Alkylation of phenolics is of great importance in synthetic chemistry and the valorization of lignocellulosic-biomass-derived streams. Here, we unravel how alkylating reactants and solvents significantly alter the reaction pathways of zeolite-catalysed alkylation of phenol in the liquid phase. The carbenium ion formed from the dehydration of cyclohexanol or from the adsorption and protonation of cyclohexene acts as the electrophile, inducing carbon–carbon bond formation. Cyclohexanol at Brønsted acid sites (BAS) forms hydrogen-bonded monomers and protonated dimers in apolar solvents. The dimer appears to generate a much lower concentration of carbenium ions compared with the monomer. Higher alkylation rates in apolar solvents than in water are caused by the energetically more-favourable carbenium ion formation from either alcohol or olefin on non-hydrated zeolite BAS than on hydronium ions produced by BAS in pores filled with water.
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Olah, G. A. Friedel-Crafts Chemistry (Wiley, 1973).
Weissermel, K. & Arpe, H.-J. in Industrial Organic Chemistry 3rd edn, 358 (VCH, 1997).
Price, C. C. Organic Reactions (John Wiley & Sons, 2004).
Ma, Q. et al. Alkylation of phenol: a mechanistic view. J. Phys. Chem. A 110, 2246–2252 (2006).
Craciun, I., Reyniers, M.-F. & Marin, G. B. Liquid-phase alkylation of benzene with octenes over Y zeolites: kinetic modeling including acidity descriptors. J. Catal. 294, 136–150 2012).
Hansen, N., Brüggemann, T., Bell, A. T. & Keil, F. J. Theoretical investigation of benzene alkylation with ethene over H-ZSM-5. J. Phys. Chem. C 112, 15402–15411 (2008).
Wilson, K. & Clark, J. H. Solid acids and their use as environmentally friendly catalysts in organic synthesis. Pure. Appl. Chem. 72, 1313–1320 (2000).
Resasco, D. E., Wang, B. & Crossley, S. Zeolite-catalyzed C–C bond forming reactions for biomass conversion to fuels and chemicals. Catal. Sci. Technol. 6, 2543–2559 (2016).
Corma, A. Organic reactions catalyzed over solid acids. Catal. Today 38, 257–308 (1997).
Dwyer, F. G., Lewis, P. J. & Schneider, F. H. Efficient, nonpolluting ethylbenzene process. Chem. Eng. 83, 90–91 (1976).
Corma, A. Inorganic solid acids and their use in acid-catalyzed hydrocarbon reactions. Chem. Rev. 95, 559–614 (1995).
Zhao, C., Camaioni, D. M. & Lercher, J. A. Selective catalytic hydroalkylation and deoxygenation of substituted phenols to bicycloalkanes. J. Catal. 288, 92–103 (2012).
Liu, Y. et al. Enhancing the catalytic activity of hydronium ions through constrained environments. Nat. Commun. 8, 14113 (2017).
Anand, R., Gore, K. U. & Rao, B. S. Alkylation of phenol with cyclohexanol and cyclohexene using HY and modified HY zeolites. Catal. Lett. 81, 33–41 (2002).
Anand, R., Daniel, T., Lahoti, R. J., Srinivasan, K. V. & Rao, B. S. Selective alkylation of phenol with cyclohexanol over large-pore zeolites. Catal. Lett. 81, 241–246 (2002).
Roberts, V. M. et al. Towards quantitative catalytic lignin depolymerization. Chem. Eur. J. 17, 5939–5948 (2011).
Zhao, C. & Lercher, J. A. Upgrading pyrolysis oil over Ni/HZSM-5 by cascade reactions. Angew. Chem. Int. Ed. 51, 5935–5940 (2012).
Huber, G. W. & Corma, A. Synergies between bio- and oil refineries for the production of fuels from biomass. Angew. Chem. Int. Ed. 46, 7184–7201 (2007).
Stöcker, M. Biofuels and biomass-to-liquid fuels in the biorefinery: catalytic conversion of lignocellulosic biomass using porous materials. Angew. Chem. Int. Ed. 47, 9200–9211 (2008).
González-Borja, M. Á. & Resasco, D. E. Reaction pathways in the liquid phase alkylation of biomass-derived phenolic compounds. AIChE. J. 61, 598–609 (2014).
Pierantozzi, R. & Nordquist, A. F. Selective O-alkylation of phenol with methanol. Appl. Catal. 21, 263–271 (1986).
Chaudhuri, B. & Sharma, M. M. Alkylation of phenol with α-methylstyrene, propylene, butenes, isoamylene, 1-octene, and diisobutylene: heterogeneous vs. homogeneous catalysts. Ind. Eng. Chem. Res. 30, 227–231 (1991).
Samolada, M. Selective O-alkylation of phenol with methanol over sulfates supported on γ-Al2O3. J. Catal. 152, 52–62 (1995).
