Hydrogen bonding in aromatic polyamine 2-guanidinobenzimidazole: Study based on density functional theory calculations

Bergero, Federico; Alvaro, Cecilia E. Silvana; Nudelman, Norma Sbarbati; Debiaggi, S. Ramos de

doi:10.1016/j.theochem.2008.10.045

Cited by 6 publications

(4 citation statements)

References 43 publications

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“…To support this interpretation of the experimental results, theoretical semi‐empirical and ab initio calculations were performed to investigate the likelihood of 2‐GB: DMSO hydrogen bond formation. It was found that 2‐GB exhibits intra‐ and intermolecular hydrogen bond formation leading to homo 2‐GB and mixed solute–solvent dimers 57…”

Section: Resultssupporting

confidence: 81%

An Original Electrochemical Pathway for the Synthesis of Porphyrin Oligomers

Schaming

Xia

Thouvenot

2012

Chemistry A European J

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An electrosynthesis process has allowed the formation of four oligomers, containing three, four, or five macrocycles. This method is based on the nucleophilic attack of porphyrins substituted by several pendant pyridyl groups to the electrogenerated radical cation of zinc β-octaethylporphyrin (ZnOEP), according to an ECEC processes. Thus, a control of the number of macrocycles and of the geometry of the oligomers can be performed. These new compounds have been characterized by HRMS as well as (1)H NMR, UV/Vis, and fluorescence spectroscopy, and electrochemistry. The results show a strong influence of the pyridinium spacers on the macrocycles.

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Section: Resultssupporting

confidence: 81%

An Original Electrochemical Pathway for the Synthesis of Porphyrin Oligomers

Schaming

Xia

Thouvenot

2012

Chemistry A European J

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“…Intramolecular H bond in 2‐GB and histamine plays an important role in stabilizing the molecules, because a pseudo‐six‐membered ring is formed between the nitrogen of the guanidine group and the benzimidazole in 2‐GB, while in histamine, the H bond is between the nitrogen of the aliphatic chain and the imidazole nitrogen.…”

Section: Resultsmentioning

confidence: 99%

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

Alvaro

Bergero

Bolcic

et al. 2015

J of Physical Organic Chem

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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 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.

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“…Though, in principle, it could be expected that the molecular structure of DMPA could be considered similar to that of ·3‐APMo it is worthwhile to note that in DMPA the N is approximately planar while the sp 3 N in the chair conformation of morpholine is more basic. Thus, the N is forced to adopt a more rigid sp 3 structure that more easily contributes to the formation of an H‐bonded structure; 3‐APMo is also too sterically hindered for another molecule to approach at the distance needed to form an intermolecular H‐bonded structure 41. The reported results afford additional evidence concerning the critical role that hydrogen‐bonding bond interactions and formation of homo ‐ and “mixed aggregates ” play in the kinetics of these reactions.…”

Section: Resultsmentioning

confidence: 73%

“…We have recently reported theoretical molecular orbital calculations on the structures of 2‐GB by ab initio and density functional theory carried out with the specific purpose of examining the likely hydrogen‐bonding interactions in vacuum and in DMSO solution. It was found that 2‐GB exhibits intra‐ and intermolecular H‐bonds, forming homo‐ and mixed solute‐solvent dimers 41. Though, in principle, it could be expected that the molecular structure of DMPA could be considered similar to that of ·3‐APMo it is worthwhile to note that in DMPA the N is approximately planar while the sp 3 N in the chair conformation of morpholine is more basic.…”

Section: Resultsmentioning

confidence: 99%

Inter‐ and intramolecular hydrogen bonds in polyamines: variable‐concentration¹H‐NMR studies

Nudelman

Alvaro

2011

J of Physical Organic Chem

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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 1 H-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 1 H-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 1 H-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.

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Hydrogen bonding in aromatic polyamine 2-guanidinobenzimidazole: Study based on density functional theory calculations

Cited by 6 publications

References 43 publications

An Original Electrochemical Pathway for the Synthesis of Porphyrin Oligomers

An Original Electrochemical Pathway for the Synthesis of Porphyrin Oligomers

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

Inter‐ and intramolecular hydrogen bonds in polyamines: variable‐concentration¹H‐NMR studies

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Hydrogen bonding in aromatic polyamine 2-guanidinobenzimidazole: Study based on density functional theory calculations

Cited by 6 publications

References 43 publications

An Original Electrochemical Pathway for the Synthesis of Porphyrin Oligomers

An Original Electrochemical Pathway for the Synthesis of Porphyrin Oligomers

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

Inter‐ and intramolecular hydrogen bonds in polyamines: variable‐concentration1H‐NMR studies

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Inter‐ and intramolecular hydrogen bonds in polyamines: variable‐concentration¹H‐NMR studies