Selective catalytic hydroalkylation and deoxygenation of substituted phenols to bicycloalkanes

Phenol and substituted phenols are hydroalkylated and hydrodeoxygenated to bi-cycloalkanes in a tandem reaction over Pd nanoclusters supported on a large-pore molecular sieve HBEA at 473–523 K using water as solvent. The HBEA-supported Pd catalyst (metal–acid ratio: 1:22 mol/mol) optimally balances the competing rates of metal catalyzed hydrogenation as well as of solid acid-catalyzed dehydration and carbon–carbon coupling to combine hydrodeoxygenation and dimerization of phenol derivatives to C12–C18 bicycloalkanes in a single reaction sequence. A detailed kinetic study of the elementary reactions of (substituted) phenol and their potential products (cyclohexanol, cyclohexanone, and cyclohexene) demonstrates that phenol selectively reacts with the in situ generated cyclohexanol or cyclohexene on Brønsted acid sites. The acid-catalyzed alkylation of phenol with alcohol intermediates and alcohol dehydration are parallel reactions, which are subtly influenced by the competing hydrogenation reactions as well as by the presence of water as solvent. IR spectroscopy of adsorbed species and preliminary molecular modeling indicate that phenol and cyclohexanol enrichment in the large pores of zeolite HBEA is critical for the high activity and hydroalkylation selectivity.

Graphical abstractPhenol and substituted phenols are hydroalkylated and hydrodeoxygenated to bi-cycloalkanes in a tandem reaction over Pd nanoclusters supported on a large-pore molecular sieve HBEA at 473–523 K using water as solvent. The HBEA-supported Pd catalyst (metal–acid ratio: 1:22 mol/mol) optimally balances the competing rates of metal catalyzed hydrogenation as well as of solid acid-catalyzed dehydration and carbon–carbon coupling to combine hydrodeoxygenation and dimerization of phenol derivatives to C12–C18 bicycloalkanes in a single reaction sequence.Figure optionsDownload full-size imageDownload high-quality image (120 K)Download as PowerPoint slideHighlights► A method has been developed on highly selective hydroalkylation and deoxygenation of substituted phenols in water. ► The acid-catalyzed alkylation and alcohol dehydration are parallel reactions in phenol hydroalkylation. ► Such competition is subtly influenced by hydrogenation and the presence of water. ► The phenol and cyclohexanol enrichment in zeolite HBEA is critical for the high activity and hydroalkylation selectivity.