- Urea as ammonia equivalent in aryl halides amination catalyzed by palladium complexes
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Urea reaction with nonactivated aryl bromides and chlorides under catalysis with palladium complexes led to the formation in 65-95% yield of triarylamines from para-and meta-substituted aryl halides and of diarylamines from ortho-isomers.
- Artamkina,Sergeev,Shtern,Beletskaya
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- Dye-sensitized electron transfer from TiO2 to oxidized triphenylamines that follows first-order kinetics
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Two sensitizers, [Ru(bpy)2(dcb)]2+ (RuC) and [Ru(bpy)2(dpb)]2+ (RuP), where bpy is 2,2′-bipyridine, dcb is 4,4′-dicarboxylic acid-2,2′-bipyridine and dpb is 4,4′-diphosphonic acid-2,2′-bipyridine, were anchored to mesoporous TiO2 thin films and utilized to sensitize the reaction of TiO2 electrons with oxidized triphenylamines, TiO2(e-) + TPA+ → TiO2 + TPA, to visible light in CH3CN electrolytes. A family of four symmetrically substituted triphenylamines (TPAs) with formal Eo(TPA+/0) reduction potentials that spanned a 0.5 eV range was investigated. Surprisingly, the reaction followed first-order kinetics for two TPAs that provided the largest thermodynamic driving force. Such first-order reactivity indicates a strong Coulombic interaction between TPA+ and TiO2 that enables the injected electron to tunnel back in one concerted step. The kinetics for the other TPA derivatives were non-exponential and were modelled with the Kohlrausch-William-Watts (KWW) function. A Perrin-like reaction sphere model is proposed to rationalize the kinetic data. The activation energies were the same for all of the TPAs, within experimental error. The average rate constants were found to increase with the thermodynamic driving force, consistent with electron transfer in the Marcus normal region.
- DiMarco, Brian N.,Troian-Gautier, Ludovic,Sampaio, Renato N.,Meyer, Gerald J.
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- Measurement and prediction of solubility of four arylamine molecules in benzene, hexane, and methanol
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In this paper, the solubility of selected arylamine molecules in methanol, hexane, and benzene has been investigated. Solubility of mmmTTA in hexane and benzene is the highest while mTTA has the lowest solubility in benzene and hexane. The UNIFAC and the UNIQUAC binary adjustable parameters have been determined. On the basis of these parameters, the solubility of these molecules has been predicted and compared with the experimental data. The effect of meta or para substitutions in arylamine molecules on their solubility in organic solvents was experimentally determined and theoretically established. The adjustable parameters of the UNIFAC equation obtained in this study will help estimate the solubility of macromolecules with the same constitutional groups or estimate the solubility of mixture of arylamine molecules. Thermal properties such as specific heat, melting point, boiling point, and heat of vaporization of the selected arylamine molecules have been determined.
- Manifar, Touraj,Rohani, Sohrab
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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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- Sensitive and Repeatable Photoinduced Luminescent Radicals from A Simple Organic Crystal
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Photoinduced organic radicals are important for chemical and physical processes of organic materials, which are extensively investigated and applied in organic synthesis, photoelectronic devices and biotechnology. However, there are rare reports of the luminescence for these photoinduced radicals, especially in the condensed state. Herein, an unexpected and interesting luminescent radical is described, which can be rapidly and reversibly generated from a simple organic crystal by gentle light irradiation in air. It was revealed that the twist and asymmetric conformation of isolated molecule in its crystal with only weak C?H???π intermolecular interactions, which led to the generation of such photoinduced luminescent radicals. In addition, dual-channel photosensitive device with rapid response and well repeatability can be obtained based on the thin film of this organic crystal, showing both photoswitching on luminescence and conducting.
