bis[2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyl]amine | 85650-01-7

• 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[2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyl]amine
• 英文别名: bis[2-(3,5-dimethylpyrazol-1-yl)ethyl]amine；bis<2-(3,5-dimethyl-1-pyrazolyl)ethyl>amine；2-(3,5-dimethylpyrazol-1-yl)-N-[2-(3,5-dimethylpyrazol-1-yl)ethyl]ethanamine
• CAS: 85650-01-7
• 化学式: C₁₄H₂₃N₅
• 分子量: 261.37
• InChiKey: AZQZJVVZBGCHSV-UHFFFAOYSA-N

物化性质

• 熔点：
  81.5-82 °C(Solv: benzene (71-43-2); hexane (110-54-3))
• 沸点：
  415.3±45.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  47.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  bis[2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyl]amine 在 硫酸 、 碘 、 碘酸 作用下， 以 溶剂黄146 为溶剂， 以58%的产率得到bis[2-(4-iodo-3,5-dimethylpyrazol-1-yl)ethyl]amine
  参考文献：
  名称：

  在超碱性介质中简便合成柔性双（吡唑-1-基）烷烃和相关配体

  摘要：

  柔性配体 1,3-双(吡唑-1-基)丙烷、双[2-(吡唑-1-基)乙基]醚和双[2-(3,5-二甲基吡唑-1-基)乙基]胺由吡唑与 1,3-二溴丙烷、双（2-氯乙基）醚或双（2-氯乙基）胺盐酸盐在超碱性介质（二甲亚砜/氢氧化钾）中反应的简便方法制备。双(2-氯乙基)胺和吡唑的反应出人意料地产生了1,4-双[2-(吡唑-1-基)乙基]哌嗪。通过在乙酸中用 I2/HIO3/H2SO4 氧化碘化制备相应的 4,4'-二碘取代的双（吡唑）衍生物。一些制备的化合物的 Vilsmeier-Haak 甲酰化产生相应的二醛。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

  DOI：

  10.1002/ejoc.200700353
• 作为产物：
  描述：

  3,5-二甲基吡唑 、 二(2-氯乙基)胺盐酸盐 在 sodium 作用下， 以 乙醇 为溶剂， 反应 13.0h， 以64%的产率得到bis[2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyl]amine
  参考文献：
  名称：

  基于7-硝基苯-2-氧杂-1,3-二唑的高灵敏性和选择性开启化学传感器，用于细胞内应用的铜（ii）离子，无细胞毒性†

  摘要：

  7-硝基苯-2-氧杂-1,3-二唑（NBD）衍生的开启式荧光探针（1）在存在其他金属离子的情况下与Cu 2+离子具有可逆结合，荧光强度增加约20倍。表观缔合常数（ķ一对Cu）2+被发现是2.62×10 4中号-1。化学传感器1在HeLa细胞上的细胞内Cu 2+成像行为通过荧光显微镜研究表明，与1个细胞温育后，外源Cu 2+会显示出强烈的荧光被引入细胞。因此，该探针具有易用性，对MeCN–中的Cu 2+具有高灵敏度和选择性的特点高氧2 （1：1，v / v）具有细胞成像的可能性，而没有或可忽略的细胞毒性。

  DOI：

  10.1039/c3ob27405e

文献信息

• A novel copper(<scp>ii</scp>) complex as a nitric oxide turn-on fluorosensor: intracellular applications and DFT calculation
  作者：Rabiul Alam、Tarun Mistri、Pallab Mondal、Dipankar Das、Sushil Kumar Mandal、Anisur Rahman Khuda-Bukhsh、Mahammad Ali

