1-isopropyl-3-(5,7-dimethyl-1,8-naphthyrid-2-yl)imidazolium bromide | 1276114-66-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 英文名称: 1-isopropyl-3-(5,7-dimethyl-1,8-naphthyrid-2-yl)imidazolium bromide
• CAS: 1276114-66-9
• 化学式: Br*C₁₆H₁₉N₄
• 分子量: 347.258
• InChiKey: NRQXAHDCEOEXRI-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -0.09
• 重原子数：
  21.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  34.59
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  1-isopropyl-3-(5,7-dimethyl-1,8-naphthyrid-2-yl)imidazolium bromide 以 二氯甲烷 、 乙腈 为溶剂， 反应 60.5h， 生成
  参考文献：
  名称：

  钌平台上的金属-配体合作：通过醇与胺的无受体脱氢偶联选择性形成亚胺

  摘要：

  金属金属单独使用键合的二钌络合物，桥接由萘啶官能化的N-杂环卡宾（NHC）配体为特色的萘啶单元上的羟基的附属物，以[钌的单罐反应，得到2（CH 3 COO）2（ CO）4 ]用1-苄基-3-（5,7-二甲基-1,8- naphthyrid -2-基）咪唑鎓溴化物（BIN ⋅的HBr）或1-异丙基-3-（5,7-二甲基-1- ，8-naphthyrid -2-基）咪唑鎓溴化物（PIN ⋅的HBr），TlBF 4，以及含有吸电子基团的取代苯甲醛。修饰的NHC-萘啶-羟基配体跨越了二氢键单元，其中NHC碳和羟基氧占据了轴向位点。在催化量的弱碱1,4-二氮杂双环[2.2.2]辛烷（DABCO）存在下，所有合成的化合物均能催化醇的无受体脱氢成相应的醛。此外，醇与胺的无受体脱氢偶联（ADHC）提供了相应的亚胺作为唯一产物。底物范围用1（BIN，对硝基苯甲醛）检查。相似的络合物[Ru 2（CO）4（CH

  DOI：

  10.1002/chem.201304403

文献信息

• Site-Directed Anchoring of an N-Heterocyclic Carbene on a Dimetal Platform: Evaluation of a Pair of Diruthenium(I) Catalysts for Carbene-Transfer Reactions from Ethyl Diazoacetate
  作者：Biswajit Saha、Tapas Ghatak、Arup Sinha、S. M. Wahidur Rahaman、Jitendra K. Bera

  DOI：10.1021/om200142p

  日期：2011.4.11

  utilities of the BArF (tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) salts of these compounds are evaluated toward carbene-transfer reactions from ethyl diazoacetate including aldehyde olefination, cyclopropanation, and X−H (X = O, N) insertions. 1-BArF is clearly shown to be the superior catalyst. DFT calculations are undertaken to understand the influence of NHC binding on the electronic structures of the

  在金属-金属单键合的二钌（I）平台上实现萘啶官能化的N-杂环卡宾（NHC）的定点锚固。用乙腈中的Ru 2（CH 3 COO）2（CO）4室温处理1-异丙基-3-（5,7-二甲基-1,8-萘-2-基）咪唑溴化铵（PIN·HBr）得到的不支持的化合物的Ru 2（CO）4（κ 2 ç 2，N 1 -PIn）2溴2（1）。NHC配体的明智改变导致桥接化合物Ru 2（CO）4（CH 3 COO）（μ2 -κ 2 Ç 2，N 1 -bin）能Br（2）（BIN = 1-苄基-3-（3-苯基-1,8- naphthyrid -2-基）咪唑-2-亚基）。X射线分析显示，每个钌在赤道位点上的PIN螯合结合为1，而跨越二钌核心的BIN的桥螯合物结合为2。对这些化合物的BAr F（四（3,5-双（三氟甲基）苯基）硼酸酯）盐的催化效用进行了评估，以进行重氮乙酸乙酯的卡宾转移反应，包括醛烯化，环丙烷化和XH（X =
• Bifunctional Water Activation for Catalytic Hydration of Organonitriles
  作者：Prosenjit Daw、Arup Sinha、S. M. Wahidur Rahaman、Shrabani Dinda、Jitendra K. Bera

  DOI：10.1021/om300297y

  日期：2012.5.14

  Treatment of [Rh(COD)(mu-Cl)](2) with excess (BuOK)-Bu-t and subsequent addition of 2 equiv of PIN center dot HBr in THF afforded [Rh(COD)(kappa C-2-PIN)Br] (1) (PIN = 1-isopropyl-3-(5,7-dimethyl-1,8-naphthyrid-2-yl)imidazol-2-ylidene, COD = 1,5-cyclooctadiene). The X-ray structure of 1 confirms ligand coordination to "Rh(COD)Br" through the carbene carbon featuring an unbound naphthyridine. Compound 1 is shown to be an excellent catalyst for the hydration of a wide variety of organonitriles at ambient temperature, providing the corresponding organoamides. In general, smaller substrates gave higher yields compared with sterically bulky nitriles. A turnover frequency of 20 000 h(-1) was achieved for the acrylonitrile. A similar Rh(I) catalyst without the naphthyridine appendage turned out to be inactive. DFT studies are undertaken to gain insight on the hydration mechanism. A 1:1 catalyst-water adduct was identified, which indicates that the naphthyridine group steers the catalytically relevant water molecule to the active metal site via double hydrogen-bonding interactions, providing significant entropic advantage to the hydration process. The calculated transition state (TS) reveals multicomponent cooperativity involving proton movement from the water to the naphthyridine nitrogen and a complementary interaction between the hydroxide and the nitrile carbon. Bifunctional water activation and cooperative proton migration are recognized as the key steps in the catalytic cycle.