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Nucleophilic Aromatic Substitution (nucleophilic + aromatic_substitution)
Terms modified by Nucleophilic Aromatic Substitution Selected AbstractsChemInform Abstract: Regioselective Nucleophilic Aromatic Substitution of Benzo[c][2,7]naphthyridines.CHEMINFORM, Issue 38 2010Charles F. Nutaitis Abstract The title reaction is studied using lithiated aromatic heterocycles as nucleophiles. [source] ChemInform Abstract: The Umpolung of Substituent Effect in Nucleophilic Aromatic Substitution.CHEMINFORM, Issue 34 2009A New Approach to the Synthesis of N, N-Disubstituted Melamines (Triazine Triskelions) under Mild Reaction Conditions. Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Nucleophilic Aromatic Substitution on 4-Fluorophenylsulfonamides: Nitrogen, Oxygen, and Sulfur Nucleophiles.CHEMINFORM, Issue 28 2005Elena Badetti Abstract For Abstract see ChemInform Abstract in Full Text. [source] N-(Nitrophenyl) Benzamide and Benzenesulfonamide Derivatives by Nucleophilic Aromatic Substitution.CHEMINFORM, Issue 10 2005Richard A. Bunce Abstract For Abstract see ChemInform Abstract in Full Text. [source] Introduction of N-Containing Heterocycles into Pyrazole by Nucleophilic Aromatic Substitution.CHEMINFORM, Issue 39 2004Min-Sup Park Abstract For Abstract see ChemInform Abstract in Full Text. [source] ChemInform Abstract: Direct Coupling of Nucleophiles with Nitroaromatic Compounds via Fluoride-Promoted Oxidative Nucleophilic Aromatic Substitution for Hydrogen.CHEMINFORM, Issue 32 2001Inma Huertas Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Alkoxy-5-nitrosopyrimidines: Useful Building Block for the Generation of Biologically Active CompoundsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 20 2010Antonio Marchal Abstract Several alkoxy-5-nitrosopyrimidines were synthesised and high regioselective and sequential nucleophilic aromatic substitution of methoxy groups in 2-amino-4,6-dimethoxy-5-nitrosopyrimidine was observed. The approach was applied to the synthesis of valuable polyfunctionalised aminopyrimidines capable of mimicking fused heterobicyclic derivatives of biological interest. In addition, new compounds were evaluated as antivirals and their usefulness as synthetic intermediates was demonstrated. [source] Spirocyclic Pyridoazepine Analogues of Galanthamine: Synthesis, Modelling Studies and Evaluation as Inhibitors of AcetylcholinesteraseEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 15 2008Sofie Vanlaer Abstract Spirocyclic pyridoazepines, designed as simplified analogues of the alkaloid galanthamine, were synthesised and evaluated as inhibitors of acetylcholinesterase. The key cyclisation step involved internal displacement of 2-chloro or 2-iodopyridine by either nucleophilic aromatic substitution or a Heck reaction. The target compounds showed significant inhibition of acetylcholinesterase but lower than that of galanthamine. This result could be rationalised by comparative docking simulation studies based on the known crystal structure of the acetylcholinesterase,galanthamine complex; multiple hydrogen bonding of a cocrystallised water molecule to both the receptor and the ligand was found to be of crucial importance for effective binding to the active site of the enzyme. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Thermodynamic Study of ,H Complexes in Nucleophilic Aromatic Substitution Reactions: Relative Stabilities of Electrochemically Generated RadicalsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 14 2008Iluminada Gallardo Abstract The mechanism for the electrochemical oxidation of ,H complexes, such as 1-hydro-1-alkoxy/sulfoxy or -fluoro-2,4-dinitro/2,4,6-trinitrocyclohexadienyl anions, has been widely studied by means of cyclic voltammetry and controlled-potential electrolysis. Previous studies have shown that the electrochemical oxidation of ,H complexes, formed by the addition of carbon or nitrogen nucleophiles followed by a two electron mechanism, corresponding to the formal elimination of the hydride anion (nucleophilic aromatic substitution of hydrogen mechanism, the NASH mechanism). For these ,H complexes (Nu, = OH,, ,OR, ,SR, ,F), the electrochemical reaction takes place by a one-electron mechanism and is followed by the radical elimination of the leaving group with the consequent recovery of the starting material. This mechanism is similar to that proposed for the electrochemical oxidation of ,X complexes (nucleophilic aromatic substitution of a heteroatom, the NASX mechanism). The operating mechanism in each case, the NASH or NASX, can be rationalized in terms of thermodynamics. The standard potentials of the , complex and/or the leaving group as well as the bond dissociation energies (BDEs) are determinant factors. This study has not led to a significant improvement in the electrochemical preparation of aromatic-substituted compounds, but does help to understand and predict the usefulness or uselessness of using the nucleophilic aromatic substitution route to obtain a desired product. Finally, the current approach extends the electrochemical methodology to different chemical fields, for example, to general nondestructive methods for the detection, identification, and quantification of either organic pollutants or explosives in different solvents. