Aromatic nucleophilic substitution in aprotic solvents using hydrogen-bonded biological amines. Kinetic studies and quantum chemical calculations

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Intermolecular and intramolecular non-bonding interactions play a crucial role in determining physical and biological properties of relevant amines, and we have recently reported that they are also responsible for changing mechanisms in aromatic nucleophilic substitution (ANS) involving amine nucleo...

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Autores principales: Alvaro, C.E.S., Bergero, F.D., Bolcic, F.M., Ramos, S.B., Sbarbati Nudelman, N.
Formato: JOUR
Materias:
aprotic solvents
aromatic nucleophilic substitution
biological amines
dimer nucleophile mechanism
hydrogen bonding
Amines
Amino acids
Aromatization
Calculations
Continuum mechanics
Copyrights
Density functional theory
Dimers
Hydrogen
Kinetic theory
Kinetics
Nucleophiles
Quantum chemistry
Solvents
Toluene
1-chloro-2 , 4-dinitrobenzene
Ab initio density functional theories (DFT)
Aprotic solvents
Aromatic nucleophilic substitution
Basis set superposition errors
Dimer nucleophile mechanisms
Quantum chemical calculations
Specific hydrogen bondings
Hydrogen bonds
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_08943230_v29_n11_p565_Alvaro
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id todo:paper_08943230_v29_n11_p565_Alvaro
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spelling todo:paper_08943230_v29_n11_p565_Alvaro2023-10-03T15:42:05Z Aromatic nucleophilic substitution in aprotic solvents using hydrogen-bonded biological amines. Kinetic studies and quantum chemical calculations Alvaro, C.E.S. Bergero, F.D. Bolcic, F.M. Ramos, S.B. Sbarbati Nudelman, N. aprotic solvents aromatic nucleophilic substitution biological amines dimer nucleophile mechanism hydrogen bonding Amines Amino acids Aromatization Calculations Continuum mechanics Copyrights Density functional theory Dimers Hydrogen Kinetic theory Kinetics Nucleophiles Quantum chemistry Solvents Toluene 1-chloro-2 , 4-dinitrobenzene Ab initio density functional theories (DFT) Aprotic solvents Aromatic nucleophilic substitution Basis set superposition errors Dimer nucleophile mechanisms Quantum chemical calculations Specific hydrogen bondings Hydrogen bonds Intermolecular and intramolecular non-bonding interactions play a crucial role in determining physical and biological properties of relevant amines, and we have recently reported that they are also responsible for changing mechanisms in aromatic nucleophilic substitution (ANS) involving amine nucleophiles, when they are carried out in solvents of low permittivity. The present work describes ANS in toluene with a series of biological amines that can set specific hydrogen bonding (H bonding) interactions due to their special molecular structures. Kinetic studies of ANS with 2-amino-5-guanidinopentanoic acid (arginine), (4-aminobutyl)guanidine (agmatine), 2,6-diaminohexanoic acid (lysine) and 3,4-dihydroxyphenethylamine (dopamine) towards 1-chloro-2,4-dinitrobenzene in toluene are reported. The kinetic results are compared with those obtained with 2-guanidinobenzimidazole and 2-(1H-imidazole-4-yl)ethanamine (histamine); both amines form intramolecular H bonds. The special types of H bonding were also investigated by ab initio density functional theory calculations, at the B3LYP/6-31++G(d,p) level, including counterpoise corrections to account for basis set superposition errors and solvent effects at the polarized continuum model level. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd. Fil:Bolcic, F.M. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Sbarbati Nudelman, N. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_08943230_v29_n11_p565_Alvaro
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic aprotic solvents
aromatic nucleophilic substitution
biological amines
dimer nucleophile mechanism
hydrogen bonding
Amines
Amino acids
Aromatization
Calculations
Continuum mechanics
Copyrights
Density functional theory
Dimers
Hydrogen
Kinetic theory
Kinetics
Nucleophiles
Quantum chemistry
Solvents
Toluene
1-chloro-2 , 4-dinitrobenzene
Ab initio density functional theories (DFT)
Aprotic solvents
Aromatic nucleophilic substitution
Basis set superposition errors
Dimer nucleophile mechanisms
Quantum chemical calculations
Specific hydrogen bondings
Hydrogen bonds
spellingShingle aprotic solvents
aromatic nucleophilic substitution
biological amines
dimer nucleophile mechanism
hydrogen bonding
Amines
Amino acids
Aromatization
Calculations
Continuum mechanics
Copyrights
Density functional theory
Dimers
Hydrogen
Kinetic theory
Kinetics
Nucleophiles
Quantum chemistry
Solvents
Toluene
1-chloro-2 , 4-dinitrobenzene
Ab initio density functional theories (DFT)
Aprotic solvents
Aromatic nucleophilic substitution
Basis set superposition errors
Dimer nucleophile mechanisms
Quantum chemical calculations
Specific hydrogen bondings
Hydrogen bonds
Alvaro, C.E.S.
