- Zero-Overlap Fluorophores for Fluorescent Studies at Any Concentration
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Fluorophores are powerful tools for the study of chemistry, biology, and physics. However, fluorescence is severely impaired when concentrations climb above 5 μM as a result of effects like self-absorption and chromatic shifts in the emitted light. Herein, we report the creation of a charge-transfer (CT) fluorophore and the discovery that its emission color seen at low concentrations is unchanged even at 5 mM, some 3 orders of magnitude beyond typical limits. The fluorophore is composed of a triphenylamine-substituted cyanostar macrocycle, and it exhibits a remarkable Stokes shift of 15 ?000 cm-1 to generate emission at 633 nm. Crucial to the performance of this fluorophore is the observation that its emission spectrum shows near-zero overlap with the absorption band at 325 nm. We propose that reducing the spectral overlap to zero is a key to achieving full fluorescence across all concentrations. The triphenylamine donor and five cyanostilbene acceptor units of the macrocycle generate an emissive CT state. Unlike closely related donor-acceptor control compounds showing dual emission, the cyanostar framework inhibited emission from the second state to create a zero-overlap fluorophore. We demonstrated the use of emission spectroscopy for characterization of host-guest complexation at millimolar concentrations, which are typically the exclusive domain of NMR spectroscopy. The binding of the PF6- anion generates a 2:1 sandwich complex with blue-shifted emission. Distinct from twisted intramolecular charge-transfer (TICT) states, experiment-supported density functional theory shows a 67° twist inside an acceptor unit in the CT state instead of displaying a twist between the donor and acceptor; it is TICT-like. Inspired by the findings, we uncovered similar concentration-independent behavior from a control compound, strongly suggesting this behavior may be latent to other large Stokes-shift fluorophores. We discuss strategies capable of generating zero-overlap fluorophores to enable accurate fluorescence characterization of processes across all practical concentrations.
- Dhara, Ayan,Flood, Amar H.,Olsson, Andrew H.,Raghavachari, Krishnan,Sadhukhan, Tumpa,Sheetz, Edward G.
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Read Online
- Conjugation-Induced Rigidity in Twisting Molecules: Filling the Gap between Aggregation-Caused Quenching and Aggregation-Induced Emission
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Conjugation-induced rigidity in twisting molecules provides a new facile but effective avenue toward solution and solid dual-state efficient luminogens. While conjugation rigidifies the molecular conformations in solution, the twisting structure prevents or alleviates detrimental close molecular packing in the solid states, thus synergistically yielding high efficiencies in both solution and solid states.
- Chen, Gan,Li, Wenbo,Zhou, Tianru,Peng, Qian,Zhai, Di,Li, Hongxiang,Yuan, Wang Zhang,Zhang, Yongming,Tang, Ben Zhong
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Read Online
- Nickel-Catalyzed Direct Cross-Coupling of Aryl Sulfonium Salt with Aryl Bromide
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The direct cross-couplings of aryl sulfonium salts with aryl halides could be achieved by using nickel as a reaction catalyst. The reactions proceeded efficiently via C-S bond activation in the presence of magnesium turnings and lithium chloride in THF at ambient temperature to afford the corresponding biaryls in moderate to good yields, potentially serving as an attractive alternative to conventional cross-coupling reactions employing preprepared organometallic reagents.
- Ma, Na-Na,Ren, Jing-Ao,Liu, Xiang,Chu, Xue-Qiang,Rao, Weidong,Shen, Zhi-Liang
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p. 1953 - 1957
(2022/03/27)
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- SOLVENT-FREE CROSS-COUPLING REACTION, AND PRODUCTION METHOD USING SAID REACTION
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Disclosed is a cross-coupling reaction method which forms a chemical bond selected from C—N, C—B, C—C, C—O and C—S bonds, the method comprising: preparing an aromatic compound (1) having a leaving group;preparing a compound (2) capable of undergoing a cross-coupling reaction selected from an aromatic amino compound (2-1), a diboronic acid ester or the like (2-2), an aromatic boronic acid or the like (2-3), an aromatic compound (2-4) having a hydroxyl group and an aromatic compound (2-5) having a thiol group; andperforming a cross-coupling reaction of the compound (1) with the compound (2) in the presence of a palladium catalyst, a base and a compound (4) having a carbon-carbon double bond or a carbon-carbon triple bond, in the absence of a solvent.