- Mu, Yingxiao,Liu, Yanyan,Tian, Haiyan,Ou, Depei,Gong, Li,Zhao, Juan,Zhang, Yi,Huo, Yanping,Yang, Zhiyong,Chi, Zhenguo
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- C-H activation and nucleophilic substitution in a photochemically generated high valent iron complex
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The photochemical oxidation of a (TAML)FeIII complex 1 using visible light generated Ru(bpy)33+ produces valence tautomers (TAML)FeIV (1+) and (TAML+)FeIII (1-TAML+), depending on the exogenous anions. The presence of labile Cl- or Br- results in a ligand-based oxidation and stabilisation of a radical-cationic (TAML+)FeIII complex, which subsequently leads to unprecedented C-H activation followed by nucleophilic substitution on the TAML aryl ring. In contrast, exogenous cyanide culminates in metal-based oxidation, yielding the first example of a crystallographically characterised S = 1 [(TAML)FeIV(CN)2]2- species. This is a rare report of an anion-dependent valence tautomerisation in photochemically accessed high valent (TAML)Fe systems with potential applications in the oxidation of pollutants, hydrocarbons, and water. Furthermore, the nucleophilic aromatic halogenation reaction mediated by (TAML+)FeIII represents a novel domain for high-valent metal reactivity and highlights the possible intramolecular ligand or substrate modification pathways under highly oxidising conditions. Our findings therefore shine light on high-valent metal oxidants based on TAMLs and other potential non-innocent ligands and open new avenues for oxidation catalyst design.
- Lim, Jia Hui,Engelmann, Xenia,Corby, Sacha,Ganguly, Rakesh,Ray, Kallol,Soo, Han Sen
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- C60 as a Photocatalyst of Electron-Transfer Processes: Reactions of Triplet C60 with Chloranil, Perylene, and Tritolylamine Studied by Flash Photolysis and FT-EPR
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Photoprocesses in benzonitrile solutions of C60 and chloranil (CA) have been studied by complementary techniques of nanosecond laser photolysis and Fourier transform EPR.Direct oxidation of 3C60 by CA is slow (k = (2.0 +/- 0.3)E7 M-1 s-1), consistent with the high oxidation potential of 3C60.However, the formation rate and yield of CA(1-) are much increased by addition of perylene (Pe) or tritolylamine (TTA) via the fast reactions 3C60 + Pe -> C60 + 3Pe, followed by 3Pe + CA -> Pe(1+) + Ca(1-), or 3C60 +TTA -> C60(1-) + TTA(1+), followed by C60(1-) + CA -> C60 + CA(1-).These reactions utilize the broad absorption and initial high triplet yield of C60, as well as the low oxidation potential of 3Pe or high reduction potential of 3C60, to catalyze efficient formation of CA(1-) and enhance separation of radicals.Triplet C60 also reacts with Pe by electron transfer, forming Pe(1+) and C60(1-) with rate one-third that of energy transfer.However, the Ca(1-) formed in the Pe-catalyzed reaction is strongly spin-polarized, indicating that it is formed primarily via the 3Pe pathway.The extinction coefficient of C60(1-) at 1080 nm is measured (ε = 18300 +/- 1100 M-1 cm-1) using the TTA reaction.
- Steren, Carlos A.,Willigen, Hans van,Biczok, Laszlo,Gupta, Neeraj,Linschitz, Henry
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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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- 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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- 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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supporting information
p. 1749 - 1754
(2017/10/06)
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- Arylation of aniline and amines by Pd-(N-Heterocyclic carbene) complexes
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Aminoarenes constitute valuable building blocks in organic synthesis and an essential skeleton ubiquitously found in ligands, agrochemicals, and pharmaceuticals. This synopsis presents recent amination methods using nitrogen-heteroatom bonds as a powerful and versatile platform to rapidly synthesize diverse aminoarenes, with transition-metal catalyzed arene C-H amination. The Buchwald-Hartwig amination has been investigated theoretically and experimentally to examine the scope of possible bases under different reaction conditions. We report examples of the palladium NHC (N-heterocyclic carbene) catalyzed amination of aryl halides with anilines and amines in the presence of dimethoxyethane solvent and potassium tertiary-butoxide as a base.
