Palladium-catalyzed Aryl Amination Reaction Research Articles

Heat resistant fluorenone-based polyimines as novel light-emitting polymers

Fluorenone-based polyamines, as novel light-emitting polymers, were synthesized by the condensation polymerization of 3,6-dibromo-9-fluorenone with different aromatic diamines by palladiumcatalyzed aryl amination reaction. The structures of the polymers were characterized by means of FT-IR, 1H NMR spectroscopy and elemental analysis. The experimental results show a good agreement with the proposed structures. TGA measurement exhibits that the polymers possess good thermal stabilities with high decomposition temperatures (T 5≥400 °C). Due to the photo-induced intramolecular charge-transfer (ICT) of fluorenone-based polyimines, these polymers show significantly strong photonic luminescence in N,Ndimethylacetamide.

Design and preparation of high-performance amine-based poly(ether ketone)s with strong photonic luminescence

Amine-based poly(ether ketone)s (A-PEKs), as novel high-performance functional polymers, have been obtained by the polycondensation of dibromo ketones with aromatic ether diamines via palladium-catalyzed aryl amination reaction. The structures of the polymers are characterized by means of FT-IR, 1H NMR spectroscopy and elemental analysis, the results show a good agreement with the proposed structures. DSC and TGA measurements exhibit that polymers possess high glass transition temperature (Tg ≥ 175 °C) and good thermal stability with high decomposition temperatures (T5 ≥ 400 °C). Based on the hydrogen bonds between the polymer chains, thin films of A-PEKs show great mechanical behaviors with high tensile strength up to 89.5 Mpa. In addition, due to the photoinduced intramolecular charge-transfer (ICT) of A-PEKs, these synthesized polymers are endowed with significantly strong photonic luminescence in N,N′-dimethylformamide.

Facile synthesis of soluble aromatic poly(amide amine)s via C-N coupling reaction: Characterization, thermal, and optical properties

Aromatic poly(amide amine)s (APAAs), as novel high-performance polymers, have been obtained by the condensation polymerization of N,N'-bis(4-bromobenzoyl)-p-phenylenediamine with two different primary aromatic diamines via palladium-catalyzed aryl amination reaction. The structures of the polymers are characterized by means of FTIR, 1H NMR spectroscopy, and elemental analysis, the results show a good agreement with the proposed structures. DSC and TGA measurements exhibit that polymers possess high glass transition temperature (Tg > 240 °C) and good thermal stability with high decomposition temperatures (T5 > 400 °C). These novel polymers also display good solubility. In addition, due to its special structure, APAA-2 is endowed with significantly strong photonic luminescence in N,N-dimethylformamide and good electroactivity. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4845–4852

Synthesis of Poly(<i>Aryl Sulfone Benzimidazole</i>) Sulfone

Sulfoned aromatic acid and o-phenylenediamine as the monomers, sulfoned-benzimidazole was obtained by condensation reaction. Poly(aryl sulfone benzimidazole) sulfone (PSBIS) as novel heat-resistant polymer was obtained by the condensation polymerization via Palladium-catalyzed aryl amination reaction of sulfoned-benzimidazole and aromatic dibromide. Differential scanning calorimetry (DSC) and thermal analysis (TG) measurements showed that the polymer synthesized possessed high glass transition temperature (Tg>321°C), good thermal stability with high decomposition temperature (TD>540°C) and good solubility.

Poly(aryl imino sulfone)s as new high-performance engineering plastics

Poly(aryl imino sulfone)s (PAISs) as novel high-performance polymers have been obtained by the condensation polymerization of 4,4′-dibromodiphenyl sulfone with different primary aromatic diamines via Palladium-catalyzed aryl amination reaction. The influence of the halogen-containing monomers, solvent, concentration, and temperature on the polycondensation reaction was investigated. The structure of polymers synthesized was characterized by means of FT–IR, NMR spectroscopy, and elemental analysis, the results showed an agreement with the proposed structure. Differential scanning calorimetry and thermal analysis measurements showed that polymers possessed high glass transition temperature (T g > 145 °C) and good thermal stability with high decomposition temperatures (T D > 450 °C). These novel polymers also exhibited good mechanical behaviors and good solubility.

