(327a) Kinetics of Friedel Crafts Acylation of 2-Methylfuran with Octanoic Anhydride and Al-MCM-41.

Authors: 
Naik, A. - Presenter, University of Minnesota
Shetty, M., Pacific Northwest National Laboratory
Ardagh, M. A., University of Minnesota
Dauenhauer, P., University of Minnesota
Friedel Crafts acylation reaction of aromatic substrates with different acylating agents produces ‘aryl alkyl ketones’. The acylation reaction of biomass derived furans and long-carbon chain (C12-C20) fatty carboxylic acids or anhydrides obtained by hydrolysis of plant -oil based triglycerides produces ‘alkyl furan ketones’. These ketone molecules are important precursors for the synthesis of renewable oleo-furan sulphonate (OFS) surfactants as demonstrated by Park et al. [1]. The exceptional stability of these OFS surfactants for use as detergents in hard water as well as other comparable detergent characteristics makes them a useful alternative to the petroleum-based surfactants. In this work, we elucidate the reaction kinetics of Friedel Crafts acylation reaction of 2-methylfuran and n-octanoic anhydride as a model system with Al-MCM-41 as a solid Brønsted acid catalyst in the presence of a non-protic solvent heptane. The apparent activation energy and the reaction rate orders are obtained in a flow reactor set-up. The experimental observations are explained using a potential mechanism and a kinetic model. The understanding of this C-C coupling reaction using long chain fatty acid derivatives will contribute to the scale-up of OFS surfactants as well as to the design of heterogeneous Friedel Crafts acylation catalysts.

Reference:

  1. Park, D. S., Joseph, K. E., Koehle, M., Krumm, C., Ren, L., Damen, J. N., Shete, M. H., Lee, H. S., Zuo, X., Lee, B., Fan, W., Vlachos, D. G., Lobo, R. F., Tsapatsis, M. and Dauenhauer, P. J. ACS Cent. Sci. 2, 820–824 (2016).