  DOI：10.1039/c3dt52521j

  日期：——

  We report, herein, the development of an easily synthesizable novel dansyl-based turn-on NO sensor L2. The UV-Vis titration data of L2 with Cu2+ display a gradual increase in absorbance at 418 nm with [Cu2+], which were analyzed by using a non-linear least-squares computer-fit program yielding K = (1.16 ± 0.36) × 106 M−1 and n = (1.28 ± 0.03) indicating a 1 : 1 complexation. The ground state geometries of L2 as well as its complex [Cu(L2)Cl]+ (1) were optimized by DFT calculations which showed that in complex 1 the central metal ion is in distorted tetrahedral geometry with bond distances very close to those found in analogous Cu2+ complexes. The fluorescence of L2 was dramatically quenched (∼60-fold) through complexation with paramagnetic Cu2+ to form [Cu(L2)Cl]+ in MeCN–H2O (9 : 1, v/v) at pH 7.2 in HEPES buffer, which on further treatment with Angeli's salt (Na2N2O3) restores its fluorescence property by ∼15-fold due to the reduction of Cu2+ to Cu+ by NO generated in solution from Na2N2O3. The lifetime measurements displayed a substantial decrease in the lifetime of free ligand L2 (τ0 = 12 ns) on complexation with Cu2+ (τ0 = 2.1 ns). The detection limit of NO calculated by the 3σ method gives a value of 1.6 nM. The NO induced fluorescence enhancement of [CuII(L2)Cl]+ was due to the reduction of [CuII(L2)Cl]+ (1) to [CuI(L2)]+ (2) and is supported by the disappearance of the d–d transition band at 850 nm as well as the X-band EPR signal of 1. The selective “turn on” fluorogenic behavior of L2 was examined on HeLa cells of human cervical cancer origin by fluorescence microscopy which showed very intense intracellular fluorescence that was strongly suppressed by the addition of Cu2+ but it regains its fluorescence property on further incubation with Angeli's salt (Na2N2O3). The existence of [CuII(L2)Cl]+ and [CuI(L2)]+ in solution was confirmed by ESI-MS+ (m/z) analysis. The effect of different biologically relevant cations and anions on the fluorescence property of L2 indicates that it was only the [CuII(L2)Cl]+ which displayed high selectivity for NO, indicating its suitability for intracellular application without much worry about its cytotoxicity in a specified dose.

  本文报道了一种易于合成的新型丹磺酰基NO开启传感器L2的开发。L2与Cu2+的紫外-可见滴定数据显示，在波长418 nm处吸收逐渐增加，与Cu2+浓度相关，通过非线性最小二乘计算机拟合程序分析，得到K = (1.16 ± 0.36) × 106 M−1和n = (1.28 ± 0.03)，表明形成了1:1的配合物。通过DFT计算优化了L2及其配合物[Cu(L2)Cl]+ (1)的基态几何结构，结果显示在配合物1中，中心金属离子呈扭曲的四面体几何结构，键长与类似Cu2+配合物中发现的键长非常接近。L2的荧光在甲腈-水(9:1, v/v)中与顺磁性Cu2+形成[Cu(L2)Cl]+时被显著淬灭(约60倍)，在HEPES缓冲液中pH 7.2下，进一步与Angeli盐(Na2N2O3)处理后恢复其荧光性质约15倍，这是由于溶液中由Na2N2O3生成的NO将Cu2+还原为Cu+。寿命测量显示，自由配体L2(τ0 = 12 ns)与Cu2+结合后寿命显著减少(τ0 = 2.1 ns)。通过3σ方法计算的NO检测限为1.6 nM。[CuII(L2)Cl]+的荧光增强是由NO诱导的[CuII(L2)Cl]+ (1)还原为[CuI(L2)]+ (2)，这通过850 nm处d–d跃迁带的消失以及X波段EPR信号的消失得到支持。通过荧光显微镜在源自人类宫颈癌的HeLa细胞上检查了L2的选择性“开启”荧光行为，结果显示强烈的细胞内荧光，在加入Cu2+后被强烈抑制，但在进一步与Angeli盐(Na2N2O3)孵育后恢复其荧光性质。通过ESI-MS+ (m/z)分析确认了溶液中[CuII(L2)Cl]+和[CuI(L2)]+的存在。不同生物相关阳离子和阴离子对L2荧光性质的影响表明，只有[CuII(L2)Cl]+对NO显示出高选择性，表明其在特定剂量下适合细胞内应用，无需过多担心其细胞毒性。
• Microwave-assisted synthesis of primary amine HX salts from halides and 7 M ammonia in methanol
  作者：Mark G. Saulnier、Kurt Zimmermann、Charles P. Struzynski、Xiaopeng Sang、Upender Velaparthi、Mark Wittman、David B. Frennesson

  DOI：10.1016/j.tetlet.2003.10.146

  日期：2004.1

  on a variety of alkyl halides, as well as mesylates and tosylates. Benzylamines are obtained from benzyl halides without significant amounts of the secondary amine side products that result without microwave heating. Direct isolation of even highly volatile primary amines as their hydrogen halide salts makes the method ideal for use in parallel synthesis.

