1,3-diisopropylimidazolium-2-carboxylate | 1173202-02-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 1,3-diisopropylimidazolium-2-carboxylate
• 英文别名: 1,3-Diisopropyl-1H-imidazol-3-ium-2-carboxylate；1,3-di(propan-2-yl)imidazol-1-ium-2-carboxylate
• CAS: 1173202-02-2
• 化学式: C₁₀H₁₆N₂O₂
• 分子量: 196.249
• InChiKey: ARVVOEJBGNPOFH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  48.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,3-diisopropylimidazolium-2-carboxylate 在 水 作用下， 以 二氯甲烷-D2 为溶剂， 生成 1,3-二异丙基咪唑鎓碳酸氢盐(含有数量不等的1,3-二异丙基咪唑鎓-2-羧酸盐)
  参考文献：
  名称：

  A Systematic Investigation of Factors Influencing the Decarboxylation of Imidazolium Carboxylates

  摘要：

  A series of 1,3-disubstituted-2-imidazolium carboxylates, an adduct of CO2 and N-heterocyclic carbenes, were synthesized and characterized using single crystal X-ray, thermogravimetric, IR, and NMR analysis. The TGA analysis of the NHC-CO2's shows that as steric bulk on the N-substituent increases, the ability of the NHC-CO2 to decarboxylate increases. The comparison of NHC-CO2's with and without methyls at the 4,5-position indicate that extra electron density in the imidazolium ring enhances the stability of an NHC-CO2 thereby making it less prone to decarboxylation. Single crystal X-ray analysis shows that the torsional angle of the carboxylate group and the C-CO2 bond length with respect to the imidazolium ring is dependent on the steric bulk of the N-substituent. Rotamers in the unit cell of a single crystal of I'BuPrCO2 (2f) indicate that the C-CO2 bond length increases as the N-substituents rotate toward the carboxylate moiety, which suggests that rotation of the N-substituents through the plane of the C-CO2 bond may be involved in the bond breaking event to release CO2.

  DOI：

  10.1021/jo901791k
• 作为产物：
  描述：

  N,N'-Diisopropylformamidin 在 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 为溶剂， 生成 1,3-diisopropylimidazolium-2-carboxylate
  参考文献：
  名称：

  Anionic Ring-Opening Homo- and Copolymerization of Lactams by Latent, Protected N-Heterocyclic Carbenes for the Preparation of PA 12 and PA 6/12

  摘要：

  Laurolactam (LL) is polymerized in the bulk using strongly basic N-heterocyclic carbenes (NHCs) as initiators at temperatures of 180-200 degrees C to prepare the corresponding polyamide (PA 12). In-situ rheology of the polymerization progress reveals that an anionic mechanism is active, which is supported by the strong dependence of initiator activity on the basicity of the NHCs. GPC data and kinetic investigations show the process to be moderately controlled and fast, allowing high or quantitative yields in short polymerization times. Fifteen different NHC-CO2-adducts and NHC-metal complexes were used as thermally labile but room temperature stable NHC-precursors. Depending on the ring size and N-substituent, some of these protected NHCs allow forming a mixture of monomer and NHC-precursor that is suitable for long-term storage and readily polymerizable by simple heating. All polymerizations are executed without activator or other additives and thus represent a true one-component system for the production of PA 12. Finally, LL is copolymerized with epsilon-caprolactam (epsilon-CLA). It is found that a copolymer with a considerable gradient is formed, with epsilon-CLA being incorporated preferentially at the onset of the polymerization.

  DOI：

  10.1021/ma4018586

文献信息

• N杂环卡宾及卡宾前体作为n型掺杂剂在半导体材料中的应用
  申请人：北京大学

  公开号：CN112645881B

  公开（公告）日：2022-12-30

  本发明公开了N杂环卡宾及卡宾前体作为n型掺杂剂在半导体材料中的应用。N杂环卡宾及卡宾前体可作为溶液稳定、高效的n型掺杂剂实现对有机小分子及聚合物材料、碳纳米管、无机半导体等半导体材料的高效n掺杂。该类n型掺杂剂化学结构简单，易于合成及衍生化，兼备较高的掺杂效率、良好的溶液稳定性及加工性和掺杂后半导体器件稳定性，同时通过调节掺杂剂浓度可以实现对半导体材料掺杂比例及电学性质的调控，可以被广泛地应用于电子学领域，例如发光二极管、太阳能电池、场效应晶体管和热电器件等。
• Highly regio- and stereoselective synthesis of cyclic carbonates from biomass-derived polyols<i>via</i>organocatalytic cascade reaction
  作者：Hui Zhou、Hui Zhang、Sen Mu、Wen-Zhen Zhang、Wei-Min Ren、Xiao-Bing Lu

  DOI：10.1039/c9gc03013a

  日期：——

  The cascade reaction of CO2, vicinal diols, and propargylic alcohol, was firstly achieved by dual Lewis base (LB) organocatalytic systems involving LB–CO2 adducts and commercially available organic amines. This methodology could overcome the chemical inertness of CO2, providing an alternative route to various functionalized five-membered cyclic carbonates in moderate to high yields under mild reaction

  CO 2，邻二醇和炔丙醇的级联反应首先通过双路易斯碱（LB）有机催化体系实现，该体系涉及LB–CO 2加合物和可商购的有机胺。该方法可以克服CO 2的化学惰性，在温和的反应条件下（25°C，1.0 atm CO 2）以中等至高收率提供各种功能化的五元环状碳酸酯的替代路线）。更重要的是，该方法还可以用于由生物质衍生的多元醇轻松有效地合成手性多环碳酸酯，并完全保留手性中心的构型。这项研究为构建具有多功能基团和​​手性中心的增值环状碳酸酯提供了一种环境友好，可扩展且具有成本效益的方案。
• Imidazolylidene Cu(II) Complexes: Synthesis Using Imidazolium Carboxylate Precursors and Structure Rearrangement Pathways
  作者：Nathalie Ségaud、Jonathan McMaster、Gerard van Koten、Martin Albrecht

