Electrocarboxylation of acetophenone in ionic liquids: the influence of proton availability on product distribution

Green Chemistry Pub Date: 2014-01-06 DOI: 10.1039/C3GC42404A

Abstract

The electroreduction of acetophenone has been investigated in two dry ionic liquids (1-butyl-2,3-dimethylimidazolium tetrafluoroborate ([BMMIM][BF4]; [H2O] = 9.2 mM) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([BMPyrd][TFSI]; [H2O] = 1.0 mM)) under both N2 and CO2 atmospheres using transient cyclic voltammetry, near steady-state voltammetry, the bulk electrolysis technique and numerical simulations. The proton availability in both solvents is low. In these dry ionic liquids under a N2 atmosphere, the sole reduction product detected is a dimer. The rate constants for dimer formation determined by comparison of experiment and simulation are 5.0 × 104 M?1 s?1 and 4.0 × 103 M?1 s?1, in [BMMIM][BF4] and [BMPyrd][TFSI], respectively. In dry [BMMIM][BF4] under a CO2 atmosphere, the products of the electroreduction of acetophenone are mixtures of 2-hydroxy-2-phenylpropionic acid, 1-phenylethanol and dimers. By contrast, the major reduction product in dry [BMPyrd][TFSI] is 2-hydroxy-2-phenylpropionic acid, suggesting that this ionic liquid is a suitable medium for electrocarboxylation. In water saturated [BMPyrd][TFSI] ([H2O] = 0.63 M), dimers are the major products under both N2 and CO2 atmospheres. The dimerization rate constant determined for this reaction under a N2 atmosphere was 1.0 × 107 M?1 s?1; more than three orders of magnitude higher than that found in dry [BMPyrd][TFSI]. Presumably strong interactions between the acetophenone radical anions and water through an extensive hydrogen bonding network lead to a larger degree of charge delocalization and thus favour dimer formation.

Graphical abstract: Electrocarboxylation of acetophenone in ionic liquids: the influence of proton availability on product distribution
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