108-69-0Relevant articles and documents
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Haller,Adams,Wherry
, p. 1842 (1920)
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First example of using a ionic liquid in electrophilic amination of arenes. Amination of methylbenzenes with the system NaN3-AlCl 3-HCl
Borodkin,Elanov,Shubin
, p. 1541 - 1542 (2004)
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Coordination or Oxidative Addition? Activation of N-H with [Tp′Rh(PMe3)]
Yuwen, Jing,Brennessel, William W.,Jones, William D.
, p. 557 - 566 (2019)
A thermal reaction of amines, anilines, and amides with Tp′Rh(PMe3)(CH3)H (1, Tp′ = tris(3,5-dimethyl-pyrazolyl)borate) is described in this report. No N-H bond cleavage was observed for reactions between ammonia or unsubstituted aliphatic amines with the reactive fragment [Tp′Rh(PMe3)]. Instead, amine coordination products (κ2-Tp′)Rh(PMe3)(NHR1R2) (R1 = H, R2 = H, nPr, iPr, octyl; R1 = R2 = Et; R1, R2: pyrrolidine) were observed, and the crystal structure of (κ2-Tp′)Rh(PMe3)(NH2iPr) is reported. No coordination products were observed when 1 was reacted with 1,1,1,3,3,3-hexafluoropropan-2-amine, anilines, and amides. Instead, the oxidative addition products (κ3-Tp′)Rh(PMe3)(NHR)H (R = CH(CF3)2, C6H5, 3,5-dimethylbenzyl, C6F5, C(O)CH3, C(O)CF3) were observed. Both RhI-N coordination products (κ2-Tp′)Rh(PMe3)(NH2CH2CF3) and RhIII N-H addition products (κ3-Tp′)Rh(PMe3)(NHCH2CF3)H were generated when 1 was reacted with 2,2,2-trifluoroethylamine. Coordination products dissociate ammonia and amines in benzene much faster than oxidative addition products eliminate anilines and amides. The relative metal-nitrogen bond energies were studied using established kinetic techniques. Analysis of the relationship between the relative M-N bond strengths and N-H bond strengths showed a linear correlation with a slope = RM-N/N-H of 0.91 (10), indicating that the Rh-N bond strength varies in direct proportion to the N-H bond strength.
Selective Reduction of Nitroarenes to Arylamines by the Cooperative Action of Methylhydrazine and a Tris(N-heterocyclic thioamidate) Cobalt(III) Complex
Ioannou, Dimitris I.,Gioftsidou, Dimitra K.,Tsina, Vasiliki E.,Kallitsakis, Michael G.,Hatzidimitriou, Antonios G.,Terzidis, Michael A.,Angaridis, Panagiotis A.,Lykakis, Ioannis N.
, p. 2895 - 2906 (2021/02/27)
We report an efficient catalytic protocol that chemoselectively reduces nitroarenes to arylamines, by using methylhydrazine as a reducing agent in combination with the easily synthesized and robust catalyst tris(N-heterocyclic thioamidate) Co(III) complex [Co(κS,N-tfmp2S)3], tfmp2S = 4-(trifluoromethyl)-pyrimidine-2-thiolate. A series of arylamines and heterocyclic amines were formed in excellent yields and chemoselectivity. High conversion yields of nitroarenes into the corresponding amines were observed by using polar protic solvents, such as MeOH and iPrOH. Among several hydrogen donors that were examined, methylhydrazine demonstrated the best performance. Preliminary mechanistic investigations, supported by UV-vis and NMR spectroscopy, cyclic voltammetry, and high-resolution mass spectrometry, suggest a cooperative action of methylhydrazine and [Co(κS,N-tfmp2S)3] via a coordination activation pathway that leads to the formation of a reduced cobalt species, responsible for the catalytic transformation. In general, the corresponding N-arylhydroxylamines were identified as the sole intermediates. Nevertheless, the corresponding nitrosoarenes can also be formed as intermediates, which, however, are rapidly transformed into the desired arylamines in the presence of methylhydrazine through a noncatalytic path. On the basis of the observed high chemoselectivity and yields, and the fast and clean reaction processes, the present catalytic system [Co(κS,N-tfmp2S)3]/MeNHNH2 shows promise for the efficient synthesis of aromatic amines that could find various industrial applications.
Ligand compound for copper catalyzed aryl halide coupling reaction, catalytic system and coupling reaction
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Paragraph 0111-0119, (2021/05/29)
The invention provides a ligand compound capable of being used for copper catalyzed aryl halide coupling reaction, the ligand compound is a three-class compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group, and the invention also provides a catalytic system for the aryl halide coupling reaction. Thecatalytic system comprises a copper catalyst, a compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group adopted as a ligand, alkali and a solvent, and meanwhile, the invention also provides a system for the aryl halide coupling reaction adopting the catalyst system. The compound containing the 2-(substituted or non-substituted) aminopyridine nitrogen oxygen group can be used as the ligand for the copper catalyzed aryl chloride coupling reaction, and the ligand is stable under a strong alkaline condition and can well maintain catalytic activity when being used for the copper-catalyzed aryl chloride coupling reaction. In addition, the copper catalyst adopting the compound as the ligand can particularly effectively promote coupling of copper catalyzed aryl chloride and various nucleophilic reagents which are difficult to generate under conventional conditions, C-N, C-O and C-S bonds are generated, and numerous useful small molecule compounds are synthesized. Therefore, the aryl halide coupling reaction has a very good large-scale application prospect by adopting the copper catalysis system of the ligand.
Porous polymeric ligand promoted copper-catalyzed C-N coupling of (hetero)aryl chlorides under visible-light irradiation
Wang, Erfei,Chen, Kaixuan,Chen, Yinan,Zhang, Jiawei,Lin, Xinrong,Chen, Mao
, p. 17 - 21 (2020/11/04)
A porous polymeric ligand (PPL) has been synthesized and complexed with copper to generate a heterogeneous catalyst (Cu@PPL) that has facilitated the efficient C-N coupling with various (hetero)aryl chlorides under mild conditions of visible-light irradiation at 80 °C (58 examples, up to 99% yields). This method could be applied to both aqueous ammonia and substituted amines, and is compatible to a variety of functional groups and heterocycles, as well as allows tandem C-N couplings with conjunctive dihalides. Furthermore, the heterogeneous characteristic of Cu@PPL has enabled a straightforward catalyst separation in multiple times of recycling with negligible catalytic efficiency loss by simple filtration, affording reaction mixtures containing less than 1 ppm of Cu residue. [Figure not available: see fulltext.]