  直接从相应的卤化物进行的伯胺卤化氢盐的原子经济合成避免了产生大量的仲胺副产物，并且仅需蒸发溶剂即可获得产物，产率通常大于90％。该程序在130°C下于7 M氨的甲醇溶液（Aldrich）中进行0.5至2.5 h的微波辐射，并处理多种烷基卤化物，甲磺酸酯和甲苯磺酸酯。从苄基卤化物获得苄胺，而没有大量的仲胺副产物，而无需微波加热即可得到。直接分离高挥发性的伯胺作为卤化氢盐，使得该方法非常适合用于平行合成。
• Structural characterization of five-coordinate copper(II), nickel(II), and cobalt(II) thiocyanato complexes derived from bis(2-(3,5-dimethyl-1-pyrazolyl)ethyl)amine
  作者：Salah S. Massoud、Lucie Le Quan、Karl Gatterer、Jörg H. Albering、Roland C. Fischer、Franz A. Mautner

  DOI：10.1016/j.poly.2011.10.011

  日期：2012.1

  observed in the nickel complex 2 , distorted trigonal bipyramidal geometry was found in 3 . Each complex forms hydrogen bonds of type N–H⋯S from the secondary amine N(3) donor atoms to the adjacent terminal S(1) acceptor atoms of the thiocyanate group. The thermal behavior of the two polymorphs 1-I and 1-II were similar and no significant differences were observed between the two complexes.

  M（ClO 4）2·6H 2 O与NH 4 NCS在空间位阻双（2-（di-3,5-二甲基-1-吡唑基）乙基）胺（bedmpza）存在下反应，得到五种配位单核二硫代氰基-M（II）配合物[M（bedmpza）（NCS）2]·x MeOH（1：M = Cu 2+，x = 0; 2：M = Ni 2+，x = 0; 3： M ＝ Co 2+，x ＝ 0.84）。证实为非电解质的化合物通过IR和UV-Vis光谱进行表征，并通过单晶X射线晶体学确定其分子结构。在这些配合物中，五配位几何是通过配体bedmpza的三个N-供体和末端硫氰酸根配体的两个N原子实现的。Cu（II）络合物以两种多晶型物1-I和1-II存在：带有两个硫氰酸根配体的中间五坐标几何结构在1-I中排列成顺式排列，而带有硫氰酸根配体的扭曲方锥几何结构在1-II中呈Transoid取向。尽管在镍络合物2中也观察到了较晚的几何形状，但在3
• Zinc and enolato-magnesium complexes based on bi-, tri- and tetradentate aminophenolate ligands
  作者：Zhanjiang Zheng、Gang Zhao、Rémy Fablet、Miloud Bouyahyi、Christophe M. Thomas、Thierry Roisnel、Osvaldo Casagrande Jr、Jean-François Carpentier

  DOI：10.1039/b812754a

  日期：——

  The coordination chemistry of a series of potentially tetra-, tri- and bi-dentate aminophenol pro-ligands ([L1]H–[L5]H) with magnesium and zinc derivatives has been studied. Reactions of the pro-ligands [L1]H, [L2]H and [L3]H with one equiv. of ZnEt2 or Zn(N(SiMe3)2)2 in toluene at room temperature afford cleanly, viaethane or amine elimination, the ethyl- and amido-zinc complexes 1–4. Complexes [L4]ZnEt (5) and [L4]Zn(N(SiMe3)2)2 (6) derived from the tridentate pro-ligand [L4]H were prepared in 84% and 76% yields, following similar alkane and amine elimination protocols, respectively. The 1 : 1 reactions of bidentate pro-ligand [L5]H with ZnEt2 or Zn(N(SiMe3)2)2 in toluene using different reaction protocols systematically yielded mixtures of the bis(ligand) complex [L5]2Zn (7) and the corresponding ethyl-[L5]ZnEt}n (8; n = 1 or 2) or amido- [L5]Zn(N(SiMe3)2)}n complexes (9; n = 1 or 2). The synthesis of magnesium-enolate complexes 10 and 11 was carried out in a one-pot, two-step procedure by first reacting pro-ligands [L1]H and [L4]H with one equiv. of Mg(n,sBu)2 to generate the corresponding [Ln]Mg(n,sBu)}n species, which were further reacted with one equiv. of 2,4,6-Me3C6H2COMe. All complexes have been characterized by multinuclear NMR, elemental analysis, and by single-crystal X-ray diffraction studies for five-coordinate magnesium complex 10, and four-coordinate Zn complexes 3–7. Preliminary studies indicate that magnesium species 10 and 11 as well as zinc complexes 1 and 5 are not active initiators for the polymerization of methyl methacrylate, even in combination with one equiv. of Li[OC(CH2)(2,4,6-Me3C6H2)], while zinc complexes 2, 4 and 6 are effective initiators for the ring-opening polymerization of ε-caprolactone and rac-lactide at 20 °C.

