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51.
Chin‐Ping Yang Ruei‐Shin Chen Ming‐Jui Wang 《Journal of polymer science. Part A, Polymer chemistry》2002,40(8):1092-1102
A novel tetraimide dicarboxylic acid was synthesized with the ring‐opening addition of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 4,4′‐oxydianiline, and trimellitic anhydride in a 1/2/2 molar ratio in N‐methyl‐2‐pyrrolidone followed by azeotropic condensation to tetraimide dicarboxylic acid. A series of poly(amide imide imide)s (PAIIs) with inherent viscosities of 0.8–1.1 dL/g were prepared from tetraimide dicarboxylic acid with various aromatic diamines by direct polycondensation. Most of the PAIIs were readily soluble in a variety of amide polar solvents and even in less polar m‐cresol and pyridine. Solvent‐cast films had tensile strengths ranging from 99 to 106 MPa, elongations at break ranging from 8 to 13%, and initial moduli ranging from 2.0 to 2.3 GPa. The glass‐transition temperatures of these PAIIs were recorded at 244–276 °C. They had 10% weight losses at temperatures above 520 °C in air or nitrogen atmospheres. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1092–1102, 2002 相似文献
52.
Highly Chemoselective Synthesis of Indolizidine Lactams by SmI2‐Induced Umpolung of the Amide Bond via Aminoketyl Radicals: Efficient Entry to Alkaloid Scaffolds
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Shicheng Shi Prof. Dr. Roger Lalancette D.Sc. Roman Szostak Prof. Dr. Michal Szostak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(34):11949-11953
Samarium(II) iodide enables a wide range of highly chemoselective umpolung radical transformations proceeding by electron transfer to carbonyl groups; however, cyclizations of important nitrogen‐containing precursors have proven limited due to their prohibitive redox potential. Herein, we report the first reductive cyclizations of unactivated cyclic imides onto N‐tethered olefins using SmI2/H2O. This new umpolung protocol leads to the rapid synthesis of nitrogen‐containing heterocycles that are of particular significance as precursors to pharmaceutical pharmacophores and numerous classes of alkaloids. The reaction conditions tolerate a wide range of functional groups. Excellent chemoselectivity is observed in the cyclization over amide and ester functional groups. Such unconventional reactivity has important implications for the design and optimization of new bond‐forming reactions by umpolung radical processes. The reaction advances the SmI2 cyclization platform to the challenging unactivated N‐tethered acyl‐type radical precursors to access nitrogen‐containing architectures. 相似文献
53.
Product Control using Substrate Design: Ruthenium‐Catalysed Oxidative C−H Olefinations of Cyclic Weinreb Amides
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Riki Das Dr. Manmohan Kapur 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(47):16986-16990
A new class of Weinreb amides has been developed as directing groups for the ruthenium‐catalysed regioselective oxidative C?H olefination. The new Weinreb amides successfully inhibit the N?O bond reductive cleavage usually associated with the cationic ruthenium system, thereby keeping intact the synthetic utility of Weinreb amides. Mechanistic studies reveal interesting aspects of the directing group capabilities of Weinreb amides when compared to simple amides of similar structures. 相似文献
54.
Synthesis and properties of novel soluble poly(amide‐imide)s with different pendant substituents
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Wenze Li Xinyu Qian Haibiao Shi Weiyi Zhou Yuting Cai Yu Liu Kunzhi Shen 《Journal of polymer science. Part A, Polymer chemistry》2017,55(19):3243-3252
Two types of novel fluorinated diimide‐diacid monomers—[2,2′‐(4,4′‐(3′‐methylbiphenyl‐2,5‐diyl)bis(oxy)bis(3‐(trifluoromethyl)‐4,1‐phenylene))bis(1,3‐dioxoisoindoline‐5‐carboxylic acid)] (III) and [2,2′‐(4,4′‐(3′‐(trifluoromethyl)biphenyl‐2,5‐diyl)bis(oxy)bis(3‐(trifluoromethyl)‐4,1‐phenylene))bis(1,3‐dioxoisoindoline‐5‐carboxylic acid)] (IV)—were respectively designed and prepared by the condensation of diamines I and II with two molar equivalents of trimellitic anhydride. From both diimide‐diacids, two series of novel poly(amide‐imide)s (PAIs) (IIIa–IIIe and IVa–IVe) bearing different pendant groups were prepared by direct polymerization with various aromatic diamines (a–e). All the PAIs had a high glass transition temperatures (Tgs, 232–265 °C), excellent thermal stability (exhibiting only 5% weight loss at 493–542 °C under nitrogen) and good solubility in various organic solvents due to the introduction of the bulky pendant groups. The cast films of these PAIs (80–90 μm) had good optical transparency (73–81% at 450 nm, 85–88% at 550 nm and 87–89% at 800 nm) and low dielectric constants (2.65–2.98 at 1 MHz). The spin‐coated films of these PAIs presented a minimum birefringence value as low as 0.0077–0.0143 at 650 nm and low optical absorption at the near‐infrared optical communication wavelengths of 1310 and 1550 nm. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3243–3252 相似文献
55.