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Nucleophilic heteroaromatic substitution: Kinetics of the reactions of nitropyridines with aliphatic amines in dipolar aprotic solventsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 3 2008Chukwuemeka Isanbor Rate data are reported for the reactions of 2-chloro-5-nitropyridine 2a, 2-chloro-3-nitropyridine 2b, and the corresponding 2-phenoxy derivatives 2c with n -butylamine, pyrrolidine and piperidine and 2d with n -butylamine and pyrrolidine in dimethyl sulfoxide (DMSO) as solvent. The same reactions in acetonitrile had been reported earlier (Crampton et al., Eur J Org Chem 2007, 1378,1383). Values in these solvents are compared with those of 2,4-dinitrochlorobenzene 3a, 2,6-dinitrochlorobenzene 3b, and the corresponding nitroactivated diphenyl ethers 3c and 3d. Reactions with n -butylamine in both solvents gave values of kobs, which increase linearly with amine concentration indicating that nucleophilic attack is rate limiting. The only exception is the reactions in acetonitrile with 2c where base catalysis was observed. Values of k1, the rate constant for the nucleophilic attack, decrease in the order pyrrolidine > piperidine > n -butylamine. In acetonitrile, kinetic data show that k/k ratios are more than unity while the inverse is the case in DMSO. With the phenoxy derivatives, substitution was the only process observed. Base catalysis detected in the reactions of the 1-phenoxy derivatives is attributed to rate-limiting deprotonation of the initially formed zwitterionic intermediate. Our results shed more light on fundamental aspects of activation, hydrogen bonding, and steric effects associated with an aza or a nitro group in the molecules investigated as it affects the nucleophilic aromatic substitution (SNAr) reaction pathways. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 125,135, 2008 [source] Synthesis and preliminary in vivo evaluation of 4-[18F]fluoro- N -{2-[4-(6-trifluoromethylpyridin-2-yl)piperazin-1-yl]ethyl}benzamide, a potential PET radioligand for the 5-HT1A receptorJOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 9 2004M. Vandecapelle Abstract 4-Fluoro- N -{2-[4-(6-trifluoromethylpyridin-2-yl)piperazin-1-yl]ethyl}benzamide is a full 5-HT1A agonist with high affinity (pKi=9.3), selectivity and a c log P of 3.045. The corresponding PET radioligand 4-[18F]fluoro- N -{2-[4-(6-trifluoromethylpyridin-2-yl)piperazin-1-yl]ethyl}benzamide was synthesized by nucleophilic aromatic substitution on the nitro precursor. The fluorinating agent K[18F]F/Kryptofix 2.2.2 was both dried (9 min, 700 W) and incorporated in the precursor (5 min, 700 W) using a commercially available microwave oven. In a total synthesis time of 60 min, an overall radiochemical yield of 18% (SD=5, n=7, EOS) was obtained. Radiochemical purity was always higher than 99% and specific activity always higher than 81.4 GBq/µmol (2.2 Ci/µmol). Initial brain uptake in mice was 2.19% ID (5.47% ID/g, 2 min) but decreased rapidly (0.17% ID, 0.45% ID/g (60 min)). During the first 20 min p.i., radioactivity concentration of the brain was significantly higher than that of blood demonstrating good brain entry of the tracer. Copyright © 2004 John Wiley & Sons, Ltd. [source] Ortho -[18F]Fluoronitrobenzenes by no-carrier-added nucleophilic aromatic substitution with K[18F]F,K222,A comparative studyJOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 13 2002M. Karramkam Abstract The scope of the nucleophilic aromatic ortho -fluorinations from the corresponding ortho -halonitrobenzene precursors (halo-to-fluoro substitutions) with no-carrier-added [18F]fluoride ion as its activated K[18F]F,K222 complex has been evaluated via the radiosynthesis of ortho -[18F]fluoronitrobenzene, chosen as a model reaction. The parameters studied include the influence of the leaving group in the ortho position of the phenyl ring (,Cl, ,Br, ,l), the quantity of precursor used, the type of activation (conventional heating or microwave irradiations), the solvent, the temperature and the reaction time. The iodo-precursor was completely unreactive and the bromo-precursor gave only low incorporation (<10%) in the optimal conditions used (conventional heating at 145°C or microwave activation, 100 W for 120 s). Only the chloro-precursor was found reactive in the conditions