH2O的约束下，阳离子和阴离子通过CH…F氢键和孤对…π相互作用组装成3D网络。两种配合物均显示出高的热稳定性。在真空下，复合物[FeL（Me，Me）2]（PF6）2·nH2O主要处于低于400 K的低自旋状态，但在较高温度下，它显示出逐渐的自旋状态转换，即使在495 K时也保持不完全。在真空中或在第一次加热运行的密
• Mono-, di-, tetra- and heptanuclear copper(II) complexes with 4-(3,5-di-R-1H-pyrazol-1-yl)-6-methyl-2-(pyridin-2-yl)pyrimidines (R=H, Me): Syntheses, crystal structures and electrospray ionization mass spectrometry
  作者：Mark B. Bushuev、Yuri V. Gatilov、Elena B. Nikolaenkova、Vladimir G. Vasiliev、Viktor P. Krivopalov

  DOI：10.1016/j.ica.2012.10.018

  日期：2013.1

  A series of mono- and oligonuclear copper(II) complexes with new hybrid NNN-tridentate 4-(1H-pyrazol-1-yl)-2-(pyridin-2-yl)pyrimidine ligands, 4-(1H-pyrazol-1-yl)-2-(pyridin-2-yl)-6-methylpyrimidine (L-1) and 4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-(pyridin-2-yl)-6-methylpyrimidine (L-2), have been synthesized. The reaction of CuCl2 with L-1 in EtOH in the 1: 1 metal-to-ligand molar ratio affords the mononuclear complex [(CuLCl2)-Cl-1]center dot 0.5H(2)O (1). An increase of the metal-to-ligand molar ratio up to 4: 1 as well as the use of less polar mixed solvent, EtOH/CHCl3, leads to mononuclear complex [(CuLCl2)-Cl-1] (2). Attempts to crystallize di- or oligonuclear copper(II) complex with L-1 (the 8:1 metal-to-ligand molar ratio, EtOH/CHCl3) resulted in the formation of ionic halocuprate compound, [(CuL14Cl12)-L-7][Cu2Cl6] (3), containing unique heptanuclear cation, [(CuL4Cl12)-L-7-Cl-1](2+), and dinuclear anion [Cu2Cl6](2) . The reaction of CuCl2 with L-2 in EtOH in the 1:1 metal-to-ligand molar ratio affords mononuclear complex [CuL2Cl2] (4). Di- and tetranuclear complexes, [Cu2L2Cl4] (5) and [(Cu4L2Cl8)-Cl-2] (6), can be crystallized from ethanolic solution when the 2: 1 metal-to-ligand molar ratio is used. The former is the product of kinetic control, while the latter is that of thermodynamic one. Being coordinated, the molecules of L-1 and L-2 adopt tridentate chelating coordination mode binding copper atoms through pyrazolyl N-2, pyrimidine N-3 and pyridinyl N atoms and forming thus two five-membered chelate rings (CuN3C and CuN2C2). Depending on the metal-to-ligand molar ratio in the solution, electrospray ionization mass spectrometry (ESI-MS) evidenced the presence of mono- and oligonuclear copper species in the CuCl2-L-1 and CuCl2-L-2 solutions. The isolation of oligonuclear species in the solid state seems to be related with the absence of hydrogen-bond donor groups in the molecules of 4-(1H-pyrazol-1-yl)-2-(pyridin-2-yl) pyrimidine ligands. (C) 2012 Elsevier B. V. All rights reserved.