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991.
Hui‐Min Wang Sheng‐Huei Hsiao 《Journal of polymer science. Part A, Polymer chemistry》2011,49(2):337-351
A new bis(triphenylamine)‐type dicarboxylic acid monomer, N,N‐bis(4‐carboxyphenyl)‐N′,N′‐bis(4‐tert‐butylphenyl)‐1,4‐phenylenediamine, was prepared by a well‐established procedure and led to a new family of redox‐active aromatic polyamides with di‐tert‐butyl‐substituted N,N,N′,N′‐tetraphenylphenylenediamine (TPPA) segments. The resulting polyamides were amorphous with good solubility in many organic solvents, and most of them could be solution cast into flexible polymer films. The polyamides exhibited high thermal stability with glass‐transition temperatures in the range of 247–293 °C and 10% weight‐loss temperatures in excess of 500 °C. They showed well‐defined and reversible redox couples during oxidative scanning, with a strong color change from a colorless or pale yellowish neutral form to green and blue oxidized forms. They had enhanced redox stability and electrochromic performance when compared with the corresponding analogs without tert‐butyl substituents on the TPPA unit. The polyamide with TPPA units in both the diacid and diamine components shows multicolored electrochromic behavior. A polyamide containing both the cathodic coloring anthraquinone chromophore and the anodic coloring TPPA chromophore has the ability to show red, green, and blue states, toward single‐component RGB electrochromics. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
992.
Brenden McDearmon Eunhee Lim Kathryn O'Hara Hidenori Nakayama Yingdong Luo Michael L. Chabinyc Craig J. Hawker 《Journal of polymer science. Part A, Polymer chemistry》2017,55(16):2618-2628
A new pentacyclic building block, benzodibenzofuranquinone (BDBFQ), is synthesized in a single step from the inexpensive and readily available feedstocks chloranil and 3‐bromophenol. This versatile repeat unit is incorporated into a series of conjugated materials as either the redox active quinone form or as an electron‐rich dialkylated benzodibenzofuran (BDBF) unit. To illustrate the performance that can be obtained from these systems, optical and electrochemical properties were studied via UV–vis–NIR spectroscopy and cyclic voltammetry. Thin‐film morphology was characterized via grazing incidence wide‐angle X‐ray scattering with thin‐film field‐effect transistor measurements further demonstrating the utility of this system. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2618–2628 相似文献
993.
Secondary alcohols are coupled with aldehydes in dioxane in the presence of a catalytic amount of a ruthenium catalyst along with KOH to give coupled ketones or coupled secondary alcohols depending on the molar ratio of secondary alcohols to aldehydes and the presence (or absence) of a sacrificial hydrogen acceptor. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
994.
D‐Glucosamine in iron‐catalysed cross‐coupling reactions of Grignards with allylic and vinylic bromides: application to the synthesis of a key sitagliptin precursor 下载免费PDF全文
A sustainable D ‐glucosamine ligand is successfully introduced into iron‐catalysed C ? C cross‐coupling reactions for the first time. The Fe(acac)2/D ‐glucosamine·HCl/Et3N catalytic system was effective at 5 mol% loading in coupling reactions of Grignard reagents with organic bromides. Moderate to high efficiency was achieved with preserved stereochemistry when allyl (Csp3) or alkenyl (Csp2) bromides were coupled with phenylmagnesium (Csp2) or benzylmagnesium (Csp3) bromides. The catalytic system developed was also successfully applied for the novel and economic preparation of a Michael‐acceptor‐like starting material used in an alternative synthesis of the drug sitagliptin, a known blockbuster for the treatment of type II diabetes mellitus. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
995.
How a Redox‐Innocent Metal Promotes the Formal Reductive Elimination of Biphenyl Using Redox‐Active Ligands 下载免费PDF全文
Daniel Charles Ashley Mu‐Hyun Baik 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(11):4308-4314
One of the most compelling strategies for utilizing redox‐active ligands is to perform redox events at the ligands to avoid accessing prohibitively high energy oxidation states at the metal center. This has been demonstrated experimentally in many systems, yet there is little understanding of the fundamental electronic structures involved with these transformations or how to control them. Here, the reductive elimination of biphenyl from [M(isq)2Ph2] (M=Ti, Zr, and Hf and isq=2,4‐di‐tert‐butyl‐6‐tert‐butyliminosemiquinone) was studied computationally. It was found that the metal remains in the +IV oxidation state and all redox chemistry was mediated by the redox‐active ligands. Two types of electron‐transfer mechanisms were identified, an asymmetric unpaired electron transfer (UET) and a symmetric pairwise electron transfer (PET), the former always being lower in energy. The energetic differences between these two mechanisms were explained through simple molecular orbital theory arguments. Despite the metal’s redox‐inactivity, it still has a marked influence on the calculated energetics of the reaction, with the Ti systems being much more reactive than the Zr/Hf systems. This primarily originates from the shorter Ti?Ph bond, which leads to a stronger filled‐filled interaction between these ligands at the reactant state. This greater reactant destabilization leads to the lower activation energies. 相似文献
996.