Preparation of Organic-Inorganic Hybrid Nanocomposites via Pd-Catalyzed Amination of Dibromobenzene with Octa(aminophenyl)silsesquioxane

Novel organic-inorganic hybrid nanocomposites have been obtained by the condensation polymerization of dibromoarene with Octa(aminophenyl)silsesquioxane via palladium-catalyzed aryl amination reaction. The structures of polymers are characterized by means of FT-IR, solid 13C, and 29Si NMR spectroscopy; the results show an agreement with the proposed structure, and the POSS building block was successfully weaved in the structure without obvious alteration of the characteristics and structure. TGA results show that polymers possess good thermal stability.

Poly(aryl Imino Sulphone)s as Novel High Performance Polymers

Poly(aryl imino sulphone)s (PAIS) as novel high-performance polymers have been obtained by the condensation polymerization of 4,4'-dibromodiphenyl solfone with different primary aromatic diamines via Palladium-catalyzed aryl amination reaction. The structure of polymers synthesized was characterized by means of FT-IR, NMR spectroscopy and elemental analysis, the results showed an agreement with the proposed structure. Differential scanning calorimetry (DSC) and thermal analysis (TG) measurements showed that polymers possessed high glass transition temperature (Tg>145°C) and good thermal stability with high decomposition temperatures (TD>450°C). These novel polymers also exhibited good mechanical behaviors and good solubility.

SYNTHESIS AND PROPERTIES OF POLY(ARYLENE IMINO ETHER KETONE) CONTAINING ISOPROPYLIDENE GROUPS

Poly(arylene imino ether ketone) containing isopropylidene group(pr-PIEK) was synthesized by the condensation polymerization of 1,4-bis-(4-bromobenzoyl)benzene and 2,2-bis[4-(4-aminophenoxy)-phenyl]-propane via Palladium-catalyzed aryl amination reaction with high molecular weight,M_n=5.15×104,M_w=1.26×105.The catalyst was tris(dibenzylideneacetone)dipalladium,and the catalyst ligand was BINAP.The monomers,1,4-bis-(4-bromobenzoyl)benzene was synthesized by Friedel-Crafts benzoylation reaction,and 2,2-bis[4-(4-aminophenoxy)phenyl]propane was obtained via two steps.The structure of pr-PIEK was characterized by means of FT-IR,1H-NMR spectroscopy and elemental analysis,and the testing results showed a good agreement with the proposed structure.XRD,DSC and TG measurements show that pr-PIEK possess amorphous nature,good thermal stability with high decomposition temperatures(T_D450℃),mechanical properties(tensile intensity=72.76 MPa,tensile modulus=1013.63 MPa,rupture tensibility=10.32%) and good solubility,pr-PIEK can be dissolved in common organic solvent CHCl_3 at room temperature and dissolved in acetone at 50℃.

Synthesis and properties of novel soluble poly(aryl amine ketone)s as high-performance polymers

A series of poly(aryl amine ketone)s have been obtained by the condensation polymerization of different aromatic dibromides with different primary aromatic diamines via palladium-catalyzed aryl amination reaction. The structures of polymers are characterized by means of FT-IR, 1H NMR spectroscopy, and elemental analysis. The results show an agreement with the proposed structures. DSC and TG measurements show that polymers possess high glass transition temperature (Tg>170°C) and good thermal stability with high decomposition temperatures (TD>450°C). These novel polymers also exhibit good mechanical behaviors and good solubility.

Synthesis of Novel High-Performance Polymers via Pd-Catalyzed Amination of Dibromoarenes with Primary Aromatic Diamines

A series of novel polymers have been obtained by the condensation polymerization of different dibromoarenes with different primary aromatic diamines via palladium-catalyzed aryl amination reaction. The structures of polymers are characterized by means of FT-IR, 1H NMR spectroscopy, and elemental analysis; the results show an agreement with the proposed structure. DSC and TG measurements show that polymers possess high glass transition temperature (Tg > 170 °C) and good thermal stability with high decomposition temperatures (TD > 450 °C). Thesis novel polymers also exhibit good mechanical behavior and good solubility.

Synthesis and Structure of P,N-Heterodifunctional Ferrocene Ligands and their Transition Metal Complexes for Palladium-Catalyzed Aryl Amination Reaction

The Staüdinger reaction of the β-ferrocenylvinylazide 1 with di- and triphosphines provided a new range of P,N- heterodifunctional ferrocene ligands bearing an iminophosphorane and at least a diphenylphosphino group; reactivity towards Pd (II) and the ability of the resulting complexes for palladium catalyzed aryl amination reaction is described. © 1997 Elsevier Science Ltd.