- Method for synthesizing diarylamine through N-arylation reaction of arylamine under copper catalysis
-
The invention provides a method for synthesizing diarylamine through an N-arylation reaction of arylamine under copper catalysis. The method comprises the following steps: S1, selecting a proper amount of a reaction reagent, a catalyst, a solvent and the like; S2, sequentially adding a reaction reagent, a catalyst, a solvent and the like into a reaction tube with a magnetic bar; S3, selecting a proper amount of AcOH, and adding the AcOH into the reaction tube; S4, heating the reaction tube; S5, performing oil bath treatment; S6, cooling to room temperature, and diluting; S7, extracting by using ethyl acetate; S8, washing the organic layer with saline water; S9, drying on anhydrous Na2SO4; S10, evaporating under vacuum; and S11, purifying the residues into the pure product through silica gel chromatography. A scheme that arylamine and an environmentally-friendly and stable aryl silicon reagent are subjected to an N-arylation reaction under the catalysis of a cheap copper reagent is provided, Cu(OAc)2 is used as a catalyst to react in DMSO in the atmosphere of O2, the conversion reactivity is good, the substrate range is wide, and the method has good tolerance to reaction substrates with various functional groups under mild reaction conditions.
- -
-
Paragraph 0062-0063; 0070; 0071; 0080; 0081
(2021/07/14)
-
- Electrochemical Reductive Arylation of Nitroarenes with Arylboronic Acids
-
The synthesis of diarylamine is extremely important in organic chemistry. Herein, a novel electrochemical reductive arylation of nitroarenes with arylboronic acids was developed. A variety of diarylamines were synthesized without the need for transition-metal catalysts. The reaction could be scaled up efficiently in a flow cell and several derivatization reactions were carried out smoothly. Cyclic voltammetry experiments and mechanism studies showed that acetonitrile, formic acid, and triethyl phosphite all played a role in promoting this reductive arylation transformation.
- Wang, Dan,Wan, Zhaohua,Zhang, Heng,Alhumade, Hesham,Yi, Hong,Lei, Aiwen
-
p. 5399 - 5404
(2021/10/20)
-
- Synthesis and characterization of new square planar heteroleptic cationic complexes [Ni(ii) β-oxodithioester-dppe]+; Their use as a catalyst for Chan-Lam coupling
-
Novel heteroleptic [Ni(ii) β-oxodithioester-dppe]+PF6- complexes (β-oxodithioester = methyl-3-hydroxy-3-benzyl-2-propenedithioate L1 1, methyl-3-hydroxy-3-(p-methoxyphenyl)-2-propenedithioate L2 2, methyl-3-hydroxy-3-(naphthyl)-2-propenedithioate L3 3, methyl-3-hydroxy-3-(p-chlorophenyl)-2-propenedithioate L4 4, methyl-3-hydroxy-3-(p-bromophenyl)-2-propenedithioate L5 5 and methyl-3-hydroxy-3-(p-cyanophenyl)-2-propenedithioate L6 6) have been synthesized and characterized by elemental (C, H, N) analysis, ESI-MS, IR, UV-visible, 1H, 13C{1H}, 31P{1H} and 19F{1H} NMR spectroscopy. The distorted square planar structures of the isomorphous cationic complexes 2, 3, 4 and 5 have been determined by X-ray crystallography. The catalytic activities of 1-6 were investigated for the Chan-Lam coupling reaction involving arylboronic acids and amines to afford N-arylated products in good to excellent yields under mild conditions with 1 mol% catalyst loading. This catalytic protocol offers significant functional group tolerance, and is endowed with a broad substrate scope. This journal is
- Kumari, Kavita,Kumar, Saurabh,Singh, Krishna Nand,Drew, Michael G. B.,Singh, Nanhai
-
p. 12143 - 12153
(2020/07/30)
-
- Copper complexes of 1,4-diazabutadiene ligands: Tuning of metal oxidation state and, application in catalytic C-C and C-N bond formation
-
Reaction of 1,4-diazabutadiene (p-RC6H4N = C(H)(H)C = NC6H4R-p; R = OCH3, CH3, H and Cl; abbreviated as L-R) with CuCl2·2H2O in methanol at ambient temperature (25 °C) affords a group of doubly chloro-bridged dicopper complexes of type [{CuI(L-R)Cl}2], designated as 1-R. Similar reaction carried out in acetonitrile furnishes a family of doubly chloro-bridged dicopper complexes of type [{CuII(L-R)Cl2}2], designated as 2-R. Molecular structures of 1-OCH3 and 2-OCH3 have been determined by X-ray crystallography. While copper(I) is having a nearly tetrahedral N2Cl2 coordination sphere in 1-OCH3, the N2Cl3 coordination sphere around copper(II) is distorted square pyramidal in nature in 2-OCH3. Isolated 2-R complexes, on dissolution in methanol, are found to undergo facile reduction of the metal center to generate the corresponding 1-R complexes. The 1-R and 2-R complexes show intense absorptions in the visible and ultraviolet regions. Cyclic voltammetry on the 1-R and 2-R complexes shows both metal-centered and ligand centered redox responses. The 1-R complexes are found to efficiently catalyze C-N cross-coupling reactions between arylboronic acids and aryl amines; while the 2-R complexes display notable catalytic efficiency for nitroaldol reactions.
