Novel alkali-promoted hydrotalcite for selective synthesis of 2-methoxy phenyl benzoate from guaiacol and benzoic anhydride

Abstract

Esters find several applications such as solvents, flavours and fragrants and intermediates in synthesis of drugs. In the present work, 2-methoxy phenyl benzoate was efficiently synthesized from guaiacol and benzoic anhydride by acylation. A variety of catalysts such as hydrotalcite and alkali-promoted hydrotalcite was synthesized. Potassium-promoted hydrotalcite (K/HT) calcined at 500 °C for 6 h was active, selective and reusable. It was characterized by different techniques. A slurry batch reactor was used to study reaction mechanism and kinetics. 2-Methoxy phenyl benzoate was efficiently obtained with 100% selectivity at guaiacol conversion of 98% over K/HT at 100 °C after 6 h. A power law model with second-order kinetics was fitted to obtain an apparent activation energy of reaction of 21.1 kcal mol−1. The process is clean and green.

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Scheme 1
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Scheme 2
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Abbreviations

A :

Reactant species A, guaiacol

B :

Reactant species B, benzoic anhydride

D :

Product species D, 2-methoxy phenyl benzoate

E :

Product species E, benzoic acid

AS 1 :

Chemisorbed guaiacol on vacant sites of type S 1

BS 2 :

Chemisorbed benzoic anhydride on vacant sites of type S 2

DS 2 :

Chemisorbed 2-methoxy phenyl benzoate on vacant sites of type S 2

ES 1 :

Chemisorbed benzoic acid on vacant sites of type S 1

C A :

Concentration of A, guaiacol (mol L−1)

\(C_{{A_{0} }}\) :

Initial concentration of A in bulk liquid phase (mol L−1)

\(C_{{AS_{1} }}\) :

Adsorption concentration of A on active site S 1 (mol g−1 of cat)

C B :

Concentration of B, benzoic anhydride (mol L−1)

\(C_{{B_{0} }}\) :

Initial concentration of B in bulk liquid phase (mol L−1)

\(C_{{BS_{2} }}\) :

Adsorption concentration of B on active site S 2 (mol g−1 of cat)

C D :

Concentration of D, 2-methoxy phenyl benzoate (mol L−1)

\(C_{{DS_{2} }}\) :

Concentration of D on active sites of type S 2 (mol g−1 of cat)

C E :

Concentration of E, benzoic acid (mol L−1)

\(C_{{ES_{1} }}\) :

Concentration of E on active sites of type S 1 (mol g−1 of cat)

\(C_{{S_{1} }}\) :

Concentration of vacant sites of type S 1 (mol g−1 of cat)

\(C_{{S_{2} }}\) :

Concentration of vacant sites of type S 2 (mol g−1of cat)

\(C_{{{\text{T}}_{1} }}\) :

Total concentration of vacant sites of type S 1 (mol g−1 of cat)

\(C_{{{\text{T}}_{2} }}\) :

Total concentration of vacant sites of type S 2 (mol g−1 of cat)

C T :

Total concentration of sites (mol g−1 of cat)

K A :

Adsorption constant for A (L mol−1)

K B :

Adsorption constant for B (L mol−1)

K D :

Adsorption constant for D (L mol−1)

K E :

Adsorption constant for E (L mol−1)

1/K D :

Desorption constant for D from catalyst site S 2 (L mol−1)

1/K E :

Desorption constant for E from catalyst site S 1 (L mol−1)

k 1 :

Forward reaction rate constant for surface reaction (L2 mol−1 s−1 g-cat−1)

\(k_{1}^{\prime }\) :

Backward reaction rate constant for surface reaction (L2 mol−1 s−1 g-cat−1)

k 2 :

Second-order rate constant (L mol−1 s−1)

M :

Molar ratio of \({{C_{{B_{0} }} } \mathord{\left/ {\vphantom {{C_{{B_{0} }} } {C_{{A_{0} }} }}} \right. \kern-0pt} {C_{{A_{0} }} }}\)

r A :

Rate of reaction (mol L−1 min−1)

w :

Catalyst loading (g L−1)

X A :

Fractional conversion of A

t :

Time (min)

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Acknowledgements

S.L.B. expresses thanks to the UGC for giving basic research (senior) fellowship. G.D.Y. acknowledges support from R. T. Mody Distinguished Professor Endowment of ICT and J. C. Bose National Fellowship of DST-GOI.

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Correspondence to Ganapati D. Yadav.

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Bhanawase, S.L., Yadav, G.D. Novel alkali-promoted hydrotalcite for selective synthesis of 2-methoxy phenyl benzoate from guaiacol and benzoic anhydride. Clean Techn Environ Policy 19, 1169–1180 (2017). https://doi.org/10.1007/s10098-016-1316-7

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Keywords

  • Guaiacol
  • Hydrotalcite
  • Catalyst Loading
  • Aromatic Ketone
  • Potassium Oxide