2-(1H-imidazol-1-yl)-N,N-dimethylaniline | 1433460-54-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 2-(1H-imidazol-1-yl)-N,N-dimethylaniline
• 英文别名: 1-(2'-(dimethylamino)phenyl)imidazole；2-imidazol-1-yl-N,N-dimethylaniline
• CAS: 1433460-54-8
• 化学式: C₁₁H₁₃N₃
• 分子量: 187.244
• InChiKey: YIDBMAGFCDITGQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  21.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(1H-imidazol-1-yl)-N,N-dimethylaniline 在 正丁基锂 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 1-(2'-(dimethylamino)phenyl)-2-diphenylphosphino-3-methylimidazolium trifluoromethanesulfonate
  参考文献：
  名称：

  Ionic Rh(I)-complexes containing π-accepting and hemilabile P,N-ligands as efficient catalysts for hydroformylation of 1-octene

  摘要：

  The ionic hybrid P,N-ligands of 1 and 2 have been synthesized as one type of unconventional tertiary phosphines with the advantages of both the pi-accepting ligands and the hemilabile ligands. The corresponding ionic Rh(I)-complexes of 1A and 2A proved to be more efficient catalysts for hydroformylation of 1-octene over isomerization than the traditional Rh-I(acac)(CO)(PPh3), due to the pi-backdonation interaction in Rh -> P linkage and the hemilabile ligation of N,P-coordinating sites to Rh-center. The in situ high-pressure FT-IR analysis indicated that: (1) the formation and lifetime of the active Rh-H species (2047 cm(-1)) derived from 1A are facilitated by the presence of ligand 1; (2) the formation of the active Rh-H species is depressed without the aid of the P,N-hemilabile ligation; and (3) the active Rh-H species derived from Rh-I(acac)(CO)(PPh3) is unstable and susceptible to the formation of the inactive carbonyl-bridged Rh-dimer. (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2014.09.021
• 作为产物：
  描述：

  咪唑 、 2-溴-N,N-二甲基苯胺 在 copper(l) iodide 、 potassium carbonate 、 L-脯氨酸 作用下， 以 二甲基亚砜 为溶剂， 反应 24.0h， 以56%的产率得到2-(1H-imidazol-1-yl)-N,N-dimethylaniline
  参考文献：
  名称：

  Ionic Rh(I)-complexes containing π-accepting and hemilabile P,N-ligands as efficient catalysts for hydroformylation of 1-octene

  摘要：

  The ionic hybrid P,N-ligands of 1 and 2 have been synthesized as one type of unconventional tertiary phosphines with the advantages of both the pi-accepting ligands and the hemilabile ligands. The corresponding ionic Rh(I)-complexes of 1A and 2A proved to be more efficient catalysts for hydroformylation of 1-octene over isomerization than the traditional Rh-I(acac)(CO)(PPh3), due to the pi-backdonation interaction in Rh -> P linkage and the hemilabile ligation of N,P-coordinating sites to Rh-center. The in situ high-pressure FT-IR analysis indicated that: (1) the formation and lifetime of the active Rh-H species (2047 cm(-1)) derived from 1A are facilitated by the presence of ligand 1; (2) the formation of the active Rh-H species is depressed without the aid of the P,N-hemilabile ligation; and (3) the active Rh-H species derived from Rh-I(acac)(CO)(PPh3) is unstable and susceptible to the formation of the inactive carbonyl-bridged Rh-dimer. (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2014.09.021

文献信息

• Synthesis of Aromatic α-Aminoesters: Palladium-Catalyzed Long-Range Arylation of Primary C sp 3H Bonds
  作者：Sam Aspin、Anne-Sophie Goutierre、Paolo Larini、Rodolphe Jazzar、Olivier Baudoin

  DOI：10.1002/anie.201206237

  日期：2012.10.22

  Remote control: The title reaction for β–ζ arylation of α‐amino esters with aryl bromides is described. This reaction, which occurs selectively at the terminal position of linear alkyl chains, gives rise to synthetically useful (hetero)arylalanines and homologues after debenzylation (see scheme).

  远程控制：描述了α-氨基酯与芳基溴的β-ζ芳基化反应的标题反应。该反应选择性地发生在线性烷基链的末端，该反应在脱苄基反应后产生合成上有用的（杂）芳基丙氨酸和同系物（参见方案）。
• Palladium-Catalyzed β-Arylation of Silyl Ketene Acetals and Application to the Synthesis of Benzo-Fused δ-Lactones
  作者：Sam Aspin、Laura López-Suárez、Paolo Larini、Anne-Sophie Goutierre、Rodolphe Jazzar、Olivier Baudoin

  DOI：10.1021/ol402398s

  日期：2013.10.4

  Silyl ketene acetals are shown to be competent nucleophiles in Pd-catalyzed migrative C(sp3)–H arylations. Compared to the parent ester lithium enolates, they possess decreased reactivity but enhanced chemoselectivity. This behavior was exploited through the synthesis of valuable benzo-fused δ-lactones such as 1-isochromanones and dihydrocoumarins.