- Mukherjee, Aparajita,Basu, Semanti,Bhattacharya, Samaresh
-
-
- Insights on bimetallic micellar nanocatalysis for buchwald-hartwig aminations
-
A nanocatalyst for micellar Buchwald-Hartwig aminations is developed, thoroughly characterized, and applied on a variety of substrates. The catalyst is stable under ambient conditions for at least six months. The catalyst retained its activity after several cycles, and its structure remained intact as confirmed by NMR spectroscopy. Association of Pd nanoparticles with Cu by a phosphine ligand is revealed by 31P NMR spectroscopy, and their linkage with the activated carbon surface is revealed by XAS analysis. Control NMR experiments revealed the binding of the ligand with both Cu and Pd, and all phosphine molecules are under the same environment. In addition to NMR and XAS analysis, the catalyst is characterized by SEM, HRTEM, XPS, and TGA. Reactions are highly reproducible at variable scales. Environmentally benign, proline-based amphiphile PS-750-M is critical for catalytic activity, which is achieved under mild conditions in water as the reaction medium. The inherent sustainability of these conditions coupled with a low E factor achievable through robust recycling of catalyst and reaction medium demonstrates the significant utility of this technology.
- Ansari, Tharique N.,Taussat, Armand,Clark, Adam H.,Nachtegaal, Maarten,Plummer, Scott,Gallou, Fabrice,Handa, Sachin
-
p. 10389 - 10397
(2019/10/14)
-
- Preparation and characterization of isatin complexed with Cu supported on 4-(aminomethyl) benzoic acid-functionalized Fe3O4 nanoparticles as a novel magnetic catalyst for the Ullmann coupling reaction
-
Isatin complexed with Cu supported on 4-(aminomethyl) benzoic acid-functionalized Fe3O4 nanoparticles (Cu-IS-AMBA-MNPs) as a new catalyst was designed, prepared and characterized by appropriate analyses. The heterogeneous reusable catalyst was successfully used for the efficient and widespread syntheses of diaryl ethers and diarylamines via the Ullmann coupling reaction. This green catalyst was easily removed, reused several times with no significant loss of its activity, and provided a clean synthesis with excellent yield and reduced time.
- Khodaei, Mohammad Mehdi,Alizadeh, Abdolhamid,Haghipour, Maryam
-
p. 2727 - 2747
(2019/02/13)
-
- Copper-Catalyzed NaBAr 4-Based N-Arylation of Amines
-
Using NaBAr 4 as an arylating agent, the formation of carbon-heteroatom bonds by a Cham-Lam cross-coupling reaction in the presence of catalytic copper(II) acetate monohydrate in acetonitrile at room temperature under air is described. The investigation of reaction scope suggests that several aliphatic and aromatic amines are compatible. In particular, the reaction of alkylamine and NaBAr 4 proceeds smoothly to offer the corresponding products in good to excellent yields.
- Yang, Qin,Lei, Xiaoli,Yin, Zhijian,Deng, Zhihong,Peng, Yiyuan
-
supporting information
p. 538 - 544
(2019/01/10)
-
- Electrochemically Enabled Chan-Lam Couplings of Aryl Boronic Acids and Anilines
-
The Chan-Lam reaction remains a highly utilized transformation for C-N bond formation. However, anilines remain problematic substrates due to their lower nucleophilicity. To address this problem, we developed an electrochemically mediated Chan-Lam coupling of aryl boronic acids and amines utilizing a dual copper anode/cathode system. The mild conditions identified have enabled the preparation of a wide range of functionalized biarylanilines in good yields and chemoselectivities.