  DOI：10.1021/acs.inorgchem.9b02568

  日期：2019.12.2

  N'-diisopropyl-imidazolylidene and N,N'-dimethyl-imidazolylidene. Spectroscopic evidence of the formation of the Cu-CNHC bond is provided by UV-vis and EPR, in particular by the 44 MHz carbene hyperfine coupling constant using a 13C-labeled imidazolylidene ligand. A variation of the nature of the carbene N-substituents and the anions bound to the Cu(II) center is possible with this methodology. These variations strongly

  通过对咪唑鎓羧酸盐进行原位脱羧制备含单齿N-杂环碳烯（NHC）的（NHC）CuX2（X = OAc，Cl，Br，BF4和NO3）型铜（II）配合物，作为Cu的新合成方法（II）-NHC配合物。与传统的去质子化方法相比，脱羧方案不需要厌氧条件，并提供了与不稳定的NHCs络合物的接触途径，这些NHCs作为游离的羧苯甲酸酯不稳定，例如N，N'-二异丙基-咪唑基亚烷基和N，N'-二甲基-咪唑基亚烷基。UV-vis和EPR，尤其是使用13C标记的咪唑基亚烷基配体的44 MHz卡宾超细偶合常数提供了Cu-CNHC键形成的光谱证据。卡宾N-取代基和与Cu（II）中心键合的阴离子的性质可能有此方法的变化。这些变化强烈影响配合物的稳定性。在重结晶过程中观察到结构重排和配体重组，这取决于不稳定的NHC配体的杂合Cu-CNHC键解离，以及取决于铜络合物中阴离子X的性质的均相Cu-X键裂解和歧化反应。
• Thermally Activated n‐Doping of Organic Semiconductors Achieved by N‐Heterocyclic Carbene Based Dopant
  作者：Yi‐Fan Ding、Chi‐Yuan Yang、Chun‐Xi Huang、Yang Lu、Ze‐Fan Yao、Chen‐Kai Pan、Jie‐Yu Wang、Jian Pei

  DOI：10.1002/anie.202011537

  日期：2021.3.8

  density of organic semiconductors thus enhancing their optoelectronic performance. However, efficient n‐doping remains challenging, especially owing to the lack of strongly reducing and air‐stable n‐dopants. Herein, an N‐heterocyclic carbene (NHC) precursor, DMImC, is developed as a thermally activated n‐dopant with the excellent stability in air. Its thermolysis in situ regenerates free NHC and subsequently

  分子掺杂在有机半导体载流子密度的改变中起着重要作用，从而增强了它们的光电性能。但是，有效的n掺杂仍然具有挑战性，特别是由于缺乏强烈还原且稳定的n掺杂剂。在此，开发了一种N-杂环卡宾（NHC）前驱体DMImC，它是一种热活化的n-掺杂剂，在空气中具有出色的稳定性。其原位热解可再生游离的NHC，并随后掺杂典型的有机半导体。在顺序掺杂的FBDPPV薄膜中，DMImC不会干扰聚合物的π-π堆积，并能与聚合物实现良好的混溶性。结果，高达8.4 S cm -1的高电导率获得。此外，热激活掺杂和出色的空气稳定性使DMImC可以与空气中的聚合物进行非交互共处理。我们的结果表明，DMImC可以用作适用于各种有机半导体的有效n掺杂剂。
• Highly Modular Piano-Stool N-Heterocyclic Carbene Iron Complexes: Impact of Ligand Variation on Hydrosilylation Activity
  作者：Pamela V. S. Nylund、Nathalie C. Ségaud、Martin Albrecht

  DOI：10.1021/acs.organomet.1c00200

  日期：2021.5.24

  with N-heterocyclic carbene (NHC) ligation constitutes an attractive scaffold for employing iron in catalysis. Here, we have expanded this scaffold by installing a pentamethyl cyclopentadienyl (Cp*) ligand as a strong electron donor compared to the traditionally used unsubstituted cyclopentadiene (Cp). Moreover, decarboxylation is introduced as a method to prepare these iron(II) NHC complexes, which

  钢琴凳构型与N-杂环卡宾（NHC）连接相结合构成了一种在催化中采用铁的有吸引力的支架。在这里，我们通过安装五甲基环戊二烯基（Cp *）配体作为强电子供体，与传统使用的未取代环戊二烯（Cp）相比，扩展了该支架。此外，引入脱羧作为制备这些铁（II）NHC络合物的方法，避免了对空气敏感的游离卡宾的分离。除了Cp / Cp *变异以外，还已经在NHC支架，NHC翼尖基团和辅助配体上对复合物进行了系统地调节，以便确定控制醛在硅氢加成中铁中心催化活性的关键因素。 。这些调节揭示了空间修整和电子密度优化对于高催化性能的重要性。数据表明，具有三唑基亚砜的NHC支架比咪唑基亚基始终具有更高的活性，并且催化活性与空间而不是电子因素之间具有相关性，因此发挥了至关重要的作用。而且，空间体积的实施强烈依赖于NHC的性质，并且受到Cp *铁前体的严格限制。性能最佳的催化系统达到周转频率，TOF 空间体积的实现在很大程度上取决于NHC的性质，并受到Cp