Physically cross‐linked networks of POSS‐capped poly(acrylate amide)s: Synthesis,morphologies, and shape memory behavior
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In this work, we synthesized a novel organic–inorganic semitelechelic polymer from polyhedral oligomeric silsesquioxane (POSS) and poly(acrylate amide) (PAA) via reversible addition‐fragmentation chain transfer (RAFT) polymerization. The organic–inorganic semitelechelic polymers have been characterized by means of nuclear magnetic resonance spectroscopy, thermal gravimetric analysis, and dynamic mechanical thermal analysis. It was found that capping POSS groups to the single ends of PAA chains caused a series of significant changes in the morphologies and thermomechanical properties of the polymer. The organic–inorganic semitelechelics were microphase‐separated; the POSS microdomains were formed via the POSS–POSS interactions. In a selective solvent (e.g., methanol), the organic–inorganic semitelechelics can be self‐assembled into the micelle‐like nanoobjects. Compared to plain PAA, the POSS‐capped PAAs significantly displayed improved surface hydrophobicity as evidenced by the measurements of static contact angles and surface atomic force microscopy. More importantly, the organic–inorganic semitelechelics displayed typical shape memory properties, which was in marked contrast to plain PAA. The shape memory behavior is attributable to the formation of the physically cross‐linked networks from the combination of the POSS–POSS interactions with the intermolecular hydrogen‐bonding interactions in the organic–inorganic semitelechelics. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 587–600 相似文献
56.
Mina Sakuragi Naoto Aoyagi Yoshio Furusho Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2014,52(14):2025-2031
In this study, we investigated the CO2‐capture/release behavior of the polystyrene‐bearing cyclic amidine pendant groups, which was synthesized via free radical polymerization of HCl salt of the corresponding styrene monomer followed by neutralization. For comparison, we also prepared the polystyrene bearing N‐formyl‐1,3‐propanediamine pendant groups through the hydrolysis of the cyclic amidine group by treatment with an alkaline solution. First, we examined the CO2‐capture/release behaviors of the amidine and amine monomers in aqueous solution in terms of conductivity. The conductivity of a wet DMSO solution of the amidine monomer increased upon CO2 bubbling at 25 °C and reached a stationary value of about 11 mS/m, which indicated the formation of the bicarbonate salt. Conversely, the conductivity decreased to its original value upon N2 bubbling at 50 °C, reflecting the complete release of the trapped CO2 molecules. Both solutions showed the changes in the conductivity with quick responses, and no appreciable difference was observed between them. We then investigated the CO2‐capture/release behaviors of the amidine and amine polymers, by taking advantage of the binary system with polyethylene glycol, and found that the binary system with the amidine polymer captured and released CO2 more efficiently than that with the amine polymer. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2025–2031 相似文献
57.
58.
Mark Farrell Bruno Melillo Amos B. Smith 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2016,128(1):240-243
The design, synthesis, and validation of new highly effective bifunctional linchpins for type II anion relay chemistry (ARC) has been achieved. The mechanistically novel negative‐charge migration that comprises the Brook rearrangement is now initiated by a stabilized tetrahedral intermediate, which is generated by nucleophilic addition to a Weinreb amide, rather than by a simple oxyanion that is generated from an epoxide. As a result, the linchpin preserves the carbonyl functionality in the ARC adducts, thus permitting access to functionally complex systems in a single flask without the need for further chemical manipulations. This tactic was validated with the one‐pot preparation of monoprotected 1,3‐diketones as well as pyran and spiroketal scaffolds, depending on the choice of nucleophile, electrophile, and work‐up conditions. 相似文献
59.
Haoquan Li Dr. Helfried Neumann Prof. Dr. Matthias Beller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(29):10050-10056
A benign and efficient palladium‐catalyzed aminocarbonylation reaction of allylic alcohols is presented. The generality of this novel process is demonstrated by the synthesis of β,γ‐unsaturated amides including aliphatic, cinnamyl, and terpene derivatives. The choice of ligand is crucial for optimal carbonylation processes: Whereas in most cases the combination of PdCl2 with Xantphos ( L6 ) gave best results, sterically hindered substrates performed better in the presence of simple triphenylphosphine ( L10 ), and primary anilines gave the best results using cataCXium® PCy ( L8 ). The reactivity of the respective catalyst system is significantly enhanced by addition of small amounts of water. Mechanistic studies and control experiments revealed a tandem allylic alcohol amination/C?N bond carbonylation reaction sequence. 相似文献
60.
The development of catalysts capable of catalyzing amidation of esters with amines to construct amides under mild conditions is of great importance. Compared to aliphatic amines, the direct catalytic amidation of esters with less nucleophilic aromatic amines is rather difficult. Employing simple lanthanide tris (amide) complexes Ln[N (SiMe3)2]3(μ-Cl)Li (THF)3 as the catalysts, it was found a broad range of aromatic amines and esters were efficiently converted into various amides in good yields under mild conditions. A plausible mechanism for this transformation was experimentally supported as starting from an amide exchange reaction between the lanthanide tris (amide) complex and the substrate amine. 相似文献