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Paragraph 0311-0314; 0318
(2021/12/30)
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- Organic electroluminescent compound, preparation method thereof and organic electroluminescent device
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The invention discloses an organic electroluminescent compound, and the structural formula of the organic electroluminescent compound is shown in the specification. The invention also discloses a preparation method of the organic electroluminescent compound, and the organic electroluminescent compound is used for preparing an organic electroluminescent device, and the prepared organic electroluminescent device shows high luminous efficiency and long service life. Driving voltage is reduced.
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Paragraph 0040-0041; 0043
(2020/12/30)
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- Nickel(II)/N-Heterocyclic Carbene Catalyzed Desulfinylative Arylation by C?S Cleavage of Aryl Sulfoxides with Phenylboronic Acids
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Suzuki-Miyaura coupling of haloarenes is the most widely used protocol for the synthesis of biphenyls. Organosulfur compounds are promising electrophiles since they are abundant in nature and versatile in organic synthesis. We report here the desulfinylative Suzuki-Miyaura coupling of aryl sulfoxides with phenylboronic acids using bench-stable nickel/5-(2,4,6-triisopropylphenyl)imidazolylidene[1,5-a]pyridines as the catalyst. The ligands are readily prepared from common commercial chemicals. The method is applicable to both symmetric and unsymmetric aryl sulfoxides, and a range of biphenyls bearing various functional groups were obtained in up to 94% yield. (Figure presented.).
- Yi, Xiaowen,Chen, Kai,Guo, Junjun,Chen, Wei,Chen, Wanzhi
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supporting information
p. 4373 - 4377
(2020/07/27)
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- Three series π-extended fluorescent compounds based on dehydroabietic acid triarylamine moiety: Syhthesis, photophysical properties and hole transporting properties
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Fluorescent compounds based on a dehydroabietic acid skeleton with favorable photophysical properties show promise for use as the hole-transporting layer in organic light-emitting diodes (OLEDs). In this work, we report the synthesis of three series of compounds (15 in total), series 1 (1a–1e), series 2 (2a–2e), and series 3 (3a–3e), by linking polycyclic aromatic hydrocarbons (PAHs) to dehydroabietic acid-based triaryamine moiety through C-C coupling reactions. The three series of compounds exhibited ultraviolet absorption, fluorescence emission, electrochemical, and thermal properties, as well as highest occupied molecular orbital levels and energy gaps that made them suitable for use as hole-transporting materials. OLEDs with 1a, 2a, or 3d as a hole-transporting layer showed better performance in terms of maximum brightness, turn-on voltage, maximum of external quantum efficiency, maximum luminous efficiency and power efficiency than that of a comparable device based on a conventional hole-transporting material. In particular, the device with 1a exhibited the most promising performance, with a high maximum brightness of 21445 cd/m2, low turn-on voltage of 2.8 V, maximum of external quantum efficiency of 1.62%, maximum luminance efficiency of 4.9 cd/A, and maximum power efficiency 3.7lm/W. The present work highlights the potential of π-extended compounds based on dehydroabietic acid for use in luminescent material applications.
- Gao, Hong,Gao, Yanan,Shang, Shibin,Song, Jie,Song, Zhanqian,Tan, Guanni,Zhang, Xinwen
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- Suzuki–Miyaura Coupling of (Hetero)Aryl Sulfones: Complementary Reactivity Enables Iterative Polyaryl Synthesis
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Ideal organic syntheses involve the rapid construction of C?C bonds, with minimal use of functional group interconversions. The Suzuki–Miyaura cross-coupling (SMC) is a powerful way to form biaryl linkages, but the relatively similar reactivity of electrophilic partners makes iterative syntheses involving more than two sequential coupling events difficult to achieve without additional manipulations. Here we introduce (hetero)aryl sulfones as electrophilic coupling partners for the SMC reaction, which display an intermediate reactivity between those of typical aryl (pseudo)halides and nitroarenes. The new complementary reactivity allows for rapid sequential cross-coupling of arenes bearing chloride, sulfone and nitro leaving groups, affording non-symmetric ter- and quateraryls in only 2 or 3 steps, respectively. The SMC reactivity of (hetero)aryl sulfones is demonstrated in over 30 examples. Mechanistic experiments and DFT calculations are consistent with oxidative addition into the sulfone C?S bond as the turnover-limiting step. The further development of electrophilic cross-coupling partners with complementary reactivity may open new possibilities for divergent iterative synthesis starting from small pools of polyfunctionalized arenes.