Natalie L. Harvey Dr. Joanna Krysiak Dr. Supakarn Chamni Dr. Sung Wook Cho Prof. Dr. Stephan A. Sieber Prof. Dr. Daniel Romo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1425-1428
An eleven‐step synthesis of (±)‐spongiolactone from 1,3‐cyclohexanedione is reported that relies on a diastereoselective, nucleophile‐catalyzed aldol lactonization (NCAL) process with an advanced ketoacid intermediate that installed the anticipated β‐lactone pharmacophore of the natural product. In addition, a stereoselective cyclohexenyl zinc addition to a substituted cyclohexanone simultaneously installed two fully substituted vicinal stereocenters. The reported synthesis enabled preliminary structure–activity studies that revealed a regio‐ and stereoisomeric derivative of spongiolactone with greater antiproliferative activity towards a leukemia (K562) cell line. Furthermore, unusual antiproliferative selectivity of these spongiolactone derivatives toward the K562 cell line was observed with no inhibition of the breast, liver, and lung cancer cell lines tested. 相似文献
997.
Ling Chen Dr. Thi Minh Thi Le Prof. Dr. Jean-Philippe Bouillon Prof. Dr. Thomas Poisson Prof. Dr. Philippe Jubault 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(42):e202201254
The catalytic asymmetric synthesis of highly functionalized cyclopropanes from α-substituted allyl sulfones and silanes is reported. The reaction, using α-aryl diazoacetates or diacceptor diazo reagents, catalyzed by a chiral rhodium complex (Rh2((S)-BTPCP)4), furnished the corresponding cyclopropanes in moderate to high yields (27–97 %), high diastereoselectivities (68 : 32 to 20 : 1 d.r.) and moderate to excellent ee (40–99 %). This methodology offers a privileged access to an underexplored class of enantioenriched cyclopropanes with a high level of functionality, an asset for further post-functionalization and their incorporation into more complex structure. 相似文献
998.
999.
《Journal of polymer science. Part A, Polymer chemistry》2018,56(4):412-419
Tuning the molecular structure is an effective strategy to modulate the electrochromic behaviors of conducting polymers. In this contribution, a novel oligoaniline‐containing polyurea ended with reactable isocyanate groups is designed and synthesized via nucleophilic polymerization. Then various functional groups such as o‐toluidine, poly(ethylene glycol) (PEG), ethoxysilane, and congo red (CR) are introduced as end groups to modulate the electrochromic performance. Hydrophilic PEG could improve the switching speed due to the rapid electrolyte ions diffusion into polymer film through the hydrophilic region. An enhanced switching stability is afforded by crosslinkable ethoxysilane end groups, ascribed to crosslinked densified surface and great adhesion force between the electrochromic layer and ITO substrate through the hydrolysis reaction. Moreover, an ample color change is achieved by introducing colored CR as end groups. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 412–419 相似文献
1000.
Yi‐Chun Kung Sheng‐Huei Hsiao 《Journal of polymer science. Part A, Polymer chemistry》2011,49(22):4830-4840
Two new aromatic poly(amide‐hydrazide)s (PAHs)‐bearing electroactive pyrenylamine units in the backbone were prepared from the phosphorylation polycondensation reactions of N,N‐di(4‐carboxyphenyl)‐1‐aminopyrene ( 1 ) with p‐aminobenzoyl hydrazide (p‐ABH) and m‐aminobenzoyl hydrazide (m‐ABH), respectively. The PAHs could be further cyclodehydrated into the corresponding poly(amide‐1,3,4‐oxadiazole)s in the range of 300–400 °C in the solid film state. All the hydrazide and oxadiazole polymers were soluble in many polar organic solvents and could afford flexible and strong films via solution casting. The poly(amide‐1,3,4‐oxdiazole)s had high glass‐transition temperatures (294–309 °C) and high thermal stability (10% weight‐loss temperature in excess of 520 °C). The dilute solutions of all the hydrazide and oxadiazole polymers showed strong fluorescence with emission maxima around 457–459 nm in the blue region. Copolymers obtained from the polycondensation of equimolar mixture of diacid 1 and 4,4′‐oxydibenzoic acid with p‐ABH or m‐ABH exhibited a significantly increased fluorescence quantum efficiency in comparison with the homopolymers. Cyclic voltammetry results indicated that all the hydrazide and oxadiazole polymers exhibited an ambipolar (n‐ and p‐doping processes) and electrochromic behavior. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011. 相似文献