- Arylation of diarylamines catalyzed by Ni(II)-PPh3 system
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(Chemical Equation Presented) The cross-coupling of bromomagnesium diarylamides, generated in situ from diarylamines, with aryl bromides or iodides can be effected with a simple NiCl2(PPh3) 2-PPh3 catalyst system under relatively mild conditions. This coupling reaction is an inexpensive, convenient, and practical method, functioning as an alternative to the corresponding Pd-catalyzed or Cu-mediated process for the synthesis of triarylamines.
- Chen, Chen,Yang, Lian-Ming
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- Polytriphenylamine derivative with high free radical density as the novel organic cathode for lithium ion batteries
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Polytriphenylamine derivative, poly[N,N,N,N-tetraphenylphenylenediamine] (PDDP), with a high free radical density, has been synthesized and studied as a cathode material for organic free radical batteries for the first time. The chemical structure, morpho
- Su, Chang,Yang, Fang,Ji, Lvlv,Xu, Lihuan,Zhang, Cheng
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- Photochemistry of Cation Radicals in Solution: Photoinduced Electron-transfer Reactions between Alcohols and the N,N,N',N'-Tetraphenyl-p-phenylenediamine Cation Radical
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Irradiation of the N,N,N',N'-tetraphenyl-p-phenylenediamine cation radical (TPPD.+) with benzyl alcohol causes its reduction to TPPD and oxidation of the alcohol into benzaldehyde; with benzhydrol and 1-phenylethanol the corresponding symmetrical ethers are formed in a photocatalytic process in which TPPD.+ is recycled via two successive electron transfers.
- Moutet, Jean-Claude,Reverdy, Gilbert
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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; 0322
(2021/12/30)
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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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- Triphenylamine structure-containing compound, and preparation method and application thereof
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The invention provides a triphenylamine structure-containing compound, and a preparation method and an application thereof, and belongs to the technical field of organic photoelectric materials. The compound has a structure represented by formula (I). Org
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Paragraph 0050; 0051-0052
(2017/12/27)
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- Synthesizing method of tetracarboxylic acid N,N,N',N'-tetra-(4'-carboxyl biphenyl)-1,4-phenylenediamine
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The invention relates to a synthesizing method of tetracarboxylic acid N,N,N',N'-tetra-(4'-carboxyl biphenyl)-1,4-phenylenediamine. The synthesizing method comprises the following steps of enabling 1,4-benzene dibromide and diphenylamine to generate N,N,N',N'-tetraphenyl-1,4-phenylenediamine (A) through arylamination reaction; enabling the N,N,N',N'-tetraphenyl-1,4-phenylenediamine (A) and NBS (N-bromosuccinimide) to generate N,N,N',N'-tetra-(4-bromophenylacetone)-1,4-phenylenediamine (B); enabling the N,N,N',N'-tetra-(4-bromophenylacetone)-1,4-phenylenediamine (B) and 4-methyl boronobenzoate to generate N,N,N',N'-tetra-(4'-methoxycarbonyl biphenyl)-1,4-phenylenediamine (C); hydrolyzing the N,N,N',N'-tetra-(4'-methoxycarbonyl biphenyl)-1,4-phenylenediamine (C), so as to generate a target compound D, namely N,N,N',N'-tetra-(4'-carboxyl biphenyl)-1,4-phenylenediamine. The synthesizing method has the advantages that the poly-benzene ring aromatic tetracarboxylic acid compound not reported in literature is synthesized; the synthesizing method is simple, the cost is low, the yield rate is high, and the purity is high. The target compound is shown as a formula shown in the attached figure.
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Paragraph 0015; 0018; 0019
(2018/01/03)
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- Quaternary carboxylic acid N, N, N', four N' - (4 - carboxyl vinyl phenyl) - 1, 4 - phenylenediamine synthetic method (by machine translation)
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The invention of a four-membered carboxylic acidN,N,N',N' - Four (4 - carboxyl vinyl phenyl) - 1, 4 - phenylenediamine synthetic method, 1, 4 - bromobenzene with two passes the amination reaction of the diphenylamineN,N,N',N' - Tetraphenyl - 1, 4 - phenyl
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Paragraph 0019; 0020
(2018/03/01)
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- Catalytic carbon-nitrogen bond-forming cross-coupling using N-trimethylsilylamines
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Carbon-nitrogen bond-forming cross-coupling reaction of haloarenes with N-trimethylsilyl (TMS)-substituted secondary and primary arylamines proceeded with the aid of a palladium catalyst and a fluoride activator. Various TMS-N(aryl)2, TMS-NH(aryl), and TMS-N(alkyl)2 reacted to give the corresponding coupled products in high yields. Multi-TMS-amine nucleophiles such as N,N-(TMS)2-aniline and N,N′-Ph2-N,N′-(TMS)2-p-phenylenediamine also participated in this C-N coupling to give multiply C-N coupled products in high yields. The novel C-N cross-coupling reaction was successfully applied to C-N bond-forming polymerization. Relative rates of the cross-coupling of p-bromotoluene with N-TMS-substituted primary and secondary amines showed that N-TMS-diphenylamine reacted faster than N-TMS-N-methylaniline or N-TMS-aniline, and N-TMS-morpholine was the least reactive, indicating that the low basicity of the nitrogen nucleophile is the key for the smooth coupling.