Gagea, B. C. et al. Alkylation of phenols and naphthols on silica-immobilized triflate derivatives. Catal. Lett. 91, 141–144 (2003).
Karthik, M. et al. Synthesis, characterization and catalytic performance of Mg and Co substituted mesoporous aluminophosphates. Micro. Mesopor. Mater. 70, 15–25 (2004).
Yadav, G. D. & Kumar, P. Alkylation of phenol with cyclohexene over solid acids: Insight in selectivity of O- versus C-alkylation. Appl. Catal. A 286, 61–70 (2005).
de Klerk, A. & Nel, R. J. J. Phenol alkylation with 1-octene on solid acid catalysts. Ind. Eng. Chem. Res. 46, 7066–7072 (2007).
Sad, M. E., Padró, C. L. & Apesteguía, C. R. Synthesis of cresols by alkylation of phenol with methanol on solid acids. Catal. Today 133–135, 720–728 (2008).
Modrogan, E., Valkenberg, M. & Hoelderich, W. Phenol alkylation with isobutene—influence of heterogeneous Lewis and/or Brønsted acid sites. J. Catal. 261, 177–187 (2009).
Zhao, Z. et al. Mechanism of phenol alkylation in zeolite H-BEA using in situ solid-state NMR spectroscopy. J. Am. Chem. Soc. 139, 9178–9185 (2017).
Alul, H. R. Solvent effects in the alkylation of benzene with 1-dodecene and trans-6-dodecene in the presence of aluminum chloride. J. Org. Chem. 33, 1522–1527 (1968).
Espeel, P. H. J., Vercruysse, K. A., Debaerdemaker, M. & Jacobs, P. A. Solvent effects in liquid phase Friedel-crafts alkylation over zeolites: control of reaction rate and selectivity by adsorption. Stud. Surf. Sci. Catal. 84, 1457–1464 (1994).
Ronchin, L., Vavasori, A. & Toniolo, L. Acid catalyzed alkylation of phenols with cyclohexene: comparison between homogeneous and heterogeneous catalysis, influence of cyclohexyl phenyl ether equilibrium and of the substituent on reaction rate and selectivity. J. Mol. Catal. A 355, 134–141 (2012).
Chiang, H. & Bhan, A. Catalytic consequences of hydroxyl group location on the rate and mechanism of parallel dehydration reactions of ethanol over acidic zeolites. J. Catal. 271, 251–261 (2010).
Zhi, Y. et al. Dehydration pathways of 1-propanol on HZSM-5 in the presence and absence of water. J. Am. Chem. Soc. 137, 15781–15794 (2015).
Knaeble, W. & Iglesia, E. Kinetic and theoretical insights into the mechanism of alkanol dehydration on solid brønsted acid catalysts. J. Phys. Chem. C. 120, 3371–3389 (2016).
Lee, K. Y. et al. Catalysis by heteropoly compounds. 20. An NMR study of ethanol dehydration in the pseudoliquid phase of 12-tungstophosphoric acid. J. Am. Chem. Soc. 114, 2836–2842 (1992).
Macht, J., Janik, M. J., Neurock, M. & Iglesia, E. Catalytic consequences of composition in polyoxometalate clusters with keggin structure. Angew. Chem. Int. Ed. 46, 7864–7868 (2007).
Macht, J., Janik, M. J., Neurock, M. & Iglesia, E. Mechanistic consequences of composition in acid catalysis by polyoxometalate keggin clusters. J. Am. Chem. Soc. 130, 10369–10379 (2008).
John, M., Alexopoulos, K., Reyniers, M.-F. & Marin, G. B. Reaction path analysis for 1-butanol dehydration in H-ZSM-5 zeolite: ab initio and microkinetic modeling. J. Catal. 330, 28–45 (2015).
Vjunov, A. et al. Following solid-acid-catalyzed reactions by MAS NMR spectroscopy in liquid phase-zeolite-catalyzed conversion of cyclohexanol in water. Angew. Chem. Int. Ed. 53, 479–482 (2013).
Y.L. gratefully acknowledges support from the Graduate School (Faculty Graduate Center of Chemistry) of the Technische Universität München. The authors thank G. L. Haller (Yale University) for his critical reading of the manuscript. The authors also thank Z. Zhao (PNNL) for performing the NMR measurements. H.S., D.M.C., J.H. and J.A.L. acknowledge support from the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multi-programme menational laboratory operated for DOE by Battelle.
The authors declare no competing financial interests.
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Liu, Y., Baráth, E., Shi, H. et al. Solvent-determined mechanistic pathways in zeolite-H-BEA-catalysed phenol alkylation. Nat Catal 1, 141–147 (2018). https://doi.org/10.1038/s41929-017-0015-z
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