- ?ahin, Neslihan,Dü?ünceli, Serpil Demir,?zdemir, ?smail
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p. 1506 - 1517
(2017/08/02)
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- Contra-thermodynamic Hydrogen Atom Abstraction in the Selective C-H Functionalization of Trialkylamine N-CH3 Groups
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We report a simple one-pot protocol that affords functionalization of N-CH3 groups in N-methyl-N,N-dialkylamines with high selectivity over N-CH2R or N-CHR2 groups. The radical cation DABCO+?, prepared in situ by oxidation of DABCO with a triarylaminium salt, effects highly selective and contra-thermodynamic C-H abstraction from N-CH3 groups. The intermediates that result react in situ with organometallic nucleophiles in a single pot, affording novel and highly selective homologation of N-CH3 groups. Chemoselectivity, scalability, and recyclability of reagents are demonstrated, and a mechanistic proposal is corroborated by computational and experimental results. The utility of the transformation is demonstrated in the late-stage site-selective functionalization of natural products and pharmaceuticals, allowing rapid derivatization for investigation of structure-activity relationships.
- Barham, Joshua P.,John, Matthew P.,Murphy, John A.
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supporting information
p. 15482 - 15487
(2016/12/09)
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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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- 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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- Nickel-catalyzed triarylamine synthesis: Synthetic and mechanistic aspects
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An improved protocol was described for the amination of chloroarenes with diarylamines under NiCl2(PCy3)2 catalysis in the presence of a Grignard reagent as base. This method fully suits bromo-/iodoarene substrates as well, and even is expanded to certain aryl tosylates. A preliminary investigation into the mechanism suggests that this amination reaction might proceed through NiI and NiIII intermediates rather than via the usually expected Ni0-Ni II cycle.
- Li, Xin-Le,Wu, Wei,Fan, Xin-Heng,Yang, Lian-Ming
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supporting information
p. 1232 - 1236
(2014/03/21)
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- Selective one-pot synthesis of symmetrical and unsymmetrical di- and triarylamines with a ligandless copper catalytic system
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The one-pot synthesis of symmetrical or unsymmetrical di- or triarylamines using aryl iodides or bromides and LiNH2 as ammonia source is reported. This highly selective method is based, for the first time, on a copper-catalyzed system, which does not require the presence of any additional ligand.
- Tlili, Anis,Monnier, Florian,Taillefer, Marc
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supporting information; experimental part
p. 6408 - 6410
(2012/07/27)
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- A reusable polymer supported copper(I) complex for the C-N bond cross-coupling reaction
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The Ullmann coupling of amines with aryl iodide as well as arylboronic acids and N(H)-heterocycles with arylboronic acids has been carried out efficiently using PS-LCu(I) catalyst. The copper complex has been prepared and characterized by using scanning electron microscope (SEM), elemental analysis, atomic absorption spectroscopy (AAS), Thermo gravimetric analysis and spectrometric methods like Fourier transform infrared spectroscopy (FTIR). The effects of various parameters such as temperature, solvent and base on the reaction system were studied. The reusability experiments show that the catalyst can be used five times without much loss in the catalytic activity.
- Islam,Mondal, Sanchita,Mondal, Paramita,Roy, Anupam Singha,Tuhina, Kazi,Mobarok, Manir
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experimental part
p. 1352 - 1357
(2011/10/12)
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- Hydroxylamine O-benzyl ether as an ammonia equivalent in the catalytic amination of aryl halides
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The palladium catalysed amination of aryl bromides with hydroxylamine O-benzyl ether leads to the formation of diaryl or triarylamines depending on the size of the aryl bromide, the number of equivalents used or the conditions employed.
- Bedford, Robin B.,Betham, Michael
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p. 8947 - 8950
(2008/03/14)
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- N-Arylation of aliphatic, aromatic and heteroaromatic amines catalyzed by copper bis(2,2,6,6-tetramethyl-3,5-heptanedionate)
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Copper bis(2,2,6,6-tetramethyl-3,5-heptanedionate) was found to be an efficient catalyst for N-arylation of aliphatic, aromatic and heteroaromatic amines with aryl iodides/bromides under mild conditions. The system tolerated a variety of hindered and functionalized amines/aryl halides and the desired N-aryl amines were obtained in good to excellent yields.