described above and up to 70% yield was observed for the formation of ortho -[18F]fluoronitrobenzene ([18F]- 1). In all the experiments, the unwanted ortho -[18F]fluoro-halobenzenes, potentially resulting from the nitro-to-fluoro substitution, could not be detected. These results will be applied for the radiosynthesis of 5-[18F]fluoro-6-nitroquipazine, a potent radioligand for the imaging of the serotonin transporter with PET. Copyright © 2002 John Wiley & Sons, Ltd. [source] Non-aqueous reverse micelles media for the SNAr reaction between 1-fluoro-2,4-dinitrobenzene and piperidine,JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 12 2006N. Mariano Correa Abstract The kinetics of the nucleophilic aromatic substitution (SNAr) reaction between 1-fluoro-2,4- dinitrobenzene (FDNB) and piperidine (PIP) in ethylene glycol (EG)/ sodium bis (2-ethyl-1-hexyl) sulfosuccinate (AOT)/n -heptane and dimethylformamide (DMF)/AOT/n -heptane non-aqueous reverse micelle systems is reported. EG and DMF were used as models for hydrogen bond donor (HBD) and non-hydrogen bond donor (non-HBD) polar solvents, respectively. The reaction was found not to be base catalyzed in these media. A mechanism to rationalize the kinetic results is proposed in which both reactants may be distributed between the two environments. The distribution constants of FDNB between the organic and each micellar pseudophases were determined by an independent fluorescence method. These results were used to evaluate the amine distribution constant and the intrinsic second-order rate coefficient of the SNAr reaction in the interface. The reaction was also studied in the pure solvents EG and DMF for comparison. The results in EG/AOT/n -heptane at Ws,=,2 give similar kinetic profiles than in water/AOT/n -hexane at W,=,10. With these HBD solvents, the interface saturation by the substrate is reached at around the same value of [AOT] and the intrinsic second-order rate coefficient in the interface, k,b, has comparable values. On the other hand, when DMF is used as a polar non-HBD solvent, the intrinsic second-order rate constant increases by a factor of about 200 as compared to the values obtained using HBD solvents as a polar core. It is concluded that higher catalytic power is obtained when non-HBD solvents are used as polar solvent in the micelle interior. Copyright © 2006 John Wiley & Sons, Ltd. [source] Synthesis of well-defined rod-coil block copolymers containing trifluoromethylated poly(phenylene oxide)s by chain-growth condensation polymerization and atom transfer radical polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 5 2010Yun Jun Kim Abstract Well-defined trifluoromethylated poly(phenylene oxide)s were synthesized via nucleophilic aromatic substitution (SNAr) reaction by a chain-growth polymerization manner. Polymerization of potassium 4-fluoro-3-(trifluoromethyl)phenolate in the presence of an appropriate initiator yielded polymers with molecular weights of ,4000 and polydispersity indices of <1.2, which were characterized by 1H nuclear magnetic resonance spectroscopy and gel permeation chromatography. Initiating sites for atom transfer radical polymerization (ATRP) were introduced at the either side of chain ends of the poly(phenylene oxide), and used for ATRP of styrene and methyl methacrylate, yielding well-defined rod-coil block copolymers. Differential scanning calorimetry study indicated that the well-defined trifluoromethylated poly(phenylene oxide)s showed high crystallinity and were immiscible with polystyrene. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1049,1057, 2010 [source] Dendrimers based on [1,3,5]-triazinesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 11 2006Mackay B. Steffensen Abstract A comprehensive and chronological account of dendrimers based on [1,3,5]-triazines is provided. Synthetic strategies to install the triazine through cycloaddition, cyclotrimerization, and nucleophilic aromatic substitution of cyanuric chloride are discussed. Motivations and applications of these architectures are surveyed, including the preparation of supramolecular assemblies in the solution and solid states and their use in medicines, advanced materials, and separations when anchored to solid supports. