1,3-Diisopropyl-4,5-dimethylimidazolium-2-carboxylate | 225931-95-3

• 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-Diisopropyl-4,5-dimethylimidazolium-2-carboxylate
• 英文别名: 4,5-dimethyl-1,3-di(propan-2-yl)imidazol-1-ium-2-carboxylate
• CAS: 225931-95-3
• 化学式: C₁₂H₂₀N₂O₂
• 分子量: 224.303
• InChiKey: DYHRKVBJXKVNJG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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-Diisopropyl-4,5-dimethylimidazolium-2-carboxylate 以 二氯甲烷 、 乙腈 为溶剂， 生成 [Cl3Ti(CH3CN)(μ-O)(μ-ImCO2)TiCl3(CH3CN)]*2CH2Cl2
  参考文献：
  名称：

  Cl3Ti (μ-O) (μ-ImCO2) 2TiCl3 和 Cl3Ti (μ-O) (μ-ImCO2) TiCl3 · 2 MeCN (Im = 2,3-dihydro-1,3-diisopropyl-4,5) 的合成和结构-二甲基咪唑-2-亚基）：作为电中性桥连配体的咪唑鎓羧酸盐 [1]

  摘要：

  1,3-二异丙基-4,5-二甲基咪唑鎓-2-羧酸盐（4，ImCO2）与TiCl4反应生成未知结构的复合物ImCO2·TiCl4（5）。5被水水解形成配合物Cl3Ti(μ-O)(μ-ImCO2)2·MeCN(6)和Cl3Ti(μ-O)(μ-ImCO2)TiCl3·2MeCN·2CH2Cl2。在图 6 和图 7 中，根据光谱和结构数据，ImCO2 充当电中性羧基配体。描述了6和7的晶体结构。Cl3Ti (μ-O) (μ-ImCO2) 2TiCl3 和 Cl3Ti (μ-O) (μ-ImCO2) TiCl3 2 MeCN (Im = 2,3-dihydro-1,3-diisopropyl-4,5 -二甲基咪唑-2-亚基)：作为电中性桥连配体的咪唑鎓羧酸盐 1,3-二异丙基-4,5-二甲基咪唑鎓-2-羧酸盐 (4, ImCO2) 与 TiCl4 反应生成未知结构的复合物 ImCO2 · TiCl4

  DOI：

  10.1002/(sici)1521-3749(199906)625:6<851::aid-zaac851>3.0.co;2-r
• 作为产物：
  描述：

  二氧化碳 、 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene 以 乙醚 为溶剂， -78.0 ℃ 、101.32 kPa 条件下， 以85%的产率得到1,3-Diisopropyl-4,5-dimethylimidazolium-2-carboxylate
  参考文献：
  名称：

  N-杂环卡宾的可逆羧化作用。

  摘要：

  对一系列咪唑羧酸盐进行的光谱分析，热重分析和交叉实验表明，羧基化是可被N-芳基取代的加合物逆转的。

  DOI：

  10.1039/b311350g
• 作为试剂：
  描述：

  二氧化碳 、 2-甲基-3-丁炔-2-醇 在 1,3-Diisopropyl-4,5-dimethylimidazolium-2-carboxylate 作用下， 40.0 ℃ 、4.5 MPa 条件下， 反应 15.0h， 以82%的产率得到4,4-二甲基-5-亚甲基-1,3-二氧戊环-2-酮
  参考文献：
  名称：

  N-Heterocyclic Carbenes as Efficient Organocatalysts for CO₂Fixation Reactions

  摘要：

  AbstractGetting a fix: N‐heterocyclic carbenes (NHCs) and NHC–CO2 adducts serve as potent organocatalysts for carbonate synthesis by the addition of a CO2 unit to propargylic alcohols or epoxides under mild and solvent‐free reaction conditions (see scheme). The enhanced Lewis basicity of imidazol‐2‐ylidenes bearing electron‐donating alkyl groups on the nitrogen atoms leads to utilizing CO2 as a nucleophilic fragment in the chemical fixation processes.magnified image

  DOI：

  10.1002/anie.200901399

文献信息

• Preparation of alpha-hydroxy ketones via carbene-catalyzed umpolung reaction of aldehydes
  申请人：Jackstell Ralf

