4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(piperidin-1-yl)pyrimidine | 357614-52-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(piperidin-1-yl)pyrimidine
• 英文别名: 4-(3,5-Diphenyl-1h-pyrazole-1-yl)-6-(piperidine-1-yl)-pyrimidine；4-(3,5-diphenylpyrazol-1-yl)-6-piperidin-1-ylpyrimidine
• CAS: 357614-52-9
• 化学式: C₂₄H₂₃N₅
• 分子量: 381.48
• InChiKey: LSJCRWOXLZDWCS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  46.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(piperidin-1-yl)pyrimidine 、 copper(ll) bromide 以 乙醇 为溶剂， 反应 0.5h， 以88%的产率得到
  参考文献：
  名称：

  带有4-（3,5-二苯基-1 H-吡唑-1-基）-6-（哌啶-1-基）的铜（II），铜（I，II）和铜（I）配合物的合成和结构嘧啶。铜（I）配合物的发光

  摘要：

  一系列的Cu（II），Cu（I，II）和Cu（I）卤化物配合物，[CuL 2 Br] 2 [Cu 2 Br 6 ]，[CuL 2 Br 2 ]，[Cu 2 L 2 Br 3 ] ·EtOH，[Cu 2 L 2 Br 3 ]·CHCl 3，[Cu 2 L 2 Cl 3 ]·MeCN，[Cu 2 L 2 Cl 3 ]·CHCl 3，[CuLCl]，[CuLBr]和[Cu 2 L 2 I 2 ]与4-（3,5-二苯基-1 H已经合成了-吡唑-1-基）-6-（哌啶-1-基）嘧啶（L）。通过CuBr 2与L在Cu：L = 1：1和1：2摩尔的条件下反应制得铜（II）化合物[CuL 2 Br] 2 [Cu 2 Br 6 ]和[CuL 2 Br 2 ]。室温下在EtOH溶液中的比率分别为。在[CuL 2 Br 2 ]的结构中，观察到N（哌啶）原子与π缺乏的嘧啶环之间存在双分子孤对相互作用。双核混合价溴化铜（I，II）化合物，[Cu

  DOI：

  10.1016/j.poly.2013.04.009
• 作为产物：
  描述：

  二苯甲酰基甲烷 、 4-肼基-6-(哌啶-1-基)嘧啶 以 乙醇 为溶剂， 反应 8.0h， 以69%的产率得到4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(piperidin-1-yl)pyrimidine
  参考文献：
  名称：

  Copper(II) complexes based on a new chelating 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(piperidin-1-yl)pyrimidine ligand: Synthesis and crystal structures. Lone pair–π, C–H···π, π–π and C–H···A (A=N, Cl) non-covalent interactions

  摘要：

  A new bidentate chelating pyrazolylpyrimidine ligand bearing a strong electron-donating substituent, i.e. 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(piperidin-1-yl) pyrimidine (L) (Scheme 1), has been synthesized and used to obtain the copper(II) complexes by reaction with CuCl2. The molar ratio Cu:L = 1: 2 leads to isolation of a complex having CuL2Cl2 empirical formula, while the molar ratio Cu:L = 1:1 gives a complex with CuLCl2 empirical formula. The crystal structure of L as well as the structures of both complexes were studied by single crystal X-ray diffraction. The crystal structure of CuL2Cl2 compound is formed by trans-[CuL2Cl2] mononuclear molecules. Surprisingly, in contrast to the previous compound having molecular structure, the crystal structure of CuLCl2 consists of mononuclear [CuL2Cl](+) complex cations and dinuclear [Cu2Cl6](2) anions. Thus, formula of CuLCl2 complex can be represented as [CuL2Cl](2)[Cu2Cl6]. In both complexes molecules of L adopt bidentate chelating coordination mode through N-2 atom of pyrazole and N-3 atom of pyrimidine rings forming five-membered CuN3C metallocycles. Owing to C-H center dot center dot center dot N interactions and pi-pi-stacking L molecules form 2D network. In the structure of trans-[CuL2Cl2] there exist double lone pair(N(piperidine))-pi(pyrimidine) interactions and C-H center dot center dot center dot Cl contacts resulting in the formation of 1D chains. Layered 2D structure of [CuL2Cl](2)[Cu2Cl6] results from C-H center dot center dot center dot Cl, C-H center dot center dot center dot pi and double lone pair (Cl([CuL2Cl](+) complex cation)-pi(pyrimidine) interactions. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2010.01.013

