- Experimental and DFT studies on the vibrational and electronic spectra of 9-p-tolyl-9H-carbazole-3-carbaldehyde
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The compound 9-p-tolyl-9H-carbazole-3-carbaldehyde (HCCD) was synthesized and characterized by X-ray diffraction, FT-IR, FT-Raman and UV-Vis spectra. The X-ray diffraction study showed that HCCD has a Z-configuration. The benzene ring including methyl is twisted from the mean plane of the carbazole group by 59.7(3)°, which is comparable with the calculated result 65° for B3LYP/6-311++G(d, p) method. Vibrational spectra and electronic spectra measurements were made for the compound. Optimized geometrical structure and harmonic vibrational frequencies were computed with B-based DFT (BLYP, B3LYP and cam-B3LYP) methods, and WB-based DFT (WB97, WB97X and WB97XD) methods and ab initio RHF method using 6-311++G(d, p) basis set. Assignments of the observed spectra were proposed. The equilibrium geometries computed by all of the methods were compared with X-ray diffraction results. The absorption spectra of the title compound were computed both in gas phase and in DMF solution using TD-(cam)B3LYP/6-311++G(d, p) and PCM-(cam)B3LYP/6-311++G(d, p) approaches, respectively. The calculated results provide good descriptions of the bands maxima in the observed electronic spectrum. Temperature dependence of thermodynamic parameters in the range of 100-1000 K was determined. The natural atomic hybrids were calculated and discussed.
- Wang, Yiwei,Zhang, Yu,Ni, Haiwei,Meng, Nana,Ma, Kuirong,Zhao, Jianying,Zhu, Dunru
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- Synthesis, optical, and antioxidant studies of anthraquinone-core-based dendrimers with N-phenylcarbazole as surface group
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Synthesis of hyperbranched dendrimers up to third generation with N-phenylcarbazole as surface group and anthraquinone as the core unit has been achieved. The fluorescence decay studies of the dendrimers indicate that generation growth alters the relaxati
- Rajakumar, Perumal,Venkatesan, Nagarathinam,Sekar, Karuppannan,Nagaraj, Subramani,Rengasamy, Ramasamy
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- Experimental and DFT studies on the vibrational and electronic spectra and NBO analysis of 2-amino-3-((E)-(9-p-tolyl-9H-carbazol-3-yl) methyleneamino) maleonitrile
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2-Amino-3-((E)-(9-p-tolyl-9H-carbazol-3-yl) methyleneamino) maleonitrile (ACMM) was synthesized and characterized by X-ray diffraction, FT-IR, FT-Raman and UV-Vis spectra. The X-ray diffraction study showed that ACMM has a Z-configuration, due to the intramolecular C18H18Aa?N2, N3H3Aa?N2 and C20H20Aa?N4 hydrogen bonds and intermolecular C10H10Aa?N4, N3H3Ba?N9 (2 - x, 2 - y, 2 - z) and N3H8Ca?N4 (2 - x, 1 - y, 2 - z) hydrogen bonds. The benzene ring including methyl is twisted from the mean plane of the carbazole group by 59.7(3). Vibrational spectra and electronic spectra measurements were made for the compound. Optimized geometrical structure and harmonic vibrational frequencies were computed with DFT (B3-based B3P86, B3LYP, B3PW91 and B-based BP86, BLYP, BPW91) methods and ab initio RHF method using 6-311++G(d, p) basis set. Assignments of the observed spectra were proposed. The equilibrium geometries computed by all of the methods were compared with X-ray diffraction results. The absorption spectra of the title compound were computed both in gas phase and in DMF solution using TD-B3LYP/6-311++G(d, p) and PCM-B3LYP/6- 311++G(d, p) approaches, respectively. The calculated results provide a good description of positions of the bands maxima in the observed electronic spectrum. Temperature dependence of thermodynamic parameters in the range of 100-1000 K were determined. The bond orbital occupancies, contribution from parent natural bond orbital (NBO), the natural atomic hybrids was calculated and discussed.
- Meng, Nana,Zhang, Yu,Wang, Yiwei,Ma, Kuirong,Zhao, Jianying,Tang, Guodong
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- A photophysical and spectroelectrochemical study on N-phenyl-carbazoles and their oxidized species
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A series of N-phenyl-carbazole derivatives namely TCz (N-tolyl-carbazol), TCz-TCz (a 3,3′-linked dimer), and CzPh-CH2-PhCz (a methylene-bridged N-phenyl-carbazole), have been synthesized and studied by means of absorption and fluorescence spect
- Ramírez, Cristina Luján,Mangione, María Inés,Bertolotti, Sonia Graciela,Arbeloa, Ernesto Maximiliano,Parise, Alejandro Rubén
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- Functionalised carbazole as a cathode for high voltage non-aqueous organic redox flow batteries
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Prospective high reduction potential cathode materials have been proposed that can be used in non-aqueous redox flow battery applications. A new class of material, 3,6-dibromo-9-(p-tolyl)-9H-carbazole(3)incorporating a carbazole core, showing a very good reversibility is employed as the cathode material and dissolved oxygen in the solvent mixture is used as the anolyte material. Labile positions of the carbazole have been substituted with electron withdrawing groups, which increases the reduction potential of the redox couple. Apart from substituting the labile positions, we have also explored the possible structural modification responsible for stabilizing the cation radical of the carbazole moiety and obtained the reversible behavior thereafter. From this, it is evident that a free radical is stabilized upon delocalization of the charge in the molecule. The mass-transport and redox parameters, diffusion coefficient and heterogeneous electron transfer rate coefficient values are high enough to realize good battery performance. A solvent mixture of acetonitrile and dichloromethane (4?:?1) has been used in this work in order to increase the solubility of electroactive materials in the medium.
