Theoretical model of internal rotation in monosubstituted derivatives of furfural.
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.
Crespo-Otero
Rachel
R
Laboratorio de Química Computacional y Teórica, Facultad de Química, Universidad de La Habana, La Habana 10400, Cuba.
Montero
Luis A
LA
Rosquete
Giselle
G
Padrón-García
J Alexander
JA
González-Jonte
Raúl H
RH