- Oxazolidin-2-one-promoted CuI-catalyzed amidation of aryl halides and cyclization of o-halobenzanilides
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Oxazolidin-2-one was found to be a versatile and efficient ligand for the CuI-catalyzed amidation of aryl halides and the cyclization of ortho-halobenzanilides. Notably, the less active halides could also be applied successfully in the synthesis of benzoxazoles and benzothiazoles. Georg Thieme Verlag Stuttgart.
- Heng, Chang Ma,Xuan, Zhen Jiang
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- Highly selective C-H functionalization/halogenation of acetanilide
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Highly regioselective C-H functionalization/halogenation of acetanilides to produce ortho-haloacetanilides was catalyzed by Pd(OAc)2 and Cu(OAc)2 with CuX2 as the halogen source. Copyright
- Wan, Xiaobing,Ma, Zhongxun,Li, Bijie,Zhang, Keya,Cao, Shaokui,Zhang, Shiwei,Shi, Zhangjie
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- TBHP-mediated highly efficient dehydrogenative cross-oxidative coupling of methylarenes with acetanilides
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A TBHP-mediated dehydrogenative cross-oxidative-coupling approach has been developed for the synthesis of N-arylbenzamides from methylarenes and acetanilides. This cross-coupling method is free of transition metal catalysts and ligands, and no extra organic solvents are required, which make it an useful and attractive strategy for the straightforward construction of C-N bonds. Besides, this conversion is an important complement to the conventional C-N forming strategies.
- Chen, Cui,Liu, Weibing,Zhou, Peng
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- Potassium Carbonate Promoted C-N Coupling Reaction between Benzamides and Aryl Iodides
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A practical and efficient method for N-arylation of benz-amides promoted by potassium carbonate in the presence of DMEDA was developed. The reaction was carried out without addition of any transition-metal catalyst to afford a variety of N-arylated products in moderate to good yields (up to 97%).
- Huang, Fei,Wu, San,Hu, Weiye,Zhang, Songlin
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- Copper catalyzed N-arylation between aryl halides and nitriles in water: An efficient tandem synthesis of benzanilides
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A series of benzanilide compounds were synthesized through copper-catalyzed tandem reactions. With the assistance of ionic liquid as phase transfer catalyst, aryl halides, and nitriles underwent a hydrolysis/coupling pathway to form benzanilides in water. Advantages of this reaction include the use of water as the environmental friendly solvent, short reaction time, and the tolerance of various functional groups. A proposed mechanism based on control experiments is also presented.
- Wang, Jichao,Yin, Xinchi,Wu, Jun,Wu, Datong,Pan, Yuanjiang
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- Halogenase-Inspired Oxidative Chlorination Using Flavin Photocatalysis
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Chlorine gas or electropositive chlorine reagents are used to prepare chlorinated aromatic compounds, which are found in pharmaceuticals, agrochemicals, and polymers, and serve as synthetic precursors for metal-catalyzed cross-couplings. Nature chlorinates with chloride anions, FAD-dependent halogenases, and O2 as the oxidant. A photocatalytic oxidative chlorination is described based on the organic dye riboflavin tetraacetate mimicking the enzymatic process. The chemical process allows within the suitable arene redox potential window a broader substrate scope compared to the specific activation in the enzymatic binding pocket. Chlorination of arenes with chloride anions: The photochemical analogue of the enzymatic chlorination of Flavin-adenine dinucleotide (FAD)-dependent halogenases is possible in the presence of riboflavin, air, acetic acid, and blue light (see scheme; RFT=riboflavin tetraacetate).
- Hering, Thea,Mühldorf, Bernd,Wolf, Robert,K?nig, Burkhard
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- Migration of the Hydroxyl Group of N-Hydroxy-N-phenylamides to the Phenyl Group with Tertiary Phosphines and Tetrachloromethane. A Novel Transhydroxylation Reaction
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The hydroxyl group of N-hydroxyl-N-phenylamides rearranges mainly to the ortho position of the N-phenyl ring by the system (n-Bu)3P-CCl4-CH3CN; use of less than a stoichiometric amount of (n-Bu)3P is effective for this reaction.
- Kikugawa, Yasuo,Mitsui, Kimiyo
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- Efficient synthesis of amides and esters from alcohols under aerobic ambient conditions catalyzed by a Au/mesoporous Al2O3 nanocatalyst
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An efficient heterogeneous Au/mesoporous alumina nanocatalyst has been successfully developed for the synthesis of amides and esters from simple building blocks of readily available alcohols and amines. The processes were simple and were performed at room temperature and atmospheric pressure of O2 to form the desired products with up to 97% isolated yield. The ability of Au/mesoporous alumina to catalyze these reactions under ambient conditions further enhances the sustainability of these chemical processes. Furthermore, the nanocatalyst was stable to air and water and could be recovered and reused easily. The enhanced catalytic activity of Au/mesoporous alumina might be attributed to the presence of negatively charged Au nanoparticles that could promote oxidation processes as well as the stability of the mesoporous alumina support calcined at a high temperature of 800°C. Gold for green: Gold nanoparticles supported on mesoporous alumina catalyze the efficient synthesis of amides and esters from simple building blocks of readily available alcohols and amines under ambient aerobic reaction conditions (R1=aryl, alkyl, and R2=H, alkyl).
