Electrocarboxylation of acetophenone in ionic liquids: the influence of proton availability on product distribution
文献信息
Mike Horne, Alan M. Bond, Jie Zhang
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.
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Green Chemistry

Green Chemistry provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on, but not limited to, the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998). Green chemistry is the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry is at the frontiers of this continuously-evolving interdisciplinary science and publishes research that attempts to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. Submissions on all aspects of research relating to the endeavour are welcome. The journal publishes original and significant cutting-edge research that is likely to be of wide general appeal. To be published, work must present a significant advance in green chemistry. Papers must contain a comparison with existing methods and demonstrate advantages over those methods before publication can be considered. For more information please see this Editorial. Coverage includes the following, but is not limited to: Design (e.g. biomimicry, design for degradation/recycling/reduced toxicity…) Reagents & Feedstocks (e.g. renewables, CO2, solvents, auxiliary agents, waste utilization…) Synthesis (e.g. organic, inorganic, synthetic biology…) Catalysis (e.g. homogeneous, heterogeneous, enzyme, whole cell…) Process (e.g. process design, intensification, separations, recycling, efficiency…) Energy (e.g. renewable energy, fuels, photovoltaics, fuel cells, energy storage, energy carriers…) Applications (e.g. electronics, dyes, consumer products, coatings, pharmaceuticals, preservatives, building materials, chemicals for industry/agriculture/mining…) Impact (e.g. safety, metrics, LCA, sustainability, (eco)toxicology…) Green chemistry is, by definition, a continuously-evolving frontier. Therefore, the inclusion of a particular material or technology does not, of itself, guarantee that a paper is suitable for the journal. To be suitable, the novel advance should have the potential for reduced environmental impact relative to the state of the art. Green Chemistry does not normally deal with research associated with 'end-of-pipe' or remediation issues.










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