Abstract
The mechanism for the decarbonylation of (E)-2-butenal and (E)-2-methyl-3-pheny-2-propenal was studied with different levels of ab initio and DFT methods. Reactants, products and transition structures were optimized for two kinds of reaction channel: a one-step reaction which involves a three-membered cyclic transition state, and a two-step reaction which involves an initial four-membered cyclic transition state. According to our calculations, these two possible mechanisms entail similar energetic costs, and there are only small differences depending on the reactant. The elimination of (E)-2-methyl-3-pheny-2-propenal yields different products depending on the channel followed. Only one of the three possible one-step mechanisms leads directly to (E)-β-methylstyrene (the main product according to experiment). This fact is reasonably well reproduced by our results, since the corresponding transition state gave rise to the lowest activation Gibbs free energy.
Similar content being viewed by others
References
Chabán OY, Domínguez RM, Herize A, Tosta M, Cuenca A, Chuchani G (2007) J Phys Org Chem 20:307–312
Fukui K (1981) Acc Chem Res 14:363–368
González C, Schlegel HB (1989) J Phys Chem 90:2154–2161
González C, Schlegel HB (1990) J Phys Chem 94:5523–5527
McQuarrie DA (1973) Statistical thermodynamics. Harper and Row, New York
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA Jr, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2004) Gaussian 03, revision C.02. Gaussian, Wallingford
Grela MA, Colussi AJ (1986) J Phys Chem 90:434–437
Fang WH (1999) J Am Chem Soc 121:8376–8384
Crawford RJ, Lutener S, Tokunaga H (1977) Can J Chem 55:3951–3954
Lin SY, Tseng JM, Lin YF, Huang WT, Shu CM (2008) J Therm Anal Cal 93:257–267
Acknowledgments
The authors thank the Xunta de Galicia for financial support (“Axuda para a Consolidación e Estructuración de unidades de investigación competitivas do Sistema Universitario de Galicia, 2007/50, cofinanciada polo FEDER 2007-2013”). The authors also wish to express their gratitude to the CESGA (Centro de Supercomputación de Galicia).
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Supporting Information Available
Geometries of reactants, products and transition structures (PDF 180 kb)
Rights and permissions
About this article
Cite this article
Erastova, V., Rodríguez-Otero, J., Cabaleiro-Lago, E.M. et al. A computational study of the mechanism of the unimolecular elimination of α,β-unsaturated aldehydes in the gas phase. J Mol Model 17, 21–26 (2011). https://doi.org/10.1007/s00894-010-0700-1
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00894-010-0700-1