- Chng, Leng Leng,Yang, Jinhua,Ying, Jackie Y.
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- Pd-Catalyzed Oxidation of Aldimines to Amides
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Methods for the synthesis of amides via the direct oxidation of imines are rarely reported. Here we report an efficient method for Pd-catalyzed oxidation of imines to amide derivatives by the use of cheap aqueous tert -butyl hydroperoxide as an oxidant through a Wacker-type reaction. This method is practically convenient and displays high functional group tolerance, allowing a variety of imines to transform into the corresponding amide derivatives in moderate to good yields.
- Gao, Shanshan,Ma, Yaorui,Chen, Weidong,Luo, Junfei
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- Iron-catalyzed N-arylations of amides
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A method was proposed for iron-catalyzed N-arylation of primary amides and its applicability to the synthesis of N-heterocycles by intramolecular ring closures. The method used a catalyst system of 10 mol % of FeCl3 and 20 mol % of N,N'-dimethylethylenediamine (DMEDA). The study found that secondary amides of N-methylbenzamide and N-benzylbenzamide produce N-arylated products in trace amounts. The method developed an iron-based catalyst system for efficient N-arylations of primary amides with aryl iodides. The study used a sealable tube equipped with a magnetic stir bar charged with amide, or K 3PO4, or K2CO3, or FeCl3. The study used NMR spectroscopic analysis to determine the identity and purity of the products. The method observed that different substituted aryl iodides made a positive impact on the reaction.
- Correa, Arkaitz,Elmore, Simon,Bolm, Carsten
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- Efficient cobalt-catalyzed C-N cross-coupling reaction between benzamide and aryl iodide in water
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A practical and efficient strategy for the N-arylation of benzamide catalysed by a Co(C2O4)·2H2O/dmeda system in water is reported. Under the optimized conditions, a wide variety of N-arylated products were obtained in good yields (up to 92%) using substituted aryl iodides.
- Tan, Bryan Yong-Hao,Teo, Yong-Chua
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- Molecular modeling studies, synthesis and biological evaluation of derivatives of N-phenylbenzamide as Plasmodium falciparum dihydroorotate dehydrogenase (PfDHODH) inhibitors
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The search for new antimalarial agents is necessary as current drugs in the market have become vulnerable due to the emergence of resistant strains of Plasmodium falciparum (Pf). The enzyme dihydroorotate dehydrogenase (PfDHODH) is a validated target for development of antimalarial agents. PfDHODH is a crucial enzyme in the de novo pyrimidine biosynthesis pathway and is essential for the growth of the parasite. In this article, we report the design, synthesis and evaluation of benzanilides as inhibitors of PfDHODH. From the pool of molecules designed using molecular modeling techniques, candidates were shortlisted for further evaluation based on docking scores and 3D-QSAR studies. The activities of these shortlisted analogs were predicted from CoMFA and CoMSIA models. The most promising molecules were synthesized using solvent-free microwave-assisted synthesis and their structures characterized by spectroscopic techniques. The molecules were screened for in vitro antimalarial activity by the whole cell assay method. Two molecules viz. KMC-3 and KMC-15 were found to be active at 8.7 and 5.7 μM concentrations, respectively. Springer Science+Business Media, LLC 2011.
- Desai, Kumar R.,Shaikh, Mushtaque S.,Coutinho, Evans C.
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- Copper(I) iodide–catalyzed amidation of phenylboronic acids/aryl bromides using 4-dimethylaminopyridine as ligand
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An efficient one-pot synthesis of N-arylbenzamide is described via reaction of phenylboronic acid/aryl bromide with benzamide in the presence of CuI (5?mol%) as catalyst, 4-dimethylaminopyridine (20?mol%) as the ligand, and Cs2CO3(2?mmol) as the base. This protocol was applied to synthesize a small library of N-arylbenzamide in high yields.
- Alapati, Mohan Lakshmi Punna Rao,Abburu, Sridhar Rao,Mutyala, Krishnaji Rao,Mukkamala, Saratchandra Babu
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- Metal-free transamidation of benzoylpyrrolidin-2-one and amines under aqueous conditions
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N-Acyl lactam amides, such as benzoylpyrrolidin-2-one, benzoylpiperidin-2-one, and benzoylazepan-2-one reacted with amines in the presence of DTBP and TBAI to afford the transamidated products in good yields. The reactions were conducted under aqueous conditions and good functional group tolerance was achieved. Both aliphatic and aromatic primary amines displayed good activity under metal-free conditions. A radical reaction pathway is proposed.