- Mirle, Chinmaya R.,M., Raja,P., Vasudevarao,S., Sankararaman,R., Kothandaraman
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- Synthesis and characterization of blue-light-emitting alternating copolymers of 9,9-dihexylfluorene and 9-arylcarbazole
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Several soluble and well-defined copolymers of 9,9-dihexyl-2,7-fluorene and 9-aryl-3,6-carbazole (aryl = phenyl, p-methylphenyl, p-methoxyphenyl) were prepared in good yields by Suzuki-type coupling polymerization of fluorene-diboronic ester with some 9-a
- Wong, Wai-Yeung,Liu, Li,Cui, Dongmui,Leung, Louis M.,Kwong, Chin-Fai,Lee, Tik-Ho,Ng, Ho-Fung
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- Microenvironment modulation of cuprous cluster enables inert aryl chlorides activation in single-molecule metallaphotoredox amination
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Amination of aryl halides is an important tool in organic synthesis and the activation of inert aryl chlorides is particular difficult. We herein report the first study of aromatic microenvironment modulation of cuprous clusters as single-molecule metalla
- Ji, Wei,Jing, Su,Li, Ai-Min,Qi, Zheng-Hang,Qiu, Wen-Jie,Zha, Guo-Jin,Zhu, Dun-Ru
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p. 313 - 321
(2022/01/03)
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- Transition-metal free synthesis of: N -aryl carbazoles and their extended analogs
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Herein, we describe a facile synthesis of N-arylated carbazoles via ladderization of fluorinated oligophenylenes. The reaction consists of two subsequent nucleophilic substitutions triggered by an electronic transfer from dimsyl anions. The reaction allows the effective one-pot formation of at least six C-N bonds with pronounced selectivity to the C-F bond placement.
- Akhmetov, Vladimir,Amsharov, Konstantin,Feofanov, Mikhail,Takayama, Ryo
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supporting information
p. 7172 - 7175
(2021/08/30)
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- Method for synthesizing carbazole derivative
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The invention aims to provide a method for synthesizing a carbazole derivative. The method is characterized in that palladium chloride is used as a catalyst, 2, 2' - dibromobiphenyl is used as an electrophilic reagent, primary amine is taken as a nucleophile, and the carbazole derivative is directly cross-coupled under the conditions of toluene as a solvent and an air atmosphere. The method has the advantages of high yield, high selectivity, simplicity and convenience in operation and the like.
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Paragraph 0013; 0018-0019
(2021/10/05)
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- Scope, Kinetics, and Mechanism of “On Water” Cu Catalysis in the C–N Cross-Coupling Reactions of Indole Derivatives
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A simple and cost-effective protocol for the C–N cross coupling of indole derivatives with aryl iodides using CuI/phenanthroline catalytic system in aqueous and DME/H2O solvent mixture is described. The reactions were performed in the absence of phase-transfer catalyst, and afforded N-arylated products in moderate to excellent yields under mild reaction conditions. A systematic tuning of reaction conditions using DME as a co-solvent enables to improve product yields of N-arylation reactions. The broad substrate scope, easy performance, and low loading of catalyst as well as ligand render this approach appropriate for large scale processes. The mechanism of “on water” Cu-catalyzed N-arylation reaction is investigated using kinetic and computational studies, which reveal interesting mechanistic aspects of the reaction. A series of kinetic experiments showed significant rate enhancement for “on water” Cu-catalyzed N-arylation over the reaction performed in the organic solvent (DME). Computational studies corroborated “on water” rate acceleration by delineating the role of water in the reaction. The water induces rate acceleration by stabilizing the transition state of oxidative addition through hydrogen bonding interactions, presumably at the oil-water interface, and thus helps to reduce the free energy of activation of oxidative addition of iodobenzene to the Cu complex, which is identified as the rate-limiting step of reaction.
- Malavade, Vrunda,Patil, Manish,Patil, Mahendra
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supporting information
p. 561 - 569
(2020/02/05)
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- Redox-neutral decarboxylative photocyclization of anthranilic acids
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A mild metal-, catalyst-, and oxidant-free photoredox neutral system has been found to efficiently enable intramolecular decarboxylative cyclization of anthranilic acids. This facile protocol provides an alternative method for the synthesis of carbazoles. Mechanistic studies reveal a key photoinduced 6π-electrocyclization process and formic acid was released as the sole byproduct.
- Huang, Huawen,Deng, Kun,Deng, Guo-Jun
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p. 8243 - 8247
(2020/12/29)
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- Palladium-catalyzed C-H bond activation for the assembly of: N -aryl carbazoles with aromatic amines as nitrogen sources
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A convenient and efficient palladium-catalyzed C-H bond activation for the assembly of N-aryl carbazole is reported, in which two C-N bonds were formed under one set of conditions. The desired carbazoles were achieved in decent yields with a wide substrate scope by utilizing readily available 2-iodo biphenyls and aromatic amines as starting materials.