- Chatelain, Paul,Sau, Abhijit,Rowley, Christopher N.,Moran, Joseph
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supporting information
p. 14959 - 14963
(2019/11/05)
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- Mixed er-NHC/phosphine Pd(ii) complexes and their catalytic activity in the Buchwald-Hartwig reaction under solvent-free conditions
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A series of novel (NHC)PdCl2-PR3 complexes were synthesized and fully characterized by 1H, 13C, 31P NMR and FT-IR spectroscopy. These complexes showed high catalytic activity toward solvent-free Buchwald-Hartwig amination. Both primary and secondary amines were efficiently utilized under the same reaction conditions. The solvent-free synthesis of valuable N-aryl carbazoles and similar N-heterocyclic systems was described.
- Ageshina, Alexandra A.,Sterligov, Grigorii K.,Rzhevskiy, Sergey A.,Topchiy, Maxim A.,Chesnokov, Gleb A.,Gribanov, Pavel S.,Nechaev, Mikhail S.,Asachenko, Andrey F.,Bermeshev, Maxim V.,Melnikova, Elizaveta K.
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supporting information
p. 3447 - 3452
(2019/04/30)
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- Solvent-free mechanochemical Buchwald-Hartwig amination of aryl chlorides without inert gas protection
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A solvent-free Buchwald-Hartwig amination had been developed under high-speed ball-milling conditions, which afforded the desired products with moderate to high yields. The addition of sodium sulfate was found to be crucial for improving both the performance and the reproducibility. Comparative solvent-free stirring experiments implicated the importance of mechanical interaction for the transformation, and the inert gas was proved to be unnecessary for this amination.
- Shao, Qiao-Ling,Jiang, Zhi-Jiang,Su, Wei-Ke
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supporting information
p. 2277 - 2280
(2018/05/16)
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- Oxidative Cross-Coupling of Boron and Antimony Nucleophiles via Palladium(I)
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The use of an isolatable, monomeric Pd(I) complex as a catalyst for the oxidative cross-coupling of aryl-antimony and aryl-boron nucleophiles is reported. This reaction tolerates a wide variety of substrates, with >20:1 selectivity for cross-coupled products. This strategy offers a new approach to achieving the selective cross-coupling of nucleophiles.
- Simpson, Quillon,Sinclair, Matthew J. G.,Lupton, David W.,Chaplin, Adrian B.,Hooper, Joel F.
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p. 5537 - 5540
(2018/09/21)
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- Electron-Catalyzed Coupling of Magnesium Amides with Aryl Iodides
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An electron was found to catalyze the coupling of magnesium diarylamides with aryl iodides giving triarylamines through a radical-anion intermediate. The transformation requires no transition metal catalysts or additives, and a wide array of products are formed in good-to-excellent yields.