- Minami, Yasunori,Komiyama, Takeshi,Shimizu, Kenta,Hiyama, Tamejiro,Goto, Osamu,Ikehira, Hideyuki
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p. 1437 - 1446
(2015/11/16)
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- Chemoselective amination of bromoiodobenzenes with diarylamines by palladium/Xantphos or ligand-free copper catalysts
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We report the chemoselective amination of bromoiodobenzenes with diarylamines by palladium/Xantphos or a ligand-free copper catalyst. The reactions by these two types of catalysts proceeded with a high chemoselectivity and afforded monobrominated triarylamines in good yields. These products are useful intermediates for the synthesis of unsymmetrical bistriarylamines.
- Kanazawa, Yoshinori,Yokota, Tomo,Ogasa, Hiroshi,Watanabe, Hirotaka,Hanakawa, Taisyun,Soga, Shinichi,Kawatsura, Motoi
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p. 1395 - 1402
(2015/02/19)
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- Silicon-based CN cross-coupling reaction
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Palladium-catalyzed CN bond-forming cross-coupling reaction of N-trimethylsilylamines with aryl bromides and chlorides is found to proceed in the presence of a fluoride activator in 1,3-dimethyl-2-imidazolidinone (DMI), giving triarylamines in excellent yields. When aryl bromide and bis(silyl)amine were used in this reaction, double CN bondforming products were obtained in high yields. The present reaction was successfully applied to CN bond-forming polymerization.
- Shimizu, Kenta,Minami, Yasunori,Goto, Osamu,Ikehira, Hideyuki,Hiyama, Tamejiro
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supporting information
p. 438 - 440
(2014/04/17)
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- Redox potential inversion by ionic hydrogen bonding between phenylenediamines and pyridines
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In electrochemical oxidations, the second oxidation potential of phenylenediamines (PD) varies because of hydrogen-bonding formation for PD +· with pyridines. A linear relationship was obtained for the potential shift as a function of pKa
- Chung, Yi-Chun,Tu, Yi-Jung,Lu, Shih-Hua,Hsu, Wan-Chi,Chiu, Kuo Yuan,Su, Yuhlong Oliver
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supporting information; experimental part
p. 2826 - 2829
(2011/08/02)
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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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- A new hybrid phosphine ligand for palladium-catalyzed amination of aryl halides
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A new hybrid phosphine was designed. The phosphine combines two common structural characteristics found among the effective phosphine ligands reported recently, namely, three tert-alkyl substituents binding to the phosphorus and an aryl group at an appropriate position. A hybrid phospine/palladium system is versatile and effective for the coupling reaction of various aryl halides with primary and secondary amines including carbazole.
- Suzuki, Ken,Hori, Yoji,Kobayashi, Tohru
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supporting information; experimental part
p. 652 - 656
(2009/05/07)
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- Two-photon photosensitized production of singlet oxygen: Sensitizers with phenylene-ethynylene-based chromophores
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(Chemical Equation Presented) Singlet molecular oxygen (a 1Δg) has been produced and optically monitored in time-resolved experiments upon nonlinear two-photon excitation of photosensitizers that contain triple bonds as an integral part of the chromophore. Both experiments and ab initio computations indicate that the photophysical properties of alkyne-containing sensitizers are similar to those in the alkene-containing analogues. Most importantly, however, in comparison to the analogue that contains double bonds, the sensitizer containing alkyne moieties is more stable against singlet-oxygen-mediated photooxygenation reactions. This increased stability can be advantageous, particularly with respect to two-photon singlet oxygen imaging experiments in which data are collected over comparatively long time periods.
- McIlroy, Sean P.,Clo, Emiliano,Nikolajsen, Lars,Frederiksen, Peter K.,Nielsen, Christian B.,Mikkelsen, Kurt V.,Gothelf, Kurt V.,Ogilby, Peter R.