- Liu, Xiaobing,Sheng, Heyun,Zhou, Yao,Song, Qiuling
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supporting information
p. 1665 - 1668
(2020/02/18)
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- 9-(p-Tolyl)-2,3,4,4a,9,9a-hexahydro-1H-carbazole—A new donor building-block in the design of sensitizers for dye-sensitized solar cells
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The novel donor building-block - 9-(p-tolyl)-2,3,4,4a,9,9a-hexahydro-1H-carbazole was designed and employed in the synthesis of dye-sensitized solar cell (DSSCs). An effective, high-yielding synthesis of 4,6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9-(p-tolyl)-1,2,3,4,4a,9a-hexahydrocarbazole from 1,2,3,4,4a,9a-hexahydrocarbazole was realized. Three new metal-free organic sensitizers, containing the new donor building block were prepared by a stepwise approach from 4,7-dibromobenzo[c][1,2,5]chacogenadiazoles. A 2,1,3-Benzothiadiazole dye containing hexahydrocarbazole donor, thiophene as π-spacer and cyanoacrylate as anchoring electron acceptor showed photovoltaic properties higher than the well-known WS-2 sensitizer with PCE = 5.86 %. Although benzoxa- and –selenadiazole dyes have a bathochromic shift (24?30 nm) in the UV–vis spectra, and smaller energy gap Eg (about 0.1 eV), they have lower photovoltaic parameters, including PCE of 1.5–2.3 %. Introducing a new donor 9-(p-tolyl)-2,3,4,4a,9,9a-hexahydro-1H-carbazole into the construction of the DSSCs has broadened possibilities for the optimization of their photovoltaic properties.
- Mikhailov, Maxim S.,Gudim, Nikita S.,Knyazeva, Ekaterina A.,Tanaka, Ellie,Zhang, Lu,Mikhalchenko, Ludmila V.,Robertson, Neil,Rakitin, Oleg A.
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- Palladium-Catalyzed C-N Cross-Coupling of NH-Heteroarenes and Quaternary Ammonium Salts via C-N Bond Cleavage
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In this paper, we extend the substrate class of Buchwald-Hartwig amination to quaternary ammonium salts. In the presence of Pd(OAc)2 and t-BuXPhos, the coupling of aryl- or arylmethyltrimethylammonium triflates with NH-heteroarenes via C-N bond cleavage affords the desired N-aryl or N-arylmethyl heteroarenes in moderate to excellent yields.
- Chen, Hongyi,Yang, Hongqin,Li, Nutao,Xue, Xinghua,He, Ze,Zeng, Qingle
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p. 1679 - 1685
(2019/08/20)
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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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p. 3447 - 3452
(2019/04/30)
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- Base-promoted SNAR reactions of fluoro- And chloroarenes as a route to N-aryl indoles and carbazoles
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KOH/DMSO-promoted C-N bond formation via nucleophilic aromatic substitution (SNAr) between chloroarenes or fluoroarenes with indoles and carbazole under transition metal-free conditions affording the corresponding N-arylated indoles and carbazoles has been developed.
- Iqbal, Muhammad Asif,Mehmood, Hina,Lv, Jiaying,Hua, Ruimao
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- Ultrafine hybrid Cu2O-Fe2O3 nanoparticles stabilized by hexaphenylbenzene-based supramolecular assemblies: A photocatalytic system for the Ullmann-Goldberg coupling reaction
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Ultrafine hybrid Cu2O-Fe2O3 NPs have been prepared using the supramolecular assemblies of hexaphenylbenzene (HPB) derivative 3 as nanoreactors and stabilizers. The as-prepared hybrid Cu2O-Fe2O3 NPs serve as an efficient and recyclable photocatalytic system for carrying out C-N coupling between aryl halides and various amines (aliphatic, aromatic and N-heterocyclic) at room temperature in mixed aqueous media under visible light irradiation. Amazingly, Cu2O-Fe2O3 NPs also exhibited high efficiency in the reactions involving the synthesis of biologically important N-substituted carbazole derivatives. The work being presented in this article demonstrates the preparation of a 'dip strip' coated with the as-prepared catalytic system and utilization of this paper strip as a recyclable and portable heterocatalytic system for carrying out the Ullmann-Goldberg coupling.
- Singh, Gurpreet,Kumar, Manoj,Bhalla, Vandana
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p. 5346 - 5357
(2018/12/05)
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- A waste-minimized protocol for copper-catalyzed Ullmann-type reaction in a biomass derived furfuryl alcohol/water azeotrope
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We report the use of biomass-derived furfuryl alcohol as an effective bidentate ligand able to promote the Ullmann-type copper-catalyzed coupling of aryl halides with heteroaromatic or aliphatic amines. Furfuryl alcohol (FA) can be mixed with water to form the corresponding azeotrope (20 wt% of FA) and therefore can be easily recovered and reused. This protocol is efficiently applied to substrates with various electronic nature and affords the expected products (27 examples) in generally good to excellent yields. It has also been demonstrated that the protocol is both chemically and environmentally effective as the azeotropic mixture can be easily and almost quantitatively recovered at the end of the process.
- Ferlin, Francesco,Trombettoni, Valeria,Luciani, Lorenzo,Fusi, Soliver,Piermatti, Oriana,Santoro, Stefano,Vaccaro, Luigi
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supporting information
p. 1634 - 1639
(2018/04/12)
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- Rh(III)-Catalyzed C-H Activation of Boronic Acid with Aryl Azide
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A Rh(III)-catalyzed C-H activation of boronic acid with aryl azide to obtain unsymmetric carbazoles, 1H-indoles, or indolines has been developed. The reaction constructs dual distinct C-N bonds via sp2/sp3 C-H activation and rhodium nitrene insertion. Synthetically, this approach represents an access to widely used carbazole derivatives. The practical application to CBP and unsymmetric TCTA derivatives has also been performed. Mechanistic experiments and DFT calculations demonstrate that a five-membered rhodacycle species is the key intermediate.
