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Theoretical model of internal rotation in monosubstituted derivatives of furfural
Author(s) -
CrespoOtero Rachel,
Montero Luis A.,
Rosquete Giselle,
PadrónGarcía J. Alexander,
GonzálezJonte Raúl H.
Publication year - 2004
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.10393
Subject(s) - furfural , internal rotation , rotation (mathematics) , computational chemistry , chemistry , organic chemistry , mathematics , catalysis , engineering , geometry , mechanical engineering
The present work explores the effect of substitution in all free positions of furfural on conformational preferences of formyl group by using ab‐initio calculations at the MP2/6‐31G( p,d ) level of theory. Theoretical modeling was made in vacuo. The selected substituents were CH 3 , NH 2 , NO 2 and F groups in 3, 4, 5 and ipso carbonyl positions. Geometries of all derivatives were analyzed and it is ascertained that substitution has not important consequences on furan ring geometry. Differences of energy between OO‐cis and trans conformers and energy barriers between them are described and extreme cases are explained. Interesting features appear in the cases of NH 2 and NO 2 groups, and particularly when the 3 and ipso carbonyl positions are substituted. Variations in energy barriers are correlated with variations in C2‐C6 distances for the transition states and planar forms. Substitution effect on Mülliken charges are analyzed and related with internal rotation energy barriers and differences between conformers. © 2003 Wiley Periodicals, Inc. J Comput Chem 25: 429–438, 2004