78287 20191127155457.0 doi 10.1021/acssuschemeng.7b03218 sideral 104587 ART-2018-104587 eng (orcid)0000-0002-0136-5138 Fraile, J.M. Universidad de Zaragoza Role of Substituents in the Solid Acid-Catalyzed Cleavage of the ß-O-4 Linkage in Lignin Models 2018 Access copy available to the general public Unrestricted The role of substituents in the acidolysis of several lignin models bearing a ß-O-4 linkage was studied through experimental (by using Nafion SAC-13 as a heterogeneous catalyst) and theoretical data (including transition state calculations). An equilibrium involving the protonation of either a-OH or ß-OH groups as well as the dehydration of the a-OH protonated form to yield a benzylic carbocation is assumed. Phenylacetaldehyde and phenol derivatives are the major reaction products for a number of lignin models, though other products have also been identified (such as enol ethers and coumaran derivatives). The high reactivity observed for lignin models bearing an ortho-methoxy group on the O-bound phenyl ring has been attributed to the methoxy anchimeric assistance to the benzylic position. On the other hand, the low formaldehyde yields observed in the acidolysis of some lignin models have been attributed to the hydrogen bond formation between the hydroxymethyl group and the base abstracting the ß- hydrogen of the carbocationic intermediate. info:eu-repo/grantAgreement/ES/DGA/E11 info:eu-repo/grantAgreement/ES/DGA/FSE info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-52367-R info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 6.97 2018 ENGINEERING, CHEMICAL 9 / 138 = 0.065 2018 Q1 T1 GREEN & SUSTAINABLE SCIENCE & TECHNOLOGY 5 / 35 = 0.143 2018 Q1 T1 CHEMISTRY, MULTIDISCIPLINARY 26 / 172 = 0.151 2018 Q1 T1 1.666 2018 Chemical Engineering (miscellaneous) 2018 Q1 Renewable Energy, Sustainability and the Environment 2018 Q1 Environmental Chemistry 2018 Q1 Chemistry (miscellaneous) 2018 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion (orcid)0000-0003-1199-2087 García, J.I. (orcid)0000-0002-8805-4374 Hormigón, Z. Universidad de Zaragoza (orcid)0000-0003-1570-4257 Mayoral, J.A. Universidad de Zaragoza Saavedra, C.J. (orcid)0000-0003-2010-9540 Salvatella, L. Universidad de Zaragoza 2013 765 Universidad de Zaragoza Dpto. Química Orgánica Área Química Orgánica 6, 2 (2018), 1837-1847 ACS sustain. chem. & eng. ACS sustainable chemistry & engineering 2168-0485 410678 http://zaguan.unizar.es/record/78287/files/texto_completo.pdf Postprint 72481 http://zaguan.unizar.es/record/78287/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:78287 articulos driver 2019-11-27-15:48:25 ARTICLE