- Kiriyama, Kazuya,Okura, Keisho,Tamakuni, Fumiko,Shirakawa, Eiji
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supporting information
p. 4519 - 4522
(2018/03/13)
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- N/O-doped carbon as a "solid ligand" for nano-Pd catalyzed biphenyl- and triphenylamine syntheses
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A series of N/O-doped porous carbon supported nanopalladium catalysts have been successfully prepared, in which the N/O doped carbons were controllably produced via polypyrrole/furan synthesis followed by carbonization. These catalysts exhibit good performance in biphenylamine and triphenylamine syntheses with nitrobenzene and cyclohexanone as starting materials. Their catalytic activity can be tuned efficiently by the N/O functional groups on the carbon surface. TEM, XRD, XPS and laser Raman methods were applied to probe the structure of these catalysts. These results indicate that the Pd nanoparticles were supported on N/O-doped porous carbon via the "coordination" between Pd nanoparticles and N/O functional groups including O-CO, CN and tertiary nitrogen, and better catalytic performance was obtained if carbon with the highest N-species loading was used as the support. In addition, a mechanistic study proved that the reaction starts with the catalytic reduction of nitrobenzene with cyclohexanone as the hydrogen source. During this reaction, aniline was formed and the cyclohexanone was transformed into phenol. Then biphenylamine and triphenylamine were generated through the reaction of aniline and cyclohexanone. This work should facilitate the controllable preparation of carbon supported nanocatalysts with specific activity, and open up a promising pathway for the development of new methodologies for N-containing fine chemical synthesis.
- Pang, Shaofeng,Zhang, Yujing,Huang, Yongji,Yuan, Hangkong,Shi, Feng
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p. 2170 - 2182
(2017/07/24)
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- Buchwald–Hartwig Amination of Nitroarenes
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The Buchwald–Hartwig amination of nitroarenes was achieved for the first time by using palladium catalysts bearing dialkyl(biaryl)phosphine ligands. These cross-coupling reactions of nitroarenes with diarylamines, arylamines, and alkylamines afforded the corresponding substituted arylamines. A catalytic cycle involving the oxidative addition of the Ar?NO2 bond to palladium(0) followed by nitrite/amine exchange is proposed based on a stoichiometric reaction.
- Inoue, Fumiyoshi,Kashihara, Myuto,Yadav, M. Ramu,Nakao, Yoshiaki
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supporting information
p. 13307 - 13309
(2017/10/17)
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- Crystalline triphenylamine substituted arenes: solid state packing and luminescence properties
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The crystal packing and solid state photophysical properties of twisted propeller-shaped triphenylamine (T) incorporated aromatic hydrocarbons [ArT where Ar = benzene (Ph), naphthalene (N), anthracene (A), phenanthrene (Phe), pyrene (Py) and perylene (Pe)] are investigated. The qualitative crystal structure and quantum theory of atoms-in-molecules (QTAIM) analyses revealed the dominant role of intermolecular C-H...C interactions in governing the three-dimensional arrangement in ArT crystals. Hirshfeld surface analyses revealed that the triphenylamine-substituted arene (ArT) crystals possess a herringbone motif with ρ (%C-H...C/%C...C) values varying from 10.4 in PeT to 101.2 in AT. A blue shift of ca. 10-28 nm in the emission maxima for PhT, NT, AT, PheT and PyT is observed in the solid state in comparison to that in dichloromethane while the solid state emission maxima is red shifted (ca. 25-71 nm) compared to that in hexane. A 2.40-fold enhancement in the quantum yield of AT is observed in the solid state relative to the solution state (dichloromethane). Solvent polarity dependent absorption and emission measurements of ArT derivatives along with Lippert-Mataga analyses evidenced the presence of charge transfer interactions between Ar and T units. A precise and systematic understanding of the influence of the crystal structure on the photophysical properties is quintessential to achieve highly efficient organic light emitting diodes and other optoelectronic devices in the near future.
- Mallia, Ajith R.,Ramakrishnan, Remya,Niyas,Hariharan, Mahesh
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p. 817 - 825
(2017/02/10)
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- Highly Emissive Organic Single-Molecule White Emitters by Engineering o-Carborane-Based Luminophores
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The development of organic single-molecule solid-state white emitters holds a great promise for advanced lighting and display applications. Highly emissive single-molecule white emitters were achieved by the design and synthesis of a series of o-carborane-based luminophores. These luminophores are able to induce multiple emissions to directly emit high-purity white light in solid state. By tuning both molecular and aggregate structures, a significantly improved white-light efficiency has been realized (absolute quantum yield 67 %), which is the highest value among the known organic single-molecule white emitters in the solid state. The fine-tuning of the packing modes from H- to J- and cross-stacking aggregates as well as intermolecular hydrogen bonds are successful in one molecular skeleton. These are crucial for highly emissive white-light emission in the solid state.