- Wexler, Ryan P.,Nuhant, Philippe,Senter, Timothy J.,Gale-Day, Zachary J.
-
supporting information
p. 4540 - 4543
(2019/06/27)
-
- Copper immobilized at a covalent organic framework: An efficient and recyclable heterogeneous catalyst for the Chan-Lam coupling reaction of aryl boronic acids and amines
-
A polyimide covalent organic framework (PI-COF) with high thermal and chemical stabilities has been readily prepared from commercially available and inexpensive reagents and was employed as an effective support for heterogeneous copper. It was demonstrated that the obtained Cu@PI-COF is a highly active heterogeneous catalyst which can effectively promote the Chan-Lam coupling reaction of aryl boronic acids and amines in an open flask without the aid of any base or additive. In addition, the catalyst could be readily recovered from the reaction mixture by simple filtration and reused for at least eight cycles without any observable change in structure and catalytic activity.
- Han, Yi,Zhang, Mo,Zhang, Ya-Qing,Zhang, Zhan-Hui
-
p. 4891 - 4900
(2018/11/21)
-
- Immobilization of nickel ions onto the magnetic nanocomposite based on cross-linked melamine groups: Effective heterogeneous catalyst for N-Arylation of Arylboronic acids
-
A new magnetic heterogeneous catalyst was synthesized by immobilization of nickel ions onto a cross-linked polymeric nanocomposite composed of cyanuric chloride, ethylenediamine and functionalized magnetic nanoparticles. The resulting nitrogen rich support was capable of adsorbing large amounts of nickel ions (1.20 mmol g?1). The synthesized catalyst was characterized using AAS, TEM, FT-IR, EDX, TGA, SEM, BET and XRD techniques. The performance of the prepared catalyst was investigated in the C-N coupling of arylamines with aryl boronic acids. The reaction was carried out under a mild condition and good to moderate to good yields of products was obtained using only 5.0 mol% of the catalyst. The catalyst was easily recovered and reused for at least 7 times without any significant loss of its activity.
- Pourjavadi, Ali,Keshavarzi, Nahid,Moghaddam, Firouz Matloubi,Hosseini, Seyed Hassan
-
-
- Palladium-catalyzed amination of aryl sulfoxides
-
Amination of diaryl sulfoxides with anilines and alkylamines has been accomplished under palladium/N-heterocyclic carbene (NHC) catalysis. Owing to its electron deficiency, the leaving arenesulfenate anion would be smoothly released from the palladium center to result in uneventful catalyst turnover under milder reaction conditions in comparison with previous C-S bond amination reactions. This amination accommodated a wider range of functional groups such as silyl, boryl, methylsulfanyl, and halogen moieties. Regioselective amination of unsymmetrical diaryl sulfoxides was also executed by means of steric bias.
- Yoshida, Yuto,Otsuka, Shinya,Nogi, Keisuke,Yorimitsu, Hideki
-
supporting information
p. 1134 - 1137
(2018/02/23)
-
- Selective Monoarylation of Primary Anilines Catalyzed by Pd(dippf) and its Application in OLED Component Synthesis
-
Palladium 1,1′-bis(diisopropylphosphino)-ferrocene [Pd(dippf)] complexes were found to promote the monoarylation of primary anilines with unprecedented selectivities. They also allow the sequential arylation of primary anilines with two different aryl bromides in one pot. The reactions can be performed at low catalyst loadings (0.2 mol%) and high substrate concentrations. The synthetic utility of the optimum catalyst was demonstrated by the synthesis of various di- and triarylamines. A particular focus was set on compounds with carbazole and fluorene moieties as employed in state-of-the-art small-molecule organic light emitting diodes (OLEDs). (Figure presented.).
- Grünberg, Matthias F.,Jia, Fan,Rivas-Nass, Andreas,Goo?en, Lukas J.