- Nandurkar, Nitin S.,Bhanushali, Mayur J.,Bhor, Malhari D.,Bhanage, Bhalchandra M.
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p. 6573 - 6576
(2008/02/12)
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- One-pot synthesis of symmetrical di- and triarylamines using urea as the source of the amino group
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A simple one-pot palladium-catalyzed reaction for the conversion of aryl halides to aryl amines using urea as an ammonia equivalent is reported. Arylation of urea in the presence of Pd2dba3, t-Bu 3P·HBF4 and t-BuOK in dioxane gives di- and triarylamines in 65-95% yields. Georg Thieme Verlag Stuttgart.
- Artamkina, Galina A.,Sergeev, Alexey G.,Stern, Mikhail M.,Beletskaya, Irina P.
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p. 235 - 238
(2007/10/03)
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- Palladium-Catalyzed Amination of Aryl Halides: Mechanism and Rational Catalyst Design
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Palladium complexes of tri-o-tolyl phosphine and bis(diphenylphospino)ferrocene catalyze the reaction between aryl halides and either tin amides or amines in the presence of base to form aryl amines by halide substitution. This account describes our mechanistic and synthetic studies related to the amination reactions. These studies include kinetic behavior of the catalytic systems as well as direct observation of the primary stoichiometric reactions comprising the catalysis - including the rare C-N bond-forming reductive eliminations - and the mechanisms of these individual reactions. This paper also describes the development of tin-free amide sources and second generation amination catalysts that have resulted from our mechanistic understanding of the amination chemistry.
- Hartwig, John F.
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p. 329 - 340
(2007/10/03)
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- Catalytic Synthesis of Triarylamines
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Condensation along Ullman reaction in the presence of copper catalysts was carried out with para-substituted arylamines and p-iodotoluene to yield the corresponding triarylamines. For preparation of diarylamines was used dehydrogenation of N-cycloalkylanilines and azomethines; diarylamines were obtained through dehydroamination of cycloaliphatic alcohols with anilines.
- Tarasievich,Mikhalevskaya,Kozlov
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p. 1100 - 1102
(2007/10/03)
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- N-ALKYLATION AND N-ARYLATION OF ANILINES STARTING FROM A MILD N-Mg REAGENT: ITS ACTIVATION CAUSING THE 'N-C' COUPLING TO EXTEND THE UNIFIED STRUCTURE-REACTIVITY RELATIONSHIP
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New N-alkylation and N-arylation procedures starting from anilinomagnesium (ArNHMgBr) are reported.For N-alkylation with alkyl bromides, addition of hexamethylphosphoramide to an ArNHMgBr solution in tetrahydrofuran (THF) is effective.After heating at 55 deg C, N-monoalkylation product was obtained in 60-90percent yield, slight dialkylation taking place.The combined use of aryliminodimagnesium with α,ω-dibromoalkanes led to N-arylazacycloalkanes.For N-arylation with iodobenzene, replacement of THF with pyridine and additional use of copper(I) iodide are effective.After heating at 115 deg C with iodobenzene, mono- and diarylation products were obtained, the former being predominant.The combined use of ArNHMgBr and N,N,N',N'-tetramethylethylenediamine as the ligand of copper species is effective for elimination of diarylation and other undesired products, and leads to diarylamines in excellent yield.The method is of advantage over the conventional Ullmann and Chapman methods.The polar solvents and copper salt are effective additives for inducing 'inert combinations' of ArNHMgBr or ArN(MgBr)2 with alkyl and aryl halides into N-C coupling, to extend the unified view proposed for the reactivity of magnesium reagents.The difference in the roles of N-Mg and N-Cu species is discussed.
