A New Method to prepare an e,e,e Trisadduct of C₆₀ Using a Protection–Deprotection Sequence

Álvaro Duarte–Ruiz,¹ Luis Echegoyen,^2* Adriana Aya,¹ and Fernando Gómez–Baquero³

¹ Universidad Nacional de Colombia, Kr 30 No 45–03, Departamento de Química, Bogotá, Colombia, phone + 571–3165000 extension 14444, fax + 571–3165220, aduarter@unal.edu.co.

² Department of Chemistry, Clemson University, 431 Hunter Laboratories Clemson, SC 29634, phone number Tel. 864–656–5030. ^*Responsible author: LECHEGOY@nsf.gov

³ College of Nanoscale Science and Engineering, University at Albany 255 Fuller Road; Suite 214, Albany, NY 12203, Phone: 518–437–8686 Fax: 518–437–8603, FGomezBaquero@uamail.albany.edu

Abstract

A racemic mixture of the e,e,e Bingel–trisadduct, tris[di(ethoxycarbonyl)methano][60]fullerene 3 was synthesized by malonate additions (Bingel reaction) following by retro Diels–Alder reactions using a C₆₀ tris–e,e,e adduct of anthracene 1 as precursor. Using this approach, the anthracenes act as protective groups and help orient the new additions so that poly–adducts with particular geometries are obtained. From the e,e,e anthracene–trisadduct 1 we also obtained the mono[di(ethoxycarbonyl)methano][60]fullerene 6 and bis [di(ethoxycarbonyl)methano][60]fullerene 7. This approach exhibits a total yield of 4,2 % for the e,e,e tris malonate adduct, gives rise to less complex reaction mixtures and makes it easier to separate and characterize the compounds than other methods. The compounds obtained where characterized by UV/VIS, FT–IR, ¹H NMR, and MALDI–TOF.

Key words: Fullerene C₆₀, Anthracene adducts, e,e,e–trisadduct, Bingel adductos.

Resumen

El trisaducto e,e,e Bingel, tris[di(etoxicarbonil)metano][ 60]fullereno 3 fue sintetizado como una mezcla racémica mediante reacciones de adición de malonatos (reacción Bingel) y retro Diels–Alder, usando el trisaducto e,e,e de antraceno y C₆₀ 1 como precursor. Utilizando este método, los antracenos actúan como grupos protectores y ayudan a orientar las nuevas adiciones, de tal forma que nuevos poliaductos con una geometría particular, pueden ser obtenidos. Del trisaducto con antraceno e,e,e 1 también se aislaron el mono[di(etoxicarbonil)metano][60]fullereno 6 y el bis[di(etoxicar–bonil)metano][60]fullereno 7. Este método tiene un rendimiento total de 4.2% para el trisaducto Bingel e,e,e 3, genera mezclas de reacción menos complejas y hace más fácil separar y caracterizar los compuestos que por otros métodos. Los compuestos obtenidos fueron caracterizados mediante UV/VIS, FT–IR, ¹H RMN, y MALDI–TOF.

Palabras claves: Fullereno C₆₀, Aductos de antraceno, trisaducto–e,e,e, Aductos Bingel.

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Aknowledgements

We would like to thank professor Eliseo Avella and Sebastián Gómez from Universidad Nacional de Colombia for the NMR analysis, and to Julio Pinzón from Clemson University for the Mass Spectroscopy analysis. A. Duarte–Ruiz would also like to acknowledge the Universidad Nacional de Colombia for its continuous support. Financial support from the National Science Foundation to L. Echegoyen (Grant DMR–0809129) is greatly appreciated.

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