文献信息

• Temperature- and excitation wavelength-dependent emission in a manganese(<scp>ii</scp>) complex
  作者：Alexey S. Berezin、Katerina A. Vinogradova、Vladimir A. Nadolinny、Taisiya S. Sukhikh、Viktor P. Krivopalov、Elena B. Nikolaenkova、Mark B. Bushuev

  DOI：10.1039/c7dt04535b

  日期：——

  halogen-to-ligand charge transfer. The emission behavior of this complex is strongly temperature-dependent: upon cooling from 300 K down to 77 K, the intensity of emission considerably increases. The enhancement of the luminescence upon cooling is accompanied by the appearance of the vibrational structure. This complex is the first example of manganese(II) complexes demonstrating excitation wavelength-dependent emission

  单核锰（II）配合物，具有螯合的4-（3,5-二苯基-1 H-吡唑-1-基）-6-（哌啶-1-基）嘧啶配体（L），[MnL 2 Cl 2 ] ·高2O表示令人感兴趣的激发波长依赖性发射。取决于激发波长，络合物显示三个发射带，其最大波长为380 nm，440 nm和495 nm。380 nm和440 nm的发射源自π→π*和n→π*以配体为中心的跃迁。具有微秒寿命的长波495 nm发射与d–d跃迁和/或金属到配体以及卤素到配体的电荷转移有关。该复合物的发射行为在很大程度上取决于温度：从300 K冷却到77 K后，发射强度会大大增加。冷却时发光的增强伴随着振动结构的出现。这种复合物是锰的第一个例子（II）配合物，显示出激发波长相关的发射。
• Zinc(II) and cadmium(II) complexes based on 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(piperidin-1-yl)pyrimidine (L): Synthesis, structure, luminescence. Double lone pair–π interactions in the structure of ZnL2Cl2
  作者：Mark B. Bushuev、Katerina A. Vinogradova、Viktor P. Krivopalov、Elena B. Nikolaenkova、Natalia V. Pervukhina、Dmitrii Yu. Naumov、Marianna I. Rakhmanova、Evgenii M. Uskov、Lilia A. Sheludyakova、Aleksei V. Alekseev、Stanislav V. Larionov

  DOI：10.1016/j.ica.2011.03.007

  日期：2011.5

  coordination cores of metal atoms in the structures of ZnL2Cl2, CdL2Cl2·0.5Me2CO·1.5H2O and CdL2Cl2·0.5CHCl3·0.5H2O are the distorted cis-MN4Cl2 (M = Zn, Cd) octahedra. In the structure of ZnL2Cl2 double lone pair(N(piperidine))–π(pyrimidine) interactions were observed. The photoluminescent properties of L, ZnLCl2, CdLCl2, ZnL2Cl2 and CdL2Cl2 were studied in the solid state under the same experimental conditions

  一系列的锌（II）和镉（II）与4-（3,5-二苯基-1 H-吡唑-1-基）-6-（哌啶-1-基）嘧啶（L），ZnLCl 2的配合物， CdLCl 2，ZNL 2氯2，CDL 2氯2，CDL 2氯2 ·0.5Me 2 CO·1.5H 2 O和CDL 2氯2 ·0.5CHCl 3 ·0.5H 2 O，已经合成。在EtOH溶液中以M：L = 1：1的摩尔比获得化合物ZnLCl 2和CdLCl 2，而ZnL 2 Cl 2和CdL在EtOH / Me 2 CO混合物中以M：L = 1：3的摩尔比分离2 Cl 2。出人意料的是，尝试从EtOH / Me 2 CO混合物中结晶CdLCl 2可以得到具有1：2的金属与配体化学计量比，CdL 2 Cl 2 ·0.5Me 2 CO·1.5H 2 O的化合物单晶。化学计量比为1：1的复合物。同时，从Me 2 CO / CHCl 3混合物中结晶CdL 2 Cl 2，得到CdL
• Halide impact on emission of mononuclear copper(<scp>i</scp>) complexes with pyrazolylpyrimidine and triphenylphosphine
  作者：Katerina A. Vinogradova、Victor F. Plyusnin、Arkady S. Kupryakov、Marianna I. Rakhmanova、Natalia V. Pervukhina、Dmitrii Yu. Naumov、Lilia A. Sheludyakova、Elena B. Nikolaenkova、Viktor P. Krivopalov、Mark B. Bushuev

