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Abstract:

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.

Registro:

Documento: Artículo
Título:Inter- and intramolecular hydrogen bonds in polyamines: Variable-concentration 1H-NMR studies
Autor:Nudelman, N.S.; Alvaro, C.E.S.
Filiación:Departamento de Química Orgánica, Facultad de Ciencias Exactas, Ciudad Universitaria, 1428 Buenos Aires, Argentina
Departamento de Química, Facultad de Ingeniería, Universidad Nacional Del Comahue, Buenos Aires 1400, 8300 Neuquén, Argentina
Palabras clave: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
Año:2011
Volumen:24
Número:11
Página de inicio:1067
Página de fin:1071
DOI: http://dx.doi.org/10.1002/poc.1832
Título revista:Journal of Physical Organic Chemistry
Título revista abreviado:J Phys Org Chem
ISSN:08943230
CODEN:JPOCE
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08943230_v24_n11_p1067_Nudelman

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Citas:

---------- APA ----------
Nudelman, N.S. & Alvaro, C.E.S. (2011) . Inter- and intramolecular hydrogen bonds in polyamines: Variable-concentration 1H-NMR studies. Journal of Physical Organic Chemistry, 24(11), 1067-1071.
http://dx.doi.org/10.1002/poc.1832
---------- CHICAGO ----------
Nudelman, N.S., Alvaro, C.E.S. "Inter- and intramolecular hydrogen bonds in polyamines: Variable-concentration 1H-NMR studies" . Journal of Physical Organic Chemistry 24, no. 11 (2011) : 1067-1071.
http://dx.doi.org/10.1002/poc.1832
---------- MLA ----------
Nudelman, N.S., Alvaro, C.E.S. "Inter- and intramolecular hydrogen bonds in polyamines: Variable-concentration 1H-NMR studies" . Journal of Physical Organic Chemistry, vol. 24, no. 11, 2011, pp. 1067-1071.
http://dx.doi.org/10.1002/poc.1832
---------- VANCOUVER ----------
Nudelman, N.S., Alvaro, C.E.S. Inter- and intramolecular hydrogen bonds in polyamines: Variable-concentration 1H-NMR studies. J Phys Org Chem. 2011;24(11):1067-1071.
http://dx.doi.org/10.1002/poc.1832