- Tu, Deshuang,Leong, Pakkin,Guo, Song,Yan, Hong,Lu, Changsheng,Zhao, Qiang
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supporting information
p. 11370 - 11374
(2017/09/11)
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- Production of the triarylamine
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PROBLEM TO BE SOLVED: To provide a method for producing a triarylamine compound by coupling an N, N-dialkyl sulfamate compound and a diaryl amide compound in the presence of a nickel catalyst.SOLUTION: A triarylamine is produced by allowing an N, N-dialkyl sulfamate represented by formula (1) (in the formula, Arrepresents a phenyl group or the like, and Rand Reach independently represents a 1-4C alkyl group that may be substituted with a fluorine atom) to react with a diarylamide in the presence of a nickel catalyst.
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Paragraph 0045-0046
(2017/01/31)
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- Palladium-catalyzed Suzuki cross-coupling of arylhydrazines via C-N bond cleavage
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The first example of Pd-catalyzed Suzuki cross-coupling of readily available arylhydrazines with arylboronic acids via C-N bond cleavage was developed under air, affording various biaryl compounds with broad substrate applicability and moderate to good yields. Moreover, the rigorous exclusion of air/moisture is not required in these transformations. Thus, the protocol represents a simple and efficient procedure to access biaryl compounds.
- Peng, Zhimin,Hu, Gaobo,Qiao, Hongwei,Xu, Pengxiang,Gao, Yuxing,Zhao, Yufen
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p. 2733 - 2738
(2014/04/17)
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- Novel bisimidazolium pincers as low loading ligands for in situ palladium-catalyzed Suzuki-Miyaura reaction in the ambient atmosphere
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A series of novel triazinonide-bridged bisimidazolium pincers were easily synthesized by quaternization of functionalized N-phenylimidazoles with highly reactive cyanuric chloride under mild conditions. The pincer 3c was proven to be a very efficient ligand for in situ Pd-catalyzed Suzuki-Miyaura reaction with ppm-level catalyst loading.
- Gao, Chao,Zhou, Hongjun,Wei, Siping,Zhao, Yinsong,You, Jingsong,Gao, Ge
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supporting information
p. 1127 - 1129
(2013/03/13)
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- Aromatic Amine Compound, and Light-Emitting Element, Light-Emitting Device, and Electronic Device Using the Aromatic Amine Compound
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Novel aromatic amine compounds are provided. Light-emitting elements having high emission efficiency and high reliability are provided. Further, light-emitting devices and electronic devices using the light-emitting devices are provided. Specifically, an aromatic amine compound represented by the general formula (1), and light-emitting elements, light-emitting devices and electronic devices that are formed using the aromatic amine compound represented by the general formula (1) are provided. By using the aromatic amine compound represented by the general formula (1) for light-emitting elements, light-emitting devices and electronic devices, the light-emitting elements, light-emitting devices and electronic devices can have high emission efficiency.
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Paragraph 0196; 0197
(2013/04/10)
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- Monovalent nickel complex bearing a bulky N-heterocyclic carbene catalyzes buchwaldhartwig amination of aryl halides under mild conditions
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Monovalent nickel complex bearing a bulky N-heterocyclic carbene (NHC) and triphenylphosphine was synthesized and demonstrated to catalyze the BuchwaldHartwig amination of aryl halides with diarylamines to form triarylamines under mild conditions.
- Nagao, Shinya,Matsumoto, Taisuke,Koga, Yuji,Matsubara, Kouki
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supporting information; experimental part
p. 1036 - 1038
(2011/12/05)
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- Iron-catalyzed direct arylation of unactivated arenes with aryl halides
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(Chemical Equation Presented) Iron tough: Various aryl halides were treated with unactivated arenes to form biaryl compounds in moderate to good yields. The reactions were carried out at relatively low temperature in the presence of a catalytic amount of FeCl3, with DMEDA as the ligand and LiHMDS as the base (see scheme; DMEDA=N,N'-dimethylethane-1,2-diamine, HDMS=hexamethyldisilazanide) .