- Xu, Shiyang,Huang, Baoliang,Qiao, Guanyu,Huang, Ziyue,Zhang, Zhen,Li, Zongyang,Wang, Peng,Zhang, Zhenhua
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p. 5578 - 5582
(2018/09/25)
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- Design, synthesis and biological evaluation of: N -arylsulfonyl carbazoles as novel anticancer agents
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In this work, a set of structurally diverse synthetic carbazoles was screened for their anticancer activities. According to structure-activity relationship studies, carbazoles with an N-substituted sulfonyl group exhibited better anticancer activity. Moreover, compound 8h was discovered to show the most potent anticancer effects on Capan-2 cells by inducing apoptosis and cell cycle arrest in G2/M phase. Finally, the in vivo study demonstrated that 8h prevented the tumor growth in PANC-1 and Capan-2 xenograft models without apparent toxicity.
- You, Xin,Zhu, Daqian,Lu, Wenhua,Sun, Yichen,Qiao, Shuang,Luo, Bingling,Du, Yongliang,Pi, Rongbiao,Hu, Yumin,Huang, Peng,Wen, Shijun
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p. 17183 - 17190
(2018/05/28)
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- Palladium-catalyzed Selective Amination of Aryl(haloaryl)amines with 9H-Carbazole Derivatives
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Palladium-catalyzed amination of aryl(haloaryl)amines with 9H-carbazole derivatives was investigated. In the amination of (4-bromophenyl)phenylamine with 9H-carbazole by the use of Pd2(dba)3/PtBu3/NaOtBu catalyst, the main product was desired 9-[4-(phenylamino)phenyl]-9H-carbazole in 60% yield with conversion of (4-bromophenyl)phenylamine >99%, and the concomitant formation of 9-[4-[phenyl[4-(phenylamino)phenyl]amino]phenyl]-9H-carbazole (15% yield), which is the consecutive by-product, was observed. When XPhos was used instead of PtBu3, the desired product was provided in 81% yield and the consecutive by-product was suppressed to 7.7%. The yield of the desired product reached 98% by the use of tBu-XPhos. Such excellent yields of the desired product were also obtained with other 2-di-tert-butyl- or 2-di(1-adamantyl)phosphino-1,1’-biaryls. Various 9-(arylamino)aryl-9H-carbazoles could be synthesized from aryl(haloaryl)amines and 9H-carbazole derivatives in high yields by the use of tBu-XPhos. The amination of 4-bromotoluene with a mixture of diphenylamine and 9H-carbazole gave only 9-o-tolyl-9H-carbazole with tBu-XPhos, while the use of PtBu3 or XPhos afforded the mixture of 9-o-tolyl-9H-carbazole and diphenyl(o-tolyl)amine, indicating that Pd2(dba)3/tBu-XPhos/NaOtBu catalyst high selectively favors 9H-carbazole over diphenylamine as an amination substrate. (Figure presented.).
- Ohtsuka, Yuhki,Yamamoto, Tetsuya,Miyazaki, Takanori,Yamakawa, Tetsu
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p. 1007 - 1018
(2018/02/06)
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- Synthesis, photoluminescence properties of novel cationic Ir(III) complexes with phenanthroimidazole derivative as the ancillary ligand
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Two novel cationic Ir(III) complexes, [(nbt)2Ir(L)](PF6) and [(CF3-bt)2Ir(L)](PF6), where nbt = 2-(1-naphthyl)benzothiazole; CF3-bt = 2-phenyl-6-(trifluoromethyl)-benzothiazole and L = 1-(4
- Yang, Fuzhi,Yu, Tianzhi,Zhao, Yuling,Zhang, Hui,Niu, Yuying
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- Highly reusable support-free copper(II) complex of para-hydroxy-substituted salen: Novel, efficient and versatile catalyst for C─N bond forming reactions
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An air-stable, highly active and versatile method for C─N bond forming reactions is reported. Under mild conditions using a highly reusable support-free Cu(II)–salen complex, structurally diverse N-aryl-substituted compounds were obtained via direct C─N bond forming reaction of HN-heterocycles with aryl iodides or three-component C─N bond forming reaction of 2-bromobenzaldehyde, aniline derivatives and sodium azide in good to excellent yields. C─N bond forming reaction for benzimidazole derivatives was also performed in the presence of the catalyst under ambient conditions. A series of hybrid benzimidazoles bearing morpholine, tetrazole and quinoxaline backbones were produced using this method. All reactions were performed in short times under air. The Cu(II) catalyst could be reused up to eight times in the direct cross-coupling reaction of 9H–carbazole with iodobenzene without any decrease in its catalytic activity.
