- The molecular structures and electrochemical response of "twisted" tetra(aryl)benzidenes
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The compounds N,N,N′,N′-tetra(4-methylphenyl)-(1,1′- biphenyl)-4,4′-diamine (4), N,N,N′,N′-tetra(4-methylphenyl)- (2,2′-dimethyl)-(1,1′-biphenyl)-4,4′-diamine (5a) and N,N,N′,N′-tetra(4-methylphenyl)-(2,2′,6,6′-tetramethyl) -(1,1′-biphenyl)-4,4′-diamine (
- Low, Paul J.,Paterson, Michael A. J.,Goeta, Andres E.,Yufit, Dmitry S.,Howard, Judith A. K.,Cherryman, Julian C.,Tackley, Daniel R.,Brown, Bev
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Read Online
- Catalytic and Aerobic Oxidative Biaryl Coupling of Anilines Using a Recyclable Heterogeneous Catalyst for Synthesis of Benzidines and Bicarbazoles
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In this study, a heterogeneous rhodium-catalyzed oxidative homocoupling reaction of anilines utilizing molecular oxygen as the sole oxidant is reported. Employing a commercially available and recyclable Rh/C catalyst enabled the oxidative dimerization of various anilines, including N,N-disubstituted and N-monosubstituted anilines, as well as diarylamines, triarylamines, and carbazoles. Additionally, the catalytic protocol was extended to the ortho-ortho coupling of anilines, affording 2,2′-diaminobiphenyls with high regioselectivity. Notably, the developed approach provides rapid access to diversely functionalized benzidines and diaminobiphenyls in an operationally simple, practical, and environmentally friendly manner.
- Matsumoto, Kenji,Toubaru, Yasunori,Tachikawa, Shohei,Miki, Ayaka,Sakai, Kentaro,Koroki, Syota,Hirokane, Tsukasa,Shindo, Mitsuru,Yoshida, Masahiro
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p. 15154 - 15166
(2020/12/23)
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- PdCl2(Ph3P)2/Salicylaldimine Catalyzed Diarylation of Anilines with Unactivated Aryl Chlorides
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Triphenylphosphine and salicylaldimine could be used as a mixed ligand system to obtain a high catalytic activity for palladium catalyzed diarylation of primary anilines with unactivated aryl chlorides by the synergistic effect of ligands. The activity and selectivity of the catalytic system could be improved by modifying the structure of salicylaldimine. In refluxing o-xylene, PdCl2(Ph3P)2 with 2,5-ditrifluoromethyl N-phenylsalicylaldimine as a coligand shows high efficiency for the diarylation of various anilines. The catalytic system shows good toleration for the steric hindrance of the substrates. The facile catalytic system works as well on the multiple arylation of 1,1′-biphenyl- 4,4′-diamine with aryl chlorides to afford N,N,N′,N′-tetraaryl-1,1′-biphenyl-4,4′-diamines which are important intermediates of organic light emitting diode (OLED) hole transport materials.
- Tao, Xiaochun,Li, Lei,Zhou, Yu,Qian, Xuanying,Zhao, Min,Cai, Liangzhen,Xie, Xiaomin
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p. 1749 - 1754
(2017/10/06)
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- Metal-Free Oxidative C-C Coupling of Arylamines Using a Quinone-Based Organic Oxidant
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A variety of arylamines are shown to undergo oxidative C-C bond formation using quinone-based chloranil/H+ reagent as the recyclable organic (metal-free) oxidant system to afford benzidines/naphthidines. Arylamines (3°/2°) designed with various substituents were employed to understand the steric as well as electronic preferences of oxidative dimerization, and a mechanism involving amine radical cation has been proposed. The tetraphenylbenzidine derivative obtained via oxidative C-C coupling has been further converted to blue-emissive hole-transporting material via a simple chemical transformation. This study highlights the preparation of novel HTMs in a simple, economic, and efficient manner.