- Matsuo, Koji,Shichida, Yoshiaki,Nishida, Hiroshi,Nakata, Satsuki,Okubo, Masao
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- Substituted Triarylamine Cation-Radical Redox Systems - Synthesis, Electrochemical and Spectroscopic Properties, Hammet Behavior, and Suitability as Redox Catalysts
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21 triarylamines (1n - 1z, 1za, 1zb) and triarylamine analogs (2a, 2b, 3a, 3b, 4a, 4b) with substituents in at least all three p positions and some of their cation-radical hexachloroantimonates have been synthesized.The electrochemical behavior has been studied by cyclic voltammetry.Most of the compounds show chemically and electrochemically reversible first oxidation waves in the formation of the cation radicals.With the exception of 4a and 4b, the second wave for the formation of the dication is chemically irreversible.The UV spectra of the triarylamine cation radicals have been obtained in the presence of a slight excess of SbCl5.A good Hammett correlation between the first anodic potential of only p-substituted triarylamines and the ?/?+ values has been established.Some redox-catalytic properties of triarylamine cation radicals are described. Key Words: Triarylamines / Cation radicals / Electrochemistry / Redox catalysts / Voltammetry, cyclic
- Dapperheld, Steffen,Steckhan, Eberhard,Grosse Brinkhaus, Karl-Heinz,Esch, Thomas
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p. 2557 - 2568
(2007/10/02)
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- Mild and Effective Removal of Dithioketal Protecting Groups by Triarylamine Cation Radicals as Homogeneous Electron Transfer Agents
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1,3-Dithianes 2 can effectively be converted into the parent carbonyl compounds 7 by a very mild oxidative procedure using tri-p-tolylammoniumyl (1a+.) or tris(4-bromophenyl)ammoniumyl (1b+.) as homogeneous electron transfer agents.The yields are equally good for the cleavage by stoichiometric amounts of the triarylammoniumyl hexachloroantimonates as well as for the indirect electrochemical procedure using catalytic amounts of the triarylamine together with electrochemical generation and regeneration of the cation radicals.In the case of 1,3-dithiolanes 3 the application of stoichiometric amounts of tris(4-bromophenyl)ammoniumyl hexa chloroantimonate is very effective while during the indirect electrochemical procedure the deposition of polymeric sulfur compounds onto the electrode surface has to be prevented by the use of a flowthrough cell.In all cases the conditions for the cleavage are so mild that hydroxy functions and double bonds are tolerated without problems.
- Platen, Martin,Steckhan, Eberhard
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p. 1679 - 1694
(2007/10/02)
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- MECHANISM OF BROMINATION OF SOME AROMATIC AMIDES BY N-BROMOSUCCINIMIDE
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It was established that in polar organic solvents N-bromosuccinimide acts as a one-electron oxidizing agent for tertiary aromatic amines and N,N-substituted dihydrophenazines.Depending on the structure of the amines and the nature of the medium, the maximum current concentration of the radical-cations in these reactions amounts to 90percent of the initial amine.It was shown that the intermediate radical-cations of the substituted amines can then be transformed into the bromination products by reaction with the bromide ion formed during dissociation of the bromosuccinimide radical- anion.The mechanism of the investigated reactions in the light and in the dark is discussed.
- Koshechko, V. G.,Inozemtsev, A. N.
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p. 315 - 318
(2007/10/02)
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- ONE-ELECTRON OXIDATION OF TRIPHENYL DERIVATIVES OF ELEMENTS OF THE NITROGEN SUBGROUP BY CATION-RADICALS OF THE TRIPHENYLAMINE SERIES
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The kinetics and mechanism of the one-electron oxidation of triphenyl derivatives of elements of the nitrogen subgroup (Ph3Y) by the cation-radicals of substituted triphenylamines (XPH)3N.(1+) were studied by ESR and electronic spectroscopy with the use of the stopped-flow technique.Possible paths for the transformations of the triphenylamine cation-radical into the tetraphenylbenzidine cation-radical were established.The effect of the electronic structure of the substituent X in (XPh)3N.(1+) and of the nature of the heteroatom Y in Ph3Y on the kinetics and mechanism of the processes was investigated.
- Atamanyuk, V. Yu.,Koshechko, V. G.,Pokhodenko, V. D.
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p. 1619 - 1626
(2007/10/02)
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