- Sharghi, Hashem,Aberi, Mahdi,Shiri, Pezhman
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- Investigation of novel carbazole-functionalized coumarin derivatives as organic luminescent materials
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Four new carbazole-based coumarin derivatives comprising a carbazole core and one or two coumarin chromophores, 7-(diethylamino)-3-(4-(9-(p-tolyl)-9H-carbazol-3-yl)phenyl)coumarin (Cz-Ph-C) and 3,3'-((9-(p-tolyl)-9H-carbazole-3,6-diyl)bis(4,4′-phenyl))bis
- Yu, Tianzhi,Zhu, Zeyang,Bao, Yanjun,Zhao, Yuling,Liu, Xiaoxiao,Zhang, Hui
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p. 260 - 269
(2017/08/23)
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- Nickel-Catalyzed N-Arylation Using N -Trimethylsilyl-carbazole
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Nickel-catalyzed N-arylation reaction of N -trimethylsilyl-carbazole using aryl bromides is found to proceed in the presence of sodium acetate, giving N -aryl-carbazoles in high yields. Under these conditions, N -trimethylsilyl-carbazole could react with aryl bromides selectively even in the presence of other N -trimethylsilyl-amines or N -H-amines. This arylation reaction was applied to the polymerization to provide a polycarbazole.
- Minami, Yasunori,Komiyama, Takeshi,Shimizu, Kenta,Uno, Shu-Ichi,Hiyama, Tamejiro,Goto, Osamu,Ikehira, Hideyuki
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supporting information
p. 2407 - 2410
(2017/09/30)
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- An electronic transmission material and its preparation and device
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The invention provides carbazole-imidazole electron transport materials. Based on triphenyl imidazole and carbazole, a kind of classic compounds is formed by connecting triphenyl imidazole and carbazole with benzene of different substituent groups. A preparation method is based on improvement of existing methods. Through repeated verification, the preparation method is simple in synthesis and purification processes and low in cost and can meet the industrial development requirements. A device prepared by using the substances has high light emitting efficiency.
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Paragraph 0041; 0043
(2017/10/14)
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- Photochemical Synthesis of Carbazoles Using an [Fe(phen)3](NTf2)2/O2 Catalyst System: Catalysis toward Sustainability
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An increasingly sustainable photochemical synthesis of carbazoles was developed using a catalytic system of Fe(phen)3(NTf2)2/O2 under continuous flow conditions and was demonstrated on gram-scale using a numbering-up strategy. Photocyclization of triaryl and diarylamines into the corresponding carbazoles occurs in general in higher yields than with previously developed photocatalysts.
- Parisien-Collette, Shawn,Hernandez-Perez, Augusto C.,Collins, Shawn K.
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supporting information
p. 4994 - 4997
(2016/10/14)
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- Strained dehydrogenative ring closure of phenylcarbazoles
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What does it take to force a rigid and strained dehydrogenative ring closure, for example, in phenylcarbazoles? Since the works of Buchwald and Fagnou, palladium-catalysed ring-closing dehydrogenative reactions are legion, but will not operate when the st
- Jones, Alexander W.,Louillat-Habermeyer, Marie-Laure,Patureau, Frederic W.
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supporting information
p. 945 - 949
(2015/03/30)
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- Visible Light-Mediated Ullmann-Type C-N Coupling Reactions of Carbazole Derivatives and Aryl Iodides
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The combined use of an iridium-based photocatalyst and a copper salt under blue light emitting diode irradiation enables the Ullmann-type C-N cross-coupling reaction between carbazole derivatives and aryl iodides to proceed under mild conditions.
- Yoo, Woo-Jin,Tsukamoto, Tatsuhiro,Kobayashi, Shu
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supporting information
p. 3640 - 3642
(2015/07/28)
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- Copper/β-diketone-catalysed N-arylation of carbazoles
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A copper-catalysed C-N bond-forming reaction of carbazoles with aryl iodides is described. Several commercially available ligands such as β-diketone and diamine, are tested in the N-arylation of carbazoles. The catalytic system generated in situ from an inexpensive copper salt, simple β-diketone and inorganic base efficiently N-arylated the carbazoles. A wide range of aryl iodides and carbazoles can be coupled to generate N-arylcarbazoles in the presence of various functional groups. However, the sterically hindered effect of aryl iodides is evident in this catalytic system. The selectivity of two iodine atoms on the aromatic ring of diiodobenzene is evaluated in the developed catalytic system. Results showed that the selectivity of diiodobenzene can be tuned by the reaction temperature.
- Chen, Fei,Liu, Ning,Ji, Enhui,Dai, Bin
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p. 51512 - 51523
(2015/06/25)
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- Transition-Metal-Free Synthesis of Carbazoles and Indoles by an SNAr-Based "aromatic Metamorphosis" of Thiaarenes
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Dibenzothiophene dioxides, which are readily prepared through oxidation of the parent dibenzothiophenes, undergo nucleophilic aromatic substitution with anilines intermolecularly and then intramolecularly to yield the corresponding carbazoles in a single operation. The "aromatic metamorphosis" of dibenzothiophenes into carbazoles does not require any heavy metals. This strategy is also applicable to the synthesis of indoles. Since electron-deficient thiaarene dioxides exhibit interesting reactivity, which is not observed for that the corresponding electron-rich azaarenes, a combination of a thiaarene-dioxide-specific reaction with the SNAr-based aromatic metamorphosis allows transition-metal-free construction of difficult-to-prepare carbazoles.
- Bhanuchandra,Murakami, Kei,Vasu, Dhananjayan,Yorimitsu, Hideki,Osuka, Atsuhiro
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supporting information
p. 10234 - 10238
(2015/09/01)
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- A tuned bicyclic proazaphosphatrane for catalytically enhanced n-arylation reactions with aryl chlorides
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The N-arylation of various amines with aryl chlorides proceeded in good-to-excellent yields in the presence of P[N{(p-NMe2)C6H4CH2}CH2CH2]3N (1e, a new electron-rich proazaphosphatrane ligand) and small amounts of Pd2(dba)3 (dba = dibenzylideneacetone). This catalytic system was also very effective for the synthesis of carbazoles. An efficient palladium-catalyzed N-arylation reaction of amines under mild conditions with a tuned bicyclic proazaphosphatrane has been developed.
