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Selective monoalkylation of hydroquinone in the presence of SO3H-functionalized ionic liquids as catalysts

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Abstract

A process aiming at O-alkylation of hydroquinone (HQ), where ionic liquids (ILs) act as catalyst is objectively described. Five SO3H-functionalized ILs having different cations were prepared and characterized by NMR and FTIR techniques. The acidity and thermal stability of ILs were determined by Hammett function and thermogravimetric analysis (TGA), respectively. The catalytic activity of these ILs were tested for O-alkylation of HQ with methanol in 4-methoxyphenol (4MP) in the presence of small amount of benzoquinone (BQ). The effect of reaction parameters such as temperature, time, catalyst loading and substrate concentration on the conversion of HQ and product distribution was examined and optimized to maximize the yield of 4MP using 1,3-disulfonic acid imidazolium hydrogen sulfate (IL2) catalyst. Maximum yield of desired product 4MP 93.79% was obtained at 338 K temperature, 5.45 × 10–2 mol HQ, 8.33 × 10–3 mol BQ, and 10.37 mol% catalyst loading in 120 min reaction time. Single-product formation was observed up to 338 K temperature but higher temperature (above 338 K) and longer reaction time resulted in the formation of 2,4-dimethoxyphenol (24DMP) as a by-product. Catalyst recyclability was also established up to the fifth run which showed no declination in its activity.

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Abbreviations

HQ:

Hydroquinone

BQ:

Benzoquinone

4MP:

4-Methoxyphenol

24DMP:

2,4-Dimethoxyphenol

IL:

Ionic liquid

IL1:

1-(4-Sulfonic acid) butyl-3-methylimidazolium hydrogen sulfate

IL2:

1,3-Disulfonic acid imidazolium hydrogen sulfate

IL3:

3-Methyl-1-sulfonic acid-imidazolium hydrogen sulfate

IL4:

1-(4-Sulfonic acid) butylpyridinium hydrogen sulfate

IL5:

N-(4-Sulfonic acid) butyl triethylammonium hydrogen sulfate

H2SO4 :

Sulfuric acid

DMSO-d6:

Deuterated dimethyl sulfoxide

FTIR:

Fourier-transform infrared

NMR:

Nuclear magnetic resonance

TGA:

Thermogravimetric analysis

KBr:

Potassium bromide

H0 :

Hammett acidity

min:

Minute

mg:

Milligram

K:

Kelvin

mM:

Millimolar

µM:

Micromolar

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Acknowledgements

Priyanka Bhongale acknowledges the support from Council of Scientific and Industrial Research (CSIR), India, for providing Senior Research Fellowship (SRF). The authors thank Academy of Scientific & Innovative Research (AcSIR) and CSIR-National Chemical Laboratory for additional support. We thank Dr. Subhash Chavan for valuable help.

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Authors and Affiliations

  1. Chemical Engineering and Process Development Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune, 411008, India

    Priyanka V. Bhongale, Sunil S. Joshi & Nilesh A. Mali

  2. Academy of Scientific and Innovative Research (AcSIR), CSIR-Human Resource Development Centre, Campus Postal Staff College Area, Ghaziabad, 201002, India

    Priyanka V. Bhongale, Sunil S. Joshi & Nilesh A. Mali

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  1. Priyanka V. Bhongale
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Correspondence to Sunil S. Joshi.

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Bhongale, P.V., Joshi, S.S. & Mali, N.A. Selective monoalkylation of hydroquinone in the presence of SO3H-functionalized ionic liquids as catalysts. Chem. Pap. 74, 4461–4471 (2020). https://doi.org/10.1007/s11696-020-01230-1

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