Aromatic nucleophilic substitution in aprotic solvents using hydrogen-bonded biological amines. Kinetic studies and quantum chemical calculations
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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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08943230_v29_n11_p565_Alvaro http://hdl.handle.net/20.500.12110/paper_08943230_v29_n11_p565_Alvaro |
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paper:paper_08943230_v29_n11_p565_Alvaro2023-06-08T15:47:48Z Aromatic nucleophilic substitution in aprotic solvents using hydrogen-bonded biological amines. Kinetic studies and quantum chemical calculations Bolcic, Federico Martín Sbarbati, Norma E. 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. 2016 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08943230_v29_n11_p565_Alvaro 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 Bolcic, Federico Martín Sbarbati, Norma E. 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. |
| author |
Bolcic, Federico Martín Sbarbati, Norma E. |
| author_facet |
Bolcic, Federico Martín Sbarbati, Norma E. |
| author_sort |
Bolcic, Federico Martín |
| 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 |
| publishDate |
2016 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08943230_v29_n11_p565_Alvaro http://hdl.handle.net/20.500.12110/paper_08943230_v29_n11_p565_Alvaro |
| work_keys_str_mv |
AT bolcicfedericomartin aromaticnucleophilicsubstitutioninaproticsolventsusinghydrogenbondedbiologicalamineskineticstudiesandquantumchemicalcalculations AT sbarbatinormae aromaticnucleophilicsubstitutioninaproticsolventsusinghydrogenbondedbiologicalamineskineticstudiesandquantumchemicalcalculations |
| _version_ |
1768545379663478784 |