1,3-diisopropyl-2-methyleneimidazoline

• 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-2-methyleneimidazoline
• 英文别名: 1,3-Diisopropyl-2-methylene-2,3-dihydro-1H-imidazole；2-methylidene-1,3-di(propan-2-yl)imidazole
• 化学式: C₁₀H₁₈N₂
• 分子量: 166.266
• InChiKey: WJHYOJPIQOOCKB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  12
• 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：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  羰基硫 、 1,3-diisopropyl-2-methyleneimidazoline 以 四氢呋喃 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 2.0h， 以53%的产率得到
  参考文献：
  名称：

  N-杂环烯烃的CO2，COS和CS2加合物及其在固定二氧化碳的有机催化剂中的应用

  摘要：

  合成了各种N-杂环烯烃（NHO）的CO2，COS和CS2加合物，并通过单晶X射线晶体学对其进行了表征。NHO-COS加合物中的CO键长度略短...

  DOI：

  10.1039/c5gc00948k
• 作为产物：
  描述：

  1-异丙基-2-甲基咪唑 在 potassium hydride 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 72.0h， 生成 1,3-diisopropyl-2-methyleneimidazoline
  参考文献：
  名称：

  Fast CO₂ Sequestration, Activation, and Catalytic Transformation Using N-Heterocyclic Olefins

  摘要：

  N-Heterocyclic Olefin (NHO) with high electronegativity at the terminal carbon atom was found to show a strong tendency for CO2 sequestration, affording a CO2 adduct (NHO-CO2). X-ray single crystal analysis revealed the bent geometry of the binding CO2 in the NHO-CO2 adducts with an O-C-O angle of 127.7-129.9 degrees, dependent on the substitute groups of N-heterocyclic ring. The length of the C-carboxylate-C-NHO bond is in the range of 1.55-1.57 angstrom, significantly longer than that of the C-carboxylate-C-NHC bond (1.52-1.53 angstrom) of the previously reported NHC-CO2 adducts. The FTIR study by monitoring the v(CO2) region of transmittance change demonstrated that the decarboxylation of NHO-CO2 adducts is easier than that of the corresponding NHC-CO2 adducts. Notably, the NHO-CO2 adducts were found to be highly active in catalyzing the carboxylative cyclization of CO2 and propargylic alcohols at mild conditions (even at ambient temperature and 0.1 MPa CO2 pressure), selectively giving alpha-alkylidene cyclic carbonates in good yields. The catalytic activity is about 10-200 times that of the corresponding NHC-CO2 adducts at the same conditions. Two reaction paths regarding the hydrogen at the alkenyl position of cyclic carbonates coming from substrate (path A) or both substrate and catalyst (path B) were proposed on the basis of deuterium labeling experiments. The high activity of NHO-CO2 adduct was tentatively ascribed to its low stability for easily releasing the CO2 moiety and/or the desired product, a possible rate-limiting step in the catalytic cycle.

  DOI：

  10.1021/ja405114e
• 作为试剂：
  描述：

  1-methyl-2-phenylaziridine 、 二氧化碳 在 1,3-diisopropyl-2-methyleneimidazoline 作用下， 反应 2.0h， 以90%的产率得到3-methyl-5-phenyloxazolidin-2-one
  参考文献：
  名称：

  N-杂环烯烃是将二氧化碳化学转化为增值化学品的可靠有机催化剂

  摘要：

  在本报告中，研究了N-杂环烯烃（NHOs）作为新兴的一类有机催化剂的活性，该方法通过与氮丙啶反应形成恶唑烷酮和胺与聚甲基氢硅氧烷（PMHS）的N-甲酰化反应来化学固定二氧化碳。在温和条件下使用9-borabicyclo [3.3.1]壬烷（9-BBN）作为还原剂。由于两个氮原子的供电子能力，NHOs的环外碳原子具有高度亲核性。NHO的这种高度亲核性激活了CO 2分子，形成了两性离子NHO-羧酸盐（NHO-CO 2）加合物，该化合物在甲酰化反应以及氮丙啶的羧基化反应生成恶唑烷酮中均具有活性。

  DOI：

  10.1002/cssc.201600467

文献信息

• CO₂, COS and CS₂ adducts of N-heterocyclic olefins and their application as organocatalysts for carbon dioxide fixation
  作者：Yan-Bo Wang、Dong-Sheng Sun、Hui Zhou、Wen-Zhen Zhang、Xiao-Bing Lu

  DOI：10.1039/c5gc00948k

  日期：——

  Various CO2, COS and CS2 adducts of N-Heterocyclic olefin (NHO) were synthesized and characterised by single crystal X-ray crystallography. The length of C-O bond in NHO-COS adducts is slightly shorter...

  合成了各种N-杂环烯烃（NHO）的CO2，COS和CS2加合物，并通过单晶X射线晶体学对其进行了表征。NHO-COS加合物中的CO键长度略短...
• Fast CO₂ Sequestration, Activation, and Catalytic Transformation Using <i>N</i>-Heterocyclic Olefins
  作者：Yan-Bo Wang、Yi-Ming Wang、Wen-Zhen Zhang、Xiao-Bing Lu

  DOI：10.1021/ja405114e

  日期：2013.8.14

  N-Heterocyclic Olefin (NHO) with high electronegativity at the terminal carbon atom was found to show a strong tendency for CO2 sequestration, affording a CO2 adduct (NHO-CO2). X-ray single crystal analysis revealed the bent geometry of the binding CO2 in the NHO-CO2 adducts with an O-C-O angle of 127.7-129.9 degrees, dependent on the substitute groups of N-heterocyclic ring. The length of the C-carboxylate-C-NHO bond is in the range of 1.55-1.57 angstrom, significantly longer than that of the C-carboxylate-C-NHC bond (1.52-1.53 angstrom) of the previously reported NHC-CO2 adducts. The FTIR study by monitoring the v(CO2) region of transmittance change demonstrated that the decarboxylation of NHO-CO2 adducts is easier than that of the corresponding NHC-CO2 adducts. Notably, the NHO-CO2 adducts were found to be highly active in catalyzing the carboxylative cyclization of CO2 and propargylic alcohols at mild conditions (even at ambient temperature and 0.1 MPa CO2 pressure), selectively giving alpha-alkylidene cyclic carbonates in good yields. The catalytic activity is about 10-200 times that of the corresponding NHC-CO2 adducts at the same conditions. Two reaction paths regarding the hydrogen at the alkenyl position of cyclic carbonates coming from substrate (path A) or both substrate and catalyst (path B) were proposed on the basis of deuterium labeling experiments. The high activity of NHO-CO2 adduct was tentatively ascribed to its low stability for easily releasing the CO2 moiety and/or the desired product, a possible rate-limiting step in the catalytic cycle.