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. 2020 Aug 4;10(1):13103.
doi: 10.1038/s41598-020-69989-7.

Solid acid catalyzed carboxymethylation of bio-derived alcohols: an efficient process for the synthesis of alkyl methyl carbonates

Kempanna S Kanakikodi  1   2 , Sathyapal R Churipard  1   2 , A B Halgeri  1 , Sanjeev P Maradur  3
Affiliations

Solid acid catalyzed carboxymethylation of bio-derived alcohols: an efficient process for the synthesis of alkyl methyl carbonates

Kempanna S Kanakikodi et al. Sci Rep. .

Abstract

Acid catalyzed carboxymethylation of alcohols is an emerging organic transformation that has grabbed the attention of scientific community in recent years. In the present study, sulfonated mesoporous polymer (MP-SO3H) is presented as a highly active solid acid catalyst to convert a wide range of alcohols into alkyl methyl carbonates. The remarkable catalytic activity of MP-SO3H is comparable to that of reported homogeneous acid catalysts. A good correlation was established between the catalytic activity and textural properties of the material. An exceptional catalytic activity of MP-SO3H was observed for DMC mediated carboxymethylation of bio-derived alcohols which is unmatchable to conventional resins and zeolites. This superior activity of MP-SO3H is ascribed to its intrinsic mesoporosity, high acid strength and uniform coverage of surface area by active sites. The catalyst is recyclable, resistant towards leaching and can be used in successive runs without losing the original activity. To the best of our knowledge, MP-SO3H is the first solid acid catalyst to exemplify highest activity for the synthesis of different alkyl methyl carbonates using DMC. The protocol developed herein opens up new avenues to transform wide range of bio-alcohols into useful organic carbonates in the future.

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Conflict of interest statement

The authors declare no competing interests.

Figures

Scheme 1
Scheme 1
Reaction scheme for DMC mediated carboxymethylation.
Figure 1
Figure 1
Characterization data of MP-SO3H, (1.1) FTIR spectra of sulfonated mesoporous polymer (MP-SO3H-8), (1.2) Thermogravimetric analysis plot of MP and MP-SO3H-8, (1.3) (a) and (b) TEM-EDS images of MP-SO3H-8, (c) and (d) transmission electron micrographs of MP-SO3H-8, (1.4): 13C MAS NMR spectrum of MP-SO3H-8, (1.5): XPS measurements (a) XPS survey, (b) binding energy peak of S2p, (c) binding energy peak of C–C and C–S.
Figure 2
Figure 2
Effect of catalyst loading. Reaction conditions: Catalyst—MP-SO3H-8, butanol:DMC—6:60 mmol, reaction time—24 h, conversions were calculated with respect to the limiting reagent (butanol), reflux condition, BMC (butyl methyl carbonate).
Figure 3
Figure 3
Effect of mole ratio between the reactants. Reaction conditions: Catalyst—MP-SO3H-8, catalyst concentration—5 mol% (w.r.t butanol), reaction time—24 h, conversions were calculated with respect to the limiting reagent (butanol), reflux condition, BMC (butyl methyl carbonate).
Figure 4
Figure 4
Effect of reaction time. Reaction conditions: Catalyst—MP-SO3H-8, catalyst concentration—5 mol% (w.r.t Butanol), mole ratio—1:12.5 (butanol:DMC), conversions were calculated with respect to the limiting reagent (butanol), reflux condition, BMC (butyl methyl carbonate), DBC (dibutyl carbonate).
Figure 5
Figure 5
Plausible reaction mechanism for acid catalyzed carboxymethylation.
Figure 6
Figure 6
Leaching studies. Reaction conditions: Catalyst—MP-SO3H-8, catalyst concentration—5 mol% (w.r.t Butanol), mole ratio—1:12.5 (butanol:DMC), reaction time—8 h, conversions were calculated with respect to the limiting reagent (butanol), reflux condition.
Figure 7
Figure 7
Recyclability studies. Reaction conditions: Catalyst—MP-SO3H-8, catalyst concentration—5 mol% (w.r.t Butanol), mole ratio—1:10 (butanol:DMC), reaction time—24 h, conversions were calculated with respect to the limiting reagent (butanol), reflux condition, BMC (butyl methyl carbonate).
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