- Kim, So Han,Kim, Min,Verkade, John G.,Kim, Youngjo
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p. 1954 - 1960
(2015/03/18)
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- An Efficient Synthesis of N-(Hetero)arylcarbazoles: Palladium-Catalyzed Coupling Reaction between (Hetero)aryl Chlorides and N-Carbazolylmagnesium Chloride
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An efficient method for the synthesis of N-(hetero)arylcarbazoles, useful compounds for functional materials, is reported. Various (hetero)aryl chlorides reacted with N-carbazolylmagnesium chloride in the presence of a palladium catalyst (0.05 to 0.2 mol%) prepared from allylpalladium(II) chloride dimer {[PdCl(allyl)]2} and di-tert-butyl(2,2-diphenyl-1-methylcyclopropan-1-yl)phosphine (cBRIDP) under mild conditions (110°C) in a short period of time (15 min to 2 h) to give N-(hetero)arylcarbazoles in high yields. The reactions of bromochlorobenzenes proceeded in favour of the bromo group to afford N-(chlorophenyl)carbazoles in a highly selective manner. Functional materials for use in organic light-emitting diodes, such as mCP, 26mcPy, CBP and TCB, were also obtained in high yields within 15 min by the reaction of (hetero)aryl polyhalides. Optimization of the reaction conditions and a postulated catalytic cycle for the reaction are also discussed.
- Nakayama, Yuji,Yokoyama, Naota,Nara, Hideki,Kobayashi, Tohru,Fujiwhara, Mitsuhiko
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supporting information
p. 2322 - 2330
(2015/07/27)
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- Optimizing the photovoltaic performance of thiocyanate-free ruthenium photosensitizers by structural modification of C^N cyclometalating ligand in dye-sensitized solar cells
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Five new thiocyanate-free ruthenium(II) complexes with different electron-donating functionalized cyclometalating ligands C^N were synthesized, characterized and applied as photosensitizers in dye-sensitized solar cells (DSSCs). Their photophysical, electrochemical, thermal and photovoltaic properties have been investigated and density functional theory (DFT) calculations have been carried out on these dyes. These dyes exhibit good thermal stability with the onset decomposition temperature at 5% weight-loss (Td) of around 330 °C. The DSSC device using the Ru(II) dye with the 9-tolylcarbazole chromophore exhibited the highest power conversion efficiency (η) up to 3.39%, with a short-circuit photocurrent density (Jsc) of 8.06 mA cm-2, an open-circuit photovoltage (Voc) of 0.62 V and a high fill factor (ff) of 0.68 under illumination of an AM 1.5 solar cell simulator.
- Siu, Chi-Ho,Ho, Cheuk-Lam,He, Jian,Chen, Tao,Majumda, Poulomi,Zhao, Jianzhang,Li, Hua,Wong, Wai-Yeung
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- A visible-light-mediated synthesis of carbazoles
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The photosynthetic preparation of N-aryl- and N-alkyl-bearing carbazoles utilizes continuous flow, visible light, and an in situ formed Cu-based sensitizer (see picture). The method is mild and efficient, and allows the straightforward synthesis of a variety of carbazoles with different substituents, heterocycles, and complex carbon architectures. Copyright
- Hernandez-Perez, Augusto C.,Collins, Shawn K.
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supporting information
p. 12696 - 12700
(2013/12/04)
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- Synthesis of carbazoles via one-pot copper-catalyzed amine insertion into cyclic diphenyleneiodoniums as a strategy to generate a drug-like chemical library
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Carbazoles have attracted high interest among synthetic chemists due to their unique structural features and potential pharmacological activities. Compared to linear aryliodoniums, cyclic diphenyleneiodoniums are more inert and have not attracted much attention to their application as building blocks. Employing our synthetic strategy, diversified carbazoles can be efficiently obtained from a single cyclic diphenyleneiodonium under mild conditions. The reactions catalyzed by cop- per(II) acetate have provided a variety of carbazoles in modest to good yields with a broad range of amines including anilines, aliphatic amines and sulfon amides. Moreover, one of the obtained carbazoles has displayed an outstanding ability to protect HT-22 neuronal cells from the damage induced by neurotoxins glutamate and homocysteic acid.
- Zhu, Daqian,Liu, Qi,Luo, Bingling,Chen, Meihui,Pi, Rongbiao,Huang, Peng,Wen, Shijun
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p. 2172 - 2178
(2013/10/01)
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- Palladium-catalyzed synthesis of N-arylated carbazoles using anilines and cyclic diaryliodonium salts
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The direct synthesis of N-arylated carbazoles through a palladium-catalyzed amination of cyclic iodonium salts with anilines is described. In particular, electron-poor aniline derivatives reacted smoothly with only 5 mol % of Pd(OAc)2 as catalyst to give the desired products in up to 71% yield. Furthermore, the reactivity of cyclic iodonium salts is compared with the reactivity of the corresponding cyclic bromonium analogues.
- Riedmueller, Stefan,Nachtsheim, Boris J.