-
supporting information
p. 1589 - 1594
(2016/10/13)
-
- Highly Chemoselective Iridium Photoredox and Nickel Catalysis for the Cross-Coupling of Primary Aryl Amines with Aryl Halides
-
A visible-light-promoted iridium photoredox and nickel dual-catalyzed cross-coupling procedure for the formation C?N bonds has been developed. With this method, various aryl amines were chemoselectively cross-coupled with electronically and sterically diverse aryl iodides and bromides to forge the corresponding C?N bonds, which are of high interest to the pharmaceutical industries. Aryl iodides were found to be a more efficient electrophilic coupling partner. The coupling reactions were carried out at room temperature without the rigorous exclusion of molecular oxygen, thus making this newly developed Ir-photoredox/Ni dual-catalyzed procedure very mild and operationally simple.
- Oderinde, Martins S.,Jones, Natalie H.,Juneau, Antoine,Frenette, Mathieu,Aquila, Brian,Tentarelli, Sharon,Robbins, Daniel W.,Johannes, Jeffrey W.
-
supporting information
p. 13219 - 13223
(2016/10/30)
-
- The solid copper-mediated C-N cross-coupling of phenylboronic acids under continuous flow conditions
-
We have developed two general methods for the C-N cross-coupling of phenylboronic acids with amines using solid copper flow reactors, in combination with an oxidant. We have developed one method for a C-N arylation reaction which employs a solid copper coil reactor, in combination with tert-butyl peroxybenzoate, to give products in moderate isolated yields. We have also developed a general method for the C-N cross coupling of phenylboronic acids using a column packed with solid copper powder, in combination with acetic acid and TEMPO, to give products in isolated yields in excess of 75+%. We have also applied our general copper powder method to generate a library of products which highlights the utility of solid copper flow reactors for C-N cross coupling reactions, generating 16 examples in good yields. Mechanistic implications and future directions are also discussed.
- Bao, Jennifer,Tranmer, Geoffrey K.
-
p. 654 - 657
(2016/01/26)
-
- Copper mediated formation of carbon-heteroatom bonds using organoboron reagents and ultrasound
-
This report summarizes research efforts focused on copper acetate mediated reactions to form new carbon-heteroatom bonds using organoboron reagents under ultrasound irradiation. The method involves the application of ultrasound irradiation to the Chan-Evans-Lam reaction to achieve O-arylation of phenols, N-arylation of anilines and indoles, and S-arylation of thiols. Ultrasound irradiation was found to decrease reaction times from 72 hours to 4 hours while improving the product yields an average of 20%.1 Representative C-O, C-N, and C-S coupling reactions were successfully scaled-up from the milligram to gram levels while maintaining good product yields offering potential applications in industrial processes.
- Musolino, Bryan J.,Kabalka, George W.
-
p. 271 - 297
(2015/03/04)
-
- Synergistic Catalysis of Ionic Br?nsted Acid and Photosensitizer for a Redox Neutral Asymmetric α-Coupling of N-Arylaminomethanes with Aldimines
-
A redox neutral, highly enantioselective coupling between N-arylaminomethanes and N-sulfonyl aldimines was developed by harnessing the efficient catalysis of P-spiro chiral arylaminophosphonium barfate and a transition-metal photosensitizer under visible
- Uraguchi, Daisuke,Kinoshita, Natsuko,Kizu, Tomohito,Ooi, Takashi
-
supporting information
p. 13768 - 13771
(2016/01/15)
-
- Visible-Light-Mediated Chan-Lam Coupling Reactions of Aryl Boronic Acids and Aniline Derivatives
-
The copper(II)-catalyzed aerobic oxidative coupling reaction between aryl boronic acids and aniline derivatives was found to be improved significantly under visible-light-mediated photoredox catalysis. The substrate scope of this oxidative Chan-Lam reaction was thus expanded to include electron-deficient aryl boronic acids as viable starting materials. Two are better than one: The copper(II)-catalyzed aerobic oxidative coupling reaction between aryl boronic acids and anilines is significantly improved by the addition of visible-light-mediated photoredox catalysts. The substrate scope of this Chan-Lam reaction was thus expanded to include electron-deficient aryl boronic acids.
