Mechanistic insights into solvent induced alkylation of p-cresol with tert-butyl alcohol using Brönsted acidic ionic liquids

Patra, Tanmoy; Parveen, Firdaus; Upadhyayula, Sreedevi

doi:10.1016/j.mcat.2016.12.006

Cited by 13 publications

(4 citation statements)

References 32 publications

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“…Pyridine can separately bind with the Brønsted and Lewis acids and produce the pyridinium cation [PyH] + and Py‐Lewis complex, respectively. Pyridine FT‐IR spectra of bifunctional ILs with both Brønsted and Lewis acidic sites show two characteristic peaks, one at around 1540 cm −1 corresponding to [PyH] + and other at around 1450 cm −1 corresponding to Py‐Lewis complex ,,. Moreover, coordinatively bonded pyridine on Lewis acid sites shows characteristic bands at 1440–1460, 1480–1500 and 1600 cm −1 ,.…”

Section: Resultsmentioning

confidence: 99%

Upgrading of HMF and Biomass‐Derived Acids into HMF Esters Using Bifunctional Ionic Liquid Catalysts under Solvent Free Conditions

et al. 2018

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Catalytic conversions of biomass‐derived compounds like 5‐hydroxymethylfurfural (HMF) and levulinic acid (LA) to value‐added compounds have drawn tremendous interest in recent years. In this study, we report the catalytic upgrading of HMF into HMF levulinate and HMF esters under solvent‐free condition using laboratory‐synthesized bifunctional ionic liquid (IL) catalysts. The synthesized ILs were characterized using 1H NMR and 13C NMR spectroscopy. Pyridine Fourier transform Infrared spectroscopy (FT‐IR) studies were carried out for their detailed Brønsted and Lewis acidity characterization. Catalytic activity of these ILs was tested in the conversion of HMF into HMF levulinate in the temperature range of 75 to 120 °C and 5 h reaction time using 150 mg each of IL catalyst and 4 Å molecular sieves with LA to HMF molar ratio of 5:1. It was found that strong dual acidic catalyst [SMIM][FeCl4] was found to exhibit highest catalytic activity with 97.0% HMF conversion and 78.1% yield of HMF levuliante. Catalytic activity decreased in the order: [SMIM][FeCl4]> [BSO3HMIm][FeCl4]> [SMIM][Cl]> [BSO3HMIm][Cl]> [BMIM][FeCl4]> [BMIM][Cl]. The reaction parameters such as reaction time, temperature, mole ratio of the reactants, and effect of catalyst loading were optimized.The recyclability of these bifunctional catalysts was also tested and found to be intact for three recycles.

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Section: Resultsmentioning

confidence: 99%

Upgrading of HMF and Biomass‐Derived Acids into HMF Esters Using Bifunctional Ionic Liquid Catalysts under Solvent Free Conditions

et al. 2018

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“…Some other homogeneous catalysts were also used in the synthesis of 2-TBM. Density functional theory was used to develop a molecular level understanding of the alkylation of p-cresol and tert-butyl alcohol catalyzed by acidic ionic liquids; an 86% conversion was obtained under a reaction temperature of 343 K [32]. The SO 3 H-functionalized ionic liquids were synthesized, and the catalytic performance for the alkylation of p-cresol and tert-butyl alcohol was evaluated, and a 79% conversion and 92% selectivity were obtained [33].…”

Section: Comparison Of Cal-tsoh With Other Catalystsmentioning

confidence: 99%

An Efficient and Mild Method for the Alkylation of p-Cresol with tert-Butyl Alcohol

Zhang

Sun

et al. 2023

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The synthesis 2-tert-butyl-4-methylphenol is of great significance because of its wide application in industry, and the development of a highly efficient catalyst is necessary for the alkylation of p-cresol and tert-butyl alcohol. Here, an efficient and mild method was established. Caprolactam was chosen as the hydrogen-bonding acceptor; p-toluenesulfonic acid was employed as the hydrogen-bonding donor, and a deep eutectic solvent (DES) was prepared to catalyze the alkylation reaction. The structure of the deep eutectic solvent catalyst was characterized by 1H NMR spectra, thermogravimetric analysis, and Fourier transform infrared spectra (FT-IR). In addition, response surface design based on the Box–Behnken method was employed to optimize the alkylation reaction process parameters, and the study of reaction kinetics was also carried out subsequently. The recycle performance of the catalyst was evaluated by recovery experiments, and a good result was obtained. By drawing comparisons with the literature reported, we provide a mild method for the synthesis of 2-tert-butyl-4-methylphenol.

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“…first reported a set of Bronsted acidic ionic liquids for acid promoted organic reactions . Since then, several research reports have been published on alkylation of phenol and alkyl phenols using these Bronsted acidic ionic liquids which function as both solvents and catalysts . However, literature reports on ionic liquid catalyzed alkylation of m‐ cresol with IPA are very few ,.…”

Section: Introductionmentioning

confidence: 99%

“…However, the potential of Lewis acidic ionic liquids was yet to be explored for efficient dehydration of IPA. Several attempts have been made to investigate the mechanism of similar alkylation reactions by correlating the product distribution with theoretical DFT and ab initio calculations . Zhou et al .…”

Section: Introductionmentioning

confidence: 99%

Synergistic Bronsted‐Lewis Acidity Effect on Upgrading Biomass‐Derived Phenolic Compounds: Statistical Optimization of Process Parameters, Kinetic Investigations and DFT Study

et al. 2018

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Biomass‐derived phenolic compounds and small oxygenates obtained from pyrolysis of lignocellulosic biomass needs to be upgraded to obtain the C10‐C13 range fuel precursors. In this context, iso‐propylation of m‐cresol was performed in batch reactors using multifunctional ionic liquids (ILs) as catalysts. Environmentally benign Bronsted‐Lewis acidic ILs were synthesized and characterized using 1H NMR, 13C NMR and Raman spectroscopic data. Relative Bronsted and Lewis acidity of these ILs were compared using UV‐Visible and FTIR spectroscopic data and the effect of acidity on the catalytic activity and product selectivity in alkylation of m‐cresol with iso‐propyl alcohol was investigated. Correlation of acidity and catalytic activity was confirmed by theoretical DFT study on IL structures. High conversion of m‐cresol (95.6%) was obtained using ZnCl2 containing IL, at 393 K temperature and 2:1:1 alcohol: m‐cresol: IL molar ratio, within 5 h of reaction time. The activity and recoverability of these ILs were retained even after 8 recycles. The effect of process parameters like reaction time, temperature, reactant mole ratio and catalyst to reactant mole ratio was investigated and optimized from design of experiments results. A plausible reaction mechanism was formulated based on the product distribution and a kinetic model was developed to estimate the activation energy (45.70 kJ mol−1) and pre‐exponential factor (247.78 lit. mol−1 min−1).

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Mechanistic insights into solvent induced alkylation of p-cresol with tert-butyl alcohol using Brönsted acidic ionic liquids

Cited by 13 publications

References 32 publications

Upgrading of HMF and Biomass‐Derived Acids into HMF Esters Using Bifunctional Ionic Liquid Catalysts under Solvent Free Conditions

Upgrading of HMF and Biomass‐Derived Acids into HMF Esters Using Bifunctional Ionic Liquid Catalysts under Solvent Free Conditions

An Efficient and Mild Method for the Alkylation of p-Cresol with tert-Butyl Alcohol

Synergistic Bronsted‐Lewis Acidity Effect on Upgrading Biomass‐Derived Phenolic Compounds: Statistical Optimization of Process Parameters, Kinetic Investigations and DFT Study

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