- Joseph, Devaneyan,Lee, Sunwoo,Park, Myeong Seong
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- Ligand-free Pd(0)/SiO2-catalyzed aminocarbonylation of aryl iodides to amides under atmospheric CO pressure
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An efficient and facile route for CO-based carbonylation of aryl iodides with amines to synthesize amides has been established by using SiO2 supported Pd(0) as the catalyst in a mild basic environment (K2CO3). This ligand-free heterogeneous reaction model can afford amide products in good to excellent yields (up to 99%) under atmospheric CO pressure and moderate temperature. The supported catalyst also displayed a broad substrate scope, good functional group tolerance and good recyclability. These features render the as-provided carbonylation approach sustainable and applicable in organic synthesis.
- Hu, Qinhua,Wang, Lele,Wang, Chen,Wu, Yubin,Ding, Zhengxin,Yuan, Rusheng
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- Ph3P/I2-Catalyzed beckmann rearrangement of ketoximes into amides
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A Beckmann rearrangement of ketoximes reaction using triphenylphosphine/ iodine as an effective catalyst in acetonitrile at reflux temperature is reported. The results indicate that conversion of oximes to amides can be reached in good to excellent yields under optimal reaction conditions within several minutes. The reaction mechanism is also proposed. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications to view the free supplemental file.
- Xu, Feng,Wang, Ni-Ge,Tian, You-Ping,Chen, Yong-Mei,Liu, Wei-Chun
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- Brine-mediated efficient benzoylation of primary amines and amino acids
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Benzoylation of primary amines and amino acids is efficiently carried out in a brine solution using a stoichiometric amount of benzoyl chloride followed by trituration with aqueous saturated bicarbonate solution. Copyright Taylor & Francis Group, LLC.
- Chattopadhyay, Gautam,Chakraborty, Suchandra,Saha, Chandan
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- Efficient one-stage procedure of Beckmann ketones rearrangement in the presence of hydroxylamine
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Ketoximes formed from ketones in the presence of hydroxylamine and silica gel in formic acid undergo in situ the Beckmann rearrangement under mild conditions affording in high yields the corresponding amides. Unsymmetrical aromatic ketones, methyl aryl ketones, and methyl cyclohexyl ketone under these conditions form as a rule amides mixtures.
- Kuksenok,Shtrykova,Filimonov,Sidel'nikova
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- Novel and efficient heterogeneous polymer supported copper catalyst for synthesis of 2-substituted Benzoxazoles from 2-Haloanilides
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A novel polymer supported copper complex is prepared by the immobilization of copper iodide on chemically modified polyacrylonitrile and its application in heterogeneous catalysis is described. The catalyst was prepared by easy method via synthetic modification of Polyacrylonitrile (PAN) using ethylene diamine followed by the complexation with CuI. After characterization, this complex was explored as a green and efficient heterogeneous catalyst for the synthesis of 2-benzoxazoles from 2-haloanilides. The reaction was performed without adding additional ligand and the catalyst shows activity over a broad range of substrates with quantitative product yields. The catalyst was easily recovered by simple filtration and reused successfully for further cycle.
- Saranya, Thachora Venu,Sruthi, Pambingal Rajan,Raj, Veena,Anas, Saithalavi
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supporting information
(2021/02/27)
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- An Environmentally Benign, Catalyst-Free N?C Bond Cleavage/Formation of Primary, Secondary, and Tertiary Unactivated Amides
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Herein, we report an operationally simple, cheap, and catalyst-free method for the transamidation of a diverse range of unactivated amides furnishing the desired products in excellent yields. This protocol is environmentally friendly and operates under extremely mild conditions without using any promoter or additives. Significantly, this strategy has been implied in the chemoselective synthesis of a pharmaceutical molecule, paracetamol, on a gram-scale with excellent yield. We anticipate that this universally applicable strategy will be of great interest in drug discovery, biochemistry, and organic synthesis.
- Kumar, Vishal,Dhawan, Sanjeev,Girase, Pankaj Sanjay,Singh, Parvesh,Karpoormath, Rajshekhar
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p. 5627 - 5639
(2021/11/11)
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- Synthesis of 2-Amino-1,3-dienes from Propargyl Carbonates via Palladium-Catalyzed Carbon-Nitrogen Bond Formation
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A catalytic method to synthesize 1,3,-dienes from propargylic precursors is reported. This palladium-catalyzed carbon-nitrogen bond-forming reaction furnishes 2-amino-1,3-dienes in excellent yields (up to 98%) and shows a broad tolerance to functional group diversity. The reaction has been demonstrated for over 30 amine substrates, including anilines and indoles, and proceeds under mild neutral conditions. The resulting 1,3-dienes are of great synthetic interest because of their further reaction potential.
- O'Broin, Calvin Q.,Guiry, Patrick J.