  在Pd催化的迁移性C（sp 3）–H芳基化反应中，甲硅烷基乙烯酮缩醛被证明是有效的亲核试剂。与母体酯烯醇锂相比，它们具有降低的反应性但增强的化学选择性。这种行为是通过合成有价值的苯并稠合的δ-内酯（例如1-isochromanones和dihydrocoumarins）来开发的。
• Copper(II)-Catalyzed Synthesis of ­Indoloquinoxalin-6-ones through Oxidative Mannich Reaction
  作者：Anupal Gogoi、Prasenjit Sau、Wajid Ali、Srimanta Guin、Bhisma K. Patel

  DOI：10.1002/ejoc.201501532

  日期：2016.3

  A Cu-catalyzed synthesis of indoloquinoxalin-6-one has been developed that starts from o-indolyl-N,N-dialkylamines through sp3 C–H bond oxidation α to the nitrogen atom with di-tert-butyl peroxide as oxidant. Other heterocycles, such as pyrrole, imidazole and benzimidazole derivatives also reacted successfully to give their respective fused quinoxalin-6-one derivatives. In this process, one of the

  已经开发了一种 Cu 催化合成吲哚喹喔啉-6-one，该合成从邻吲哚基-N,N-二烷基胺开始，通过 sp3 C-H 键将 α 氧化为氮原子，并使用二叔丁基过氧化物作为氧化剂。其他杂环，如吡咯、咪唑和苯并咪唑衍生物也成功地反应得到它们各自的稠合喹喔啉-6-one衍生物。在这个过程中，甲基之一转化为羰基。
• Imidazolio-substituted secondary phosphine oxides as potential carbene reagents
  作者：Yu-Chang Chang、Chih-Hung Chang、Lyu-Wei Wang、Ya-Han Liang、Dan-Fu Hu、Chia-Ming Weng、Kuo-Chung Mao、Fung-E Hong

  DOI：10.1016/j.poly.2015.08.041

  日期：2015.11

  New pre-ligands of 1-aryl-1H-imidazol-2-yl substituted secondary phosphine oxides (HRP(=O)-Im:SPO-Im) were prepared and characterized by spectroscopic means. The SPO-Im pre-ligands are able to tautomerize to their corresponding genuine ligands, the 1-aryl-1H-imidazol-2-yl substituted phosphinous acids ((HO)RP-Im:PA-Im) while the condition permitted. Further reactions of selected SPO-Im pre-ligands toward Pd(COD)Cl-2 or PdBr yielded bis-(PA-Im)-coordinated cis-palladium dichloride or dibromide complexes, respectively. These cis-palladium dihalide complexes are all having an intramolecular hydrogen bond between two coordinated PA-Im ligands (R(Im(H)(+))P-O-center dot center dot center dot HO-PRIm) by transferring a proton from one of the two P-OH groups to its free nitrogen site of imidazolyl substituents; and, therefore, imposes the formation of zwitterionic cis-form palladium complexes. Three crystal structures of these square-planar zwitterionic palladium complexes were determined by the X-ray diffraction methods. Additionally, two novel NHC carbene coordinated palladium complexes were obtained from the crystal-growing process of the above-mentioned zwitterionic cis-palladium dihalide complexes. The crystal structures of two NHC carbene coordinated palladium complexes were also successfully determined. Density-functional theory (DFT) calculations were carried out to substantiate the feasibility of the proposed reaction pathways for the formation of NHC carbene coordinated palladium complexes. Finally, applying selected SPO-Im pre-ligands to Heck reactions with pre-optimized reaction conditions exhibited satisfactory performances. (C) 2015 Elsevier Ltd. All rights reserved.
• Ionic Rh(I)-complexes containing π-accepting and hemilabile P,N-ligands as efficient catalysts for hydroformylation of 1-octene
  作者：Sheng-Jie Chen、Yong-Qi Li、Yong-Yong Wang、Xiao-Li Zhao、Ye Liu

  DOI：10.1016/j.molcata.2014.09.021

  日期：2015.1

  The ionic hybrid P,N-ligands of 1 and 2 have been synthesized as one type of unconventional tertiary phosphines with the advantages of both the pi-accepting ligands and the hemilabile ligands. The corresponding ionic Rh(I)-complexes of 1A and 2A proved to be more efficient catalysts for hydroformylation of 1-octene over isomerization than the traditional Rh-I(acac)(CO)(PPh3), due to the pi-backdonation interaction in Rh -> P linkage and the hemilabile ligation of N,P-coordinating sites to Rh-center. The in situ high-pressure FT-IR analysis indicated that: (1) the formation and lifetime of the active Rh-H species (2047 cm(-1)) derived from 1A are facilitated by the presence of ligand 1; (2) the formation of the active Rh-H species is depressed without the aid of the P,N-hemilabile ligation; and (3) the active Rh-H species derived from Rh-I(acac)(CO)(PPh3) is unstable and susceptible to the formation of the inactive carbonyl-bridged Rh-dimer. (C) 2014 Elsevier B.V. All rights reserved.