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3411,3433, 2006 [source] Development of an efficient route to hyperbranched poly(arylene ether sulfone)sJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 14 2005Patrick Himmelberg Abstract A two-step route to an AB2 monomer that underwent polymerization via nucleophilic aromatic substitution to afford hyperbranched poly(arylene ether sulfone)s (HB PAES) was developed. The synthesis of 3,5-difluoro-4,-hydroxydiphenyl sulfone (4) was accomplished by the reaction of 3,5-difluorophenylmagnesium bromide with 4-methoxyphenylsulfonyl chloride, followed by deprotection of the phenol group with HBr in acetic acid. The polymerization of 4 in the presence of 3,4,5-trifluorophenylsulfonyl benzene or tris(3,4,5-trifluorophenyl)phosphine oxide as a core molecule afforded HB PAES with number-average molecular weights ranging from 3400 to 8400 Da and polydispersity index values ranging from 1.5 to 4.8. The presence of cyclic oligomeric species, formed by an intramolecular cyclization process, was a contributing factor to the relatively low molecular weights. The degree of branching (DB) of the HB PAES samples was estimated by a comparison of the 19F NMR spectra of the polymer samples with those of a series of model compounds, and DB values ranging from 0.51 to 0.70 were determined. The glass-transition temperatures for the HB PAES samples were in the range of 205,222 °C, as determined by differential scanning calorimetry. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43:3178,3187, 2005 [source] Synthesis and optical properties of fluorinated poly(arylene ether phosphine oxide)sJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 10 2003Jae-Pil Kim Abstract Fluorinated dihydroxy phosphine oxide monomers were synthesized via chlorination, Grignard, and demethylation techniques. The prepared monomer was successfully polymerized with each of the three perfluorinated monomers (decafluorobiphenyl, decafluorobenzophenone, and pentafluorophenylsulfide) by nucleophilic aromatic substitution. The average molecular weight ranged between 7800 and 14,900 g/mol. The glass-transition temperatures of the polymers were registered in the range of 185,235 °C, and all the polymers exhibited high thermal stability up to 326,408 °C. The results of the refractive-index measurements indicated control of the refractive index between 1.5181 and 1.5536 and an optical loss of 0.53 dB/cm at 1550 nm. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1497,1503, 2003 [source] Phthalide as an activating group for the synthesis of poly(aryl ether phthalide)s by nucleophilic aromatic substitutionJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 17 2002Daniel M. Knauss Abstract The phthalide ring was examined as an activating group for nucleophilic aromatic substitution. The proposed mechanism by which activation occurs is through a ring opening of the phthalide ring to form a Meisenheimer-like , complex. 3,3-Bis(4-fluorophenyl)phthalide was synthesized and examined under different reaction conditions to determine its suitability for polymer formation. Semiempirical calculations at the PM3 level suggested that 3,3-bis(4-fluorophenyl)phthalide is only moderately activated, whereas 1H, 13C, and 19F NMR spectroscopy suggested that the monomer was not sufficiently activated for nucleophilic aromatic substitution. However, low-molecular-weight polymers (number-average molecular weight < 7000 g/mol) were produced from bisphenol A, hydroquinone, and phenolphthalein. The polymers were characterized by gel permeation chromatography, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, NMR spectroscopy, and differential scanning calorimetry. The polymers displayed relatively high glass-transition temperatures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3046,3054, 2002 [source] Fabrication of Aromatic-Aliphatic Aminoketone Polymers with Terminal Fluorine GroupsMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 14 2010Susann Anders Abstract A procedure for synthesis aromatic-aliphatic PAK, completely functionalized with p- fluorophenyl terminal groups, is presented. This synthesis uses the nucleophilic aromatic substitution of DFB with various secondary aliphatic diamines [CH3NH(CH2)mNHCH3] (m,=,3, 6, and 8) and cesium fluoride as the base catalyst in the melt. The linearity and the complete functionalization of the PAK compounds with p- fluorophenyl terminal groups are demonstrated with the aid of MALDI TOF mass spectrometry. PAK compounds are semi-crystalline as shown by WAXS and DSC measurements. The degree of crystallinity ranges between 2 and 25%. Nucleophilic aromatic substitution reactions in the fluorine end groups are demonstrated by reaction of PAK (m,=,6) with the strong S- nucleophile mercaptoacetic acid. [source] Computational chemistry study of the environmentally important acid-catalyzed hydrolysis of atrazine and related 2-chloro- s -triazinesPEST MANAGEMENT SCIENCE (FORMERLY: PESTICIDE SCIENCE), Issue 8 2002Phillip Sawunyama Abstract Many chlorine-containing pesticides, for example 2-chloro- s -triazines, are of great concern both environmentally and toxicologically. As a result, ascertaining or predicting the fate and transport of these compounds in soils and water is of current interest. Transformation pathways for 2-chloro- s -triazines in the environment include dealkylation, dechlorination (hydrolysis), and