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Pseudo-cyclic structures of mono- and di-azaderivatives of malondialdehydes. Synthesis and conformational disentanglement by computational analyses

Pseudo-cyclic structures of mono- and di-azaderivatives of malondialdehydes. Synthesis and conformational disentanglement by computational analyses
Pseudo-cyclic structures of mono- and di-azaderivatives of malondialdehydes. Synthesis and conformational disentanglement by computational analyses
Mono- and diaza-derivatives of malondialdehydes, namely 3-alkyl(aryl)amino-2-arylacroleins and 1,5-dialkyl(aryl)-3-arylvinamidines are open-chain systems in which extended electron delocalization and pseudoaromaticity can be envisaged. A set of diversely functionalized compounds has been synthesized and characterized by spectroscopic data and X-ray diffractometry. Quantum-chemical calculations were performed for all possible neutral tautomers and conformers in the gas phase and compared to those in polar solvents (CHCl3, DMSO, and EtOH) at the M06-2X/6-311++G(d,p) level. Tautomeric equilibria and conformational preferences can be rationalized in terms of structural factors, which can be roughly estimated as summation or subtractions of intramolecular interactions. As expected, a key role is played by intramolecular hydrogen bonds whose strength varies from the gas phase to polar ethanol. This issue also delves into the concept of resonance-assisted H-bond, where the donor and acceptor atoms are connected by a π-conjugated system. The most stable conformers (structures a and c) possess a high degree of pseudoaromaticity as inferred from HOMA indexes and other delocalization parameters.
1477-0520
8997-9010
Romero-Fernández, María P.
eaeec9b0-e560-4798-a854-92877fa6cb2b
Ávalos, Martín
2d0b39c7-15a3-4f90-bdfb-8e4b6e69c64a
Babiano, Reyes
b7ffd91c-bacd-4372-ab99-fc30ac2450ae
Cintas, Pedro
29979233-8382-47a8-bde7-1faf4869308c
Jiménez, José L.
074cc8fd-9ea1-41fc-b8b6-551d26e5fcd3
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Palacios, Juan C.
2c06e379-89b3-46b1-95c8-7f5057732f9f
Romero-Fernández, María P.
eaeec9b0-e560-4798-a854-92877fa6cb2b
Ávalos, Martín
2d0b39c7-15a3-4f90-bdfb-8e4b6e69c64a
Babiano, Reyes
b7ffd91c-bacd-4372-ab99-fc30ac2450ae
Cintas, Pedro
29979233-8382-47a8-bde7-1faf4869308c
Jiménez, José L.
074cc8fd-9ea1-41fc-b8b6-551d26e5fcd3
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Palacios, Juan C.
2c06e379-89b3-46b1-95c8-7f5057732f9f

Romero-Fernández, María P., Ávalos, Martín, Babiano, Reyes, Cintas, Pedro, Jiménez, José L., Light, Mark E. and Palacios, Juan C. (2014) Pseudo-cyclic structures of mono- and di-azaderivatives of malondialdehydes. Synthesis and conformational disentanglement by computational analyses. Organic & Biomolecular Chemistry, 12 (44), 8997-9010. (doi:10.1039/c4ob01507j).

Record type: Article

Abstract

Mono- and diaza-derivatives of malondialdehydes, namely 3-alkyl(aryl)amino-2-arylacroleins and 1,5-dialkyl(aryl)-3-arylvinamidines are open-chain systems in which extended electron delocalization and pseudoaromaticity can be envisaged. A set of diversely functionalized compounds has been synthesized and characterized by spectroscopic data and X-ray diffractometry. Quantum-chemical calculations were performed for all possible neutral tautomers and conformers in the gas phase and compared to those in polar solvents (CHCl3, DMSO, and EtOH) at the M06-2X/6-311++G(d,p) level. Tautomeric equilibria and conformational preferences can be rationalized in terms of structural factors, which can be roughly estimated as summation or subtractions of intramolecular interactions. As expected, a key role is played by intramolecular hydrogen bonds whose strength varies from the gas phase to polar ethanol. This issue also delves into the concept of resonance-assisted H-bond, where the donor and acceptor atoms are connected by a π-conjugated system. The most stable conformers (structures a and c) possess a high degree of pseudoaromaticity as inferred from HOMA indexes and other delocalization parameters.

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More information

Accepted/In Press date: 12 September 2014
e-pub ahead of print date: 25 September 2014
Published date: 28 November 2014

Identifiers

Local EPrints ID: 385736
URI: http://eprints.soton.ac.uk/id/eprint/385736
ISSN: 1477-0520
PURE UUID: 4d237a03-76f1-4514-8f09-e65b72d94723
ORCID for Mark E. Light: ORCID iD orcid.org/0000-0002-0585-0843

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Date deposited: 21 Jan 2016 14:46
Last modified: 15 Mar 2024 03:01

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Contributors

Author: María P. Romero-Fernández
Author: Martín Ávalos
Author: Reyes Babiano
Author: Pedro Cintas
Author: José L. Jiménez
Author: Mark E. Light ORCID iD
Author: Juan C. Palacios

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