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p. 1134 - 1146
(2007/10/03)
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- Triamino-s-triazine triradical trications. An experimental study of triazine as a magnetic coupling unit
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(equation presented) Triamino-s-triazine derivatives 3a, 4, and 5 have been prepared, and their cationic states have been analyzed electrochemically. At 298 K, 3a+ has a limited lifetime in CH2CI2 solution. However, 4+ and 5+ are long-lived under such conditions, and quartet states of 43+ and 53+ are observed by ESR spectroscopy. Variable-temperature ESR analysis and NMR shift susceptibility measurements indicate that 53+ is a doublet ground state with a populated quartet state.
- Selby, Trent D.,Stickley, Kurt R.,Blackstock, Silas C.
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p. 171 - 174
(2007/10/03)
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- Transition metal-catalyzed process for preparing N-aryl amine compounds
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Disclosed is a process for the preparation of N-aryl amine compounds, comprising reacting an amine compound with an arylating compound in the presence of a base and a transition metal catalyst under reaction conditions effective to form an N-aryl amine compound, the transition metal catalyst comprising a Group 8 metal and P(t-Bu)3 as a ligand, and wherein the ratio of the ligand to the Group 8 metal is in the range of about 3:1 to about 0.25:1, and wherein the reaction temperature is less than 100 DEG C. The process of the present invention provides a useful general method of N-arylation for the manufacture of pharmaceuticals, polymers, and the like.
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- Influence of methyl substituents in phenylenediamine derivatives on the properties of electrophotographic layers
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Substituent effects on the electrophotographic properties of N,N,N′,N′-tetraarylphenylenediamines 1a-i derivatives have been investigated to obtain a molecular design guide to enhance photosensitivity of hole transporting materials for organic photorecept
- Getautis,Stanisauskaite,Paliulis,Uss,Uss
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- Room-temperature palladium-catalyzed amination of aryl bromides and chlorides and extended scope of aromatic C-N bond formation with a commercial ligand
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The reactions of aryl bromides with amines occurs at room temperature when using Pd(0) and P(t-Bu)3 in a 1:1 ratio, and the reactions of aryl chlorides occur at room temperature or 70 °C. The arylation of indoles and the new arylation of carbamates also occur when using P(t-Bu)3 as ligand.
- Hartwig, John F.,Kawatsura, Motoi,Hauck, Sheila I.,Shaughnessy, Kevin H.,Alcazar-Roman, Luis M.
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p. 5575 - 5580
(2007/10/03)
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- Mechanism and Models for Copper Mediated Nucleophilic Aromatic Substitution. 2. A Single Catalytic Species from Three Different Oxidation States of Copper in an Ullmann Synthesis of Triarylamines
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Ullmann condensations of diarylamines with iodobenzenes has been investigated under homogeneous and a heterogeneous catalytic conditions with cupruos and cupric salts, as well as powered copper metal.Copper catalyzed condensation of diarylamines with iodoaromatics is relatively insensitive to substituent (for substituted iodobenzenes p=-0.25; for substituted diphenylamines p=1.09) but quite sensitive to halogen (k1/kBr.200).The first direct evidence for solution catalysis after filtration of a metal catalyzed reactions was obtained.Quantitative analysis of reaction rates, product yields, and catalyst characteristics leads to a comprehensive picture of the formation of soluble cuprous ions as the single active catalytic species under all conditions investigated.This hypothesis rationalizes many of the perplexing results which typify the literature associated with copper catalyzed nucleophilic aromatic substitution.
- Paine, Anthony James
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p. 1496 - 1502
(2007/10/02)
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- Condensations of 1,4-Cyclohexanediones and Secondary Aromatic Amines. II. N-Phenylation of Diarylamines
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The condensations of 1,4-cyclohexanedione with several diphenylamines were investigated in order to determine the limit of the utility of this reaction for the N-phenylation of aromatic secondary amines. 4-Methoxy-, 4,4'-dimethyl-, and 4,4'-dibromodiphenylamines produced their N-phenylated compounds in fairly good yields, but 4-hydroxy-, 3-methoxy-, and 4,4'-bis(dimethylamino)diphenylamines produced poor yields.Nitro-substituted diphenylamines gave N-phenyl derivatives in low yields along with N-4-hydroxyphenyl derivatives.N,N'-Diphenyl-p-phenylenediamine and N,N'-diphenylbenzidine gave correspondig tetra-N-phenyl diamines in good yields.The condensation of N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, di-2-pyridylamine, phenothiazine, and carbazole with 1,4-cyclohexanedione were also examined.
- Haga, Kazuo,Iwaya, Katsumasa,Kaneko, Ryohei
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p. 803 - 808
(2007/10/02)
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