1-(1,3-dimethyl-1H-pyrazol-4-yl)-4,4,4-trifluorobutane-1,3-dione | 758709-44-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(1,3-dimethyl-1H-pyrazol-4-yl)-4,4,4-trifluorobutane-1,3-dione
• 英文别名: 1-(1,3-dimethylpyrazol-4-yl)-4,4,4-trifluorobutane-1,3-dione
• CAS: 758709-44-3
• 化学式: C₉H₉F₃N₂O₂
• mdl: MFCD03419772
• 分子量: 234.178
• InChiKey: YOUQVUDXGZRPNP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  52
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1-环丙基-1-亚硝基脲 、 1-(1,3-dimethyl-1H-pyrazol-4-yl)-4,4,4-trifluorobutane-1,3-dione 在 potassium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 2.25h， 以15%的产率得到2-[2-(1,3-dimethyl-1H-pyrazol-4-yl)-2-oxoethyl]-2-(trifluoromethyl)-1-oxaspiro[2.2]penatne
  参考文献：
  名称：

  氟化β-二酮与原位生成的重氮环丙烷反应

  摘要：

  用环丙基重氮中间体 2 和 3 处理 1,1-二-和 1,1,1-三氟烷烃-2,4-二酮 10-13，中间体 2 和 3 通过 N-环丙基-N-亚硝基脲 1 的分解原位生成潮湿的 K2CO3 没有导致预期的环丙基重氮离子的偶氮偶联，但提供了相应的氧杂环戊烷 14-17 作为重氮环丙烷 (3) 添加到其中一个羰基上的产物。此外，反应选择性地在与二氟甲基或三氟甲基取代基相邻的羰基上进行。1,1-二氟丙酮与原位生成的重氮环丙烷 (3) 类似地反应，以大约 50% 的产率得到稳定的 2-(二氟甲基)-2-甲基氧杂环戊烷。加热或在碘化锂存在下，生成的氧杂环戊烷 14-17，选择性地重排成环丁酮 20-23，而在 Al2O3 的存在下，它们形成了大约等量的相应环丁酮和 1-乙烯基环丙醇 24-27 的混合物。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim

  DOI：

  10.1002/ejoc.200400110
• 作为产物：
  描述：

  三氟乙酸乙酯 、 1-(1,3-二甲基-1H-吡唑-4-基)乙酮 在 乙醇 、 sodium hydride 作用下， 以 vaseline oil 、 乙醚 为溶剂， 反应 4.0h， 以82%的产率得到1-(1,3-dimethyl-1H-pyrazol-4-yl)-4,4,4-trifluorobutane-1,3-dione
  参考文献：
  名称：

  合成N-取代的（1 H-吡唑基）丙烷-1,3-二酮异构体的改进方法

  摘要：

  以NaH为碱，研究了异构的N-取代的（1 H-吡唑-4-基）乙酮与吡唑羧酸和氟乙酸乙酯的缩合反应。在优化的条件下，它被证明是合成N-取代的（1 H-吡唑基）丙烷-1,3-二酮和（1 H-吡唑基）-4-多氟丁烷-1,3-二酮的简便方法。

  DOI：

  10.1007/s10593-011-0821-1

文献信息

• Effect of ancillary ligands on visible and NIR luminescence of Sm3+ β-diketonate complexes
  作者：V.S. Sizov、D.A. Komissar、D.A. Metlina、D.F. Aminev、S.A. Ambrozevich、S.E. Nefedov、E.A. Varaksina、M.T. Metlin、V.V. Mislavskií、I.V. Taydakov

  DOI：10.1016/j.saa.2019.117503

  日期：2020.1

  obtained for the compounds by the Judd-Ofelt calculations were of the order of 5.5%, whereas the measured external quantum yields were 0.75% and 1.5% for Sm3+ complexes involving 2,2'-bipyridine and 1,10-phenanthroline ancillary ligands, respectively, with the corresponding sensitization efficiencies calculated as 0.16 and 0.26. It was demonstrated that replacing the 1,10-phenanthroline ancillary ligand

