title: Production of p-Methylstyrene and p-Divinylbenzene from Furanic Compounds.
abstract: A four-step catalytic process was developed to produce p-methylstyrene from methylfuran, a biomass-derived species. First, methylfuran was acylated over zeolite H-Beta with acetic anhydride. Second, the acetyl group was reduced to an ethyl group with hydrogen over copper chromite. Third, p-ethyltoluene was formed through Diels-Alder cycloaddition and dehydration of 2-ethyl-5-methyl-furan with ethylene over zeolite H-Beta. Dehydrogenation of p-ethyltoluene to yield p-methylstyrene completes the synthesis but was not investigated because it is a known process. The first two steps were accomplished in high yield (>88 %) and the Diels-Alder step resulted in a 67 % yield of p-ethyltoluene with a 99.5 % selectivity to the para isomer (final yield of 53.5 %). The methodology was also used for the preparation of p-divinylbenzene. It is shown that acylation of furans over H-Beta zeolites is a highly selective and high-yield reaction that could be used to produce other valuable molecules from biomass-derived furans.
authors.affiliation: Catalysis Center for Energy Innovation, U.S. Department of Energy-Energy Frontier Research Center, University of Delaware, 150 Academy St., Newark, DE, 19716, USA.|Department of Chemical and Biomolecular Engineering, University of Delaware, 150 Academy St., Newark, DE, 19716, USA.
authors.forename: Maura
authors.identifier: http://orcid.org/0000-0002-4592-0770
authors.initials: M
authors.lastname: Koehle
authors.affiliation: Catalysis Center for Energy Innovation, U.S. Department of Energy-Energy Frontier Research Center, University of Delaware, 150 Academy St., Newark, DE, 19716, USA.|Department of Chemical and Biomolecular Engineering, University of Delaware, 150 Academy St., Newark, DE, 19716, USA.
authors.forename: Erisa
authors.initials: E
authors.lastname: Saraçi
authors.affiliation: Catalysis Center for Energy Innovation, U.S. Department of Energy-Energy Frontier Research Center, University of Delaware, 150 Academy St., Newark, DE, 19716, USA.|Department of Chemical Engineering and Materials Science, University of Minnesota, 421 Washington Ave. SE, Minneapolis, MN, 55455, USA.
authors.forename: Paul
authors.initials: P
authors.lastname: Dauenhauer
authors.affiliation: Catalysis Center for Energy Innovation, U.S. Department of Energy-Energy Frontier Research Center, University of Delaware, 150 Academy St., Newark, DE, 19716, USA.|Department of Chemical and Biomolecular Engineering, University of Delaware, 150 Academy St., Newark, DE, 19716, USA.
authors.forename: Raul F
authors.identifier: http://orcid.org/0000-0003-4027-3129
authors.initials: RF
authors.lastname: Lobo
mesh_terms: D000107:Acetylation; D002384:Catalysis; D005663:Furans / Q000737:chemistry*; D007536:Isomerism; D010100:Oxygen / Q000737:chemistry; D013343:Styrenes / Q000737:chemistry*; D014753:Vinyl Compounds / Q000737:chemistry*
chemical_list: D005663:Furans; D013343:Styrenes; D014753:Vinyl Compounds; C027142:vinyltoluene; C004985:divinyl benzene; D010100:Oxygen
keywords: acylation; furans; para selectivity; sustainable chemistry; zeolites