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p. 1202 - 1209
(2013/07/26)
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- Discovery of novel N-substituted carbazoles as neuroprotective agents with potent anti-oxidative activity
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Carbazole moiety is an important scaffold with a variety of biological applications, for example, anti-oxidative stress. Our previous synthesized carbazoles were screened for their neuroprotective properties against two individual oxidative stresses. Some of the new carbazole derivatives were observed with modest to good neuroprotective effects on neuronal cells HT22 against cell injury induced by glutamate or homocysteic acid (HCA). Substituents introduced to the carbazole ring system play crucial roles in their biological activities. In particular, a bulky group favors the neuroprotective activity of the compounds. One of the new compounds, 6, showed the best neuroprotective effects, which might result from its anti-oxidative activity with a GSH-independent mechanism. These findings might provide an alternative strategy for the development of novel carbazole derivatives for the treatment of CNS diseases such as Alzheimer's disease.
- Zhu, Daqian,Chen, Meihui,Li, Min,Luo, Bingling,Zhao, Yang,Huang, Peng,Xue, Fengtian,Rapposelli, Simona,Pi, Rongbiao,Wen, Shijun
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- PROCESS FOR PRODUCING N-(HETERO)ARYLAZOLES
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The present invention provides a process for effectively producing an N-(hetero)arylazole with high yield, which is useful as a medical or agrochemical product, an organic photoconductor material, an organic electroluminescent element material, or the like. The present invention relates to a process for producing an N-(hetero)arylazole, which includes reacting a (hetero)aryl (pseudo)halide with an NH-azole in the presence of: a catalyst including a palladium compound and a coordination compound; and a basic magnesium compound.
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Page/Page column 30; 31
(2013/03/28)
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- N-PHENYL TRISCARBAZOLE
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The present invention relates to a novel triscarbazole compound having substituent on N-phenyl, which can be represented by Formula (I). wherein R1 is selected from the group consisting of hydrogen, halogen or alkyl or alkoxy group having 1 to 20 carbon atoms wherein at least one hydrogen atom is optionally replaced by halogen; RA, RB, RC, RD and RE are any of substituents other than hydrogen wherein at least two of R1 and RA may further form a fused ring; and i, j, k, l and m are same or different at each occurrence and represent an integer from 0 to 4, with the proviso that when R1 is hydrogen, i is not 0. By introduction of the substituent on N-phenyl, the device efficiency, stability and lifetime can be increased while maintaining the solubility. These compounds can be used in various organic devices such as organic light emitting diodes, photovoltaic cells or organic semiconductor devices.
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Page/Page column 14
(2012/03/26)
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- N-phenyl triscarbazole
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The present invention relates to a novel triscarbazole compound having substituent on N-phenyl, which can be represented by Formula (I). wherein R1 is selected from the group consisting of halogen or alkyl or alkoxy group having 1 to 20 carbon atoms wherein one or more hydrogen atom may be replaced by halogen; RA, RB, Rc, RD and RE are any of substituents; and i, j, k, l and m are same or different at each occurrence and represent an integer from 0 to 4. By introduction of the substituent on N-phenyl, the device efficiency, stability and lifetime can be increased while maintaining the solubility. These compounds can be used in various organic devices such as organic light emitting diodes, photovoltaic cells or organic semiconductor devices.
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Page/Page column 10
(2012/04/10)
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- Electrochemical and spectral characterizations of 9-phenylcarbazoles
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A series of 9-phenylcarbazoles have been synthesized and characterized for their electrochemical as well as spectral properties. For 3,6-substituted carbazoles, the oxidation is reversible and the potential is affected by the substituents. For 3,6-unprotected carbazoles, on the other hand, the oxidized forms can undergo dimerization. Their corresponding dimers have been independently synthesized by chemical methods and have exhibited identical spectral properties. The para position of the 9-phenyl group is relatively insensitive for redox and chemical reactions. The amino derivatives are unstable in carbazole cation radical form compared with their triphenylamine counterparts.
- Chiu, Ssu-Kai,Chung, Yi-Chun,Liou, Guey-Sheng,Su, Yuhlong Oliver
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scheme or table
p. 331 - 337
(2012/07/03)
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- Benzotriazol-1-ylmethanol: An excellent bidentate ligand for the copper/palladium-catalyzed C-N and C-C coupling reaction
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An efficient benzotriazole based N,O bidentate ligands for the Cu-catalyzed N-arylation of π-excessive nitrogen heterocycles is described. This ligand accomplishes C-N coupling of Nheterocycles and C-C coupling of boronic acids with a variety of hindered, functionalized aryl/heteroaryl halides under mild reaction conditions in good to excellent yields. Using his ligand C-N and C-C (Suzuki) couplings with bromoarenes could be conducted with less catalyst loading. A wide array of deactivated and hindered aryl halides react cleanly to afford the functionalized biaryl derivatives in high yields. ARKAT-USA, Inc.
- Jha, Rajeev R.,Singh, Jaspal,Tiwari, Rakesh K.,Verma, Akhilesh K.
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p. 228 - 248
(2013/02/23)
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- Blue fluorescence from the ligand and yellow phosphorescence from the iridium complex: High-efficiency wet-processed white organic light-emitting device
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We synthesized four carbazole modified blue-emitting fluorescent ligands. These ligands coordinated with Ir3+ and four yellow-emitting phosphorescent complexes were obtained. A high-efficiency (current efficiency 20.6 cd/A) yellow electrophosphorescence device was wet-fabricated using the complex as a guest. The ligands can harvest and transfer energy to the complexes and a high efficiency (~18 cd/A) white-light emitting device (CIE 0.31, 0.39) was obtained using the ligand as the blue-fluorescence emitter and the complex as the yellow-phosphorescence emitter. Therefore, the ligand can be a coordinator, an emitter and partly, a host. This is beneficial to device efficiency and saving cost for large-scale manufacturing.