  DOI：10.1039/c3dt53040j

  日期：——

  A series of mononuclear heteroleptic copper(I) halide complexes, [CuL(PPh3)X] (X = Cl, Br, I), based on 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(piperidin-1-yl)pyrimidine (L) and triphenylphosphine, have been synthesized by reaction between CuX (X = Cl, Br, I), L and PPh3 in a molar ratio of 1/1/1 in MeCN solutions. The copper atom, showing the distorted tetrahedral environment, is bound by the N,N-chelating ligand L, triphenylphosphine and a halide ion. The complexes [CuL(PPh3)Cl] and [CuL(PPh3)Br] are isostructural. In CH2Cl2 solutions, L and the complexes [CuL(PPh3)X] (X = Cl, Br, I) display a luminescence band with λmax = 377 nm and a lifetime of 1.9 ns (ligand-based luminescence (LL*)). However, the complex [CuL(PPh3)I] has an additional weak luminescence band with λmax = 681 nm and a lifetime of 96 ns of 3MLCT origin. In the solid state, L shows the splitting of the luminescence band to λmax = 365 and 384 nm and a slight increase of the lifetime to 2.66 ns. Solid samples of the complexes [CuL(PPh3)X] demonstrate 3MLCT luminescence bands at 620 nm (X = Cl), 605 nm (X = Br) and 559 nm (X = I) with lifetimes in the range 3.6–11.2 μs, whereas the LL* band (377 nm) is absent. Quantum yields and rate constants of radiative and nonradiative processes were determined in CH2Cl2 solutions and in the solid state for all complexes. The luminescence quantum yield and lifetimes for the solid samples increase in the order [CuL(PPh3)Cl] < [CuL(PPh3)Br] < [CuL(PPh3)I]. This is due to the increase of radiative decay and simultaneous suppression of nonradiative decay. The complex [CuL(PPh3)I] shows a high quantum yield of 29.4% and an excited state lifetime of 11.2 μs.

  通过 CuX（X = Cl、Br、I）、L 和 PPh3 在 MeCN 溶液中以 1/1/1 的摩尔比发生反应，合成了一系列基于 4-(3,5-二苯基-1H-吡唑-1-基)-6-(哌啶-1-基)嘧啶（L）和三苯基膦的单核异极铜(I)卤化物配合物 [CuL(PPh3)X]（X = Cl、Br、I）。铜原子显示出畸变的四面体环境，并与 N,N-螯合配体 L、三苯基膦和卤离子结合。[CuL(PPh3)Cl]和[CuL(PPh3)Br]复合物结构相同。在 CH2Cl2 溶液中，L 和配合物 [CuL(PPh3)X]（X = Cl、Br、I）显示出一条发光带，λmax = 377 nm，寿命为 1.9 ns（配体发光（LL*））。然而，[CuL(PPh3)I] 复合物还有一个额外的弱发光带，λmax = 681 nm，寿命为 96 ns（3MLCT）。在固态下，L 显示发光带分裂为 λmax = 365 和 384 nm，寿命略微延长至 2.66 ns。复合物[CuL(PPh3)X]的固体样品在 620 nm（X = Cl）、605 nm（X = Br）和 559 nm（X = I）处显示出 3MLCT 发光带，寿命范围为 3.6-11.2 μs，而 LL* 发光带（377 nm）不存在。测定了所有复合物在 CH2Cl2 溶液和固态下辐射和非辐射过程的量子产率和速率常数。固体样品的发光量子产率和寿命按照 [CuL(PPh3)Cl] < [CuL(PPh3)Br] < [CuL(PPh3)I] 的顺序增加。这是由于辐射衰变的增加和非辐射衰变的同时抑制。复合物 [CuL(PPh3)I] 的量子产率高达 29.4%，激发态寿命为 11.2 μs。
• Copper(II) and copper(I) tetrafluoroborate complexes with 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(piperidin-1-yl)pyrimidine (L): Synthesis, structures and luminescence
  作者：Katerina A. Vinogradova、Viktor P. Krivopalov、Elena B. Nikolaenkova、Natalia V. Pervukhina、Dmitrii Yu. Naumov、Lilia A. Sheludyakova、Mark B. Bushuev