- Maddala, Sudhakar,Mallick, Sudesh,Venkatakrishnan, Parthasarathy
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p. 8958 - 8972
(2017/09/11)
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- Oxidative Dimerization of Triarylamines Promoted by WCl6, Including the Solid State Isolation and the Crystallographic Characterization of a Triphenylammonium Salt
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The triphenylammonium salt [NHPh3][WCl6], 1, and the product of the C-C dimerization of triphenylamine, Ph2N(C6H4)2NPh2, 2, were afforded from the reaction between WCl6 and NPh3 in CH2Cl2. Compound 2 was isolated in 43% yield upon hydrolysis of the reaction mixture. The X-ray structure of 1 provides the first crystallographic characterization of the triphenylammonium ion. Combined EPR and DFT studies gave insight into the reaction mechanism, and allowed the identification of WCl5···[Cl(C6H4)NPh2] as a presumable key intermediate. The reactions of WCl6 with 4-bromotriphenylamine, 4,4′-dimethyltriphenylamine, 9-phenylcarbazole, followed by hydrolytic treatment, led to the dimerization products 3-6, in admixture with variable amounts of the parent amines. N,N,N′,N′-tetrakis(4-bromophenyl)-[1,1′-biphenyl]-4,4′-diamine, 3, was isolated in 60% yield from the reaction of WCl6 with 4,4′-dibromotriphenylamine.
- Bortoluzzi, Marco,Marchetti, Fabio,Pampaloni, Guido,Pinzino, Calogero,Zacchini, Stefano
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p. 887 - 893
(2016/02/03)
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- Method of manufacturing hydroxytriarylamine compd.
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PROBLEM TO BE SOLVED: To provide a method for producing an arylamine compound, capable of avoiding bumping during reaction even with a reduced amount of reaction solvent, increasing an amount obtained per one batch, achieving excellent productivity, and producing an arylamine compound of high quality at a low cost.SOLUTION: In a method for producing an arylamine compound, an aryl halide compound and an amine compound are reacted in presence of a palladium catalyst and at least one base selected from alkali metal hydroxide and alkaline earth metal hydroxide, while distilling off by-produced water.
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Paragraph 0069-0072; 0073; 0085-0086
(2018/03/13)
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- Effects of solvent and base on the palladium-catalyzed amination: PdCl 2(Ph3P)2/Ph3P-catalyzed selective arylation of primary anilines with aryl bromides
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A readily accessible catalytic system, PdCl2(Ph 3P)2/Ph3P, was developed for the selective arylation of primary anilines with aryl bromides. The strong influence of solvents and bases on the catalytic activity was observed. In refluxing o-xylene, triphenylphosphine shows high efficiency for Pd-catalyzed intermolecular amination reactions. By changing the bases, mono- and diarylation of primary amines could be selectively achieved in high yields. Moreover, the catalytic system showed good toleration for the steric hindrance of anilines. A series of N,N,N′,N′-tetraaryl-1,1′-biphenyl-4,4′- diamines, important intermediates of OLED hole transport materials, were synthesized facilely via coupling reactions between 4,4′-diaminobiphenyls and aryl bromides.
- Cai, Liangzhen,Qian, Xuanying,Song, Wenjing,Liu, Taoping,Tao, Xiaochun,Li, Wanfang,Xie, Xiaomin
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p. 4754 - 4759
(2014/06/24)
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- Composition for conductive layers in electronic devices
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A composition for conductive materials comprises a compound represented by the following general formula (A1): wherein: R1 is the same or different and each independently represents a C2-C8 straight-chain alkyl group;R2 is the same or different and each independently represents a hydrogen atom, a methyl group or an ethyl group;Y represents a group containing at least one substituted or unsubstituted aromatic hydrocarbon ring, or substituted or unsubstituted heterocyle; andX1 is the same or different and each represents a substituent represented by the following general formula (A2): wherein n1 is an integer of from 2 to 8.