- Liu, Wei,Cao, Hao,Lei, Aiwen
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supporting information; scheme or table
p. 2004 - 2008
(2010/06/20)
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- P-phenyl-2,2,6,6-tetramethylphosphorinan-4-ol: An air-stable p,o-type ligand for palladium-mediated cross-coupling reactions
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A two-step entry to a chemically robust, hindered P,O-type phosphorinane-based ligand and its application toward Pd-mediated cross-coupling reactions of unactivated aryl chlorides is presented. A two-step entry to a chemically robust, hindered P,O-type phosphorinane-based ligand and its application toward Pd-mediated cross-coupling reactions of unactivated aryl chlorides is presented. Copyright
- Ullah, Ehsan,McNulty, James,Larichev, Vladimir,Robertson, Al J.
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experimental part
p. 6824 - 6830
(2011/03/19)
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- Clean synthesis of triarylamines: Buchwald-Hartwig reaction in water with amphiphilic resin-supported palladium complexes
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Catalytic aromatic amination was achieved in water under heterogeneous conditions by the use of palladium complexes anchored to the amphiphilic PS-PEG resin with little palladium leaching to provide a green and clean (metal-uncontaminated) protocol for the preparation of triarylamines, including the optoelectronically active N,N,N′,N′-tetraaryl-1,1′- biphenyl-4,4′-diamines (TPDs).
- Hirai, Yoshinori,Uozumi, Yasuhiro
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supporting information; experimental part
p. 1103 - 1105
(2010/06/18)
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- Heterogeneous aromatic amination of aryl halides with arylamines in water with PS-PEG resin-supported palladium complexes
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Catalytic aromatic amination is achieved in water under heterogeneous conditions by the use of immobilized palladium complexes coordinated with the amphiphilic polystyrene-poly-(ethylene glycol) resin-supported di(tert-butyl)phosphine ligand. Aromatic amination of aryl halides with diphenylamine and N,N-double arylation of anilines with bromobenzene were found to proceed in water with broad substrate tolerance to give the triarylamines in high yield with high recyclability of the polymeric catalyst beads. Very little palladium leached from the polymeric catalyst under the waterbased reaction conditions to provide a green and clean (metal-uncontaminated) protocol for the preparation of triarylamines, including the optoelectronically active N,N,N',N'-tetraaryl-1,1'-biphenyl-4,4'-diamines (TPDs).
- Hirai, Yoshinori,Uozumi, Yasuhiro
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supporting information; experimental part
p. 1788 - 1795
(2011/04/16)
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- Cp2Ni-KOt-Bu-BEt3 (or PPh3) catalyst system for direct C - H arylation of benzene, naphthalene, and pyridine
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Ni-catalyzed direct C - H arylation of benzene and naphthalene using aryl halides was investigated. For the first time, the arylation was successfully catalyzed by Cp2Ni (5 mol %) in the presence of KOt-Bu and BEt 3. This Ni catalyst system was also applied to direct C - H arylation of pyridine, an electron-deficient heteroarene; PPh3 was used instead of BEt3 in this case.
- Kobayashi, Osamu,Uraguchi, Daisuke,Yamakawa, Tetsu
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supporting information; experimental part
p. 2679 - 2682
(2009/10/10)
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- CARBAZOLE DERIVATIVE, AND LIGHT-EMITTING ELEMENT, LIGHT-EMITTING DEVICE, AND ELECTRONIC DEVICE USING CARBAZOLE DERIVATIVE
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To provide a light-emitting element having high luminous efficiency and to provide a light-emitting device and an electronic device which consumes low power and is driven at low voltage, a carbazole derivative represented by the general formula (1) is provided. In the formula, α1, α2, α3, and α4 each represent an arylene group having less than or equal to 13 carbon atoms; Ar1 and Ar2 each represent an aryl group having less than or equal to 13 carbon atoms; R1 represents any of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted biphenyl group; and R2represents any of an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted biphenyl group. In addition, l, m, and n are each independenly 0 or 1.
