1-(2-iodophenyl)-1H-pyrazole | 1419605-60-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 1-(2-iodophenyl)-1H-pyrazole
• 英文别名: 1-(2-Iodophenyl)pyrazole
• CAS: 1419605-60-9
• 化学式: C₉H₇IN₂
• 分子量: 270.072
• InChiKey: GIWCESQCQKTPMF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  17.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-(2-iodophenyl)-1H-pyrazole 在 copper(l) iodide 、 potassium carbonate 、 L-脯氨酸 作用下， 以 二甲基亚砜 、 乙腈 为溶剂， 反应 72.0h， 生成 N-[2-(pyrazol-1-yl)phenyl]-N'-benzylimidazolium chloride
  参考文献：
  名称：

  Synthesis and catalytic activity of N-heterocyclic carbene silver complexes derived from 1-[2-(pyrazol-1-yl)phenyl]imidazole

  摘要：

  Six mono-and dinuclear N-heterocyclic carbene (NHC) silver complexes based on 1-[2-(pyrazol-1-yl) phenyl] imidazole have been synthesized and characterized by elemental analysis and NMR spectroscopy, and their structures have been confirmed by single crystal X-ray diffraction. The N-functionalized carbene ligands exhibit versatile coordination modes in these silver complexes. N-[2-(3,5-Dimethylpyrazol-1-yl)phenyl]-N-benzylimidazol-2-ylidene (L) acts as a monodentate ligand through the carbene carbon in mononuclear LAgCl. While in dinuclear L2Ag2(PF6)(2) and L'Ag-2(2)(PF6)(2) (L' = N-[2-(pyrazol-1-yl) phenyl]-N-benzylimidazol-2-ylidene), L and L' act as bridging bidentate ligands through the pyrazolyl nitrogen and the carbene carbon atoms to two silver atoms. Though, these two silver atoms have different coordination environments. In the former, one silver atom coordinates with two carbene carbons, the other coordinates with two pyrazolyl nitrogen atoms. In the latter, each silver atom coordinates with one carbene carbon and one pyrazolyl nitrogen atom, respectively. A dinuclear macrocyclic structure is observed in m-xylyl bridging tetradentate bis-NHC complexes L2Ag2(BF4)(2) and (L)CH2C6H4CH2(L)Ag-2(BF4)(2), in which the coordination mode of carbene ligands is similar with that in L2Ag2(PF6)(2). Preliminary catalytic tests show that all these complexes exhibit highly effective catalytic activity in the three-component coupling reaction of alkyne, aldehyde and amine forming propargylamines. (C) 2012 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2012.12.008
• 作为产物：
  描述：

  1-苯基吡唑 在 dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer 、 碘苯二乙酸 、 三氟乙酸 、 sodium iodide 作用下， 以 丙酮 为溶剂， 反应 12.0h， 以67%的产率得到1-(2-iodophenyl)-1H-pyrazole
  参考文献：
  名称：

  卤化钠作为卤化试剂：铑（III）催化的芳基化合物的通用卤化和实用卤化

  摘要：

  AbstractWe report a concise, versatile and practical method for the ortho‐chlorination, ortho‐bromination and ortho‐iodination of aryl compounds. The significant advantage of this transformation is the creation of the carbon‐halogen bond by use of readily available and cheap halide salts as formal nucleophilic halogenating reagents under mild reaction conditions.magnified image

  DOI：

  10.1002/adsc.201400590

文献信息

• N‐Heterocycle‐Stabilized Iodanes: From Structure to Reactivity
  作者：Andreas Boelke、Enno Lork、Boris J. Nachtsheim

  DOI：10.1002/chem.201804957

  日期：2018.12.12

  throughout shelf‐stable solids is robust and can be achieved on a large scale. Their reactivity is highly tunable, depending on the stabilizing heterocycle. Solid state structures of selected derivatives are reported and their reactivity in a model oxygen transfer reaction is compared. Further derivatization reactions to N‐heterocycle‐stabilized pseudocyclic diaryliodonium salts and cyclic iodoso species

  Pseudocyclic芳基λ 3由于稳定性，溶解性和反应性之间的平衡关系良好，碘代烷是用于各种氧化转化的优良试剂。它们的性质基本上受路易斯碱（通常是羧酸或酰胺的氧原子）与中心高价碘原子之间的相互作用的影响。这项工作是对伪环N杂环稳定的碘化物（NHIs）的首次系统研究。这些在整个储存稳定的固体中的合成都是可靠的，可以大规模实现。它们的反应性是高度可调的，具体取决于稳定的杂环。报告了所选衍生物的固态结构，并比较了它们在模型氧转移反应中的反应性。
• Thermal stability of <i>N</i>-heterocycle-stabilized iodanes – a systematic investigation
  作者：Andreas Boelke、Yulia A Vlasenko、Mekhman S Yusubov、Boris J Nachtsheim、Pavel S Postnikov