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supporting information
p. 879 - 883
(2020/02/04)
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- Silver-Catalyzed Cascade Cyclization Reaction of Isocyanides with Sulfoxonium Ylides: Synthesis of 3-Aminofurans and 4-Aminoquinolines
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A silver-catalyzed cascade cyclization reaction of isocyanides with sulfoxonium ylides has been developed for the first time. This reaction provides a new and efficient method for the construction of highly functionalized 3-aminofurans and 4-aminoquinolines from readily available starting materials in a single step.
- Liang, Yong-Xin,Yang, Ming,He, Bo-Wen,Zhao, Yu-Long
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supporting information
p. 7640 - 7644
(2020/10/09)
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- Catalyst- And oxidant-free electrochemical: para -selective hydroxylation of N -arylamides in batch and continuous-flow
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Hydroxyl compounds serve as key building blocks in the preparation of biologically active natural products and drugs. Traditionally, hydroxylation of the aromatic ring is achieved using stoichiometric amounts of oxidants, which leads to low atom-economy, undesired by-products, potential explosion risk and environmental pollution. Recently, electrosynthesis has attracted increasing attention as it employs clean electrical energy to promote redox reactions avoiding the use of oxidants. However, due to the poor mass and heat transfers of batch cells, low productivity and selectivity limit its further application. Herein, we develop a catalyst-, oxidant-, acidic solvent- and quaternary ammonium salt-free electrochemical para-selective hydroxylation of N-arylamides at room temperature in batch and continuous-flow. This proposal features excellent position control and water, air and functional group tolerance. Also, it is easy to scale up with higher productivity and selectivity using a flow electrolysis cell.
- Chen, Meng-Yi,Fang, Zheng,Guo, Kai,Lin, Xin-Xin,Liu, Cheng-Kou
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supporting information
p. 6437 - 6443
(2020/11/09)
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- Copper-catalyzed aerobic oxidative C-C bond cleavage of simple ketones for the synthesis of amides
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A Cu-catalyzed oxidative amidation of simple ketones with amines via carbon-carbon (C-C) bond cleavage has been developed. A number of aryl and alkyl ketones could be easily converted to amides using cheap copper salt as the catalyst and O2 as the oxidant with a wide range of amines, including primary and secondary amines. This method shows a notable advantage of the broad scope for the substrate, thus providing a practical approach to amides. A plausible mechanism is proposed based on the preliminary experiments.
- Li, Ke,Liu, Wei,Liu, Yu-Feng,Yang, Guo-Ping,Zeng, Kai
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p. 6958 - 6964
(2020/10/02)
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- Graphene oxide-catalyzed CSp3–H activation of methylarenes in aqueous medium: A unified metal-free access to amides and benzimidazoles
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Graphene oxide (GO)-catalyzed selective synthesis of amides via CSp3–H activation of methylarenes and consequent C–N bond formation with anilines under aqueous medium has been described. Oxygen functionality allied with GO surface played a dual role both as acid catalyst and oxidizing agent to some extent. However, GO has a copious effect on the reaction, shown by a high TOF value with TBHP as co-oxidant. The decisive role of carboxylic acid functional groups on GO nanosheets in this metal-free strategy has been confirmed and was monitored by various analytic techniques viz. Fourier transform-infrared, UV–Vis, Raman and XPS. A plausible mechanism was proposed by control experiments and by the isolation of the intermediate. Over-oxidation of methylarenes was not detected, and high recyclability of the carbocatalyst with its heterogeneous behavior facilitated the isolation and purification of the desired products. We have further explored the utility of this process for the chemoselective synthesis of benzimidazoles.
- Dandia, Anshu,Mahawar, Dinesh Kumar,Sharma, Ruchi,Badgoti, Ranveer Singh,Rathore, Kuldeep S.,Parewa, Vijay
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- Method for preparing derivatives of benzamide under microwave condition in aqueous phase
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The invention discloses a method for preparing derivatives of benzamide under a microwave condition in an aqueous phase. A coupling reaction is carried out between substituted benzoic acid and amine under the microwave condition in the aqueous phase. The method for preparing the derivatives of benzamide is environmentally friendly, easy and convenient to operate, safe, low in cost and efficient. Compared with the prior art, the method can be applicable to a large number of functional groups, is high in yield, produces fewer by-products, and further is easy to operate, safe, low in cost and environmentally friendly. A formula is shown in the description.
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Paragraph 0019; 0061
(2019/03/28)
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- Method for synthesizing amide compound through photocatalysis in water phase
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The invention discloses a method for synthesizing an amide compound through photocatalysis in a water phase. The method comprises the following steps: putting catalysis amounts of a free radical initiator, an amine derivative, a carboxylic acid derivative, a phase transfer catalyst, an inorganic base and water into a reaction container, carrying out a reaction in a photocatalysis reaction instrument at certain power under a room temperature condition, after a certain time, carrying out extraction by using a small amount of ethyl acetate, and carrying out recrystallization, so as to obtain theamide compound, wherein the free radical initiator is eosin, methyl orange, sodium persulfate, ammonium persulfate or potassium peroxodisulfate, the phase transfer catalyst is tetrabutylammonium bromide, and the power of the photocatalytic reaction instrument is 5W. By adopting the method disclosed by the invention, toxic thionyl chloride or phosphorus oxychloride is not needed for a chlorinationreaction, water is adopted as a solvent, a novel photocatalysis method is used, and the amide compound with a high yield can be prepared through a room-temperature reaction for 2-5 hours with an incandescent light bulb of 5W, and in addition, the method is simple in aftertreatment, and low in cost and is an ideal green synthesis method of amide compounds.