- Yoo, Woo-Jin,Tsukamoto, Tatsuhiro,Kobayashi, Shu
-
supporting information
p. 6587 - 6590
(2015/06/02)
-
- Application of nanoparticle mediated N-arylation of amines for the synthesis of pharmaceutical entities using vit-E analogues as amphiphiles in water
-
The first CuI-nanoparticle catalyzed inter and intramolecular N-arylation of amines using vitamin E analogues (TPGS) as amphipiles has been developed in water. Application of this transition metal-amphiphile C-N bond formation methodology is further extended for the synthesis of substituted indoles, bioactive natural product tryptanthrin and intermediates of pharmaceutical entities such as imatinib, nilotinib, selective D3 agonist/antagonist ligands, and oxacarbazepine. This journal is
- Kumar, Atul,Bishnoi, Ajay Kumar
-
p. 20516 - 20520
(2015/03/30)
-
- Stable nickel(0) phosphites as catalysts for C-N cross-coupling reactions
-
Herein we describe the design and preparation of inexpensive, air-stable nickel phosphite-based catalysts for use in the C-N cross-coupling reaction. The combination of nickel tetrakis(triphenyl phosphite) {Ni[P(OPh) 3]4} and 1,1'-bis(diphenylphosphino)ferrocene (dppf), and in particular a newly developed catalyst (dppf)Ni[P(OPh)3] 2, were found to be extremely effective in catalyzing a range of amination reactions of anilines and amines with aryl chlorides. This new catalyst system offers an alternative to the bis(cyclooctadienyl)nickel [Ni(COD)2] and palladium(0) catalysts commonly used for C-N bond formation.
- Kampmann, Sven S.,Sobolev, Alexandre N.,Koutsantonis, George A.,Stewart, Scott G.
-
supporting information
p. 1967 - 1973
(2014/07/07)
-
- Effects of solvent and base on the palladium-catalyzed amination: PdCl 2(Ph3P)2/Ph3P-catalyzed selective arylation of primary anilines with aryl bromides
-
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
-
p. 4754 - 4759
(2014/06/24)
-
- Synthesis, characterization and catalytic application of some novel binuclear transition metal complexes of bis-(2-acetylthiophene) oxaloyldihydrazone for CN bond formation
-
In the present work, synthesis, characterization and catalytic properties of some novel complexes derived from a Schiff base bis-(2-acetylthiophene) oxaloyldihydrazone with various transition metal ions and precursors have been reported. The complexes were characterized by IR, NMR, ESR, electronic and mass spectroscopy, magnetic moments and TGA studies. Molecular structures of the ligand and its Cu(I) complex are determined by single crystal X-ray diffraction. Electronic spectral studies exhibit a 6-coordinated geometry around metal centers for Co(II), Ni(II) and Cu(II) complexes, whereas 4-coordinated geometry for Cu(I) and Zn(II) complexes. ESR spectra indicate a distorted octahedral geometry for Cu(II) complex in DMSO frozen solution. The electro-chemical studies of Ni(II) and Cu(II) complexes reveal a metal based reversible redox behavior. The catalytic activity of the complexes has been demonstrated for the cross-coupling of arylboronic acids with various N-nucleophiles. Ni(II) complex exhibited the maximum impact on catalytic activity with the product yields ranging from 62% to 82%.
- Singh, Divya Pratap,Raghuvanshi, Dushyant S.,Singh,Singh, Vinod P.
-
-
- N(2)-Monosubstituted bishydrazides of oxalic acid as new efficient components of the system for the copper-catalyzed C-N cross-coupling in water
-
N(2)-Monosubstituted bishydrazides of oxalic acid in the presence of hexane-2,5-dione in situ form efficient ligands for the copper catalyzed C-N cross-coupling. A scaled pre-parative method for the synthesis of diarylamines was developed based on the results obtained.
- Kurandina,Eliseenkov,Petrov,Boyarskiy
-
p. 1009 - 1013
(2013/07/25)
-
- Nickel-mediated N-arylation with arylboronic acids: An avenue to Chan-Lam coupling
-
An efficient use of NiCl2·6H2O, for the cross-coupling of arylboronic acids with various N-nucleophiles, has been demonstrated. The method is practical and offers an alternative to the corresponding Cu-mediated Chan-Lam process for the construction of the C-N bond.
