Preparation of Polyaminopyridines Using a CuI/l-Proline-Catalyzed C-N Polycoupling Reaction

Reis, Lindomar Augusto dos; Ligiéro, Carolina B. P.; Andrade, Acácio A.; Taylor, Jason G.; Miranda, Paulo C. M. L.

doi:10.3390/ma5112176

Cited by 10 publications

(6 citation statements)

References 40 publications

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“…In general, the reaction mechanism consists of oxidative addition followed by reductive elimination steps, which is well-known for most of the metal-catalyzed coupling reactions. The role of the L-Proline ligand is to maintain the copper (I) catalytic reactivity, give a high-yield product and permit the use of mild reaction conditions since the ligand-free method requires a high stoichiometric amount of the catalyst and high reaction temperature that might reach 200 • C [30][31][32][33].…”

Section: Synthesis and Physical Propertiesmentioning

confidence: 99%

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Post-Functionalization of Bromo-Substituted Ether-Linked Polymers via Ullman Coupling Reaction: Synthesis, Characterization and Their Role toward Carbon Dioxide Capture

et al. 2022

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A new open-chain ether-linked polymer has been prepared via nucleophilic aromatic substitution reaction on a C-F bond of 1,4-dibromo-2,5-difluorobenzene by using 2,2-bis(4-hydroxyphenyl) hexafluoropropane (bisphenol AF or BAF). The new polymer (PE-AF) has shown a good solubility in non-polar solvents, good thermal stability (up to 300 °C) and random surface morphology. Tailoring these properties has been achieved by utilizing the post-modification synthetic methodology on the bromo-sites of the polymer backbone via the application of an Ullmann coupling reaction with aniline to form the polymer (PE-Sec-NHPh). The successful synthesis of the polymers has been confirmed by elemental analysis, infrared spectroscopy (IR), 1H- and 13C-NMR and 13C CP-MAS solid state. Upon incorporation of the aniline linker, the nitrogen content increased when compared with the parent polymer chain, and thus PE-Sec-NHPh revealed a higher thermal stability up to 350 °C and a more uniformly aggregated morphology (spherical particles ca. 0.3–0.1 µm). A further evaluation has been conducted on the polymers by measuring their surface tendency toward carbon dioxide capture. Interestingly, despite their non-porous nature, the polymers demonstrated a reasonable amount of gas capture that reached 90.0 and 41.0 mg/g for PE-Sec-NHPh and PE-AF, respectively. Furthermore, the calculated CO2 binding affinities of the polymers are consistent with data reported previously in the literature.

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Section: Synthesis and Physical Propertiesmentioning

confidence: 99%

“…the ligand-free method requires a high stoichiometric amount of the catalyst and high reaction temperature that might reach 200 °C [30][31][32][33].…”

Section: Synthesis and Physical Propertiesmentioning

confidence: 99%

Post-Functionalization of Bromo-Substituted Ether-Linked Polymers via Ullman Coupling Reaction: Synthesis, Characterization and Their Role toward Carbon Dioxide Capture

et al. 2022

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“…Post-functionalization of PE-A has been achieved applying the Ullmann-coupling reaction between the aryl-halide part of the polymer and aromatic primary amine [11,18] . Ani-A.…”

Section: Resultsmentioning

confidence: 99%

“…When the LOI value exceeds 28, then the polymer is considered as a good flame-retardant candidate. Examples on these polymers include poly(brominated) polymers, poly(ether-amine), poly(aminopyridines), poly(ether-sulfone), poly-(ether-imide), poly(imnies) with LOI values of 49, 33, 32, 35, 46 and 32, respectively [10][11][12][13] . The high LOI values support the fact that the incorporation of halogens or heterocycles within an ether-linked chain improves the thermal stability and the flame-retardancy of polymers.…”

Section: Introductionmentioning

confidence: 99%

Post-functionalization of Ether-linked Polymer via the Application of Ullmann-coupling Reaction: Synthesis, Characterization and Thermal Degradation Kinetics

2021

JJC

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A new ether-linked polymer (PE-A) was synthesized via the polycondensation of 1,4-dibromo-2,5-difluorobenzene with biphenol (A). The new polymer has shown a good solubility in non-polar solvents, as well as moderate thermal stability (up to 300 °C). The parent PE-A was subjected to post-functionalization modification applying the Ullmann-coupling reaction on the C-Br bonds of PE-A, where the bromo-sites have been replaced by aniline-linked moieties. The resulting polymer (PE-Ani-A) shows slight solubility in several solvents. Its thermal stability was enhanced by 36% when compared with PE-A. To ensure the significant impact of the inclusion of the aniline group on thermal stability, a thermal degradation kinetics study was performed and the Coats-Redfren and Broido theoretical models were applied to explore the degradation process. The calculated activation energy for PE-Ani-A degradation was thereby found to be higher than that of PE-A, which indicates the higher thermal stability of PE-Ani-A. For further insights into the thermal stability of the polymers, the limited oxygen index (LOI), which represents the flame-retardant property of the polymers, was calculated. The results indicate that PE-A is a promising candidate as a flame-retardant polymer (LOI = 46.7), since it has a high bromo-content. On the other hand, PE-Ani-A has a lower LOI although it has a higher thermal stability.

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“…For the preparation of polyaminopyridines, Miranda et al used a CuI/ L ‐proline catalytic system for Ullman‐like polymerization 115. As previously reported by Kanbara et al,109 3‐amino‐6‐bromopyridine ( 161 ) proved to be much more reactive than 2‐amino‐5‐bromopyridine.…”

Section: C–n Cross‐couplingmentioning

confidence: 96%

Metal‐Catalyzed Cross‐Coupling Reactions of Aminopyridines

2015

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The aminopyridines are key building blocks in the synthesis of bioactive heterocyclic compounds such as azaindoles and imidazopyridines. The role of metal-catalyzed methods in aminopyridine functionalization, in particular the catalytic systems used, reaction conditions and the influence of aminopyridine substituents on the reaction outcome, is outlined. The review covers different metal-catalyzed reactions developed for C-C and C-N bond formation. One-pot and multicomponent reactions directed towards aminopyridine-

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Preparation of Polyaminopyridines Using a CuI/l-Proline-Catalyzed C-N Polycoupling Reaction

Cited by 10 publications

References 40 publications

Post-Functionalization of Bromo-Substituted Ether-Linked Polymers via Ullman Coupling Reaction: Synthesis, Characterization and Their Role toward Carbon Dioxide Capture

Post-Functionalization of Bromo-Substituted Ether-Linked Polymers via Ullman Coupling Reaction: Synthesis, Characterization and Their Role toward Carbon Dioxide Capture

Post-functionalization of Ether-linked Polymer via the Application of Ullmann-coupling Reaction: Synthesis, Characterization and Thermal Degradation Kinetics

Metal‐Catalyzed Cross‐Coupling Reactions of Aminopyridines

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