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Paragraph 0061-0062
(2019/10/01)
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- Revisiting 1-chloro-1,2-benziodoxol-3-one: Efficient: ortho -chlorination of aryls under aqueous conditions
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The application of 1-chloro-1,2-benziodoxol-3-one as a powerful chlorinating agent as well as oxidant for aniline derivatives is explored. The amide directing group assisted radical mediated ortho-selective chlorination proceeds in the absence of a radical initiator. Various electronically differentiated anilides and sulfonamides are tolerated under aqueous conditions.
- Vinayak, Botla,Ravindrakumar, Pardhi Vishal,Ramana, Daggupati V.,Chandrasekharam, Malapaka
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p. 8953 - 8959
(2018/06/08)
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- Cross-Dehydrogenating Coupling of Aldehydes with Amines/R-OTBS Ethers by Visible-Light Photoredox Catalysis: Synthesis of Amides, Esters, and Ureas
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A straightforward synthesis of amides, ureas, and esters is reported by visible-light cross-dehydrogenating coupling (CDC) of aldehydes (or amine carbaldehydes) and amines/R-OTBS ethers by photoredox catalysis. The reaction is found to be general and high yielding. A plausible mechanistic pathway has been proposed for these transformations and is supported by appropriate controlled experiments.
- Pandey, Ganesh,Koley, Suvajit,Talukdar, Ranadeep,Sahani, Pramod Kumar
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supporting information
p. 5861 - 5865
(2018/09/21)
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- Unexpected Rearrangement of 2-Bromoaniline under Biphasic Alkylation Conditions
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Alkylation of 2-bromoaniline with benzyl bromide under ostensibly basic N-alkylation conditions resulted in migration of bromine from the 2- to the 4-aryl position. Herein we report our studies to elucidate the mechanism of this rearrangement with the objective of suppressing this unexpected outcome. We find that careful choice of reagents is critical, and that this behavior may be extrapolated to alkylation reactions of electron-rich bromo- and iodoanilines in general.
- Barraza, Scott J.,Denmark, Scott E.
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supporting information
p. 2891 - 2895
(2017/10/06)
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- Palladium-Catalyzed Direct Synthesis of Phenanthridones from Benzamides through Tandem N–H/C–H Arylation
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We report a palladium-catalyzed method for the direct synthesis of phenanthridones from benzamides in a single step. Unlike previous reports, the current protocol does not need any directing groups or any harsh conditions. This methodology has a wide functional group tolerance therefore a series of phenanthridones were synthesized with a yield up to 87 %. The efficacy of this protocol was further explored by synthesizing some important naturally occurring amaryllidaceae alkaloids in a single step with very good yields.
- Banerji, Biswadip,Chatterjee, Satadru,Chandrasekhar,Nayan, Chinmay,Killi, Sunil Kumar
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supporting information
p. 5214 - 5218
(2017/09/29)
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- Unmasking Amides: Ruthenium-Catalyzed Protodecarbonylation of N-Substituted Phthalimide Derivatives
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The unprecedented transformation of a wide range of synthetically appealing phthalimides into amides in a single-step operation has been achieved in high yields and short reaction times using a ruthenium catalyst. Mechanistic studies revealed a unique, homogeneous pathway involving five-membered ring opening and CO2 release with water being the source of protons.
- Yuan, Yu-Chao,Kamaraj, Raghu,Bruneau, Christian,Labasque, Thierry,Roisnel, Thierry,Gramage-Doria, Rafael
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supporting information
p. 6404 - 6407
(2017/12/08)
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- Copper-Catalyzed Coupling Reaction of (Hetero)Aryl Chlorides and Amides
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Cu2O/N,N′-bis(thiophen-2-ylmethyl)oxalamide is established to be an effective catalyst system for Goldberg amidation with inferior reactive (hetero)aryl chlorides, which have not been efficiently documented by Cu-catalysis to date. The reaction is well liberalized toward a variety of functionalized (hetero)aryl chlorides and a wide range of aromatic and aliphatic primary amides in good to excellent yields. Furthermore, the arylation of lactams and oxazolidinones is achieved. The present catalytic system also accomplished an intramolecular cross-coupling product.
