Conversion of Fusel Oil Alcohols to Alkyl Carbonates By Carbon Dioxide Fixation

Advanced Fossil Energy Utilization
AIChE Annual Meeting
November 8, 2013 - 10:00am-10:30am

The development of suitable methods for the preparation of interesting CO2-containing compounds, like organic carbonates, is an alternative to recycling CO2 and using it as a substitute for the highly toxic phosgene and its derivatives.1–4 The selectivity and nature of the capture products are two of the most important aspects of the CO2 fixation.5,6 Organic carbonates can be synthesized by reaction of alcohols with CO2 under catalytical conditions.7,8 This process is relevant since both CO2 and fusel oil are by-products from the sugar cane and ethanol production. Alkylcarbonates among other products have wide industrial applications, such as chemical,9 medicinal10 and fuel additives.11 The present work describes the preparation of alkyl carbonates from reaction of fusel oil alcohols with carbon dioxide in the presence of 1.8-diazabicycloundecene (DBU) and 1.5-diazabicyclononene (DBN) and an alkylating agent. The capture of CO2 by alcohols was carried out with nucleophilic activation of the isopentyl and isobutyl alcohols with the amidines DBU or DBN. The carbon dioxide fixation was accomplished by subsequent alkylation under pressurized-CO2 conditions. The synthesis of butyl-isopentylcarbonate and butyl-isobtuylcarbonate were confirmed by FT-IR ana, lysis and GC-MS with EI ionization mode. In order to establish the conditions for better yields of the alkylcarbonates, it was investigated the influence of temperature, concentration of reagents, time of reaction and gas pressure in the synthesis.

[1] E. R. Pérez, M. O. da Silva, V. C. Costa, U. P. Rodrigues-Filho and D. W. Franco, Tetrahedron Lett., 2002, 43, 4091–4093.

[2] P. Alessio, D. M. Ferreira, A. E. Job, R. F. Aroca, A. Riul, C. J. L. Constantino and E. R. P. González, Langmuir, 2008, 24, 4729–4737.

[3] C. R. Gomes, D. M. Ferreira, C. J. L. Constantino and E. R. P. Gonzalez, Tetrahedron Lett., 2008, 49, 6879–6881.

[4] J.M. Hooker,A. T.Reibel, S.M.Hill, M. J. Schueller and J. S. Fowler, Angew. Chem., Int. Ed., 2009, 48, 3482–3485.

[5] Pereira, F. S.; DeAzevedo, E. R.; Silva, E. F.; Bonagamba, T. J.; Agostini, D.; Magalhães, A.;  Job, A. e Pérez, E. R. Tetrahedron, 2008, 64, 10097-10106.

 [6] Pereira, F. S.; Agostini, D.; Santo, R.D.E.; deAzevedo, E. R.; Bonagamba, T.J.; Job, A.; Pérez, E. R. Green Chemistry, 2011, 13, 2146-2153.

[7] Sankar, M.; Madhavan, C. N.; Murty, K. V. G. K.; Manikandan  P. Applied Catalysis A: General, 2006, 312, 108–114.

[8] Park, D. W.; Jeong, E. S.; Kim, K. H.; Bineesh, K. V.; Lee, J. W.; Park, S. W. Studies in Surface Science and Catalysis, 2006, 159, 329–332.

[9] a. Schaffner, B.; Andrushko, V.; Bayardon, J.; Holz, J.; Borner, A. Chirality, 2009, 21, 857-861. b. Vollmer, C.; Thomann, R.; Janiak, C. Dalton Trans., 2012, 41, 9722-9727.

[10] Ghosh, A. K.; Duong, T. T.; Mckee, S. P.; Thompson, W. J. Tetrahedron Lett. 1992, 32, 2781. 

[11] Carbon Dioxide Recovery and Utilization, Aresta, M. Ed., Kluwer Academic Publishers, London,  2003.

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