1,3-dimethylimidazolidin-2-ylidene | 202584-80-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: 1,3-dimethylimidazolidin-2-ylidene
• 英文别名: 1,3-dimethylimidazoline；1,3-dimethyl-4,5-dihydro-2H-imidazol-1-ium-2-ide
• CAS: 202584-80-3
• 化学式: C₅H₁₀N₂
• 分子量: 98.1478
• InChiKey: CFQXZFHOLVNEQO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  6.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1,3-dimethylimidazolidin-2-ylidene 60.0 ℃ 、13.33 Pa 条件下， 生成 2-(1,3-二甲基咪唑烷-2-亚基)-1,3-二甲基-咪唑烷
  参考文献：
  名称：

  Steric Stabilization of Nucleophilic Carbenes

  摘要：

  DOI：

  10.1002/anie.199726071
• 作为产物：
  描述：

  1,3-二甲基咪唑烷-2-硫酮 在 氢化钾 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 1,3-dimethylimidazolidin-2-ylidene
  参考文献：
  名称：

  Steric Stabilization of Nucleophilic Carbenes

  摘要：

  DOI：

  10.1002/anie.199726071
• 作为试剂：
  描述：

  3,4-二氯苯腈 在 1,3-dimethylimidazolidin-2-ylidene 、 potassium fluoride 作用下， 以 水 、 甲苯 为溶剂， 以93%的产率得到3,4-二氟苯腈
  参考文献：
  名称：

  一种3,4-二氟苯腈工艺生产方法

  摘要：

  本发明涉及化合物生产工艺领域，尤其是一种3,4‑二氟苯腈工艺生产方法，具体包括如下步骤：S1：添加原料：S2：加入氟化钾和催化剂：S3：脱甲苯：S4：收集粗品3，4‑二氟苯腈：S5：离心分离：S6：得成品3，4‑二氟苯腈。通过使用高温热稳定性好、活性高的相转移催化剂N‑双（二甲胺基）‑1,3‑二甲基咪唑啉，降低了反应需要的温度，提高了反应速率；同时，通过控制反应深度（3，4‑二氟苯腈含量在89.0‑89.5%），降低了体系在高温下的存在时间，从而有效的减少聚合、脱卤、焦化现象，提高了产品收率，最大限度地减轻环保压力。

  公开号：

  CN110804001A

文献信息

• A New Route to Acyclic Diaminocarbenes via Lithium−Halogen Exchange
  作者：David R. Snead、Ion Ghiviriga、Khalil A. Abboud、Sukwon Hong

  DOI：10.1021/ol9013156

  日期：2009.8.6

  (ADC) from chloroamidinium salts. Convenient access to various ADC complexes (B, Rh, Ir, Pd) stems from a one-pot transmetalation protocol. Formation of a carbenoid species is suggested by 1D and 2D NMR studies with a 13C-labeled chloroamidinium precursor and also by X-ray structures of transition metal−carbene complexes. Rh-ADC complex 4 is an effective catalyst for the 1,2-addition of aryl boronic acids

  已开发出锂-卤素交换路线，可从氯ami盐生成无环二氨基卡宾（ADC）。方便地访问各种ADC配合物（B，Rh，Ir，Pd）来自于一锅式金属转移协议。通过13 C标记的氯ami鎓前体的1D和2D NMR研究以及过渡金属-卡宾配合物的X射线结构，表明类胡萝卜素物质的形成。Rh-ADC配合物4是芳基硼酸1,2-加成芳基醛的有效催化剂。
• Ambident Reactivities of Carbenium Salts Possessing a Thiocarbonyl Group at the<i>β</i>-Position
  作者：Juzo Nakayama、Taku Kitahara、Yoshiaki Sugihara、Akihiko Ishii

  DOI：10.1246/cl.1999.187

  日期：1999.2

  A stable, crystalline carbenium iodide, which possesses a thiocarbonyl group at the β-position, shows ambident reactivities, thereby reacting with a hard nucleophile OH− at the carbenium carbon atom and with a soft nucleophile RLi at the thiocarbonyl sulfur atom. Thermal dissociation of the MeLi adduct to a carbene and a ketene dithioacetal is also presented.

  一种稳定的晶体碘化碳鎓在 β 位上具有一个硫代羰基，显示出不同时的反应活性，从而与碳鎓碳原子上的硬亲核体 OH- 和硫代羰基硫原子上的软亲核体 RLi 发生反应。此外，还介绍了 MeLi 加合物热解生成碳烯和烯酮二硫代乙缩醛的情况。
• Hydrolysis of Imidazole-2-ylidenes
  作者：Oldamur Hollóczki、Péter Terleczky、Dénes Szieberth、Georgios Mourgas、Dietrich Gudat、László Nyulászi

  DOI：10.1021/ja103578y

  日期：2011.2.2

  The direct reaction of an imidazole-2-ylidene in a predominantly aqueous environment [about 0.1 M solution in a H2O (>60%)/THF solvent system] was investigated for the first time. The reaction yielded a stable solution of the corresponding imidazolium-hydroxide of pH 13, which is in agreement with results from an ab initio molecular dynamics simulation. In contrast, hydrolysis of the carbene in a mainly aprotic environment (>80% THF) gives a hydrogen-bridged carbene water complex which could be detected by NMR and IR spectroscopies for the first time. This complex converts slowly to two isomeric ring opened products and is at higher water concentration in dynamic equilibrium with the imidazolium hydroxide. A computational mechanistic study of the carbene hydrolysis with a gradually increasing number of water molecules revealed that the imidazolium hydroxide structure can only be optimized with three or more water molecules as reactants, and with the increasing number of water molecules its stability is increasing with respect to the carbene water complex. In agreement with the experimental results, these findings point out that solvent stabilization and basicity of the hydroxide ion plays a crucial role in the reaction. With increasing number of water molecules the barriers connecting the reaction intermediates are getting smaller, and the ring opened hydrolysis products can be derived from imidazolium hydroxide type intermediates. Computational studies on the hydrolysis of a nonaromatic imidazolidine-2-ylidene analogue clearly indicated the analogous ring-opened product to be by 10-12 kcal/mol more stable than the appropriate ion pair and the carbene water complex, in agreement with the known aromatic stabilization of imidazol-2-ylidenes. Accordingly, these molecules hydrolyze with exclusive formation of the ring-opened product.
• Metal Complexes of N-Heterocyclic Carbenes—A New Structural Principle for Catalysts in Homogeneous Catalysis
  作者：Wolfgang A. Herrmann、Martina Elison、Jakob Fischer、Christian Köcher、Georg R. J. Artus

  DOI：10.1002/anie.199523711

  日期：1995.11.17