- De, Subhadip,Yin, Junli,Ma, Dawei
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supporting information
p. 4864 - 4867
(2017/09/23)
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- Highly ortho-Selective Chlorination of Anilines Using a Secondary Ammonium Salt Organocatalyst
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An organocatalytic, highly facile, efficient, and regioselective ortho-chlorination of anilines is described. A secondary ammonium chloride salt has been employed as the catalyst and the reaction can be conducted at room temperature without protection from air and moisture. In addition, the reaction is readily scalable and the catalyst can be recycled and reused. This catalytic protocol has been applied to the efficient synthesis of a highly potent c-Met kinase inhibitor. Mechanistic studies revealed that unique structural features of the secondary ammonium chloride salt are important for both the catalysis and regioselectivity of the electrophilic ortho-chlorination.
- Xiong, Xiaodong,Yeung, Ying-Yeung
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supporting information
p. 16101 - 16105
(2016/12/26)
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- A PROCESS FOR THE SYNTHESIS OF CARBOXYLIC ACID DERIVATIVES
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The present invention discloses one-pot synthesis of various carboxylic acid derivatives using copper catalyst and sodium cyanide as the cyanide source for bringing in carbonylative coupling in a single step.
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Page/Page column 7-8; 11
(2015/05/19)
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- Imidazolium Salt Catalyzed para -Selective Halogenation of Electron-Rich Arenes
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A highly para-selective halogenation of arenes bearing coordinating groups in the presence of a dimidazolium salt as a catalyst is reported. A series of electron-rich p-haloarenes were prepared in good yields and good to excellent selectivities. We also propose a plausible mechanism for the catalytic reaction.
- Chen, Jie,Xiong, Xiaoyu,Chen, Zenghua,Huang, Jianhui
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supporting information
p. 2831 - 2834
(2015/12/18)
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- Carboxyl activation of 2-mercapto-4,6-dimethylpyrimidine through n-acyl-4,6-dimethylpyrimidine-2-thione: A chemical and spectrophotometric investigation
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2-Mercapto-4,6-dimethylpyrimidine, as effective carboxyl activating group, has been successfully proved by converting it into respective acyl derivatives and the subsequent conversion to the amides and esters respectively using amines, amino alcohols and alcohols. The aminolysis and esterification were monitored chemically and spectrophotometrically. This paved way to establish that the above mercaptopyrimidine derivative is an efficient carboxyl activating group applicable in solid phase peptide synthesis.
- Rajan
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p. 287 - 291
(2015/01/30)
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- Copper(I) bromide-catalyzed carbonylative coupling of aryl halides with phenols, alcohols and amines using sodium cyanide as C1 source: A synthesis of carboxylic acid derivatives
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A new carbon monoxide-free synthesis of carboxylate derivatives via carbonylative coupling of aryl bromides with phenols, alcohols, amines and acids in the presence of copper(I) bromide as catalyst and sodium cyanide in a stoichiometric amount has been developed. Its intramolecular version provides for the preparation of lactones (e.g., isochroman-1-ones and isobenzfuranones), imides, anhydrides and lactams in excellent yields (73-96%).
- Prasad, Pragati K,Sudalai, Arumugam
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supporting information
p. 2231 - 2238
(2014/07/21)
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- Direct N-cyclopropylation of secondary acyclic amides promoted by copper
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The N-cyclopropylation of aromatic and aliphatic secondary acyclic amides, known to be poor nucleophiles, has been accomplished using a simple and cheap copper system. The corresponding tertiary acyclic amides, which constitute a wide family of biologically active compounds, have been obtained in good to excellent yields.
- Racine, Emilie,Monnier, Florian,Vors, Jean-Pierre,Taillefer, Marc
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supporting information
p. 7412 - 7414
(2013/09/23)
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- Palladium-catalyzed synthesis of benzimidazoles and quinazolinones from common precursors
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N-(o-Halophenyl)imidoyl chlorides and the corresponding imidates are easily prepared and can be utilized as complementary precursors for the synthesis of important heterocycles. The synthesis of N-substituted benzimidazoles was possible from the palladium
- Sadig, Jessie E. R.,Foster, Radleigh,Willis, Michael C.,Wakenhut, Florian
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p. 9473 - 9486,14
(2012/12/12)
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- Thermally induced cyclization of electron-rich N-arylthiobenzamides to benzothiazoles
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Heating N-(2-methoxyphenyl)benzenecarbothioamides in refluxing nitrobenzene for 24 hours gives the corresponding benzothiazoles with intramolecular ipso substitution of the ortho-methoxy substituent. The thermal cyclization of various other N-arylthiobenzamides is also explored. Georg Thieme Verlag Stuttgart · New York.
- Barrett, Oscene V.,Downer-Riley, Nadale K.,Jackson, Yvette A.
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experimental part
p. 2579 - 2586
(2012/09/07)
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- Pd(OAc)2-catalyzed carbonylative coupling of aryl iodide with ortho-haloamines in water
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The carbonylative cross coupling of aryl iodide with ortho-haloaniline to ortho-haloanilide using phosphine-free Pd(OAc)2 catalyst in water as a reaction medium has been studied. The present protocol facilitated the reaction of o-haloanilines with a wide variety of hindered and functionalized aryl iodides, affording good yields of the desired products. The protocol was also extended for the synthesis of benzoxazoles through cyclization of ortho-haloanilide using Cu(acac)2 catalyst. Taylor & Francis Group, LLC.