  研究了两个新的Sm3 +配合物，它们以带有CF3基团的吡唑基β-二酮为主要配体，并以2,2'-联吡啶或1,10-菲咯啉为辅助配体，并建立了它们的能级结构。在复合物的光致发光光谱中观察到的斯塔克分裂表明了它们的非立方对称性，这由计算得出的贾德-奥费尔特强度参数证实。通过Judd-Ofelt计算得出的化合物的内部量子产率约为5.5％，而对于涉及2,2'-联吡啶和1,10-菲咯啉辅助化合物的Sm3 +配合物，测得的外部量子产率分别为0.75％和1.5％。分别以0.16和0.26计算出相应的敏化效率。结果表明，用2,2'代替了1,10-菲咯啉辅助配体 -联吡啶使Sm3 +配合物的650 nm发射强度增加，支化率达到55％。所研究的复合物在650 nm处的强发射为其用作光谱纯的红色发射体提供了希望。
• Impact of ligand-centered excited states on luminescence sensitization in <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" altimg="si65.svg"><mml:mrow><mml:msup><mml:mrow><mml:mi mathvariant="normal">Pr</mml:mi></mml:mrow><mml:mrow><mml:mn>3</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:mrow></mml:math> complexes with <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" altimg="si66.svg"><mml:mrow><mml:mi>β</mml:mi></mml:mrow></mml:math>-diketones
  作者：V.M. Korshunov、M.T. Metlin、S.A. Ambrozevich、I.S. Golovanov、V.E. Gontcharenko、A.S. Selyukov、I.V. Taydakov

  DOI：10.1016/j.saa.2021.119863

  日期：2021.11

  In this study, two novel Pr3+ complexes with different 1,3-diketonate ligands were synthesized and investigated. To study the effect of the ancillary ligand on the energy transfer mechanisms in the complexes, a phenanthroline ligand was introduced. To take into account the influence of the ligand environment composed of different ligands on the energy transfer and relaxation processes, we compared

  在这项研究中，两本小说 镨3+合成并研究了具有不同1,3-二酮酸酯配体的配合物。为了研究辅助配体对复合物中能量转移机理的影响，引入了菲咯啉配体。考虑到由不同配体组成的配体环境对能量转移和弛豫过程的影响，我们将合成的化合物与含有邻菲咯啉配体的类似配合物进行了比较。DFT和TD-DFT计算补充了可见光和近红外光谱区域的光谱研究。我们发现了两个配体到配体的电荷转移（LLCT）状态，一种状态对应于1,3-二酮之间的能量转移，另一种状态对应于从1,3-二酮到菲咯啉基序的能量转移。π--π∗1,3-二酮过渡。此外，LLCT的两个状态都提供了对镨3+发光涉及3P0和3P1个 水平。
• Vanadyl heterosubstituted 1,3-β-diketonate complexes: Synthesis, characterization and catalytic applications for the selective oxidation and detoxification of sulfur compounds
  作者：Andrea Di Giuseppe、Francesco Taglieri、Ilya V. Taydakov、Yuriy A. Belousov、Mikhail A. Kiskin、Ivan V. Kurganskii、Matvey V. Fedin、Marcello Crucianelli

  DOI：10.1016/j.cattod.2023.01.012

  日期：2023.1

  as primary oxidant. The effects of oxidant to substrate molar ratio, catalyst amount, solvent and temperature have been studied. The high activity and selectivity showed by the complexes, prompted us to apply, successfully, the catalyst in the challenging decontamination of the mustard gas simulants CEES and CEPS, towards their corresponding sulfoxide derivatives, under mild conditions. A rationale

