Inter- and intramolecular hydrogen bonds in polyamines: Variable-concentration 1H-NMR studies
Inter- and intramolecular hydrogen bonding play an important role in determining the arrangement, physical properties, and reactivity of a great diversity of structures in chemical and biological systems. Several aromatic nucleophilic substitutions (ANS) in nonpolar aprotic, (non-HBD), solvents rece...
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todo:paper_08943230_v24_n11_p1067_Nudelman2023-10-03T15:42:04Z Inter- and intramolecular hydrogen bonds in polyamines: Variable-concentration 1H-NMR studies Nudelman, N.S. Alvaro, C.E.S. 1H-NMR studies on amine solutions ANS in non-HBD solvents dimer nucleophile mechanism dimerization equilibrium constants hydrogen-bonded nucleophiles hydrogen-bonding effects on 1H-NMR Amine solutions ANS in non-HBD solvents dimer nucleophile mechanism Hydrogen-bonded nucleophiles Hydrogen-bonding effects Amines Association reactions Dimerization Dimers Equilibrium constants Hydrogen Nucleophiles Hydrogen bonds Inter- and intramolecular hydrogen bonding play an important role in determining the arrangement, physical properties, and reactivity of a great diversity of structures in chemical and biological systems. Several aromatic nucleophilic substitutions (ANS) in nonpolar aprotic, (non-HBD), solvents recently studied in our laboratory have demonstrated the importance of self-association of amines by hydrogen-bond interactions. In this paper, we describe 1H-NMR studies carried out at room temperature on bi- and polyfunctionalized amines, namely: N-(3-amino-1-propyl)morpholine (3-APMo), histamine, 2-guanidinobenzimidazole (2-GB), 1,2-diaminoethane (EDA), 3-dimethylamino-l-propylamine (DMPA), and 1-(2-aminoethyl)piperidine (2-AEPip). By 1H-NMR measurements of amine solutions at variable concentrations we have shown that 3-APMo, histamine and 2-GB are able to form a six-membered ring by intramolecular hydrogen bonding, while EDA, DMPA, and 2-AEPip form dimers by intermolecular hydrogen bonds. Likewise, variable concentration 1H-NMR studies allowed estimation of the corresponding equilibrium constants for the dimerization. These results are correlated with experimental kinetic results of ANS, confirming hereto the relevance of the "dimer mechanism" in reactions involving these amines. Copyright © 2011 John Wiley & Sons, Ltd. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_08943230_v24_n11_p1067_Nudelman |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
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R-134 |
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
1H-NMR studies on amine solutions ANS in non-HBD solvents dimer nucleophile mechanism dimerization equilibrium constants hydrogen-bonded nucleophiles hydrogen-bonding effects on 1H-NMR Amine solutions ANS in non-HBD solvents dimer nucleophile mechanism Hydrogen-bonded nucleophiles Hydrogen-bonding effects Amines Association reactions Dimerization Dimers Equilibrium constants Hydrogen Nucleophiles Hydrogen bonds |
| spellingShingle |
1H-NMR studies on amine solutions ANS in non-HBD solvents dimer nucleophile mechanism dimerization equilibrium constants hydrogen-bonded nucleophiles hydrogen-bonding effects on 1H-NMR Amine solutions ANS in non-HBD solvents dimer nucleophile mechanism Hydrogen-bonded nucleophiles Hydrogen-bonding effects Amines Association reactions Dimerization Dimers Equilibrium constants Hydrogen Nucleophiles Hydrogen bonds Nudelman, N.S. Alvaro, C.E.S. Inter- and intramolecular hydrogen bonds in polyamines: Variable-concentration 1H-NMR studies |
| topic_facet |
1H-NMR studies on amine solutions ANS in non-HBD solvents dimer nucleophile mechanism dimerization equilibrium constants hydrogen-bonded nucleophiles hydrogen-bonding effects on 1H-NMR Amine solutions ANS in non-HBD solvents dimer nucleophile mechanism Hydrogen-bonded nucleophiles Hydrogen-bonding effects Amines Association reactions Dimerization Dimers Equilibrium constants Hydrogen Nucleophiles Hydrogen bonds |
| description |
Inter- and intramolecular hydrogen bonding play an important role in determining the arrangement, physical properties, and reactivity of a great diversity of structures in chemical and biological systems. Several aromatic nucleophilic substitutions (ANS) in nonpolar aprotic, (non-HBD), solvents recently studied in our laboratory have demonstrated the importance of self-association of amines by hydrogen-bond interactions. In this paper, we describe 1H-NMR studies carried out at room temperature on bi- and polyfunctionalized amines, namely: N-(3-amino-1-propyl)morpholine (3-APMo), histamine, 2-guanidinobenzimidazole (2-GB), 1,2-diaminoethane (EDA), 3-dimethylamino-l-propylamine (DMPA), and 1-(2-aminoethyl)piperidine (2-AEPip). By 1H-NMR measurements of amine solutions at variable concentrations we have shown that 3-APMo, histamine and 2-GB are able to form a six-membered ring by intramolecular hydrogen bonding, while EDA, DMPA, and 2-AEPip form dimers by intermolecular hydrogen bonds. Likewise, variable concentration 1H-NMR studies allowed estimation of the corresponding equilibrium constants for the dimerization. These results are correlated with experimental kinetic results of ANS, confirming hereto the relevance of the "dimer mechanism" in reactions involving these amines. Copyright © 2011 John Wiley & Sons, Ltd. |
| format |
JOUR |
| author |
Nudelman, N.S. Alvaro, C.E.S. |
| author_facet |
Nudelman, N.S. Alvaro, C.E.S. |
| author_sort |
Nudelman, N.S. |
| title |
Inter- and intramolecular hydrogen bonds in polyamines: Variable-concentration 1H-NMR studies |
| title_short |
Inter- and intramolecular hydrogen bonds in polyamines: Variable-concentration 1H-NMR studies |
| title_full |
Inter- and intramolecular hydrogen bonds in polyamines: Variable-concentration 1H-NMR studies |
| title_fullStr |
Inter- and intramolecular hydrogen bonds in polyamines: Variable-concentration 1H-NMR studies |
| title_full_unstemmed |
Inter- and intramolecular hydrogen bonds in polyamines: Variable-concentration 1H-NMR studies |
| title_sort |
inter- and intramolecular hydrogen bonds in polyamines: variable-concentration 1h-nmr studies |
| url |
http://hdl.handle.net/20.500.12110/paper_08943230_v24_n11_p1067_Nudelman |
| work_keys_str_mv |
AT nudelmanns interandintramolecularhydrogenbondsinpolyaminesvariableconcentration1hnmrstudies AT alvaroces interandintramolecularhydrogenbondsinpolyaminesvariableconcentration1hnmrstudies |
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1782026455400579072 |