Bergero, F.D.
Bolcic, F.M.
Ramos, S.B.
Sbarbati Nudelman, N.
Aromatic nucleophilic substitution in aprotic solvents using hydrogen-bonded biological amines. Kinetic studies and quantum chemical calculations
topic_facet aprotic solvents
aromatic nucleophilic substitution
biological amines
dimer nucleophile mechanism
hydrogen bonding
Amines
Amino acids
Aromatization
Calculations
Continuum mechanics
Copyrights
Density functional theory
Dimers
Hydrogen
Kinetic theory
Kinetics
Nucleophiles
Quantum chemistry
Solvents
Toluene
1-chloro-2 , 4-dinitrobenzene
Ab initio density functional theories (DFT)
Aprotic solvents
Aromatic nucleophilic substitution
Basis set superposition errors
Dimer nucleophile mechanisms
Quantum chemical calculations
Specific hydrogen bondings
Hydrogen bonds
description Intermolecular and intramolecular non-bonding interactions play a crucial role in determining physical and biological properties of relevant amines, and we have recently reported that they are also responsible for changing mechanisms in aromatic nucleophilic substitution (ANS) involving amine nucleophiles, when they are carried out in solvents of low permittivity. The present work describes ANS in toluene with a series of biological amines that can set specific hydrogen bonding (H bonding) interactions due to their special molecular structures. Kinetic studies of ANS with 2-amino-5-guanidinopentanoic acid (arginine), (4-aminobutyl)guanidine (agmatine), 2,6-diaminohexanoic acid (lysine) and 3,4-dihydroxyphenethylamine (dopamine) towards 1-chloro-2,4-dinitrobenzene in toluene are reported. The kinetic results are compared with those obtained with 2-guanidinobenzimidazole and 2-(1H-imidazole-4-yl)ethanamine (histamine); both amines form intramolecular H bonds. The special types of H bonding were also investigated by ab initio density functional theory calculations, at the B3LYP/6-31++G(d,p) level, including counterpoise corrections to account for basis set superposition errors and solvent effects at the polarized continuum model level. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.
format JOUR
author Alvaro, C.E.S.
Bergero, F.D.
Bolcic, F.M.
Ramos, S.B.
Sbarbati Nudelman, N.
author_facet Alvaro, C.E.S.
Bergero, F.D.
Bolcic, F.M.
Ramos, S.B.
Sbarbati Nudelman, N.
author_sort Alvaro, C.E.S.
title Aromatic nucleophilic substitution in aprotic solvents using hydrogen-bonded biological amines. Kinetic studies and quantum chemical calculations
title_short Aromatic nucleophilic substitution in aprotic solvents using hydrogen-bonded biological amines. Kinetic studies and quantum chemical calculations
title_full Aromatic nucleophilic substitution in aprotic solvents using hydrogen-bonded biological amines. Kinetic studies and quantum chemical calculations
title_fullStr Aromatic nucleophilic substitution in aprotic solvents using hydrogen-bonded biological amines. Kinetic studies and quantum chemical calculations
title_full_unstemmed Aromatic nucleophilic substitution in aprotic solvents using hydrogen-bonded biological amines. Kinetic studies and quantum chemical calculations
title_sort aromatic nucleophilic substitution in aprotic solvents using hydrogen-bonded biological amines. kinetic studies and quantum chemical calculations
url http://hdl.handle.net/20.500.12110/paper_08943230_v29_n11_p565_Alvaro
work_keys_str_mv AT alvaroces aromaticnucleophilicsubstitutioninaproticsolventsusinghydrogenbondedbiologicalamineskineticstudiesandquantumchemicalcalculations
AT bergerofd aromaticnucleophilicsubstitutioninaproticsolventsusinghydrogenbondedbiologicalamineskineticstudiesandquantumchemicalcalculations
AT bolcicfm aromaticnucleophilicsubstitutioninaproticsolventsusinghydrogenbondedbiologicalamineskineticstudiesandquantumchemicalcalculations
AT ramossb aromaticnucleophilicsubstitutioninaproticsolventsusinghydrogenbondedbiologicalamineskineticstudiesandquantumchemicalcalculations
AT sbarbatinudelmann aromaticnucleophilicsubstitutioninaproticsolventsusinghydrogenbondedbiologicalamineskineticstudiesandquantumchemicalcalculations
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