  已经合成了六种新型氧钒基杂环/芳族取代的1,3-β-二酮配合物，其含有双齿配体，并且通过单晶X射线分析（配合物）、玻璃态（100 K）或作为状态的EPR光谱充分表征了它们的结构粉末、FT-IR 和 UV-Vis 分析。配合物的配位环境（扭曲的八面体）由赤道面上的两个螯合二阴离子以平面构型形成。这些新型氧化钒(IV)络合物的催化活性已在一系列含硫底物选择性氧化为其相应的硫化物和/或砜的过程中进行了研究，使用正丁基过氧化氢作为主要氧化剂。研究了氧化剂与底物摩尔比、催化剂用量、溶剂和温度的影响。该配合物表现出的高活性和选择性，促使我们成功地将该催化剂应用于芥子气模拟物 CEES 和 CEPS 的挑战性净化，在温和的条件下对其相应的亚砜衍生物进行净化。对底物转化率和亚砜（或砜）选择性方面的主要观察结果进行了合理分析。
• Novel β-diketonate complexes of <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" altimg="si1.gif" overflow="scroll"><mml:mrow><mml:msup><mml:mrow><mml:mtext>Eu</mml:mtext></mml:mrow><mml:mrow><mml:mn>3</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:mrow></mml:math> bearing pyrazole moiety for bright photo- and electroluminescence
  作者：V.M. Korshunov、S.A. Ambrozevich、I.V. Taydakov、A.A. Vashchenko、D.O. Goriachiy、A.S. Selyukov、A.O. Dmitrienko

  DOI：10.1016/j.dyepig.2018.12.006

  日期：2019.4

  Four novel 1,3-diketonate Eu3+ complexes bearing pyrazole moieties as main ligands and a 4,7-Diphenyl-1,10-phenanthroline (bathophenanthroline) ancillary ligand were synthesized. The number of fluorine atoms in the main ligand was varied from 3 to 13. From spectroscopic studies of the synthesized complexes we conclude that increasing the degree of fluorination results in a significant rise in the quantum yield and sensitization efficiency. With further extension of the fluorinated chain length, saturation of these characteristics was observed. The maximum obtained values of the quantum yield and sensitization efficiency were 56% and 99%, respectively. In order to reveal the potential of the complexes for OLED applications, electroluminescent devices based on these compounds were fabricated and their performance was studied. It was found that the quantum efficiencies of the OLEDs and the sensitization efficiencies exhibit similar behaviour depending on the degree of fluorination of the ligands in the complexes.
• Bright NIR-luminescent <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline" id="d1e655" altimg="si55.svg"><mml:msup><mml:mrow><mml:mi mathvariant="normal">Nd</mml:mi></mml:mrow><mml:mrow><mml:mn>3</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math> complexes with pyrazole-substituted 1,3-diketones demonstrated an unusual spectral lines branching ratios
  作者：D.A. Metlina、M.T. Metlin、S.A. Ambrozevich、A.S. Selyukov、N.P. Datskevich、D.F. Aminev、D.O. Goryachii、K.A. Lyssenko、A.A. Pavlov、A.O. Dmitrienko、I.V. Taydakov

  DOI：10.1016/j.dyepig.2020.108558

  日期：2020.10

  A series of novel highly NIR-emitting Nd3+ complexes with specially designed 1,3-diketones bearing a pyrazole moiety and a linear CxF2x+1 group (x = 1, 3,6) was obtained and exhaustively investigated. It was demonstrated that for the complexes with an increased number of fluorine atoms, the triplet level energy of the ligands is decreased and phonon relaxation processes are suppressed. This provides a remarkable increase in the photoluminescence quantum yield up to 1.1%, which is close to the highest values reported for Nd3+ complexes with 1,3-diketones. The photoluminescence spectra of the complexes exhibited the Stark splitting indicative of non-cubic symmetry. Low symmetry of coordination environment was confirmed by the X-ray structural data and analysis of calculated Judd-Ofelt intensity parameters. Besides, it was revealed that the most intense band in the PL spectrum is attributed to the F-4(3/2) -> I-4(9/2) transition (at 880 nm) which is commonly rather weak for simple diketonate complexes. The calculations showed that the unexpectedly high branching ratio of the F-4(3/2) -> (4)I9/ transition raises with elongation of the fluorinated chain and reaches 59% for the complex with x = 6. The studies were conducted for solutions of the complexes as well as for solid samples, and the corresponding changes in their optical behavior were discussed. Uncommon properties of the synthesized Nd3+ complexes make them promising materials for various state-of-the-art luminescent applications, e.g., luminescent markers with an unusual spectral intensity distribution. Based on the electroluminescence studies, we also estimated the potential of the complexes for purely NIR-emitting OLEDs fabrication.