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Journal of the Mexican Chemical Society
versão impressa ISSN 1870-249X
J. Mex. Chem. Soc vol.50 no.2 Ciudad de México Abr./Jun. 2006
Article
Effect of Aryl Substituents on the Reactivity of the Captodative Olefins 1-Acetylvinyl Arenecarboxylates
Jorge A. Mendoza, Enrique García-Pérez, Hugo A. Jiménez-Vázquez*, and Joaquín Tamariz*
Departamento de Química Orgánica, Escuela Nacional de Ciencias Biológicas, Instituto Politécnico Nacional, Prol. de Carpio y Plan de Ayala, 11340 México, D.F., México. Tels: (+5255) 5729-6300/62411 and (+5255) 5729-6300/62412; Fax: (+5255) 5396-3503; jtamariz@woodward.encb.ipn.mx and hjimenez@woodward.encb.ipn.mx
Recibido el 23 de abril del 2006.
Aceptado el 6 de junio del 2006.
Abstract
With the aim of evaluating the effect of substitution at the aryl moiety of the aroyloxy group of captodative olefins 1 on their reactivity in Diels-Alder and other reactions, the new series of olefins 1-acetylvinyl arenecarboxylates 1c-1k were prepared. No correlation was found between 13C NMR chemical shifts of the carbon atoms of the double bond and the electronic effects of the diverse substituents. However, an excellent correlation was observed between the energies of the FMOs (HF/6-31G*), or the corresponding atomic coefficients or the Mülliken charges at the carbon atoms of the double bond, and the Hammett σm and σp constants of the phenyl ring substituents of some members of the series, and of some other calculated analogues. These results strongly suggest that, in addition to the major effect of the electron-withdrawing group, the reactivity of captodative olefins 1 is also controlled by the long-range inductive effects of the substituent at the phenyl ring of the aroyloxy group.
Key words: Captodative olefins, 1-acetylvinyl arenecarboxylates, FMO, Hammett constants, inductive effects.
Resumen
Con el objeto de evaluar el efecto de la sustitución del fragmento arilo del grupo aroiloxi de las olefinas captodativas 1 sobre su reactividad en reacciones de Diels-Alder y otras reacciones, se preparó la nueva serie de olefinas 1-acetilvinil arencarboxilatos 1c-1k. No se encontró correlación alguna entre los desplazamientos químicos en RMN de 13C de los átomos de carbono del doble enlace y los efectos electrónicos de los diversos sustituyentes. Sin embargo, se encontró una excelente correlación entre las energías de los OMF (HF/6-31G*), o los coeficientes atómicos correspondientes o las cargas de Mülliken en los átomos de carbono del doble enlace, y las constantes de Hammett σm y σp de los sustituyents del grupo fenilo de algunos miembros de la serie, y para algunos otros compuestos análogos que fueron calculados. Estos resultados sugieren fuertemente que además del efecto dominante del grupo electroatractor, la reactividad de las olefinas captodativas 1 está también controlada por el efecto inductivo a larga distancia de los sustituyentes en el fenilo del grupo aroiloxi.
Palabras clave: Olefinas captodativas, 1-acetilvinil arencarboxilatos, OMF, constantes de Hammett, efectos inductivos.
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Acknowledgments
We thank Fernando Labarrios for his help in spectrometric measurements. J.T. would like to acknowledge SIP-IPN (Grants 921769 and 200410) and CONACYT (Grants 1570P, 32273-E, and 43508-Q) for financial support. H.A.J.-V. thanks CONACYT (Grant 3251P) for financial support. J.M. and E.G.-P, are grateful to CONACYT (Grants 86038 and 91989) for graduate fellowships, and to the PIFI-IPN program for scholarships. J.M. also thanks the Ludwig K. Hellweg Foundation for a partial scholarship. J.T. and H.A.J.-V. are fellows of the EDI/IPN and COFAA/IPN programs.
References and Notes
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