- Raghuvanshi, Dushyant Singh,Gupta, Amit Kumar,Singh, Krishna Nand
-
supporting information
p. 4326 - 4329
(2012/10/29)
-
- Pentavalent organoantimony compounds as mild N-arylating agents for amines: Cu-mediated ullmann-type N-arylation with tetraarylantimony(V) acetates
-
Simple and mild Cu-mediated arylation of various amines by use of tetraarylantimony acetate (Ar4SbOAc) is described. The Ullmann-type condensation of Ar4SbOAc with aliphatic and electron rich aromatic amines proceeded efficiently in
- Qin, Weiwei,Kakusawa, Naoki,Wu, Yichen,Yasuike, Shuji,Kurita, Jyoji
-
scheme or table
p. 436 - 438
(2009/12/25)
-
- Polymer-supported copper complex for C-N and C-O cross-coupling reactions with aryl boronic acids
-
(Chemical Equation Presented) Immobilization of copper onto modified Wang resin provided a polymer-supported copper catalyst, which is effective in cross-coupling reactions between N- or O-containing substrates and arylboronic acids. The copper catalyst is air stable and can be recycled with minimal loss of activity.
- Chiang, Gary C. H.,Olsson, Thomas
-
p. 3079 - 3082
(2007/10/03)
-
- Copper-catalyzed coupling of arylboronic acids and amines.
-
[reaction: see text] A general catalytic coupling of arylboronic acids and amines is reported. This room-temperature coupling was realized through the use of catalytic copper(II) acetate, 2,6-lutidine as base, and myristic acid as an additive. Functionalized aniline substrates provided the diarylamine coupling products in good yield (58-91%). A variety of alkylamines were also successfully coupled to give N-alkyl anilines in moderate yield (50-64%).
- Antilla,Buchwald
-
p. 2077 - 2079
(2007/10/03)
-
- Palladium-Catalyzed Amination of Aryl Halides: Mechanism and Rational Catalyst Design
-
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.
-
p. 329 - 340
(2007/10/03)
-
- 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
-
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
-
-
- ALIPHATIC C-H, N-INSERTION VERSUS AROMATIC N-SUBSTITUTION IN THE REACTION OF ARYLNITRENIUM-BORON TRIFLUORIDE COMPLEXES WITH METHYLATED BENZENES
-
The boron trifluoride promoted decomposition of a number of substituted phenyl azides in toluene, para-xylene, meta-xylene or mesitylene at 60 gradC, leads preferentially to N-benzylamines or diarylamines depending on both ring substituent effect and nucleophilic character of the solvent.
- Spagnolo, Piero,Zanirato, Paolo
-
p. 961 - 964
(2007/10/02)
-
- Nucleophilic Displacements of N-Aryl and Heteroaryl Groups. Part 3. Pyrylium-mediated Synthesis of Unsymmetrical Diarylamines from Anilines
-
2-Ethoxycarbonyl-4,6-diphenylpyrylium salts (1) reacted with various ring-substituted anilines to give the corresponding pyridinium salts (2) (average yield 90percent); these were hydrolysed to the pyridinium betaines (3) (75percent) and treated with thionyl chloride followed by an aniline to give the amides (4) (70percent).Refluxing in toluene with sodium hydride for 12 h transfers intramolecularly the 1-aryl group of the pyridinium salt(4) to the nitrogen of the amide.Aqueous work-up cleaves (6) and the diarylamine is purified by sublimation (60percent) (overall yield ca. 30percent).
- Katritzky, Alan R.,Cozens, Andrew J.
-
p. 2611 - 2615
(2007/10/02)
-
- THE DIHYDROPHENOPHOSPHAZINE RING SYSTEM. 2. THE REACTION OF PHOSPHORUS TRIHALIDES WITH HALOSUBSTITUTED AND STERICALLY HINDERED DIARYLAMINES
-
The reaction of phosphorus trichloride with three p-chloro-substituted diarylamines gave the expected ring-substituted derivatives of the secondary phosphine oxide 1 and spirophosphonium chloride 2. 4,4'-Dibromodiphenylamine was converted in part to a tribromo derivative, but 2,2',4,4'-tetrabromodiphenylamine did not react at all with phosphorus trichoride or tribromide.N-Phenyl-o-toluidine and phosphorus trichloride gave a moderate yield of the expected phosphine oxide but no spirophosphonium chloride.Di-o-tolylamine gave only a very small yield of phosphine oxide.All of the phosphine oxides obtained in this study were oxidized to the corresponding phosphinic acids.
- Butler, Jack R.,Freeman, Harold S.,Freedman, Leon D.
-
p. 269 - 272
(2007/10/02)
-