- Tambade, Pawan J.,Patil, Yogesh P.,Qureshi, Ziyauddin S.,Dhake, Kishor P.,Bhanage, Bhalchandra M.
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supporting information; experimental part
p. 176 - 185
(2011/10/31)
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- Synthesis and biological evaluation of a series of 2-(Substitutedphenyl) benzothiazoles
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A series of 2-phenylbenzothiazoles has been synthesized either by i) condensation of different aromatic aldehydes with 2-aminothiophenol or ii) condensation of N-(2-chlorophenyl)benzothioamides in KOH catalyzed by potassium fericyanide. The structures of
- Nam, Nguyen Hai,Dung, Phan Thi Phuong,Thuong, Phuong Thien
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p. 127 - 134
(2013/01/10)
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- A simple copper-catalyzed synthesis of tertiary acyclic amides
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The N-arylation of aromatic and aliphatic secondary acyclic amides, known to be poor nucleophiles, has been accomplished using a simple and cheap copper catalytic system. The corresponding tertiary acyclic amides, which can be found in numerous biologically active compounds, have been obtained in good to excellent yields.
- Racine, Emilie,Monnier, Florian,Vors, Jean-Pierre,Taillefer, Marc
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supporting information; experimental part
p. 2818 - 2821
(2011/07/09)
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- Copper-catalyzed domino annulation approaches to the synthesis of benzoxazoles under microwave-accelerated and conventional thermal conditions
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(Chemical Equation Presented) Two domino annulation approaches for benzoxazole synthesis have been developed. In the first approach, copper-catalyzed intermolecular cross-coupling of 1,2-dihaloarenes with primary amides initially forms the Ar-N bond of the benzoxazole ring, followed by copper-catalyzed intramolecular cyclization to form the Ar-O bond. Benzoxazoles were formed in good yields for the reaction of 1,2-dibromobenzene, but the reaction was not regioselective for the reaction of 3,4-dibromotoluene. Furthermore, the method is limited by the availability of 1,2-dihaloarenes. As a result of these limitations, an alternative more versatile one-pot domino annulation strategy was developed involving reaction of 2-bromoanilines with acyl chlorides in the presence of Cs2CO3, catalytic CuI, and the non-acylatable ligand 1,10-phenanthroline. Under these conditions initial acylation of the aniline is followed by copper-catalyzed intramolecular cyclization of the resultant 2-haloanilide to form the Ar-O bond of the benzoxazole ring. Optimized conditions using microwave irradiation achieved much shorter reaction times than conventional heating (i.e., 210 °C for 15 min versus 95 °C for 24 h) and were applied to the synthesis of a small library of benzoxazoles. These copper-catalyzed approaches complement existing strategies for benzoxazole synthesis, which typically utilize 2-aminopheonls as precursors.
- Viirre, Russell D.,Evindar, Ghotas,Batey, Robert A.
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p. 3452 - 3459
(2008/09/20)
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- Copper-catalysed intramolecular O-arylation of aryl chlorides and bromides: a straightforward approach to benzo[d]oxazoles in water
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A general, efficient and more sustainable protocol for the copper-catalysed intramolecular O-arylation of o′-haloanilides leading to the benzo[d]oxazole core is reported. Remarkably, the optimised conditions allowed for the use of inexpensive and easily available aryl chlorides as arylating agents. Moreover, all reactions were carried out employing exclusively water as the solvent, rendering the methodology presented herein highly valuable from both environmental and economic points of view.
- Barbero, Nekane,Carril, Mónica,SanMartin, Raul,Domínguez, Esther
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p. 10425 - 10432
(2008/02/12)
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- Mild, powerful, and robust methods for esterification, amide formation, and thioesterification between acid chlorides and alcohols, amines, thiols, respectively
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We developed two efficient practical methods for esterification, amide formation, and thioesterification between acid chlorides and alcohols, amines, thiols, respectively. The present mild and robust reaction was performed by two separate methods both by combining cheap and readily available amines, N-methylimidazole, and N,N,N′,N′-tetramethylethylenediamine (TMEDA). Method A uses catalytic N-methylimidazole and TMEDA with an equimolar amount of K2CO3, whereas Method B uses equimolar amounts of N-methylimidazole and TMEDA. The salient features are as follows. (i) With regard to reactivity, Method B was superior to Method A for esterification and thioesterification, whereas cost-effective Method A was superior to Method B for amide formation. (ii) Amide formation proceeded smoothly between acid chlorides and less nucleophilic and stereocongested amines such as 2,6-dichloroaniline. (iii) This protocol was applied to the successful synthesis of two agrochemicals, bromobutide and carpropamid.