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Page/Page column 197-198
(2009/07/17)
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- TRIARYLAMINE DERIVATIVE, LIGHT-EMITTING SUBSTANCE, LIGHT-EMITTING ELEMENT, LIGHT-EMITTING DEVICE, AND ELECTRONIC DEVICE
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A triarylamine derivative represented by a general formula (G1) given below is provided. Note that in the formula, Ar represents either a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group; α represents a substituted or unsubstituted naphthyl group; β represents either hydrogen or a substituted or unsubstituted naphthyl group; n and m each independently represent 1 or 2; and R1 to R8 each independently represent any of hydrogen, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
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Page/Page column 77-78
(2009/12/23)
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- MICROREACTOR TECHNOLOGY TO BUCHWALD-HARTWIG AMINATION
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A process for forming an arylamine compound, including reacting an arylamine and an aryl halide in the presence of a palladium ligated catalyst, a base and a suitable solvent in a microreactor.
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Page/Page column 4-5
(2009/05/28)
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- Evaluation of aromatic amination catalyzed by palladium on carbon: A practical synthesis of triarylamines
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A heterogeneous palladium on carbon (Pd/C)-catalyzed coupling between amines and aromatic halides including aromatic chlorides has been achieved using sodium tert-butoxide (NaO-t-Bu) and 1,1′-bis(diphenylphosphino)ferrocene (dppf) as a ligand in cyclopentyl methyl ether (CPME). The use of potassium tert-butoxide (KO-t-Bu) in place of NaO-t-Bu brought about the benzyne-mediated aromatic amination even without Pd/C and dppf, giving a mixture of regioisomers when 4-substituted bromobenzenes were employed as the substrate. The combination of Pd/C, dppf, NaO-t-Bu could be utilized for the syntheses of a broad range of triarylamines by replacing CPME with mesitylene which can provide a higher reaction temperature. The Pd/C could be quantitatively recovered and reused until at least the fourth cycle without any loss in catalytic activity. The quite low leaching of palladium (1.1%) was demonstrated by an inductively coupled plasma-atomic emission spectrometric analysis.
- Monguchi, Yasunari,Kitamoto, Katsunori,Ikawa, Takashi,Maegawa, Tomohiro,Sajiki, Hironao
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supporting information; experimental part
p. 2767 - 2777
(2009/12/08)
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- System and method for producing arylamine compounds
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Improved methods for making hole transport molecules (HTMs) that are incorporated into imaging members, such as layered photoreceptor devices, to increase the photoreceptor's “hole mobility,” or its ability to move charge, across its charge transport laye
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Page/Page column 5
(2008/12/07)
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- Nickel(II)-aryl complexes as catalysts for the Suzuki cross-coupling reaction of chloroarenes and arylboronic acids
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A series of air- and moisture-stable Ni(II)-(σ-aryl) complexes, Ni(PPh3)2(aryl)X (X = Cl, Br), were employed as catalyst precursors in the Ni-catalyzed Suzuki cross-coupling reaction. These pre-catalysts easily form the catalytically active Ni(0) species in situ without the need of additional reducing agents. A general catalytic system involving Ni(PPh3)2(1-naph)Cl and PPh3 proved to be highly effective for the Suzuki reaction of aryl chlorides under mild conditions (at 60 °C in THF in the presence of K2CO3 as the base).
- Chen, Chen,Yang, Lian-Ming
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p. 2427 - 2430
(2007/10/03)
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- Arylamine processes
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A process for the preparation of the tertiary arylamine compound, comprising reacting and arylhalide, such as am arylbromide, and an arylamine in an ionic liquid in the presence of a catalyst.
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Page/Page column 12
(2008/06/13)
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- A pronounced anionic effect in the Pd-catalyzed Buchwald-Hartwig animation reaction revealed in phosphonium salt ionic liquids
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The Pd-mediated Buchwald-Hartwig animation reaction of aryl halides in a phosphonium salt ionic liquid consisting of a trihexyl(tetradecyl)phosphonium cation with a range of anions has been investigated. A pronounced anionic effect was uncovered with the reaction proceeding readily with weakly nucleophilic diarylamines only in the presence of noncoordinating anions. A mechanism is postulated to explain these results and it involves a rate-limiting ligand exchange step that proceeds through a dissociative pathway. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
- McNulty, James,Cheekoori, Sreedhar,Bender, Timothy P.,Coggan, Jennifer A.