  DOI：10.3762/bjoc.15.223

  日期：——

  The thermal stability of pseudocyclic and cyclic N-heterocycle-stabilized (hydroxy)aryl- and mesityl(aryl)-λ³-iodanes (NHIs) through thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) is investigated. Peak decomposition temperatures (T_peak) were observed within a wide range between 120 and 270 °C. Decomposition enthalpies (ΔH_dec) varied from −29.81 to 141.13 kJ/mol. A direct comparison between pseudocyclic and cyclic NHIs revealed high T_peak but also higher ΔH_dec values for the latter ones. NHIs bearing N-heterocycles with a high N/C-ratio such as triazoles show among the lowest T_peak and the highest ΔH_dec values. A comparison of NHIs with known (pseudo)cyclic benziodoxolones is made and we further correlated their thermal stability with reactivity in a model oxygenation.

  本文研究了假环和环状N-杂环稳定的(羟基)芳基和二甲基(芳基)-λ3-碘烷（NHIs）的热稳定性，通过热重分析（TGA）和差示扫描量热法（DSC）进行了研究。峰值分解温度（Tpeak）在120℃至270℃之间。分解焓（ΔHdec）变化从-29.81至141.13 kJ/mol。假环和环状NHIs之间的直接比较显示出后者有更高的Tpeak和更高的ΔHdec值。具有高N/C比率的N-杂环的NHIs，如三唑衍生物，显示出最低的Tpeak和最高的ΔHdec值。本文还将NHIs与已知的(伪)环状苯碘氧烷进行了比较，并进一步将它们的热稳定性与模型氧化反应的反应性相关联。
• Stabilization of Ethynyl‐Substituted Aryl‐λ ³ ‐Iodanes by Tethered <i>N</i> ‐Heterocylces**
  作者：Thomas J. Kuczmera、Andreas Boelke、Boris J. Nachtsheim

  DOI：10.1002/ejoc.202200276

  日期：2022.6.13

  A new class of ethynyl N-heterocycle-substituted-λ3-iodanes (ENHIs) is presented. The (pseudo)cyclic iodanes were synthesized using a one-pot protocol with a variety of heterocycles and substituents and could be used for well-established alkynylation reactions with a comparable reactivity to TIPS-EBX. Moreover, an unexpected self-reactivity was found, which leads to a new alkynylation method and the

  提出了一类新的乙炔基N-杂环取代-λ 3 -碘烷(ENHIs)。（伪）环状碘烷是使用具有各种杂环和取代基的一锅法合成的，可用于与 TIPS-EBX 具有相当反应性的成熟炔基化反应。此外，发现了一种意想不到的自反应性，这导致了一种新的炔基化方法和新型杂芳族化合物的合成。
• Nickel-catalyzed [2 + 2 + 2] benzannulation of alkynes: a new route to the synthesis of highly substituted naphthalenes
  作者：Sampath Thavaselvan、Kanniyappan Parthasarathy

  DOI：10.1039/d2ob00513a

  日期：——

  directing groups with alkynes to afford highly substituted naphthalene products via C–X bond cleavage followed by alkyne insertion and C–H activation is described. This reaction proceeded with a wide range of directing groups such as pyrazoles, imidazopyridines, benzoimidazothiazoles, thiazoles and triazoles with alkynes to afford highly substituted naphthalenes in moderate to good yields. This transformation

  描述了 Ni( II ) 催化的各种导向基团与炔烃的芳族同系化，通过C-X 键断裂、炔烃插入和 C-H 活化提供高度取代的萘产物。该反应在吡唑类、咪唑并吡啶类、苯并咪唑并噻唑类、噻唑类和三唑类等多种导向基团与炔烃的作用下进行，以中等至高产率提供高度取代的萘。Ni( II )-络合物、锌粉和碱的简单、直接组合促进了这种转变。
• Site Selective Concerted Nucleophilic Aromatic Substitutions of Azole‐Ligated Diaryliodonium Salts
  作者：Yulia A. Vlasenko、Thomas J. Kuczmera、Nikita S. Antonkin、Rashid R. Valiev、Pavel S. Postnikov、Boris J. Nachtsheim

  DOI：10.1002/adsc.202201001

  日期：2023.2.21

  Diaryliodonium salts are electrophilic arylation reagents in transition metal-catalyzed and transition metal-free reaction methods. Herein we present the application of azole-stabilized diaryliodonium salts with additional thiophene-2-yl-ligands as substrates for metal-free nucleophilic arylations. Besides their synthesis, we demonstrate their application in chemoselective nitrations, oxygenations

  二芳基碘盐是过渡金属催化和无过渡金属反应方法中的亲电芳基化试剂。在这里，我们介绍了唑稳定的二芳基碘盐与额外的噻吩-2-基配体作为无金属亲核芳基化底物的应用。除了它们的合成外，我们还展示了它们在 umpolung 条件下在化学选择性硝化、氧化、胺化和硫醇化中的应用。还讨论了基于原位形成的方便的一锅法程序。