A highly
modular electrochemical flow cell and its application
in electroorganic synthesis is reported. This innovative setup facilitates
many aspects: an easy adjustment of electrode distance, quick exchange
of electrode material, and the possibility to easily switch between
a divided or undivided cell. However, the major benefit of the cell
is the exact thermal positioning of the electrode material into a
Teflon piece. Thereby, the application of expensive and nonmachinable
electrode materials like boron-doped diamond or glassy carbon can
easily be realized in flow cells. By this geometry, the maximum surface
of such valuable electrode materials is exploited. The cell size can
compete with classical preparative approaches in terms of performance
and productivity. The optimization of reaction parameters and an easy
up-scaling to larger flow cells is possible. By using this cell, the
starting material can be saved in the development of the electroorganic
transformations. To demonstrate the utility of this particular cell,
two transformations of important building blocks for the fine chemical
and pharmaceutical industry were established including an efficient
and simple workup protocol.
Lignin represents
the largest renewable resource of aromatic moieties
on earth and harbors a huge potential as a sustainable feedstock for
the synthesis of biobased aromatic fine chemicals. Due to the complex,
heterogeneous, and robust chemical structure of the biopolymer, the
valorization is associated with significant challenges. Unfortunately,
technical lignins, which are a large side stream of the pulp and paper
industries, are mainly thermally exploited. In this study, technical
Kraft lignin was selectively electrochemically depolymerized to the
aroma chemical vanillin. Using electricity, toxic and/or expensive
oxidizers could be replaced. The electrodegradation of Kraft lignin
was performed at 160 °C in a simple undivided high-temperature
electrolysis cell and studied in respect to several reaction parameters.
At optimized electrolytic conditions vanillin could be obtained in
high selectivity with 67% efficiency compared to the common nitrobenzene
oxidation. Additionally, the established high-temperature electrolysis
indicated a reliable process and could be easily adapted to a variety
of different Kraft lignins.
The successive scale-up of electrochemical reactions is crucial with regard to the implementation of technical electro-organic syntheses. Therefore, we developed a scalable modular parallel-plate electrochemical flow cell. One distinctive feature of this flow cell is that the temperature of the electrodes can be easily controlled from the back side via an external cooling circuit, enabling high reproducibility of electrochemical conversions. Because the gap between the electrodes is kept narrow, small amounts or no supporting electrolyte is required. The practicability and performance of the novel flow cell were validated by three different anodic phenol−phenol cross-couplings as test reactions.
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