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p. 1423 - 1428
(2008/09/18)
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- Arylamine processes
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A method for bisformylation an arylamine compound by reacting an arylamine compound with an alkyleneamine in a reaction mixture while refluxing an acid in the reaction mixture.
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Page/Page column 6-7
(2008/06/13)
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- Process for arylamine production
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A tertiary arylamine compound, such as N,N-diphenyl-4-aminobiphenyl, is Formed by reacting an arylbromidem such as 4-bromobiphenyl, and an arylamine, such as Diphenylamine, preferably in the presence of a palladium ligated catalyst.
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Page/Page column 16; title page; 3/4
(2008/06/13)
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- PROCESS FOR PREPARING IODOAROMATIC COMPOUNDS AND USING THE SAME
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The present invention provides a process for preparing monoiodinated aromatic compounds that are useful as intermediates for preparing charge transporting and hole transporting amino compounds and have high purity with high yield and at low cost. A process for preparing aryl iodide compounds comprises reacting an aryl halide compound with a metal iodide, a metal catalyst and a catalyst coordinating ligand in at least one solvent to form an aryl iodide; and purifying the aryl iodide. A triarylamine compound and a process for preparing a triarylamine compounds reacting the aryl iodide with a diarylamine is also provided. Further, a photoconductive imaging member comprising a charge transport layer that comprises at least one triarylamine compound prepared reacting the aryl iodide with a diarylamine is provided.
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Page/Page column 5
(2008/06/13)
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- PROCESS FOR PRODUCING AROMATIC AMINES
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The present invention provides an activator in arylamination using a palladium compound as a catalyst, which is superior to conventional phosphines in stability and performance. With the phosphine sulfide as an activator, an arylamination reaction achieve
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- Process for producing aromatic amines
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The present invention provides an activator in arylamination using a palladium compound as a catalyst, which is superior to conventional phosphines in stability and performance. With the phosphine sulfide as an activator, an arylamination reaction achieve
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Page column 9
(2008/06/13)
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- The use of palladium chloride as a precatalyst for the amination of aryl bromides
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The use of palladium chloride as a precatalyst for the amination of aryl bromides is reported. To overcome the poor solubility of palladium chloride in commonly used solvents, a procedure was developed in which PdCl2 was preheated with neat amine in the presence of a phosphine ligand before the addition of the other reaction components. This protocol is effective for a broad range of substrate combinations using several types of phosphine ligands.
- Zhang, Xiao-Xiang,Harris, Michele C.,Sadighi, Joseph P.,Buchwald, Stephen L.
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p. 1799 - 1805
(2007/10/03)
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- Electron-transfer process in layered photoreceptors containing azo compounds
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Photoinduced electron transfer (ET) is the most essential process for carrier photogeneration in organic optoelectronic devices. In azo compound- based layered photoreceptors, carrier photogeneration is sensitized by hole transport material (HTM) incorporation. We investigated this process to elucidate the highly sensitizing mechanism. First, the photoinduced ET efficiency and overall quantum efficiency were measured and compared for the layered photoreceptor and the carrier generation layer. The result that the HTM enhances the photoinduced ET implies that the HTM works catalytically to diminish the activation energy. Although such extrinsic ET takes place independently of an electric field, the subsequent geminate pair dissociation depends on the electric field. Next, the energy-gap dependence of the ET was investigated by employing more than 50 photoreceptors to vary the energy gap over a wide range. The measured efficiency was plotted against the energy gap, in which an inverted region was not observed.
- Shimada, Tomoyuki,Sasaki, Masaomi,Aruga, Tamotsu,Umeda, Minoru
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p. 785 - 793
(2007/10/03)
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- A highly active palladium catalyst system for the arylation of anilines
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The chelating ligand bis[2-(diphenylphosphino)phenyl] ether (DPEphos), in combination with palladium acetate, forms a highly active catalyst system for the coupling of anilines with aryl bromides. The bisphosphine is easily prepared in large quantity and
- Sadighi, Joseph P.,Harris, Michele C.,Buchwald, Stephen L.
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p. 5327 - 5330
(2007/10/03)
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