- Nakatsuji, Hidefumi,Morimoto, Mami,Misaki, Tomonori,Tanabe, Yoo
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p. 12071 - 12080
(2008/03/13)
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- CeCl3·7H2O-NaI/SiO2 promoted Beckmann rearrangement (under solvent-free and microwave irradiation)
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CeCl3·7H2O-NaI/SiO2 system promoted Beckmann rearrangement of a variety of aldoximes and ketoximes was efficiently conducted under solvent-free and microwave irradiation conditions. This protocol afforded an alternative method for the preparation of amides by Beckmann rearrangement with advantages of short reaction time, high yield, no pollution, simple operation and easy work-up.
- Li, Zheng,Lu, Zhong,Ding, Runbo,Yang, Jingya
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p. 668 - 670
(2007/10/03)
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- Parallel synthesis of a library of benzoxazoles and benzothiazoles using ligand-accelerated copper-catalyzed cyclizations of ortho-halobenzanilides
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A general method for the formation of benzoxazoles via a copper-catalyzed cyclization of ortho-haloanilides is reported. This approach complements the more commonly used strategies for benzoxazole formation which require 2-aminophenols as substrates. The reaction involves an intramolecular C-O cross-coupling of the ortho-haloanilides and is believed to proceed via an oxidative insertion/reductive elimination pathway through a Cu(I)/Cu(III) manifold. The reaction is also applicable to the formation of benzothiazoles. A variety of ligands including 1,10-phenanthroline and N,N′- dimethylethylenediamine were shown to provide ligand acceleration/stabilization in the reaction. Optimal conditions for cyclization used a catalyst combination of CuI and 1,10-phenanthroline (10 mol %). The method was amenable to a parallel-synthesis approach, as demonstrated by the synthesis of a library of benzoxazoles and benzothiazoles substituted at various positions in the ring. Most examples utilized the cyclization of ortho-bromoanilides, but orthoiodoanilides and ortho-chloroanilides also undergo a reaction under these conditions. The rate of reaction of the ortho-haloanilides follows the order I > Br > Cl, consistent with oxidative addition being the rate-determining step.
- Evindar, Ghotas,Batey, Robert A.
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p. 1802 - 1808
(2007/10/03)
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- Infrared spectra of N-aryl substituted amides 2/4-XC6H 4NHCOR (R = H, CH3-iXi, C6H 5 or C6H5Cl; X = H, Cl or CH3 and i = 0, 1, 2 or 3)
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Several N-(aryl)-substituted amides of the general formula, 2/4-XC 6H4NHCOR (where X = H, Cl or CH3 and R = H, CH3, CH2CH3, CH(CH3)2, C(CH3)3, C6H5 or C6H 5Cl) are prepared, characterised and their infrared spectra measured in the solid state and analysed. Generally chloro substitution in the side chain increases the C=O absorptions, while that of methyl groups lower the wave numbers. Amides with trimethyl substituted side chains absorb at higher wavenumbers. But the N-H and C-N stretching vibrations do not show particular trends on side chain substitution. This may be due to the fact that the spectra were recorded in the solid state and the compounds may crystallise in different forms in the solid state. The intercorrelations of C=O and N-H absorption frequencies of all the amides have been made. The correlations are reasonably linear with some exceptions for the reasons stated above.
- Gowda, B. Thimme,Jyothi,Jayalakshmi,Damodara
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p. 564 - 568
(2007/10/03)
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- Activation of the aryl hydrocarbon receptor by methyl yellow and related congeners: structure-activity relationships in halogenated derivatives.
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The aryl hydrocarbon receptor (AhR) is a ligand-activated transcription factor that mediates the biological action of many environmental compounds. Methyl yellow (4-dimethylaminoazobenzene; MY) is a principal azo-dye, and structurally related compounds were subjected to analysis of structure-activity relationships as AhR ligands by using a yeast AhR signaling assay. The effects of halogen-substitution among 23 halogenated MYs on the AhR ligand activity can be summarized as follows: enhancement by halogen-substitution at the ortho-position (2'- and 6'-position), and reduction by substitution at the para-position (4'-position). The greatest enhancement of the ligand activity was observed in 2',6'-dichlorinated MY (13.5-fold of MY), and its AhR ligand activity was very close to that of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in the present assay system. In the study of compounds structurally related to MY, benzanilide (BA) showed almost the same AhR ligand activity as azobenzene and trans-stilbene. Furthermore, 4'-chlorobenzanilide, in which the length of the molecule is similar to that of MY, enhanced the AhR ligand activity by ortho(2')-chlorine-substitution, and the AhR ligand activity of 2',4'-dichlorobenzanilide was similar to that of 2'-chloro-MY. These results suggest that the amide bond is equivalent to the -N=N- or -CH=CH- double bond for recognition as the ligand by AhR in 1,2-diphenyl-1,2-ene derivatives.
- Kato, Taka-aki,Matsuda, Tomonari,Matsui, Saburo,Mizutani, Takaharu,Saeki, Ken-ichi
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p. 466 - 471
(2007/10/03)
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