  公开号：US20080051608A1

  公开（公告）日：2008-02-28

  The present invention relates to the preparation of α-hydroxy ketones of the general formula I. In particular, the invention relates to novel imidazolinium carboxylate adducts and to a novel process for using catalytic amounts of imidazolium and imidazolinium carboxylate adducts in the acyloin reaction of aldehydes to prepare hydroxy ketones of the general formula I, where R and R′ are the same or different and are each H or a straight-chain or branched and optionally substituted C 1 -C 12 -alkyl radical, and R″═H 3 CSCH 2 CH 2 , t-butyl, n-butyl, sec-butyl, n-propyl, i-propyl, an optionally heteroatom-substituted C 6 -C 18 -aryl, heteroaryl, C 6 -C 18 -arylalkyl, especially phenylmethyl, where phenyl may again be heteroatom-substituted, or heteroalkyl.

  本发明涉及通式I的α-羟基酮的制备。特别是，本发明涉及新型咪唑啉酮酸盐加合物以及一种新的过程，该过程利用咪唑和咪唑啉酮酸盐加合物的催化量在醛的酰乙醇反应中制备通式I的羟基酮，其中R和R′相同或不同，每个都是H或直链或支链且可选择取代的C1-C12烷基基团，而R″=H3CSCH2CH2、叔丁基、正丁基、异丁基、正丙基、异丙基、可选择杂原子取代的C6-C18芳基、杂原子芳基、C6-C18芳基烷基，特别是苯甲基，其中苯可能再次被杂原子取代，或者杂原子烷基。
• NHC‐Coordinated Diphosphene‐Stabilized Gold(I) Hydride and Its Reversible Conversion to Gold(I) Formate with CO ₂
  作者：Debabrata Dhara、Shubhajit Das、Swapan K. Pati、David Scheschkewitz、Vadapalli Chandrasekhar、Anukul Jana

  DOI：10.1002/anie.201909798

  日期：2019.10.21

  hydride, which readily adds CO2 at room temperature yielding the corresponding AuI formate. The reversible reaction can be expedited by the addition of NHC, which induces β-hydride shift and the removal of CO2 from equilibrium through the formation of an NHC-CO2 adduct. The AuI formate is alternatively formed by dehydrogenative coupling of the AuI hydride with formic acid (HCO2 H), thus in total establishing

  将NHC配位的二膦用作配体，用于合成烃溶性单体AuI氢化物，该氢化物在室温下容易添加CO2，得到相应的AuI甲酸酯。可通过添加NHC来加快可逆反应，NHC会诱导β氢化物转移，并通过形成NHC-CO2加合物来从平衡中除去CO2。可替代地，AuI甲酸酯是通过AuI氢化物与甲酸（HCO2 H）的脱氢偶联形成的，因此，总的来说，建立了由AuI氢化物介导的作为化学储氢材料的HCO2 H脱氢的反应顺序。
• CATALYST FOR DISSOCIATION OF BLOCKING AGENT FOR BLOCKED ISOCYANATES, AND THERMOSETTING COMPOSITION CONTAINING SAID CATALYST FOR DISSOCIATION OF BLOCKING AGENT
  申请人：Koei Chemical Company, Limited

  公开号：EP3689931A1

  公开（公告）日：2020-08-05

  A blocking agent dissociation catalyst for blocked isocyanates comprising a nitrogen-containing compound represented by Formula (1a): wherein D is represented by Formula (2): wherein R1, R2, R3, R4, and a are as described in the specification.

  一种用于封端异氰酸酯的封端剂解离催化剂，由式（1a）代表的含氮化合物组成： 其中 D 由式（2）表示： 其中 R1、R2、R3、R4 和 a 如说明书所述。
• A Systematic Investigation of Factors Influencing the Decarboxylation of Imidazolium Carboxylates
  作者：Bret R. Van Ausdall、Jeremy L. Glass、Kelly M. Wiggins、Atta M. Aarif、Janis Louie

  DOI：10.1021/jo901791k

  日期：2009.10.16

  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.
• Kuhn, Norbert; Steimann, Manfred; Weyers, Gerd, Zeitschrift fur Naturforschung, B: Chemical Sciences, 1999, vol. 54, # 4, p. 427 - 433
  作者：Kuhn, Norbert、Steimann, Manfred、Weyers, Gerd

  DOI：——

  日期：——