  一系列潜在的四齿、三齿和二齿氨基酚前配体([L1]H–[L5]H)与镁和锌衍生物的配位化学已被研究。前配体[L1]H、[L2]H和[L3]H与等量的ZnEt2或Zn(N(SiMe3)2)2在室温下在甲苯中反应，通过乙烷或胺消除，干净地得到乙基和酰胺基锌配合物1–4。从三齿前配体[L4]H衍生的配合物[L4]ZnEt(5)和[L4]Zn(N(SiMe3)2)2(6)分别通过类似的烷烃和胺消除协议，以84%和76%的产率制备。二齿前配体[L5]H与ZnEt2或Zn(N(SiMe3)2)2在甲苯中的1:1反应，采用不同的反应协议，系统地生成了双(配体)配合物[L5]2Zn(7)和相应的乙基-[L5]ZnEt}n(8; n = 1或2)或酰胺- [L5]Zn(N(SiMe3)2)}n配合物(9; n = 1或2)的混合物。镁醇盐配合物10和11的合成采用了一锅法两步程序，首先将前配体[L1]H和[L4]H与等量的Mg(n,sBu)2反应生成相应的[Ln]Mg(n,sBu)}n物种，然后进一步与等量的2,4,6-Me3C6H2COMe反应。所有配合物均通过多核NMR、元素分析以及五配位镁配合物10和四配位锌配合物3–6的单晶X射线衍射研究进行了表征。初步研究表明，镁物种10和11以及锌配合物1和5即使与等量的Li[OC(CH2)(2,4,6-Me3C6H2)]结合，也不是甲基丙烯酸甲酯聚合的有效引发剂，而锌配合物2, 4和6在20°C下对于ε-己内酯和rac-乳酸的环开聚合是有效的引发剂。
• Slow magnetic relaxation in penta-coordinate cobalt(<scp>ii</scp>) field-induced single-ion magnets (SIMs) with easy-axis magnetic anisotropy
  作者：Salah S. Massoud、Zoe E. Perez、Jessica R. Courson、Roland C. Fischer、Franz A. Mautner、Ján Vančo、Michal Čajan、Zdeněk Trávníček

  DOI：10.1039/d0dt02338h

  日期：——

  square-pyramidal geometry in [Co(L1)(NCS)]ClO4·MeOH (1), while the vicinity of the central atom can be described as a distorted trigonal–bipyramidal geometry in [Co(L2)(NCS)]ClO4 (2) as revealed using the SHAPE analysis. Differences in interatomic parameters among the cobalt(II) and donor atoms in 1 and 2 have definite impact on the magnetic features of both compounds. The complexes show an easy-axis magnetic

  通式为[Co（L n）（NCS）] ClO 4的两个五坐标配合物，其中L 1 = 双[（3,5-二甲基-1 H-吡唑-1-基）乙基]-[（ 3,4-二甲氧基吡啶-2-基）甲基]}胺和L 2 = 双[（3,5-二甲基-1 H-吡唑-1-基）乙基]-[（4-甲氧基-3,5-二甲基吡啶-2-基）甲基]}胺，已经合成并充分表征。每个钴（II）原子在CoN 5 }供体集中以[Co（L 1）（NCS）] ClO 4 ·MeOH（1），而中心原子的附近可以用SHAPE分析显示为[Co（L 2）（NCS）] ClO 4（2）中扭曲的三角-双锥体几何形状。钴（II）和供体原子中的原子间参数的差异（1和2）对这两种化合物的磁性都具有确定的影响。该配合物显示的易轴的磁各向异性（d = -38.5厘米-1为1和d = -8.5为2），并且两个配合揭示大rhombicity与Ë / d = 0.21为1和E /