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Page/Page column 51
(2010/12/29)
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- Cu(II)-mediated generation of triarylamine radical cations and their dimerization. An easy route to tetraarylbenzidines
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(Chemical Equation Presented) Triphenylamine (TPA) derivatives react with Cu2+ in acetonitrile to give TPA radical cations which undergo dimerization and deprotonation reactions to yield tetraphenylbenzidines (TPB). Synthetic utility of this reaction is demonstrated using several triphenylamine derivatives, and yields in excess of 80% are obtained in most cases. Involvement of the amine radical cations in these reactions was confirmed by ESR and absorption spectroscopic studies. A mechanism consistent with all observations is proposed. This study also revealed a very good correlation between the free energy change for radical cation formation and product yields.
- Sreenath, Kesavapillai,Suneesh, Chettiyam Veettil,Ratheesh Kumar, Venugopal K.,Gopidas, Karical R.
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p. 3245 - 3251
(2008/09/20)
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- RAPID COST EFFECTIVE METHOD FOR THE SYNTHESIS OF TPD-TYPE ARYLAMINES
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A process for forming a tetra(aryl)-biphenyldiamine compound, including reacting a dibromobiphenyl compound and a diarylamine compound in the presence of a palladium ligated catalyst and a base.
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Page/Page column 8
(2008/12/05)
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- Diazabutadiene: a simple and efficient ligand for copper-catalyzed N-arylation of aromatic amines
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Diazabutadienes (DABs) were chosen as ancillary ligands in the Cu-catalyzed C-N coupling reaction for the synthesis of triarylamines. A combination of CuI/DAB (1) [1: N,N′-bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene] was found to be an efficient catalyst system for N-arylation of diarylamines and anilines with aryl iodides, affording the desired products in good to excellent yields.
- Liu, Yu-Hua,Chen, Chen,Yang, Lian-Ming
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p. 9275 - 9278
(2007/10/03)
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- Method for the production of aryl-aryl coupled compounds
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The present invention relates to a process for preparing aryl-aryl-coupled compounds and materials. These materials play an important role in industry, for instance as liquid crystals, pharmaceuticals, agrochemicals and as organic semiconductors. The aryl
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Page/Page column 7-9
(2010/10/20)
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- Towards an understanding of structure-property relationships in holetransport materials: The influence of molecular conformation on oxidation potential in poly(arvl)amines
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The influence of molecular conformation on the oxidation (ionisation) potential and electronic structure associated with several TPD-style hole transport materials has been assessed through a combination of single crystal X-ray diffraction, electrochemical and spectroelectrochemical methods and DFT calculations. The introduction of methyl groups can be used to tune the ionisation potential of these molecular species through a combination of electronic (inductive) and thermodynamic effects, while the conformation of the biphenyl portion of the molecular framework is found to play the greatest role in determining the Marcus-type reorganisation energy associated with the charge transport process on the molecular level. The Royal Society of Chemistry 2005.
- Low, Paul J.,Paterson, Michael A. J.,Yufit, Dmitry S.,Howard, Judith A. K.,Cherryman, Julian C.,Tackley, Daniel R.,Brook, Robert,Brown, Bev
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p. 2304 - 2315
(2007/10/03)
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- Electrophotographic member
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Disclosed is an electrophotographic member containing as a charge transport material a fluorine-containing N,N,N',N'-tetraarylbenzidine derivative which is remarkably excellent in solubility in an organic solvent and/or a binder such as polycarbonate resin, etc., can show very excellent electrophotographic properties such as high sensitivity, low residual potential and high durability. Further, a fluorine-containing N,N,N',N'-tetraarylbenzidine derivative usable as a charge transport material, and a process for producing the same are disclosed. Furthermore, a fluorine-containing diarylamine usable for producing the fluorine-containing N,N,N',N'-tetraarylbenzidine derivative, and a process for producing the same are disclosed.
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