ring cleavage. This study explored the feasibility of using computational chemistry, specifically the hybrid density functional theory method, B3LYP, to predict hydrolysis trends of atrazine (2-chloro- N4 -ethyl- N6 -isopropyl-1,3,5-triazine-2,4-diamine) and related 2-chloro- s -triazines to the corresponding 2-hydroxy- s -triazines. Gas-phase energetics are described on the basis of calculations performed at the B3LYP/6-311++G(d,p)//B3LYP/6-31G* level of theory. Calculated free energies of hydrolysis (,hG298) are nearly the same for simazine (2-chloro- N4,N6 -diethyl-1,3,5-triazine-2,4-diamine), atrazine, and propazine (2-chloro- N4,N6 -di-isopropyl-1,3,5-triazine-2,4-diamine), suggesting that hydrolysis is not significantly affected by the side-chain amine-nitrogen alkyl substituents. High-energy barriers also suggest that the reactions are not likely to be observed in the gas phase. Aqueous solvation effects were examined by means of self-consistent reaction field methods (SCRF). Molecular structures were optimized at the B3LYP/6-31G* level using the Onsager model, and solvation energies were calculated at the B3LYP/6-311++G(d,p) level using the isodensity surface polarizable continuum model (IPCM). Although the extent of solvent stabilization was greater for cationic species than neutral ones, the full extent of solvation is underestimated, especially for the transition state structures. As a consequence, the calculated hydrolysis barrier for protonated atrazine is exaggerated compared with the experimentally determined one. Overall, the hydrolysis reactions follow a concerted nucleophilic aromatic substitution (SNAr) pathway. Published in 2002 for SCI by John Wiley & Sons, Ltd [source] Porphyrin-Functionalized Dendrimers: Synthesis and Application as Recyclable Photocatalysts in a Nanofiltration Membrane ReactorCHEMISTRY - A EUROPEAN JOURNAL, Issue 22 2005Suhas A. Chavan Dr. Abstract The convergent synthesis of a series of porphyrin-functionalized pyrimidine dendrimers has been accomplished by a procedure involving the nucleophilic aromatic substitution (NAS) as a key reaction step. The resulting dendritic porphyrin catalysts show high activity in the light-induced generation of singlet oxygen (1O2) from ground-state oxygen. These materials are synthetically useful photosensitizers for the oxidation of various olefinic compounds to the corresponding allylic hydroperoxides. Catalytic activities and regio- and stereoselectivities of the dendritic photosensitizers are comparable to those observed for mononuclear porphyrin catalysts. Recycling of the dendrimer-enlarged homogeneous photocatalysts was possible by solvent-resistant nanofiltration (SRNF) by using an oxidatively stable membrane consisting of a polysiloxane polymer and ultrastable Y zeolite as inorganic filler. Moreover, this membrane technology provides a safe way to isolate the hydroperoxide products under very mild conditions. The membrane showed high retention for the macromolecular catalysts, even in chlorinated solvents, but some oxidative degradation of the porphyrin units of the dendrimer was observed over multiple catalytic runs. [source] Alkylations of N4 -(4-Pyridyl)-3,5-di(2-pyridyl)-1,2,4-triazole: First Observation of Room-Temperature Rearrangement of an N4 -Substituted Triazole to the N1 AnalogueCHEMISTRY - AN ASIAN JOURNAL, Issue 4 2010Jonathan Abstract Attempts to use alkylation to introduce a positive charge at the nitrogen atom of the 4-pyridyl ring in the bis(bidentate) triazole ligand N4 -(4-pyridyl)-3,5-di(2-pyridyl)-1,2,4-triazole (pydpt) were made to ascertain what effect a strongly electron-withdrawing group would have on the magnetic properties of any subsequent iron(II) complexes. Alkylation of pydpt under relatively mild conditions led in some cases to unexpected rearrangement products. Specifically, when benzyl bromide is used as the alkylating agent, and the reaction is carried out in refluxing acetonitrile, the N4 substituent moves to the N1,position. However, when the same reaction is performed in dichloromethane at room temperature, the rearrangement does not occur and the desired product containing an alkylated N4 substituent is obtained. Heating a pure sample of N4 -Bzpydpt,Br to reflux in MeCN resulted in clean conversion to N1 -Bzpydpt,Br. This is consistent with N4 -Bzpydpt,Br being the kinetic product whereas N1 -Bzpydpt,Br is the thermodynamic product. When methyl iodide is used as the alkylating agent, the N4 to N1 rearrangement occurs even at room temperature, and at reflux pydpt is doubly alkylated. The observation of the lowest reported temperatures for an N4 to N1 rearrangement is due to this particular rearrangement involving nucleophilic aromatic substitution: a possible mechanism for this transformation is suggested. [source] | |||||||||||||||||||||||||