  DOI：10.1016/j.ica.2012.02.004

  日期：2012.5

  Copper(II) and copper(I) complexes, [(CuL2)-L-II(BF4)(2)]center dot 0.5H(2)O, [CuIL2](BF4)center dot 2MeCN and [CuIL2](BF4)center dot H2O, with 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(piperidin-1-yl)pyrimidine (L) have been synthesized. The compound [(CuL2)-L-II(BF4)(2)]center dot 0.5H(2)O was obtained in the M:L = 1: 1 and 1: 2 molar ratios in EtOH solutions. It represents an example of a complex containing coordinated BF4 anion. The Cu-F(BF3) distances, 1.964(2) and 2.000(2) angstrom, are the shortest for copper tetrafluoroborate complexes. The compounds [(CuL2)-L-I](BF4)center dot 2MeCN and [(CuL2)-L-I](BF4)center dot H2O were obtained in the M:L = 1: 1 and 1: 2 molar ratios in MeCN solutions. According to X-ray data, the molecules of L in the structures of [(CuL2)-L-II(BF4)(2)]center dot 0.5H(2)O and [(CuL2)-L-I](BF4)center dot 2MeCN are coordinated to the copper atoms through N-2(pyrazole) and N-3(pyrimidine) atoms. The complex [(CuL2)-L-I](BF4)center dot 2MeCN is unstable in the ambient air and transforms into [(CuL2)-L-I(BF4)]center dot H2O. The complex [(CuL2)-L-I](BF4)center dot H2O was found to display orange photoluminescence. (C) 2012 Elsevier B. V. All rights reserved.
• Synthesis and structures of copper(II), copper(I,II) and copper(I) complexes with 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(piperidin-1-yl)pyrimidine. Luminescence of copper(I) complexes
  作者：Katerina A. Vinogradova、Viktor P. Krivopalov、Elena B. Nikolaenkova、Natalia V. Pervukhina、Dmitrii Yu. Naumov、Mariana I. Rakhmanova、Evgenii G. Boguslavsky、Lilia A. Sheludyakova、Mark B. Bushuev

  DOI：10.1016/j.poly.2013.04.009

  日期：2013.7

  series of Cu(II), Cu(I,II) and Cu(I) halide complexes, [CuL2Br]2[Cu2Br6], [CuL2Br2], [Cu2L2Br3]·EtOH, [Cu2L2Br3]·CHCl3, [Cu2L2Cl3]·MeCN, [Cu2L2Cl3]·CHCl3, [CuLCl], [CuLBr] and [Cu2L2I2] with 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(piperidin-1-yl)pyrimidine (L) have been synthesized. Copper(II) compounds, [CuL2Br]2[Cu2Br6] and [CuL2Br2], were obtained by the reactions of CuBr2 with L in the Cu:L = 1:1 and

  一系列的Cu（II），Cu（I，II）和Cu（I）卤化物配合物，[CuL 2 Br] 2 [Cu 2 Br 6 ]，[CuL 2 Br 2 ]，[Cu 2 L 2 Br 3 ] ·EtOH，[Cu 2 L 2 Br 3 ]·CHCl 3，[Cu 2 L 2 Cl 3 ]·MeCN，[Cu 2 L 2 Cl 3 ]·CHCl 3，[CuLCl]，[CuLBr]和[Cu 2 L 2 I 2 ]与4-（3,5-二苯基-1 H已经合成了-吡唑-1-基）-6-（哌啶-1-基）嘧啶（L）。通过CuBr 2与L在Cu：L = 1：1和1：2摩尔的条件下反应制得铜（II）化合物[CuL 2 Br] 2 [Cu 2 Br 6 ]和[CuL 2 Br 2 ]。室温下在EtOH溶液中的比率分别为。在[CuL 2 Br 2 ]的结构中，观察到N（哌啶）原子与π缺乏的嘧啶环之间存在双分子孤对相互作用。双核混合价溴化铜（I，II）化合物，[Cu