- Yu, Fang-Fang,Fan, He-Liang,Huang, Hai-Fang,Cao, Qian-Yong,Dai, Yan-Feng,Gao, Xi-Cun,Shang, Yu-Zhu,Zhang, Min-Yan,Long, Li,Xu, Hong,Li, Xi-Feng,Wei, Bin
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scheme or table
p. 119 - 122
(2012/07/31)
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- Cu(OAc)2·H2O-catalyzed N-arylation of nitrogen-containing heterocycles
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In the absence of any additional ligands, the efficient N-arylation of nitrogen-containing heterocycles with aryl iodides catalyzed by relative low catalyst amount of Cu(OAc)2·H2O was developed. This simple catalytic system is involved in the C-N cross-coupling reaction and works for a variety of pyrazole, pyrrole, imidazole, triazole, indole, benzoimidazole, benzotriazole, carbazole, and anilines as well as aryl iodides with different electronic properties. Highly efficient copper(II)-catalyzed N-arylation protocol was established.
- Xu, Zhong-Lin,Li, Hong-Xi,Ren, Zhi-Gang,Du, Wei-Yuan,Xu, Wei-Chang,Lang, Jian-Ping
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supporting information; experimental part
p. 5282 - 5288
(2011/08/04)
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- Efficient copper-catalyzed N-arylations of nitrogen-containing heterocycles and aliphatic amines in water
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A simple and efficient copper-catalyzed method has been developed for N-arylations of nitrogen-containing heterocycles and aliphatic amines in water. The protocol uses (1E,2E)-oxalaldehyde dioxime (OADO) as the ligand, and water as the solvent, and shows good tolerance towards various functional groups.
- Li, Xufeng,Yang, Daoshan,Jiang, Yuyang,Fu, Hua
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experimental part
p. 1097 - 1105
(2010/08/06)
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- Copper-catalyzed double N-vinylation of aromatic amines: An efficient synthesis of various substituted N-arylpyrroies
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A simple and efficient approach to various substituted N-arylpyrroles has been developed. The method is based on the copper-catalyzed sequential inter- and intramolecular Nvinylation of aromatic amines. The reactions proceed to afford substituted N-arylpyrroles in good-to-excellent yields using CuI as the precatalyst, iBuONa as the base, and N1,N2dimethylethane- l,2-diamine (DMEDA) as the ligand. Ani-lines with electron-donating and -withdrawing substituents as well as a heteroaromatic amine performed very well under the conditions used. Tri- and tetrasubstituted dienyl diiodides also performed well under the reaction conditions and afforded the corresponding substituted N-arylpyrroles in good yields, Products were also obtained in high yields with CuBr or CuCl as precatalyst.
- Liao, Qian,Zhang, Liyun,Wang, Fei,Li, Shutao,Xi, Chanjuan
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experimental part
p. 5426 - 5431
(2010/11/18)
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- Highly efficient ligands for the palladium-assisted double N-arylation of primary amines for one-sep construction of carbazoles
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A highly efficient one-pot synthesis of carbazoles via palladium-catalyzed double N-arylation of primary amines with 2,2'-dihalobiphenyls is described using a catalyst system comprised of tris(dibenzylideneacetone)dipalladium(O) (Pd2dba3) and the proazaphosphatrane P(i-BuNCH 2CH2)3N (8) or its derivative (t-Bu) 2P=N-P(iBuNCH2CH2)3N (9a) as the ligand. The process is effective for double N-arylation of 2,2'-biphenyl dibromide, diiodide, and even dichloride with a variety of primary amines including neutral, electronrich, electron-deficient, and sterically hindered anilines as well as aliphatic amines.
- Zhou, Yibo,Verkade, John G.
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supporting information; experimental part
p. 616 - 620
(2010/07/03)
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- DICARBAZOLE AROMATIC AMINE POLYMERS AND ELECTRONIC DEVICES
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A conjugated or partially conjugated polymer comprising a structural unit of Formula I: I Wherein Ar1 is an aromatic group which contains one or more heteroatoms, or an aromatic group which comprises one or more fused aromatic or non-aromatic rings, said aromatic group may be substituted or unsubstituted; and R1 is alkyl, alkoxy, and aryl group, cyano, or F.
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- Synthesis and characterization of deep blue emitters from starburst carbazole/fluorene compounds
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A series of well-defined, highly fluorescent starburst compounds with a carbazole core and oligo(2,7-fluorene ethynylene) arms have been synthesized by Sonogashira coupling reaction and fully characterized. These conjugated compounds exhibit good solubility, high thermal stability, and excellent fluorescence quantum yields (up to 0.99). The incorporation of carbazole core interrupted the main-chain conjugation and resulted in blue-shifted absorption and emission. Moreover, deep blue light has been approached from organic light-emitting diodes (OLEDs) adopting these compounds as emitting layer.
- Zhao, Zujin,Xu, Xinjun,Chen, Xiaopeng,Wang, Xiaoming,Lu, Ping,Yu, Gui,Liu, Yunqi
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p. 2658 - 2668
(2008/09/19)
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